Method for treating copper-containing etching waste liquid

Abstract

The invention relates to the technical field of chemical engineering, and provides a method for treating a copper-containing etching waste liquid, and the method for treating the copper-containing etching waste liquid comprises the following steps: S1, mixing an etching liquid with ammonia water; s2, stirring and carrying out reaction treatment; s4, carrying out filter pressing treatment; s5, evaporating and crystallizing the second filtrate; the method comprises the following steps: mixing a copper-containing alkaline etching solution with ammonia water with a certain concentration to obtain a stable alkaline copper-nitrogen etching solution; the method comprises the following steps: mixing the copper-containing acidic etching waste liquid with an alkaline copper ammonia etching liquid, and carrying out suction filtration, washing and suction filtration to obtain a basic copper chloride product and a first filtered liquid; mixing the solution with sodium sulfide, diluted hydrochloric acid and a flocculating agent, and carrying out filter pressing to obtain a copper sulfide product and a second filtered solution; and evaporating and condensing the second filtered liquid to obtain the product refined ammonium chloride. According to the technical scheme, the problems that an existing treatment method for recycling the copper-containing etching waste liquid adopts iron powder for replacement, the process is simple, operation is easy, and the defect is that discharged waste water and waste gas pollute the environment are solved.

Description

Technical Field

[0001] The present invention relates to the field of chemical engineering technology, and specifically, to a method for treating copper-containing etching waste liquid. Background Art

[0002] Copper-containing etching waste liquid is acidic and alkaline etching waste liquid generated after the etching process, and its main components are Cu 2+ , Cl - , NH 4+ etc.; it is discarded because it cannot meet the requirements of the industrial production etching process and is listed in the national hazardous waste list. If it is directly discharged without treatment, it will not only cause serious environmental pollution but also result in a huge waste of resources;

[0003] After retrieval, for the method for treating copper-containing etching waste liquid with the authorized announcement number of CN109319823B, this method mixes acidic etching waste liquid with a first pH regulator, hydrogen peroxide, and a first flocculant and filters to obtain a copper chloride solution; mixes alkaline etching waste liquid with a second pH regulator, magnesium chloride, and a second flocculant and filters to obtain a copper ammonia solution; mixes a part of the copper chloride solution, a part of the copper ammonia solution, and ammonia water, presses, washes, and presses again to obtain a third filter cake and a first filtrate after filtration; beats the third filter cake to obtain a fourth mixed solution; mixes concentrated sulfuric acid and the fourth mixed solution and cools to obtain copper sulfate pentahydrate crystals; filters and dehydrates the copper sulfate pentahydrate crystals to obtain copper sulfate products; mixes another part of the copper chloride solution, another part of the copper ammonia solution, and ammonia water and dehydrates to obtain basic copper chloride hydrate and a second filtrate after filtration; dries the basic copper chloride hydrate to obtain basic copper chloride; mixes the first filtrate after filtration, the second filtrate after filtration, and an alkaline solution to obtain an alkaline etching solution;

[0004] However, the current treatment method for the recovery of copper-containing etching waste liquid is to displace it with iron powder. This method has a simple process and is easy to operate, but the disadvantage is that the discharged wastewater and waste gas pollute the environment. For this reason, we have proposed a method for treating copper-containing etching waste liquid. Summary of the Invention

[0005] The present invention proposes a method for treating copper-containing etching waste liquid, which solves the problem that the existing treatment method for the recovery of copper-containing etching waste liquid in the background art is to displace it with iron powder. This method has a simple process and is easy to operate, but the disadvantage is that the discharged wastewater and waste gas pollute the environment.

[0006] The technical solution of the present invention is as follows:

[0007] A method for treating copper-containing etching waste liquid, the treatment method comprising the following steps:

[0008] S1. Mix the copper-containing alkaline etching solution with ammonia water;

[0009] S2. Stir, react, filter by suction, wash, and then filter by suction to obtain a first filtrate and basic copper chloride;

[0010] S3. React by adding a sodium sulfide solution and dilute hydrochloric acid;

[0011] S4. Press-filter to obtain copper sulfide products and a second filtered liquid;

[0012] S5. Evaporate and crystallize the second filtered liquid to obtain refined ammonium chloride;

[0013] The device for reaction stirring is a mixing device. The mixing device includes a bracket. The outer surface of the bracket is fixedly connected with a mixing box. The center of the mixing box is rotatably connected with a central shaft. The outer surface of the central shaft is connected with a stirring structure. The outer surface of the mixing box is connected with an aeration structure. The inside of the mixing box is connected with a feeding structure;

[0014] The stirring structure is used to adjust the stirring length of the stirring member. The aeration structure includes an air inlet pipe fixedly connected to the outer surface of the mixing box. The inner end of the air inlet pipe is fixedly connected with a fixed ring. The lower end of the fixed ring is rotatably connected with a rotating ring. The lower end of the rotating ring is fixedly connected with a connecting pipe. The lower end of the connecting pipe is fixedly connected with an aeration ring. The inner side of the connecting pipe is fixedly connected with an adapter ring. The inner side of the adapter ring is fixedly connected with a baffle. Air is injected through the air inlet pipe for aeration. When the stirring structure rotates to the maximum length, it drives the baffle to rotate, realizing the common rotation of the baffle, the adapter ring, the connecting pipe, the aeration ring and the rotating ring;

[0015] The feeding structure is used to evenly supply materials while cooperating with the rotation of the stirring structure for stirring.

[0016] As a further technical solution of the present invention, S1 specifically includes: mixing a copper-containing alkaline etching solution with ammonia water; wherein copper in the alkaline etching solution exists in the form of copper ammine complex ions. After mixing with ammonia water, the ammonia concentration increases, which is used to further stabilize the copper ammine complex ions, inhibit the precipitation of copper, and maintain the dissolution ability and stability of the etching solution;

[0017] S2 specifically includes: mixing a copper-containing acidic etching solution with a basic copper ammine etching solution at 50°C to 60°C, adjusting the pH value between 9.5 and 10.5, allowing them to react fully, then performing suction filtration, washing, and then suction filtration again to obtain the product basic copper chloride and a first filtered liquid;

[0018] The reaction formula is: 2[Cu(NH)] 2+ +3H2O+Cl - →Cu2(OH)3Cl↓+4NH4 + +NH3↑;

[0019] This reaction needs to control the pH and temperature to avoid excessive dissolution;

[0020] S3 specifically includes: The first filtered liquid mainly contains HN4Cl and trace amounts of Cu 2+ , sodium sulfide solution is added to generate Cu2S precipitate, and then dilute hydrochloric acid is added to inhibit the hydrolysis of S 2+ , avoiding the generation of toxic gas H2S and ensuring the complete precipitation of Cu 2+ ;

[0021] The reaction formula is: ZCu + +S 2- →Cu2S↓;

[0022] S4 specifically includes: Pressuring and filtering this mixed solution to obtain copper sulfide products and the second filtered liquid NH4Cl;

[0023] S5 specifically includes: Evaporating, condensing and crystallizing the second filtered liquid NH4Cl to obtain refined ammonium chloride.

[0024] As a further technical solution of the present invention, the stirring structure includes a stirring frame fixedly connected to the outer surface of the central shaft. A chute is provided on the surface of one end of the stirring frame away from the central shaft. A sliding frame is slidably connected to the inner side of the stirring frame. A reinforcing plate is fixedly connected to the outer end of the sliding frame. A spring is connected between the inner end of the sliding frame and the inner wall of the stirring frame. A heating pipe for heating the inside of the mixing box is fixedly connected inside the mixing box. A second discharge pipe is fixedly connected to the lower end of the mixing box. A solenoid valve is fixedly connected to the outer surface of the second discharge pipe.

[0025] As a further technical solution of the present invention, a stirring motor for driving the rotation of the central shaft is fixedly connected to the outer surface of the bracket. The rotation speed of the stirring motor is adjusted by a frequency converter. A first hopper and a second hopper are respectively arranged on both sides of the bracket. Feeding pipes are fixedly connected between the first hopper and the second hopper and the mixing box. The feeding structure includes a feeding ring fixedly connected between the lower end of the feeding pipe corresponding to the first hopper and the inner wall of the lower end of the mixing box. The lower end of the feeding ring is rotatably connected with a discharging ring. A first discharge pipe is fixedly connected to the lower end of the discharging ring. The central shaft is divided into upper and lower parts, and the upper and lower parts are plug-in structures. The stirring structure is arranged on the lower half of the central shaft. A connecting column is fixedly connected to the lower end of the upper half of the central shaft. A connecting groove is provided at the upper end of the lower half of the central shaft. A telescopic cylinder is fixedly connected to the lower end of the mixing box corresponding to the lower half of the central shaft.

[0026] As a further technical solution of the present invention, an annular slide rail and a slider are fixedly connected to the inner wall surface of the mixing box. There is a connection between the annular slide rail, the slider and the aeration ring. The aeration ring is fixedly connected by screws. It slides along the length direction of the slider of the annular slide rail.

[0027] As a further technical solution of the present invention, the intake pipe is connected to the inside of the fixed ring, a mechanical seal is provided between the rotating ring and the fixed ring, the number of the connecting pipes is several groups and they are distributed in an annular array, and the smaller the distance between the connecting pipes and the intake pipe, the smaller the opening through which the connecting pipes communicate with the rotating ring.

[0028] As a further technical solution of the present invention, the number of the connecting rings is several groups and they are vertically spaced apart. The connecting rings are used to connect several groups of connecting pipes. The baffle is connected to the inner side of the connecting ring near the connecting pipes, and the aeration ring is in a circular ring structure.

[0029] As a further technical solution of the present invention, one end of the stirring frame is in a comb-like structure. The sliding groove is opened inside the comb teeth. The sliding frame together with the reinforcing plate is swung outward by the centrifugal force generated by the rotation of the stirring frame, and the spring is used to pull to prevent the sliding frame from disengaging from the inside of the sliding groove.

[0030] As a further technical solution of the present invention, a mechanical seal is provided between the discharge ring and the feeding ring. The guide pipe corresponding to the first hopper is connected to the inside of the feeding ring. The guide pipe corresponding to the second hopper is directly connected to the inside of the mixing tank. The first discharge pipe is connected to the discharge ring, and the number of the first discharge pipes is several groups and they are distributed in an annular array.

[0031] As a further technical solution of the present invention, the connecting post is in a regular quadrangular prism structure. The opening shape of the connecting groove matches that of the connecting post. The output end of the telescopic cylinder is embedded inside the lower half of the central shaft, and the output end of the telescopic cylinder is rotatably connected to the central shaft through a bearing.

[0032] The method for treating copper-containing etching waste liquid provided by the present invention has low energy consumption, the copper recovery rate can reach more than 99%, stable basic salts are generated, ammonium chloride can be regenerated and refined at the same time, and the process wastewater can meet the discharge standards, with remarkable economic, social and environmental benefits.

[0033] The working principle and beneficial effects of the present invention are as follows:

[0034] 1. The method for treating copper-containing etching waste liquid provided by the present invention has low energy consumption, the copper recovery rate can reach more than 99%, stable basic salts are generated, ammonium chloride can be regenerated and refined at the same time, and the process wastewater can meet the discharge standards, with remarkable economic, social and environmental benefits.

[0035] 2. Through the action of the stirring structure of the present invention, the stirring range of the stirring structure can be automatically adjusted according to the rotation speed of the central shaft, so as to achieve a better stirring and mixing effect, promote the reaction process, and can be freely adjusted according to the actual needs of the user, realizing the purpose of adjustable stirring effect. Description of the Drawings

[0036] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0037] Figure 1 It is a flow chart of the method for treating copper-containing etching waste liquid of the present invention;

[0038] Figure 2 It is a schematic structural diagram of the mixing device in the method for treating copper-containing etching waste liquid of the present invention;

[0039] Figure 3 For the present invention Figure 2 partial structural schematic diagram;

[0040] Figure 4 For the present invention Figure 2 partial structural schematic diagram of the mixing tank cut open;

[0041] Figure 5 For the present invention Figure 3 partial structural schematic diagram of the stirring structure cut open;

[0042] Figure 6 For the present invention Figure 3 partial structural schematic diagram of the upper half of the aeration structure cut open;

[0043] Figure 7 For the present invention Figure 3 partial structural schematic diagram of the lower half of the aeration structure cut open;

[0044] Figure 8 For the present invention Figure 3 partial structural schematic diagram of the feeding ring cut open;

[0045] Figure 9 For the present invention Figure 3 partial structural schematic diagram of the area near the telescopic cylinder cut open.

[0046] In the figure: 1, support; 2, mixing tank; 3, first hopper; 4, second hopper; 5, central shaft; 6, guide pipe; 7, stirring structure; 71, stirring frame; 72, chute; 73, sliding frame; 74, reinforcing plate; 75, spring; 8, aeration structure; 81, intake pipe; 82, fixed ring; 83, rotating ring; 84, connecting pipe; 85, aeration ring; 86, connecting ring; 87, baffle; 88, annular slide rail; 89, slider; 9, material spreading structure; 91, feeding ring; 92, discharging ring; 93, first discharging pipe; 94, connecting groove; 95, connecting column; 96, telescopic cylinder; 10, heating pipe; 11, stirring motor; 12, second discharging pipe; 13, solenoid valve. Specific embodiments

[0047] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0048] Example 1

[0049] As Figure 1 shown, this embodiment proposes a method for treating copper-containing etching waste liquid. The treatment method includes the following steps:

[0050] S1. Mix the copper-containing alkaline etching solution with ammonia water;

[0051] S2. Stir, react, perform suction filtration, washing, and then suction filtration to obtain a first filtrate and basic copper chloride;

[0052] S3. React by adding a sodium sulfide solution and dilute hydrochloric acid;

[0053] S4. Perform pressure filtration to obtain a copper sulfide product and a second filtered liquid;

[0054] S5. Evaporate and crystallize the second filtered liquid to obtain refined ammonium chloride;

[0055] S1 specifically includes: Mix the copper-containing alkaline etching solution with ammonia water; wherein the copper in the alkaline etching solution exists in the form of copper ammine complex ions. After mixing with ammonia water, the ammonia concentration increases, which is used to further stabilize the copper ammine complex ions, inhibit the precipitation of copper, and maintain the solubility and stability of the etching solution;

[0056] S2 specifically includes: Mix and stir the copper-containing acidic etching solution with the alkaline copper ammine etching solution at 50 °C to 60 °C, adjust the pH value between 9.5 and 10.5, allow them to react fully, and then perform suction filtration, washing, and then suction filtration to obtain the product basic copper chloride and a first filtered liquid;

[0057] The reaction formula is: 2[Cu(NH)] 2+ +3H2O+Cl - →Cu2(OH)3Cl↓+4NH4 + +NH3↑;

[0058] This reaction needs to control the pH and temperature to avoid excessive dissolution;

[0059] S3 specifically includes: The first filtered liquid mainly contains HN4Cl and trace amounts of Cu 2+ , add a sodium sulfide solution to form a Cu2S precipitate, and then add dilute hydrochloric acid to inhibit the hydrolysis of S 2+ , avoid generating toxic gas H2S, and ensure the complete precipitation of Cu 2+ ;

[0060] The reaction formula is: ZCu + +S 2- →Cu2S↓;

[0061] Specifically, S4 includes: pressure-filtering this mixed solution to obtain copper sulfide products and the second filtered liquid NH4Cl;

[0062] Specifically, S5 includes: evaporating, condensing and crystallizing the second filtered liquid NH4Cl to obtain refined ammonium chloride.

[0063] In this embodiment, the method has low energy consumption, the copper recovery rate can reach more than 99%, stable basic salts are generated, refined ammonium chloride can be regenerated at the same time, and the process wastewater can meet the discharge standards, with remarkable economic, social and environmental benefits.

[0064] Example 2

[0065] As Figures 2 to 5 shown, on the basis of Example 1, in this embodiment, the reaction stirring equipment proposed is a mixing device, and the mixing device includes a bracket 1. A mixing tank 2 is fixedly connected to the outer surface of the bracket 1. A central shaft 5 is rotationally connected to the center of the mixing tank 2. A stirring structure 7 is connected to the outer surface of the central shaft 5. An aeration structure 8 is connected to the outer surface of the mixing tank 2. A feeding structure 9 is connected to the inside of the mixing tank 2;

[0066] The stirring structure 7 is used to adjust the stirring length of the stirring member. The stirring structure 7 includes a stirring frame 71 fixedly connected to the outer surface of the central shaft 5. A chute 72 is provided on the surface of one end of the stirring frame 71 away from the central shaft 5. A sliding frame 73 is slidably connected to the inside of the stirring frame 71. A reinforcing plate 74 is fixedly connected to the outer end of the sliding frame 73. A spring 75 is connected between the inner end of the sliding frame 73 and the inner wall of the stirring frame 71. A heating pipe 10 for heating the inside of the mixing tank 2 is fixedly connected to the inside of the mixing tank 2. A second discharge pipe 12 is fixedly connected to the lower end of the mixing tank 2. An electromagnetic valve 13 is fixedly connected to the outer surface of the second discharge pipe 12.

[0067] One end of the stirring frame 71 is a comb-like structure, and the chute 72 is opened inside the comb teeth. The sliding frame 73 together with the reinforcing plate 74 is swung outward by the centrifugal force of the rotation of the stirring frame 71, and the spring 75 is used to pull to prevent the sliding frame 73 from disengaging outward from the inside of the chute 72.

[0068] In this embodiment, the stirring range of the stirring structure 7 can be automatically adjusted according to the rotation speed of the central shaft 5, so as to achieve a better stirring and mixing effect, promote the reaction process, and can be freely adjusted according to the actual needs of the user, realizing the purpose of adjustable stirring effect.

[0069] Example 3

[0070] As Figures 6 to 7 shown, based on Embodiment 2, this embodiment proposes that the aeration structure 8 includes an air inlet pipe 81 fixedly connected to the outer surface of the mixing tank 2. The inner end of the air inlet pipe 81 is fixedly connected with a fixed ring 82. The lower end of the fixed ring 82 is rotatably connected with a rotating ring 83. The lower end of the rotating ring 83 is fixedly connected with a connecting pipe 84. The lower end of the connecting pipe 84 is fixedly connected with an aeration ring 85. The inner side of the connecting pipe 84 is fixedly connected with an adapter ring 86. The inner side of the adapter ring 86 is fixedly connected with a baffle 87. Air is injected through the air inlet pipe 81 for aeration. When the stirring structure 7 rotates to the maximum length, it drives the baffle 87 to rotate, realizing the common rotation of the baffle 87, the adapter ring 86, the connecting pipe 84, the aeration ring 85 and the rotating ring 83;

[0071] The feeding structure 9 is used to uniformly supply materials while cooperating with the rotation of the stirring structure 7 for stirring.

[0072] The inner wall surface of the mixing tank 2 is fixedly connected with an annular slide rail 88. A slider 89 is connected between the annular slide rail 88 and the aeration ring 85. The aeration ring 85 is fixedly connected with the slider 89 by screws. The slider 89 slides along the length direction of the annular slide rail 88. The air inlet pipe 81 is communicated with the inside of the fixed ring 82. A mechanical seal is provided between the rotating ring 83 and the fixed ring 82. The number of the connecting pipes 84 is several groups and is distributed in a circular array. And the smaller the distance between the connecting pipe 84 and the air inlet pipe 81 is, the smaller the opening through which the connecting pipe 84 communicates with the rotating ring 83 is. The number of the adapter rings 86 is several groups and is vertically spaced. The adapter rings 86 are used to connect several groups of connecting pipes 84. The baffle 87 is connected to the inner side of the adapter ring 86 near the connecting pipe 84. The aeration ring 85 is of a circular ring structure.

[0073] In this embodiment, during the process of the stirring structure 7 mixing and stirring the internal solution of the mixing tank 2, the mixing effect can be enhanced by means of aeration. At the same time, according to the adjustment of the rotation speed of the stirring structure 7, the aeration ring 85 for aeration can be made to rotate synchronously with the rotating stirring structure 7, so as to achieve a better aeration effect and improve the mixing effect.

[0074] Embodiment 4

[0075] As Figures 8 to 9As shown, on the basis of Example 3, this embodiment proposes that the outer surface of the bracket 1 is fixedly connected with a stirring motor 11 for driving the central axis 5 to rotate, and the stirring motor 11 adjusts the speed through a frequency converter. A No. 1 hopper 3 and a No. 2 hopper 4 are respectively arranged on both sides of the bracket 1, and a guide pipe 6 is fixedly connected between the No. 1 hopper 3 and the No. 2 hopper 4 and the mixing box 2. The spreading structure 9 includes a feeding ring 91 fixedly connected between the lower end of the guide pipe 6 corresponding to the No. 1 hopper 3 and the inner wall of the lower end of the mixing box 2, and the lower end of the feeding ring 91 is rotatably connected with a discharge ring 92, and the lower end of the discharge ring 92 is fixedly connected with a No. 1 discharge pipe 93, the central axis 5 is divided into an upper and lower part, and the upper and lower parts are plug-in structures, the stirring structure 7 is arranged at the lower half of the central axis 5, the lower end of the upper half of the central axis 5 is fixedly connected with a connecting column 95, and the upper end of the lower half of the central axis 5 is provided with a connecting groove 94, and the lower end of the mixing box 2 is fixedly connected with a telescopic cylinder 96 corresponding to the lower half of the central axis 5.

[0076] There is a mechanical seal between the discharge ring 92 and the feed ring 91, the guide pipe 6 corresponding to the No. 1 hopper 3 is connected to the interior of the feed ring 91, the guide pipe 6 corresponding to the No. 2 hopper 4 is directly connected to the interior of the mixing box 2, the No. 1 discharge pipe 93 is connected to the discharge ring 92, and the number of No. 1 discharge pipes 93 is several groups and distributed in a ring array; the connecting column 95 is a regular quadrangular prism structure, the opening shape of the connecting groove 94 matches the connecting column 95, the output end of the telescopic cylinder 96 is embedded in the lower half of the central shaft 5, and the output end of the telescopic cylinder 96 is rotatably connected to the central shaft 5 through a bearing.

[0077] In this embodiment, the method of adding ammonia water to the etching liquid can be adjusted. The ammonia water can be dripped directly downward from the No. 1 discharge pipe 93, or the No. 1 discharge pipe 93 can be rotated by the stirring frame 71 to allow the ammonia water to be added to the etching liquid more quickly and evenly, thereby effectively improving the stirring and mixing effect and making the reaction between the two faster and more complete.

[0078] In summary, the use principle of the present invention is as follows:

[0079] S1 specifically includes: mixing a copper-containing alkaline etching solution with ammonia water; wherein the copper in the alkaline etching solution exists in the form of copper-ammonia-chromium ions, and after mixing with ammonia water, the ammonia concentration increases, which is used to further stabilize the copper-ammonia complex ions, inhibit copper precipitation, and maintain the solubility and stability of the etching solution; when used, the user first pours the etching solution into the interior of the mixing box 2 through the second hopper 4;

[0080] S2 specifically includes: mixing the copper-containing acidic etching solution and the alkaline copper ammonia etching solution at 50°C to 60°C, stirring, adjusting the pH value to be between 9.5 and 10.5, allowing them to react fully, then performing suction filtration, washing, and then suction filtration again to obtain the product basic copper chloride and the first filtrate; in specific use, first control the temperature to the stirring temperature, which is achieved by heating with the heating tube 10. Then, slowly pour an appropriate amount of ammonia water from the inside of the first hopper 3, supply the ammonia water through the spreading structure 9, and while supplying, drive the central shaft 5 to rotate by the stirring motor 11, and perform stirring and mixing through the stirring structure 7. While stirring and mixing, perform aeration operation through the aeration structure 8 to promote the mixing process. When needed, promote the operation effects of the aeration structure 8 and the spreading structure 9 by the stirring structure 7 separately or simultaneously in cooperation with the aeration structure 8 and the spreading structure 9;

[0081] The reaction formula is: 2[Cu(NH)] 2+ +3H2O+Cl - →Cu2(OH)3Cl↓+4NH4 + +NH3↑;

[0082] This reaction needs to control the pH and temperature to avoid excessive dissolution;

[0083] S3 specifically includes: The first filtrate mainly contains HN4Cl and trace amounts of Cu 2+ , adding a sodium sulfide solution to form a Cu2S precipitate, and then adding dilute hydrochloric acid to inhibit the hydrolysis of S 2+ to avoid generating toxic H2S gas and ensure the complete precipitation of Cu 2+ ;

[0084] The reaction formula is: ZCu + +S 2- →Cu2S↓;

[0085] S4 specifically includes: filtering this mixed solution under pressure to obtain the copper sulfide product and the second filtrate NH4Cl;

[0086] S5 specifically includes: evaporating, condensing, and crystallizing the second filtrate NH4Cl to obtain refined ammonium chloride.

[0087] During the use of the stirring structure 7, the central shaft 5 is driven to rotate by the stirring motor 11, and the stirring frame 71 is driven to rotate by the central shaft 5. The rotation of the stirring frame 71 drives the sliding frame 73 together with the reinforcing plate 74 to rotate. At this time, under the action of centrifugal force, the sliding frame 73 can stretch the spring 75 to expand a part. At this time, the overall stirring member composed of the stirring frame 71, the sliding frame 73, and the reinforcing plate 74 becomes larger, and the area that can be stirred is larger, which can achieve a better stirring effect. And according to the rotation speed of the central shaft 5, different stirring effects of the stirring structure 7 can be adjusted, so as to form a better mixing and reaction effect;

[0088] During the process of the stirring structure 7 mixing and stirring ammonia water and etching solution, air can be injected into the interior of the air inlet pipe 81 through an air pump. The air flows through the air inlet pipe 81 into the interior of the fixed ring 82, then enters the interior of the rotating ring 83 via the fixed ring 82, and then enters the interior of the connecting pipe 84 from the rotating ring 83. Finally, it enters the interior of the aeration ring 85 through the connecting pipe 84 for aeration. The structural design that the closer the connecting pipe 84 is to the air inlet pipe 81, the smaller the communication opening with the rotating ring 83 can make the air flow injected into the interior of the aeration ring 85 more uniform, thereby making the aeration effect better. And at the maximum rotational speed of the central shaft 5, the reinforcing plate 74 pulls the sliding frame 73 to move outward to the maximum distance, and the reinforcing plate 74 will be blocked by the connecting ring 86. At the same time, the reinforcing plate 74 will push the baffle plate 87, causing the baffle plate 87, together with the connecting pipe 84, the connecting pipe 84, the connecting ring 86, and the connecting pipe 84, to rotate, so that the aeration ring 85 for aeration rotates, which can make the aeration effect better. And through the action of the slider 89 and the annular slide rail 88, the rotational aeration of the aeration ring 85 can be made more stable and reliable;

[0089] During the process of adding ammonia water, the ammonia water entering from the first hopper 3 will enter the interior of the guide pipe 6. The ammonia water is poured into the interior of the feeding ring 91 through the guide pipe 6, flows into the interior of the discharging ring 92 via the feeding ring 91, and finally flows into the interior of the mixing tank 2 through the first discharging pipe 93 to be mixed with the etching solution. During the mixing process, it is synchronously stirred by the stirring structure 7 to complete the mixing. When it is necessary to enhance the mixing effect, the user can control the telescopic cylinder 96 to extend. The output end of the telescopic cylinder 96 pushes the lower half of the central shaft 5 upward. The lower half of the central shaft 5 moves upward by a certain distance, so that the rotation of the stirring frame 71 can push the first discharging pipe 93, causing the first discharging pipe 93 and the discharging ring 92 to rotate relative to the feeding ring 91. The ammonia water is thrown into the etching solution in the interior of the mixing tank 2 by the rotation of the first discharging pipe 93, so that the mixing effect is better. Combined with the existing stirring and aeration effects, the final mixing can be made faster and the reaction effect is better;

[0090] At the same time, the telescopic cylinder 96 can be periodically pushed and contracted, which can achieve the effect of differential speed between the rotational supply of ammonia water by the first discharging pipe 93 and the stirring of the stirring structure 7, and further can make the mixing and stirring effect better.

[0091] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for treating copper-containing etching waste liquid, characterized in that, The treatment method includes the following steps: S1. Mix the copper-containing alkaline etching solution with ammonia water; S2. Stir, react, perform suction filtration, washing, and then suction filtration to obtain a first filtrate and basic copper chloride; S3. React by adding a sodium sulfide solution and dilute hydrochloric acid; S4. Perform pressure filtration to obtain a copper sulfide product and a second filtrate; S5. Evaporate and crystallize the second filtrate to obtain refined ammonium chloride; The device for reaction stirring is a mixing device. The mixing device includes a support (1). The outer surface of the support (1) is fixedly connected with a mixing tank (2). The center of the mixing tank (2) is rotatably connected with a central shaft (5). The outer surface of the central shaft (5) is connected with a stirring structure (7). The outer surface of the mixing tank (2) is connected with an aeration structure (8). The inside of the mixing tank (2) is connected with a feeding structure (9); The stirring structure (7) is used to adjust the stirring length of the stirring member. The aeration structure (8) includes an air inlet pipe (81) fixedly connected to the outer surface of the mixing tank (2). The inner end of the air inlet pipe (81) is fixedly connected with a fixed ring (82). The lower end of the fixed ring (82) is rotatably connected with a rotating ring (83). The lower end of the rotating ring (83) is fixedly connected with a connecting pipe (84). The lower end of the connecting pipe (84) is fixedly connected with an aeration ring (85). The inner side of the connecting pipe (84) is fixedly connected with an adapter ring (86). The inner side of the adapter ring (86) is fixedly connected with a baffle (87). Air is injected through the air inlet pipe (81) for aeration. When the stirring structure (7) rotates to the maximum length, it drives the baffle (87) to rotate, realizing the common rotation of the baffle (87), the adapter ring (86), the connecting pipe (84), the aeration ring (85), and the rotating ring (83); The feeding structure (9) is used to uniformly supply materials while cooperating with the rotation of the stirring structure (7) for stirring.

2. The method for treating copper-containing etching waste liquid according to claim 1, wherein S1 specifically includes: Mix the copper-containing alkaline etching solution with ammonia water. Among them, copper in the alkaline etching solution exists in the form of copper ammonia chromium ions. After mixing with ammonia water, the ammonia concentration increases, which is used to further stabilize the copper ammonia complex ions, inhibit the precipitation of copper, and maintain the dissolution ability and stability of the etching solution; S2 specifically includes: Mix and stir the copper-containing acidic etching solution and the alkaline copper ammonia etching solution at 50°C to 60°C, adjust the pH value between 9.5 and 10.5, make them fully react, and then perform suction filtration, washing, and then suction filtration to obtain the product basic copper chloride and a first filtrate; The reaction formula is: 2[Cu(NH)] 2+ + 3H2O + Cl - → Cu2(OH)3Cl↓ + 4NH4 + + NH3↑; The reaction needs to control the pH and temperature to avoid excessive dissolution; S3 specifically includes: The first filtered liquid mainly contains HN4Cl and trace amounts of Cu 2+ , adding a sodium sulfide solution to form a Cu2S precipitate, and then adding dilute hydrochloric acid to inhibit the hydrolysis of S 2+ to avoid the generation of toxic H2S gas and ensure complete precipitation of Cu 2+ ; The reaction formula is: ZCu + +S 2- →Cu2S↓; S4 specifically includes: Perform pressure filtration on this mixed solution to obtain a copper sulfide product and a second filtrate NH4Cl; S5 specifically includes: Evaporate, condense, and crystallize the second filtrate NH4Cl to obtain refined ammonium chloride.

3. The method for treating copper-containing etching waste liquid according to claim 1, wherein The stirring structure (7) includes a stirring frame (71) fixedly connected to the outer surface of the central shaft (5). A chute (72) is formed on the surface of one end of the stirring frame (71) away from the central shaft (5). A sliding frame (73) is slidably connected to the inner side of the stirring frame (71). A reinforcing plate (74) is fixedly connected to the outer end of the sliding frame (73). A spring (75) is connected between the inner end of the sliding frame (73) and the inner wall of the stirring frame (71). A heating pipe (10) for heating the inside of the mixing tank (2) is fixedly connected to the inside of the mixing tank (2). A second discharge pipe (12) is fixedly connected to the lower end of the mixing tank (2). A solenoid valve (13) is fixedly connected to the outer surface of the second discharge pipe (12).

4. The method for treating copper-containing etching waste liquid according to claim 3, wherein, A stirring motor (11) for driving the rotation of the central shaft (5) is fixedly connected to the outer surface of the bracket (1). The rotation speed of the stirring motor (11) is adjusted by a frequency converter. A first hopper (3) and a second hopper (4) are respectively arranged on both sides of the bracket (1). Feeding pipes (6) are fixedly connected between the first hopper (3) and the second hopper (4) and the mixing tank (2). The feeding structure (9) includes a feeding ring (91) fixedly connected between the lower end of the feeding pipe (6) corresponding to the first hopper (3) and the inner wall of the lower end of the mixing tank (2). The lower end of the feeding ring (91) is rotatably connected to a discharge ring (92). A first discharge pipe (93) is fixedly connected to the lower end of the discharge ring (92). The central shaft (5) is divided into upper and lower parts, and the upper and lower parts are in a plug-in structure. The stirring structure (7) is arranged in the lower half of the central shaft (5). A connecting column (95) is fixedly connected to the lower end of the upper half of the central shaft (5). A connecting groove (94) is formed in the upper end of the lower half of the central shaft (5). A telescopic cylinder (96) is fixedly connected to the lower end of the mixing tank (2) corresponding to the lower half of the central shaft (5).

5. The method for treating copper-containing etching waste liquid according to claim 3, characterized in that An annular slide rail (88) is fixedly connected to the inner wall surface of the mixing tank (2). A slider (89) is connected between the annular slide rail (88) and the aeration ring (85). The aeration ring (85) is fixedly connected to the slider (89) by screws. The slider (89) slides along the length direction of the annular slide rail (88).

6. The method for treating copper-containing etching waste liquid according to claim 5, wherein The intake pipe (81) is communicated with the inside of the fixed ring (82). A mechanical seal is provided between the rotating ring (83) and the fixed ring (82). The number of connecting pipes (84) is several groups and is distributed in a circular array. And the smaller the distance between the connecting pipe (84) and the intake pipe (81), the smaller the opening of the connecting pipe (84) communicating with the rotating ring (83).

7. The method for treating copper-containing etching waste liquid according to claim 3, wherein The number of connecting rings (86) is several groups and is vertically spaced. The connecting rings (86) are used to connect several groups of connecting pipes (84). A baffle (87) is connected to the inner side of the connecting ring (86) near the connecting pipe (84). The aeration ring (85) is in a circular ring structure.

8. The method for treating copper-containing etching waste liquid according to claim 3, wherein One end of the stirring frame (71) is a comb-like structure, and the sliding groove (72) is formed inside the comb teeth. The sliding frame (73) together with the reinforcing plate (74) is swung outward by the centrifugal force generated by the rotation of the stirring frame (71), and the spring (75) is used to pull to prevent the sliding frame (73) from disengaging outward from the inside of the sliding groove (72).

9. The method for treating copper-containing etching waste liquid according to claim 4, characterized in that, A mechanical seal is provided between the discharge ring (92) and the feed ring (91). The guide pipe (6) corresponding to the first hopper (3) is communicated with the inside of the feed ring (91). The guide pipe (6) corresponding to the second hopper (4) is directly communicated with the inside of the mixing tank (2). The first discharge pipe (93) is communicated with the discharge ring (92), and the number of the first discharge pipes (93) is several groups and is distributed in an annular array.

10. The method for treating copper-containing etching waste liquid according to claim 9, wherein The connecting column (95) has a regular square prism structure. The opening shape of the connecting groove (94) matches the connecting column (95). The output end of the telescopic cylinder (96) is embedded inside the lower half of the central shaft (5), and the output end of the telescopic cylinder (96) is rotatably connected to the central shaft (5) through a bearing.

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