Semiconductor wastewater magnetoelectric sub-tank treatment system

Abstract

The utility model discloses a kind of semiconductor wastewater magnetoelectric sub-tank processing systems, and the system includes the pulse electrochemical reactor, magnetic separation system, sub-tank electrodeposition system and reverse osmosis membrane system connected in turn.Pulse electrochemical reactor is degraded organic matter and pre-enriched heavy metal under the action of pulse power by BDD anode and rotating titanium mesh cathode;Magnetic separation system is deeply removed heavy metal by adding mercapto functionalized Fe3O4 nanoparticles and under the action of magnetic field;Sub-tank electrodeposition system realizes high-purity metal recovery by independently controlled copper, nickel, tin deposition tank;Reverse osmosis membrane system is equipped with flux monitoring and self-cleaning module, effectively delays membrane pollution.The utility model realizes the integrated processing of the deep removal of heavy metal in semiconductor wastewater, high-purity resource recovery and membrane pollution control.

Description

Technical Field

[0001] This utility model relates to the field of semiconductor wastewater treatment technology. Specifically, it relates to a magnetoelectric separator system for semiconductor wastewater treatment. Background Technology

[0002] As semiconductor manufacturing technology continues to evolve towards 3nm and more advanced processes, the wastewater generated during wafer production is becoming increasingly complex. It not only contains high concentrations of heavy metal ions such as copper, nickel, and tin, but also contains organic solvents such as isopropanol, forming a difficult-to-treat complex pollution system that places extremely high demands on wastewater treatment processes. Currently, existing technologies for the treatment and resource recovery of heavy metals in semiconductor wastewater still have significant limitations. For example, when using a single-tank pulse electrodeposition process to recover metals, the competition for electrode potential between different metal ions leads to severe co-deposition, often resulting in copper products containing impurities such as nickel, with a purity typically not exceeding 95%, failing to meet the semiconductor industry's standards for high-purity metal reuse. In the deep treatment stage, while the widely used Fe3O4 magnetic adsorption material has a certain heavy metal removal capacity, the particles are prone to agglomeration and caking, resulting in a recycling rate generally less than 10 times. Furthermore, its removal efficiency for heavy metal ions with concentrations below 1 ppm is low, making deep purification difficult. Furthermore, organic solvents in wastewater easily adsorb and accumulate on the surface of reverse osmosis membranes, causing severe membrane fouling, a sharp decline in flux, shortened membrane element lifespan, and frequent replacements that increase maintenance costs. In summary, existing technologies struggle to simultaneously achieve the multiple objectives of "deep removal of heavy metals, high-purity metal recovery, and long-term membrane fouling control" when treating high-performance semiconductor wastewater. Therefore, there is an urgent need to develop an integrated, high-efficiency, and fouling-resistant novel treatment system. Utility Model Content

[0003] The present invention aims to provide a magnetoelectric separation tank treatment system for semiconductor wastewater to solve the problems of incomplete removal of heavy metals, low purity of multiple metals recovery, and easy fouling of reverse osmosis membranes in existing semiconductor wastewater treatment technologies.

[0004] The technical solution of this utility model is as follows: A semiconductor wastewater magnetoelectric separation tank treatment system includes a pulsed electrochemical reactor, a magnetic separation system, a separate tank electrodeposition system, a UF ultrafiltration system, and a reverse osmosis membrane system connected in sequence; the pulsed electrochemical reactor includes a BDD anode, a rotating titanium mesh cathode, and a pulsed power supply; the magnetic separation system includes a nanoparticle dosing device, a mixing reaction tank, and a permanent magnet separator; the separate tank electrodeposition system includes independently set copper deposition tank, nickel deposition tank, and tin deposition tank; the reverse osmosis membrane system includes a real-time flux monitor, a self-cleaning trigger module, a UV lamp, an oxidant dosing device, and a reverse osmosis membrane.

[0005] Preferably, the pulse power supply parameters of the pulse electrochemical reactor are: voltage 12V, frequency 100Hz, and duty cycle 30%; the reaction temperature of the pulse electrochemical reactor is 50±2℃, and the hydraulic residence time is 30 minutes; the rotation speed of the rotating titanium mesh cathode is 120rpm.

[0006] Preferably, the nanoparticles added in the nanoparticle addition device of the magnetic separation system are thiol-functionalized Fe3O4 nanoparticles with a particle size of 50±5nm and an addition amount of 50mg / L; the magnetic field strength of the permanent magnet separator is 0.5T.

[0007] Preferably, the electrolyte in the copper deposition tank contains 180 g / L H2SO4 and 0.1 g / L thiourea, and the operating conditions are 50°C and a current density of 200 A / m. 2 The electrolyte in the nickel deposition tank is 40 g / L H3BO3 and 0.15 g / L succinyl oxime, and the operating conditions are 60°C and a current density of 150 A / m. 2 The electrolyte in the tin deposition tank is 120 g / L methanesulfonic acid with added gelatin, and the operating conditions are 30°C and a current density of 100 A / m. 2 .

[0008] Preferably, the triggering condition of the self-cleaning trigger module in the reverse osmosis membrane system is that the flux of the reverse osmosis membrane (45) decreases by 15.0%, the wavelength of the UV lamp is 365nm and the power is 300W, the oxidant added by the oxidant dosing device is 50ppm H2O2 solution, and the cleaning time is 30 minutes; the concentrate produced by the reverse osmosis membrane system is returned to the pulse electrochemical reactor through the pipeline.

[0009] Preferably, the UF ultrafiltration unit is disposed between the magnetic separation system and the reverse osmosis membrane system, and has a pore size of 0.02 μm.

[0010] Compared with existing technologies, this invention achieves high-purity recovery of copper, nickel, and tin through segmented electrodeposition, solving the problem of co-deposited impurities; it employs magnetic separation and functionalized nanoparticles for deep purification, stably reducing heavy metals to below 1 ppm; and it integrates a UV-catalyzed self-cleaning reverse osmosis system, effectively controlling membrane fouling, extending membrane life, and reducing operation and maintenance costs. The entire system is highly efficient and synergistic, achieving the integrated goal of deep heavy metal removal, high-purity resource recovery, and long-term stable operation. Attached Figure Description

[0011] Figure 1 This is a flowchart illustrating the overall processing system of this application.

[0012] Figure 2 This is a structural diagram of the pulsed electrochemical reactor in this application;

[0013] Figure 3 This is a structural diagram of the magnetic separation system in this application;

[0014] Figure 4 This is a structural diagram of the cell electrodeposition system in this application;

[0015] Figure 5 This is a structural diagram of the reverse osmosis module in this application;

[0016] In the diagram: 1. Pulsed electrochemical reactor; 11. BDD anode; 12. Rotating titanium mesh cathode; 13. Pulsed power supply; 2. Magnetic separation system; 21. Nanoparticle dosing device; 22. Mixing reaction tank; 23. Permanent magnet separator; 3. Separate electrodeposition system; 31. Copper deposition tank; 32. Nickel deposition tank; 33. Tin deposition tank; 4. Reverse osmosis membrane system; 41. Real-time flux monitor; 42. Self-cleaning trigger module; 43. UV lamp; 44. Oxidant dosing device; 45. Reverse osmosis membrane; 5. UF ultrafiltration. Detailed Implementation

[0017] To make the purpose, technical solution, and advantages of this utility model clearer, the following description is provided in conjunction with the appendix. Figure 1-5 The present invention provides a detailed description of a semiconductor wastewater magnetoelectric separation tank treatment system. It should be noted that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention.

[0018] Please see Figure 1-5 The system of this utility model mainly includes a pulsed electrochemical reactor 1, a magnetic separation system 2, a multi-slot electrodeposition system 3, and a reverse osmosis membrane system 4. The pulsed electrochemical reactor 1 and the magnetic separation system 2 are connected in sequence through pipelines. The multi-slot electrodeposition system 3 and the UF ultrafiltration system 5 are connected in parallel at the outlet of the magnetic separation system 2. The reverse osmosis membrane system 4 is connected to the outlet of the UF ultrafiltration system 5 through pipelines.

[0019] The pulsed electrochemical reactor 1 includes a BDD anode 11, a rotating titanium mesh cathode 12, and a pulsed power supply 13. The pulsed electrochemical reactor 1 degrades organic matter and pre-deposits and recovers some metals.

[0020] The magnetic separation system 2 includes a nanoparticle dosing device 21, a mixing reaction tank 22, and a permanent magnet separator 23. The magnetic separation system 2 removes and concentrates heavy metal ions through magnetic flocculation technology.

[0021] The separate electrodeposition system 3 includes a copper deposition tank 31, a nickel deposition tank 32, and a tin deposition tank 33. The separate electrodeposition system 3 electrodeposits and recovers high-purity copper, nickel, and tin metals respectively.

[0022] The reverse osmosis membrane system 4 includes a real-time flux monitor 41, a self-cleaning trigger module 42, a UV lamp 43, an oxidant dosing device 44, and a reverse osmosis membrane 45. The reverse osmosis membrane system 4 purifies water quality and achieves stable operation by self-cleaning and draining water.

[0023] In this embodiment, as Figure 2 As shown, the semiconductor wastewater to be treated is at a concentration of 50m³. 3 A constant flow rate of [flow rate] / h enters the pulsed electrochemical reactor 1. The BDD anode 11 and the titanium mesh cathode 12, rotating at 120 rpm, operate under the action of a pulsed power supply 13. The parameters of the pulsed power supply 13 are set as follows: voltage 12V, frequency 100Hz, duty cycle 30%. The reaction temperature is maintained at 50±2℃, and the hydraulic residence time is 30 minutes. During this process, the BDD anode 11 undergoes anodizing reaction: C3H8O (isopropanol) + 8H2O → 3CO2 + 24H2O. + +24e - Rotating cathode reduction reaction: Cu 2+ +2e - →Cu, after treatment, the isopropanol concentration in the effluent is <0.1ppm, the TOC is reduced to 52ppm, and a copper layer with a thickness of about 0.2mm is pre-deposited on the cathode surface.

[0024] like Figure 3 As shown, the effluent from the pulsed electrochemical reactor 1 enters the magnetic separation system 2. A pre-prepared suspension of thiol-functionalized iron(III) oxide (Fe3O4@-SH) nanoparticles is injected into the nanoparticle dosing device 21 at a dosage of 50 mg / L. The suspended particles have a particle size of 50 ± 5 nm. In the mixing reaction tank 22, the nanoparticles react with residual Cu in the water. 2+ Ni 2+ Sn 2+ The plasmas come into full contact and undergo a complexation reaction: Fe3O4@-SH+Cu 2+ →Fe3O4@-SCu generates magnetically loaded heavy metal flocs with a relatively high specific gravity. When the water flows through the permanent magnet separator 23 with a magnetic field strength of 0.5T, the magnetically loaded heavy metal flocs are captured. The concentration of copper ions in the separated water decreases from 1200ppm to 0.1ppm, and the concentrations of nickel and tin ions decrease to 0.3ppm and 0.4ppm, respectively. This purified water then enters the subsequent ultrafiltration unit.

[0025] like Figure 4 As shown, the magnetic flocculent concentrate containing high concentrations of heavy metals generated by the magnetic separation system 2 is diverted to the separate electrodeposition system 3 for resource recovery. The three deposition tanks operate independently, taking into account the deposition characteristics of different metals.

[0026] Copper Deposition Tank 31: This tank is specifically designed for copper recovery. The electrolyte is 180 g / L H₂SO₄, with 0.1 g / L thiourea added as a masking agent. Thiourea preferentially reacts with Ni. 2+ A stable complex [Ni(SCN2H4)2] is formed. 2+ This stabilizes it in the electrolyte, inhibiting its co-deposition with copper at the cathode. The copper deposition tank is operated at 50℃ and a current density of 200 A / m. 2 Under certain conditions, high-purity electrolytic copper is deposited on the cathode plate.

[0027] Nickel deposition tank 32: This tank is specifically designed for nickel recovery. The electrolyte is a 40 g / L H3BO3 solution, which acts as a pH buffer. 0.15 g / L succinyl oxime is added, and the succinyl oxime reacts with Sn... 2+ The reaction produces Sn(C4H7N2O2)2 precipitate to eliminate the interference of tin on nickel deposition. The nickel deposition tank is operated at a temperature of 60℃ and a current density of 150 A / m. 2 Under these conditions, it produces electrolytic nickel plates with a purity of 99.91%.

[0028] Tin deposition tank 33: This tank is specifically designed for tin recovery. The electrolyte is 120 g / L methanesulfonic acid, with the addition of an appropriate amount of gelatin to improve the density of the tin deposition layer and inhibit dendrite growth. The tin deposition tank operates at a temperature of 30℃ and a current density of 100 A / m. 2 Under these conditions, it produces electrolytic tin plates with a purity of 99.86%.

[0029] like Figure 5 As shown, the qualified purified water produced by the magnetic separation system 2 is pretreated by a UF ultrafiltration membrane 5 with a pore size of 0.02 μm to remove any possible residual trace suspended solids or particulate matter before entering the reverse osmosis membrane system 4. The flux real-time monitor 41 monitors the permeate flux of the reverse osmosis membrane 45 in real time, with an initial flux of 15.2 L / (m²). 2 •h). Under normal flux conditions, the effluent from UF ultrafiltration 5 is treated by reverse osmosis membrane 45, and the permeate meets discharge standards. The concentrate is returned to pulse electrochemical reactor 1 for recycling. After approximately 72 hours of operation, the flux drops to 12.9 L / (m³). 2 When the membrane flux decreases by more than 15% (·h), the self-cleaning trigger module 42 is activated. During cleaning, a 365nm wavelength, 300W UV lamp 43 is turned on, and simultaneously, the oxidant dosing device 44 injects 50ppm of H2O2 solution. UV photocatalysis generates hydroxyl radicals (·OH) from H2O2: H2O2 + hν(UV) → 2·OH. These strong oxidizing free radicals decompose the organic matter adhering to the membrane surface. After cleaning for approximately 30 minutes, the membrane flux recovers to 14.9 L / (m²). 2 ·h).

[0030] The above description is merely an embodiment of this utility model and does not limit the patent scope of this utility model. Any equivalent modifications made based on the content of this utility model specification and drawings, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of this utility model.

Claims

1. A semiconductor wastewater magnetoelectric separation tank treatment system, characterized in that, The system includes a pulsed electrochemical reactor (1), a magnetic separation system (2), a multi-tank electrodeposition system (3), an ultrafiltration (UF) system (5), and a reverse osmosis membrane system (4) connected in sequence. The pulsed electrochemical reactor (1) includes a BDD anode (11), a rotating titanium mesh cathode (12), and a pulse power supply (13). The magnetic separation system (2) includes a nanoparticle dosing device (21), a mixing reaction tank (22), and a permanent magnet separator (23). The multi-tank electrodeposition system (3) includes independently set copper deposition tank (31), nickel deposition tank (32), and tin deposition tank (33). The reverse osmosis membrane system (4) includes a real-time flux monitor (41), a self-cleaning trigger module (42), a UV lamp (43), an oxidant dosing device (44), and a reverse osmosis membrane (45).

2. The semiconductor wastewater magnetoelectric separator treatment system according to claim 1, characterized in that, The nanoparticles added in the nanoparticle addition device (21) of the magnetic separation system (2) are thiol-functionalized Fe3O4 nanoparticles with a particle size of 50±5nm and an addition amount of 50mg / L; the magnetic field strength of the permanent magnet separator (23) is 0.5T.

3. The semiconductor wastewater magnetoelectric separator treatment system according to claim 1, characterized in that, The UF ultrafiltration (5) is located between the magnetic separation system (2) and the reverse osmosis membrane system (4), and has a pore size of 0.02 μm.

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