Developing waste liquid recycling device and method

Abstract

The application relates to the technical field of semiconductor waste liquid treatment, and particularly provides a developing waste liquid quality-based recovery device and method.The device comprises an electrodialysis assembly, a first circulation assembly, an oxidation assembly and a second circulation assembly; the electrodialysis assembly is used for receiving developing waste liquid and performing cyclic electrodialysis to obtain first circulation liquid and second circulation liquid; the first circulation assembly is used for receiving the first circulation liquid and detecting the TMAH concentration; when the concentration is higher than a first preset range, the first circulation liquid is sent to the electrodialysis assembly for cyclic removal; when the concentration meets the first preset range, target fresh water is output to the oxidation assembly; the oxidation assembly oxidizes and degrades TMAH to output first target liquid; and the second circulation assembly is used for receiving the second circulation liquid and detecting the TMAH concentration; when the concentration is lower than a second preset range, the second circulation liquid is sent to the electrodialysis assembly for cyclic accumulation; and when the concentration meets the second preset range, second target liquid is output. The application takes into account high resource utilization rate and low energy consumption and cost.

Description

Technical Field

[0001] This invention relates to the field of semiconductor waste liquid treatment technology, and in particular to a device and method for the fractional recovery of developing waste liquid. Background Technology

[0002] Tetramethylammonium hydroxide (TMAH) is widely used as an alkaline developer in semiconductor manufacturing. Developing wastewater is generated after the developing process, and the TMAH concentration in this wastewater is typically lower than the standard developer concentration of 2.38 wt%.

[0003] If the developer waste liquid is directly discharged or only treated at the end of the process, effective recovery of TMAH (Transient Acid-Based Hydrate) cannot be achieved, which can easily lead to resource waste and environmental burden. If evaporation technology is used to concentrate the developer waste liquid to the standard developer concentration, the energy consumption is significant and the economic efficiency is poor. Summary of the Invention

[0004] The developer waste liquid fractionation and recovery device and method provided in this invention at least solve the problem that related waste liquid recovery methods are difficult to balance high resource utilization and low energy consumption and cost. By performing electrodialysis fractionation treatment on the developer waste liquid, high resource utilization and low energy consumption and cost can be balanced.

[0005] In a first aspect, the present invention provides a developer wastewater fractionation and recovery device, comprising: an electrodialysis component for receiving developer wastewater and performing cyclic electrodialysis treatment to obtain a first circulating liquid and a second circulating liquid; the TMAH concentration of the first circulating liquid is lower than the TMAH concentration of the second circulating liquid; a first circulation component for receiving the first circulating liquid and detecting the TMAH concentration; when the TMAH concentration of the first circulating liquid is higher than a first preset range, the first circulating liquid is fed to the electrodialysis component for cyclic removal; when the TMAH concentration of the first circulating liquid meets the first preset range, target fresh water is output; an oxidation component for receiving the target fresh water and performing oxidative degradation of TMAH treatment to output a first target liquid; and a second circulation component for receiving the second circulating liquid and detecting the TMAH concentration; when the TMAH concentration of the second circulating liquid is lower than a second preset range, the second circulating liquid is fed to the electrodialysis component for cyclic accumulation; when the TMAH concentration of the second circulating liquid meets the second preset range, a second target liquid is output.

[0006] In one embodiment of the present invention, the freshwater inlet of the oxidation component is connected to the first outlet of the first circulation component to receive the target freshwater; the target freshwater carries sensible heat within a target temperature range, which is generated by the electrodialysis component during cyclic electrodialysis; the ozone inlet of the oxidation component is used to receive ozone; a heterogeneous iron-based catalyst is disposed within the oxidation component, and the surface catalysis of the heterogeneous iron-based catalyst synergistically with the strong oxidation of the ozone to oxidize and degrade TMAH in the target freshwater; the sensible heat maintains the oxidation reaction temperature to obtain the first target liquid.

[0007] In one embodiment of the invention, an ozone generator is further included, which is used to receive oxygen and generate ozone; the ozone inlet of the oxidation component is connected to the ozone outlet of the ozone generator to receive the ozone.

[0008] In one embodiment of the present invention, a conditioning component is further included; the inlet of the conditioning component is connected to the gas outlet of the electrodialysis component to receive oxygen-containing gas for conditioning and to obtain the oxygen; the outlet of the conditioning component is connected to the oxygen inlet of the ozone generator to output the oxygen; wherein the oxygen-containing gas is generated by the oxidation reaction of the electrodialysis component.

[0009] In one embodiment of the present invention, the conditioning component includes a gas-liquid separator, a dryer, and a filter; the inlet of the gas-liquid separator is connected to the gas outlet of the electrodialysis component to receive the oxygen-containing gas and perform gas-liquid separation to output humidified oxygen; the inlet of the dryer is connected to the gas outlet of the gas-liquid separator to receive the humidified oxygen and perform drying to output impure oxygen; the inlet of the filter is connected to the outlet of the dryer to receive the impure oxygen and perform filtration to output the oxygen; and the oxygen inlet of the ozone generator is connected to the outlet of the filter.

[0010] In one embodiment of the present invention, the electrodialysis assembly includes a circulation sub-assembly, an anode sub-assembly, and a cathode sub-assembly; the circulation sub-assembly is used to receive the developing waste liquid, a first circulating liquid with a TMAH concentration higher than a first preset range, and a second circulating liquid with a TMAH concentration lower than a second preset range; the anode sub-assembly and the cathode sub-assembly are respectively disposed on both sides of the circulation sub-assembly; the anode sub-assembly is used to pass electricity and undergo an oxidation reaction to generate the oxygen-containing gas; the cathode sub-assembly is used to pass electricity and undergo a reduction reaction to cooperate with the anode sub-assembly, causing the tetramethylammonium cations in the circulation sub-assembly to migrate towards the cathode sub-assembly, causing the hydroxide anions to migrate towards the anode sub-assembly, and generating heat to obtain the first circulating liquid and the second circulating liquid.

[0011] In one embodiment of the present invention, the circulation sub-assembly includes a plurality of cation exchange membranes and a plurality of anion exchange membranes; along the arrangement direction of the anode sub-assembly and the cathode sub-assembly, the plurality of cation exchange membranes and the plurality of anion exchange membranes are arranged alternately, and a first water chamber or a second water chamber is provided between two adjacent exchange membranes; the first water chamber is used to receive the developing waste liquid and the first circulating liquid with a TMAH concentration higher than the first preset range, and the outlet of the first water chamber is connected to the inlet of the first circulation assembly; the second water chamber is used to receive the second circulating liquid with a TMAH concentration lower than the second preset range, and the outlet of the second water chamber is connected to the inlet of the second circulation assembly.

[0012] In one embodiment of the present invention, the heterogeneous iron-based catalyst is a catalyst of ferric oxide or ferric oxide supported on activated carbon.

[0013] In one embodiment of the present invention, the iron loading in the heterogeneous iron-based catalyst is 1 wt% to 10 wt%.

[0014] In one embodiment of the present invention, the heterogeneous iron-based catalyst has a particle size of 0.1 mm to 10 mm.

[0015] In one embodiment of the present invention, the heterogeneous iron-based catalyst is configured as a fixed bed or fluidized bed structure.

[0016] In one embodiment of the present invention, the target temperature range is 30°C to 40°C.

[0017] In one embodiment of the present invention, the first circulation component includes a first water tank, a first splitter, and a first concentration detector; the first water tank is used to receive the developing waste liquid, and the outlet of the first water tank is connected to the inlet of the first water chamber in the electrodialysis component; the inlet of the first splitter is connected to the outlet of the first concentration detector, the first outlet of the first splitter is connected to the freshwater inlet of the oxidation component, and the second outlet of the first splitter is connected to the inlet of the first water tank; the inlet of the first concentration detector is connected to the outlet of the first water chamber, and the first concentration detector is used to detect the TMAH concentration of the first circulation liquid; the first concentration detector is signal-connected to the first splitter, and when the TMAH concentration of the first circulation liquid is higher than the first preset range, the inlet of the first splitter is disconnected from the first outlet of the first splitter, and the inlet of the first splitter is connected to the second outlet of the first splitter; when the TMAH concentration of the first circulation liquid meets the first preset range, the inlet of the first splitter is connected to the first outlet of the first splitter, and the inlet of the first splitter is disconnected from the second outlet of the first splitter.

[0018] In one embodiment of the present invention, a nanofiltration device is further included, which is used to receive and retain developer waste liquid; the outlet of the nanofiltration device is connected to the inlet of the first water tank so as to input the retained developer waste liquid into the first water tank.

[0019] In one embodiment of the present invention, the nanofiltration device includes a polypiperazine amide composite nanofiltration membrane, wherein the polypiperazine amide composite nanofiltration membrane has a molecular weight cutoff of 250 Da to 350 Da and an operating pressure of 0.6 MPa to 1.0 MPa.

[0020] In one embodiment of the present invention, the first preset range is 45ppm to 55ppm.

[0021] In one embodiment of the present invention, the second circulation component includes a second splitter, a second concentration detector, and a second water tank; the inlet of the second splitter is connected to the outlet of the second concentration detector, the first outlet of the second splitter is connected to the inlet of the second water tank, and the second outlet of the second splitter is used to output the second target liquid; the outlet of the second water tank is connected to the inlet of the second water chamber in the electrodialysis component; the inlet of the second concentration detector is connected to the outlet of the second water chamber, and the second concentration detector is used to detect the TMAH concentration of the second circulating liquid; the second concentration detector is signal-connected to the second splitter, and when the TMAH concentration of the second circulating liquid is lower than the second preset range, the inlet of the second splitter is connected to the first outlet of the second splitter, and the inlet of the second splitter is disconnected from the second outlet of the second splitter; when the TMAH concentration of the second circulating liquid meets the second preset range, the inlet of the second splitter is disconnected from the first outlet of the second splitter, and the inlet of the second splitter is connected to the second outlet of the second splitter.

[0022] In one embodiment of the present invention, the second preset range is 2.37wt% to 2.39wt%.

[0023] In one embodiment of the present invention, a first purifier is further included, the inlet of which is connected to the outlet of the oxidation component to receive the first target liquid and purify it with metal ions to output pure water.

[0024] In one embodiment of the present invention, a second purifier is further included, the inlet of which is connected to the second outlet of the second circulation component to receive the second target liquid and perform metal ion purification to output a TMAH solution.

[0025] Secondly, the present invention also provides a method for the fractional recovery of developer waste liquid, applied to the developer waste liquid fractional recovery device as described in any one of the above claims, comprising the steps of: controlling an electrodialysis component to receive developer waste liquid and performing cyclic electrodialysis treatment to obtain a first circulating liquid and a second circulating liquid; the TMAH concentration of the first circulating liquid is lower than the TMAH concentration of the second circulating liquid; controlling the first circulating component to receive the first circulating liquid and detecting the TMAH concentration; when the TMAH concentration of the first circulating liquid is higher than a first preset range, sending the first circulating liquid to the electrodialysis component for cyclic removal; when the TMAH concentration of the first circulating liquid meets the first preset range, outputting target fresh water; controlling an oxidation component to receive the target fresh water and performing oxidative degradation of TMAH treatment to output a first target liquid; controlling the second circulating component to receive the second circulating liquid and detecting the TMAH concentration; when the TMAH concentration of the second circulating liquid is lower than a second preset range, sending the second circulating liquid to the electrodialysis component for cyclic accumulation; when the TMAH concentration of the second circulating liquid meets the second preset range, outputting a second target liquid.

[0026] Compared with the prior art, the above-described technical solution of the present invention has the following advantages: The developer wastewater fractionation and recovery device of this invention includes an electrodialysis unit to perform cyclic electrodialysis treatment on the developer wastewater, resulting in two circulating solutions with different TMAH concentrations. For the first circulating solution with a lower TMAH concentration, the first circulating unit returns the TMAH concentration (higher than a first preset range) to the electrodialysis unit for further removal, continuously reducing the TMAH concentration. The target freshwater with a TMAH concentration within the first preset range is then oxidized and degraded by an oxidation unit, outputting the first target liquid. For the second circulating solution with a higher TMAH concentration, the second circulating unit returns the TMAH concentration (lower than a second preset range) to the electrodialysis unit for accumulation, continuously increasing the TMAH concentration. The second target liquid with a TMAH concentration within the second preset range is then output. Thus, through fractionation treatment, the concentration and treatment method are effectively matched, ensuring high resource utilization while maintaining low energy consumption and cost. Attached Figure Description

[0027] The accompanying drawings, which are provided to further illustrate the invention and constitute a part of this invention, are illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention.

[0028] Figure 1 This is one of the structural schematic diagrams of the developing waste liquid fractionation and recovery device in a preferred embodiment of the present invention.

[0029] Figure 2This is one of the partial structural schematic diagrams of the developing waste liquid separation and recovery device in a preferred embodiment of the present invention.

[0030] Figure 3 This is a partial structural schematic diagram of the developing waste liquid fractionation and recovery device in a preferred embodiment of the present invention.

[0031] Figure 4 This is a schematic diagram of the structure of the loop sub-component in a preferred embodiment of the present invention.

[0032] Figure 5 This is a schematic diagram of the structure of the first circulation component in a preferred embodiment of the present invention.

[0033] Figure 6 This is a schematic diagram of the structure of the second circulation component in a preferred embodiment of the present invention.

[0034] Figure 7 This is the second schematic diagram of the developing waste liquid fractionation and recovery device in a preferred embodiment of the present invention.

[0035] Figure 8 This is a schematic flowchart of the developing waste liquid fractionation and recovery method in a preferred embodiment of the present invention.

[0036] The above-mentioned figures include the following reference numerals: 10, electrodialysis assembly; 11, circulation subassembly; 111, cation exchange membrane; 112, anion exchange membrane; 113, first water chamber; 114, second water chamber; 12, anode subassembly; 121, anode body; 122, anode electrode water chamber; 13, cathode subassembly; 131, cathode body; 132, cathode electrode water chamber; 14, electrode water tank; 20, first circulation assembly; 21, first water tank; 22, first splitter; 23, first concentration detector; 30, oxidation assembly; 40, second circulation assembly; 41, second splitter; 42, second concentration detector; 43, second water tank; 50, ozone generator; 60, conditioning assembly; 61, gas-liquid separator; 62, dryer; 63, filter; 70, nanofiltration unit; 80, first purifier; 90, second purifier. Detailed Implementation

[0037] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0038] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0039] Unless otherwise specifically stated, the relative arrangement, numerical expressions, and values ​​of the components and steps set forth in these embodiments do not limit the scope of the invention. It should also be understood that, for ease of description, the dimensions of the various parts shown in the drawings are not drawn to actual scale. Techniques, methods, and devices known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques, methods, and devices should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar reference numerals and letters in the following drawings denote similar items; therefore, once an item is defined in one drawing, it need not be further discussed in subsequent drawings.

[0040] To address the issues of low resource utilization, high energy consumption, and high cost in developing waste liquid recovery methods in related technologies, this paper refers to... Figure 1 As shown, this embodiment of the invention provides a developer waste liquid fractionation and recovery device, including an electrodialysis component 10, a first circulation component 20, an oxidation component 30, and a second circulation component 40.

[0041] In this embodiment of the invention, the developing waste liquid includes TMAH, and the concentration of TMAH in the developing waste liquid is less than 2.38 wt%.

[0042] The electrodialysis unit 10 is used to receive the developer waste liquid and perform cyclic electrodialysis treatment to obtain a first circulating liquid and a second circulating liquid. The core principle of the electrodialysis unit 10 is based on the selective permeability of the ion exchange membrane, which enables the directional migration and separation concentration of TMAH under the drive of a DC electric field.

[0043] Specifically, after the developing waste liquid is fed into the electrodialysis unit 10 and energized, tetramethylammonium cations (TMA) are generated. + The hydroxide ion (OH-) will migrate towards the cathode. - The TMAH will migrate towards the anode, resulting in two solutions with different TMAH concentrations: the first circulating solution and the second circulating solution. The TMAH concentration in the first circulating solution is lower than that in the second circulating solution.

[0044] During the electrodialysis process of the electrodialysis unit 10, multiple batches of developing waste liquid can be fed to achieve the cyclic accumulation or removal of TMAH concentration.

[0045] It is worth noting that as the difference in TMAH concentration between the two solutions gradually increases, if the residual TMAH concentration is further reduced by electromigration, the conductivity, current utilization, and unit processing energy consumption may change.

[0046] Therefore, in this embodiment of the invention, by performing separate treatment on two solutions with different TMAH concentrations, the concentration and treatment method are matched to ensure high resource utilization while taking into account low energy consumption and cost.

[0047] Specifically, the first circulating liquid with a low TMAH concentration is treated by the first circulating component 20 and the oxidation component 30 working together, while the second circulating liquid with a high TMAH concentration is treated by the second circulating component 40.

[0048] Specifically, the first circulation component 20 is connected to the electrodialysis component 10, and the first circulation component 20 is used to receive the first circulating liquid output by the electrodialysis component 10. After receiving the first circulation component 20, the first circulation component 20 first detects the TMAH concentration of the first circulating liquid.

[0049] There are two scenarios: the TMAH concentration of the first circulating solution is higher than the first preset range, and the TMAH concentration of the first circulating solution meets the first preset range.

[0050] The first preset range can be set according to actual needs. In this embodiment of the invention, the first preset range is preferably set to 45 ppm (parts per million) to 55 ppm. During actual recycling, a value can be selected from the first preset range as the threshold for switching the first circulation component 20, such as 45 ppm, 46 ppm, 47 ppm, 48 ppm, 49 ppm, 50 ppm, 51 ppm, 52 ppm, 53 ppm, 54 ppm, 55 ppm, etc.

[0051] When the TMAH concentration in the first circulating solution drops to a first preset range, it can be considered as the target freshwater. If the target freshwater is further subjected to electrodialysis through the electrodialysis unit 10, the overall energy consumption is too high and uneconomical. Therefore, the first circulation unit 20 can directly output the target freshwater.

[0052] Conversely, electrodialysis can continue through the electrodialysis unit 10. That is, if the TMAH concentration of the first circulating solution is higher than the first preset range, the first circulation unit 20 will transport the first circulating solution back to the electrodialysis unit 10 for circulation and removal, and continue to reduce the TMAH concentration.

[0053] The TMAH concentration detection and diversion of the first circulating fluid can be achieved by installing a concentration sensor and a reversing valve on the pipeline. For example, a controller can be installed and electrically connected to the concentration sensor and the solenoid reversing valve.

[0054] During operation, the concentration of TMAH in the first circulating liquid in the pipeline is detected by a concentration sensor, and the concentration detection signal is fed back to the controller. In the initial stage, the TMAH concentration of the first circulating liquid may be high. After receiving the concentration detection signal, the controller controls the solenoid reversing valve to directly send the first circulating liquid, whose TMAH concentration has not dropped to the first preset range, back to the electrodialysis unit 10 for TMAH removal.

[0055] After a certain period of electrodialysis removal, the TMAH concentration has dropped to the first preset range. After receiving the concentration detection signal, the controller controls the electromagnetic reversing valve to output the target fresh water.

[0056] In this embodiment of the invention, the target freshwater output from the first circulation component 20 is received and processed by the oxidation component 30. Specifically, the oxidation component 30 receives the target freshwater and performs oxidative degradation of TMAH to output the first target liquid.

[0057] For example, the oxidation component 30 can employ methods such as ozone oxidation alone, combined ultraviolet / ozone oxidation, or electrochemical oxidation to generate highly oxidizing species that degrade TMAH. After oxidative degradation, the TMAH in the first target liquid has been largely decomposed. Excluding other impurities, the first target liquid can be considered as pure water. Pure water can be directly reused or discharged in compliance with regulations.

[0058] Compared to continuing electrodialysis of the target freshwater, oxidizing and degrading the TMAH in the target freshwater using the oxidation component 30 can effectively decompose the TMAH to obtain the first target liquid that meets the requirements, improve the resource utilization rate of the developing waste liquid, and effectively save energy consumption and cost in treating TMAH, ensuring that the entire recycling process is energy-saving and environmentally friendly.

[0059] Preferably, in this embodiment of the invention, 50 ppm is selected as the threshold for switching the first circulation component 20. Actual testing shows that the electrodialysis component 10 reduces the TMAH concentration of the first circulating solution from 200 ppm to 50 ppm with an energy consumption of approximately 6 kWh / m³. 3Meanwhile, the energy consumption for further reduction from 50 ppm to 0.5 ppm surged to 35 kWh / m³. 3 When the TMAH concentration is below 50 ppm, it has little impact on the removal efficiency of the oxidation component 30 and can stably meet the standard within a reasonable residence time.

[0060] Next, the second circulation component 40 is also connected to the electrodialysis component 10, and the second circulation component 40 is used to receive the second circulating liquid output by the electrodialysis component 10. After receiving the second circulation component 40, the second circulation component 40 first detects the TMAH concentration of the second circulating liquid.

[0061] There are two scenarios: the TMAH concentration of the second circulating solution is lower than the second preset range, and the TMAH concentration of the second circulating solution meets the second preset range.

[0062] The second preset range can be set according to actual needs. In this embodiment of the invention, the second preset range is preferably set to 2.37wt% to 2.39wt%. During actual recycling, a value can be selected from the second preset range as the threshold for switching the second circulation component 40, for example, 2.37wt%, 2.371wt%, 2.372wt%, 2.373wt%, 2.374wt%, 2.375wt%, 2.376wt%, 2.377wt%, 2.378wt%, 2.379wt%, 2.38wt%, 2.381wt%, 2.382wt%, 2.383wt%, 2.384wt%, 2.385wt%, 2.386wt%, 2.387wt%, 2.388wt%, 2.389wt%, 2.39wt%, etc.

[0063] If the TMAH concentration in the second circulating liquid meets the second preset range, it indicates that there is sufficient TMAH and the concentration requirement of the standard developer is basically met, and it can be regarded as the second target liquid. Excluding other impurities, the second target liquid can be considered as the alkaline developer required in semiconductor manufacturing, i.e., a TMAH solution. The second circulation assembly 40 can output the second target liquid.

[0064] Conversely, electrodialysis can continue through the electrodialysis unit 10. That is, if the TMAH concentration of the second circulating liquid is lower than the second preset range, the second circulation unit 40 will transport the second circulating liquid back to the electrodialysis unit 10 for circulation and accumulation, and continue to increase the TMAH concentration.

[0065] The TMAH concentration detection and diversion of the second circulating fluid can also be achieved by installing a concentration sensor and a reversing valve on the pipeline. For example, a controller can be installed and electrically connected to the concentration sensor and the solenoid reversing valve.

[0066] During operation, the concentration of TMAH in the second circulating liquid in the pipeline is detected by a concentration sensor, and a concentration detection signal is fed back to the controller. In the initial stage, the TMAH concentration of the second circulating liquid may be low. After receiving the concentration detection signal, the controller controls the solenoid reversing valve to directly send the second circulating liquid, whose TMAH concentration has not risen to the second preset range, back to the electrodialysis unit 10 for TMAH circulation and accumulation.

[0067] After a certain period of electrodialysis accumulation, the TMAH concentration has risen to the second preset range. After receiving the concentration detection signal, the controller controls the electromagnetic reversing valve to output the second target liquid.

[0068] In this way, differentiated treatment of two solutions with different TMAH concentrations can effectively meet the TMAH removal requirements of the first circulating liquid with a lower TMAH concentration and the TMAH recovery requirements of the second circulating liquid with a higher TMAH concentration, achieving optimal matching of the treatment path and obtaining two target liquids.

[0069] In summary, the developer waste liquid fractionation and recovery device of the present invention uses an electrodialysis component 10 to perform cyclic electrodialysis treatment on the developer waste liquid, resulting in two circulating liquids with different TMAH concentrations. For the first circulating liquid with a lower TMAH concentration, the first circulating component 20 returns the first circulating liquid with a TMAH concentration higher than a first preset range to the electrodialysis component 10 for further cyclic removal, continuing to reduce the TMAH concentration; the target freshwater with a TMAH concentration within the first preset range is then oxidized and degraded by the oxidation component 30, outputting the first target liquid. For the second circulating liquid with a higher TMAH concentration, the second circulating component 40 returns the second circulating liquid with a TMAH concentration lower than the second preset range to the electrodialysis component 10 for cyclic accumulation, continuing to increase the TMAH concentration; the second target liquid with a TMAH concentration within the second preset range is then output. Thus, through fractionation treatment, the concentration and treatment method are effectively matched, ensuring high resource utilization while maintaining low energy consumption and cost.

[0070] Reference Figure 2 As shown, in some embodiments of the developer waste liquid fractionation and recovery device of the present invention, the oxidation component 30 has an ozone inlet, a fresh water inlet, and an outlet. The ozone inlet of the oxidation component 30 is used to receive ozone for the degradation of TMAH by ozone.

[0071] The freshwater inlet of the oxidation component 30 is connected to the first outlet of the first circulation component 20 to receive the target freshwater. The target freshwater is the feedstock that needs to be degraded by TMAH.

[0072] The target freshwater carries sensible heat within the target temperature range, which is generated by the electrodialysis unit 10 during cyclic electrodialysis. For example, the Joule heat generated by the electrodialysis unit 10 during electrodialysis due to resistance and ion migration resistance can cause the temperature of the first circulating liquid to rise.

[0073] Sensible heat can be used to maintain the oxidation reaction temperature. A suitable reaction temperature can effectively improve the overall degradation efficiency and realize the resource utilization of waste heat in the process.

[0074] In addition, a heterogeneous iron-based catalyst is provided within the oxidation component 30. During operation, the surface catalysis of the heterogeneous iron-based catalyst synergistically with the strong oxidation of ozone to oxidize and degrade TMAH in the target freshwater. Simultaneously, sensible heat maintains the reaction temperature for ozone catalytic oxidation, ensuring the reaction continues. After a certain period of time, the first target liquid is obtained.

[0075] Preferably, the heterogeneous iron-based catalyst is a catalyst in which ferric oxide or ferric oxide is supported on activated carbon.

[0076] During operation, ozone decomposes at the active sites of the heterogeneous iron-based catalyst to generate hydroxyl radicals (·OH). The activated carbon support adsorbs and enriches TMAH molecules, enabling efficient contact and rapid degradation of reactants on the catalyst surface. The CN bond of TMAH breaks under the attack of ·OH, decomposing into harmless products such as carbon dioxide, water, and inorganic nitrogen.

[0077] The sensible heat carried by the target freshwater directly maintains the reaction temperature, increases the ·OH generation rate and mass transfer efficiency, shortens the residence time and reduces ozone consumption, thus achieving efficient removal of residual TMAH.

[0078] In this way, by recycling the sensible heat of the freshwater generated by electrodialysis to maintain the reaction temperature of ozone catalytic oxidation, it is possible to fully oxidize and degrade TMAH in the target freshwater to obtain the desired first target liquid, and effectively improve the overall resource utilization rate. There is no need to provide an independent heat source for ozone catalytic oxidation, which is energy-saving, environmentally friendly, and effectively reduces recycling costs.

[0079] Preferably, the specific surface area of ​​activated carbon in the heterogeneous iron-based catalyst is greater than 1500 m². 2 / g. Preferably, the iron loading in the heterogeneous iron-based catalyst is 1wt% to 10wt%. The loading can be 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, etc. Preferably, the catalyst particle size of the heterogeneous iron-based catalyst is 0.1mm to 10mm. The catalyst particle size can be 0.1mm, 0.5mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, etc. Preferably, the heterogeneous iron-based catalyst is configured as a fixed bed or fluidized bed structure.

[0080] Preferably, the target temperature range is 30℃ to 40℃, which is conducive to increasing the oxidation reaction rate and achieving synergy between waste heat utilization and reaction efficiency. Among them, the sensible heat temperature can be 30℃, 31℃, 32℃, 33℃, 34℃, 35℃, 36℃, 37℃, 38℃, 39℃, 40℃, etc.

[0081] Actual tests showed that the catalytic ozone oxidation rate at 35℃ was about 30% to 40% higher than at 25℃. However, excessively high temperatures, such as above 50℃, can lead to decreased ozone solubility, accelerated self-decomposition, and a reduced effective ozone concentration in the liquid phase, thereby weakening the removal efficiency and potentially damaging the catalyst structure.

[0082] Furthermore, refer to Figure 2 As shown, in some embodiments of the developer waste liquid separation and recovery device of the present invention, an ozone generator 50 is further included. The ozone generator 50 is used to receive oxygen and generate ozone. The oxygen for the ozone generator 50 can be provided by an independent gas source.

[0083] The ozone generator 50 primarily uses high-voltage electricity to break down oxygen molecules into oxygen atoms. These oxygen atoms then combine with intact oxygen molecules to produce ozone. The workload of the ozone generator 50 can be dynamically adjusted based on parameters such as the target freshwater flow rate and TMAH concentration, which will not be elaborated further.

[0084] Compared to the combined use of ultraviolet (UV) and ozone, ozone generator 50 does not require an additional UV component; compared to electrochemical oxidation, ozone generator 50 does not require a separate reactor. This effectively reduces the device size and improves space utilization.

[0085] The ozone inlet of the oxidation component 30 is connected to the ozone outlet of the ozone generator 50 to receive ozone. The ozone, in synergy with the heterogeneous iron-based catalyst, oxidizes and degrades TMAH in the target freshwater to obtain the first target liquid.

[0086] Preferably, the anode of the electrodialysis component 10 can generate oxygen-containing gas, which can be used to supply oxygen to the ozone generator 50, thereby realizing the resource utilization of the gas produced by electrodialysis.

[0087] Considering that the oxygen-containing gas at the anode may contain droplets, water vapor, or gaseous components related to influent impurities, therefore, refer to Figure 2 As shown, the developer waste liquid separation and recovery device of the present invention, in some embodiments, further includes a conditioning component 60.

[0088] The inlet of the conditioning component 60 is connected to the gas outlet of the electrodialysis component 10 to receive oxygen-containing gas for conditioning, removing these gaseous components, and obtaining oxygen. The outlet of the conditioning component 60 is connected to the oxygen inlet of the ozone generator 50 to output oxygen. The oxygen-containing gas is produced by the oxidation reaction in the electrodialysis component 10.

[0089] The anode of the electrodialysis unit 10 can generate oxygen-containing gas. By setting the conditioning unit 60 to condition it, the oxygen required by the ozone generator 50 can be obtained, so that the ozone generator 50 can provide the ozone required for catalytic oxidation of the oxidation unit 30.

[0090] In this way, the oxygen-containing gas at the anode and the sensible heat of the freshwater generated by the electrodialysis unit 10 can be utilized in a dual way. The oxygen-containing gas, after conditioning, is used as the gas source for the ozone generator 50 to provide ozone for catalytic oxidation; the sensible heat can be directly used to maintain the temperature of the catalytic oxidation reaction, ensuring that the oxidation unit 30 fully oxidizes and degrades TMAH in the target freshwater.

[0091] Based on this, the device does not require additional gas or heat sources, which ensures high overall resource utilization, small device size, and high space utilization, enabling efficient fractional recovery of developing waste liquid.

[0092] The structure of the conditioning component 60 can be configured according to actual needs. Preferably, refer to... Figure 2 and Figure 3 As shown, in some embodiments of the developer waste liquid separation and recovery device of the present invention, the conditioning component 60 includes a gas-liquid separator 61, a dryer 62, and a filter 63.

[0093] The inlet of gas-liquid separator 61 is connected to the gas outlet of electrodialysis component 10 to receive oxygen-containing gas and perform gas-liquid separation, outputting moist oxygen. The inlet of dryer 62 is connected to the gas outlet of gas-liquid separator 61 to receive moist oxygen and perform drying, outputting impurity-containing oxygen. The inlet of filter 63 is connected to the outlet of dryer 62 to receive impurity-containing oxygen and perform filtration, outputting oxygen. Gas-liquid separator 61, dryer 62, and filter 63 are all conventional structures, and their specific principles will not be elaborated further.

[0094] The oxygen inlet of the ozone generator 50 is connected to the outlet of the filter 63 to receive conditioned oxygen. In this way, the oxygen-containing gas at the anode produced by the electrodialysis component 10, after being conditioned through gas-liquid separation, drying, and filtration, can be used as a stable intake gas for the ozone generator 50, facilitating the generation of ozone by the ozone generator 50 to produce the ozone required for catalytic oxidation by the oxidation component 30, thereby achieving TMAH oxidative degradation.

[0095] In addition, the temperature of the oxygen-containing gas at the anode is usually high. After conditioning through gas-liquid separation, drying, and filtration, its temperature can be reduced to a suitable range. This avoids the impact of high gas temperature on ozone generation and improves ozone production.

[0096] Reference Figure 4 As shown, in some embodiments of the developing waste liquid fractionation and recovery device of the present invention, the electrodialysis component 10 includes a circulation sub-component 11, an anode sub-component 12, and a cathode sub-component 13.

[0097] The circulation sub-assembly 11 is used to receive developer waste liquid, a first circulation liquid with a TMAH concentration higher than a first preset range, and a second circulation liquid with a TMAH concentration lower than a second preset range. The anode sub-assembly 12 and the cathode sub-assembly 13 are respectively disposed on both sides of the circulation sub-assembly 11, and the components can be connected to each other through corresponding ion exchange membranes.

[0098] The anode sub-assembly 12 is used for energizing and initiating an oxidation reaction. Preferably, the anode sub-assembly 12 includes an anode body 121 and an anode electrode water chamber 122. The anode body 121 is disposed on the side of the anode electrode water chamber 122 away from the cathode sub-assembly 13. The anode body 121 is electrically connected to a power source to enable energizing. The anode electrode water chamber 122 is provided with electrode water to cooperate with the anode body 121 in initiating the oxidation reaction. The gas outlet of the anode electrode water chamber 122 is connected to the inlet of the gas-liquid separator 61.

[0099] The cathode sub-assembly 13 is used for energizing and initiating a reduction reaction. Preferably, the cathode sub-assembly 13 includes a cathode body 131 and a cathode electrode water chamber 132. The cathode body 131 is disposed on the side of the cathode electrode water chamber 132 away from the anode sub-assembly 12. The cathode body 131 is electrically connected to a power source to enable energizing. The cathode electrode water chamber 132 is provided with electrode water to cooperate with the cathode body 131 in initiating a reduction reaction. Preferably, the electrodialysis assembly 10 also includes an electrode water tank 14 to provide electrode water to the anode electrode water chamber 122 and the cathode electrode water chamber 132.

[0100] The cathode sub-assembly 13 works in conjunction with the anode sub-assembly 12 to cause the tetramethylammonium cations in the circulation sub-assembly 11 to migrate toward the cathode sub-assembly 13 and the hydroxide anions to migrate toward the anode sub-assembly 12, thus obtaining the first circulation liquid and the second circulation liquid.

[0101] Among them, the electrode water of the cathode sub-assembly 13 undergoes an electrochemical reaction to produce hydrogen-containing gas, which can be separated into gas and liquid phases. The liquid phase can be recycled, while the hydrogen gas in the gas phase is discharged or collected after safe treatment.

[0102] An electrochemical reaction occurs in the electrode water of the anode assembly 12, producing oxygen-containing gas. After conditioning by the conditioning assembly 60, this gas can supply oxygen to the ozone generator 50. Furthermore, heat is generated during electrodialysis due to membrane stack resistance and ion migration resistance, causing the circulating liquid temperature to rise. The sensible heat carried by the first circulating liquid can provide a suitable temperature for catalytic ozone oxidation, realizing the resource utilization of process waste heat. Thus, the triple-coupling utilization of materials, gas, and waste heat can be achieved.

[0103] Furthermore, refer to Figure 4 As shown, in some embodiments of the developer waste liquid fractionation and recovery device of the present invention, the circulation sub-component 11 includes multiple cation exchange membranes 111 and multiple anion exchange membranes 112.

[0104] Along the arrangement direction of the anode sub-assembly 12 and the cathode sub-assembly 13, multiple cation exchange membranes 111 and multiple anion exchange membranes 112 are arranged alternately, and a first water chamber 113 or a second water chamber 114 is provided between two adjacent exchange membranes.

[0105] For example, in Figure 4 In the process, an anion exchange membrane 112 is provided between the anode water chamber 122 and the first first water chamber 113, a cation exchange membrane 111 is provided between the first first water chamber 113 and the first second water chamber 114, an anion exchange membrane 112 is provided between the first second water chamber 114 and the second first water chamber 113, and so on.

[0106] Among them, cation exchange membrane 111 allows cations to pass through while blocking anions, and anion exchange membrane 112 allows anions to pass through while blocking cations.

[0107] The first water chamber 113 is used to receive developer waste liquid and a first circulating liquid with a TMAH concentration higher than a first preset range. The outlet of the first water chamber 113 is connected to the inlet of the first circulating component 20. The second water chamber 114 is used to receive a second circulating liquid with a TMAH concentration lower than a second preset range. The outlet of the second water chamber 114 is connected to the inlet of the second circulating component 40.

[0108] Specifically, after power is supplied, the TMA in the first water chamber 113... + It will migrate towards the cathode, pass through the cation exchange membrane 111 and enter the second water chamber 114, where it will be blocked and retained by the anion exchange membrane 112. Simultaneously, OH- in the first water chamber 113... -It will migrate towards the anode, pass through the anion exchange membrane 112 and enter the second water chamber 114, where it will be blocked and retained by the cation exchange membrane 111.

[0109] In this way, TMAH continuously migrates out of the first water chamber 113 and its concentration decreases, while the second water chamber 114 continuously receives migrating ions and its concentration increases, thus achieving the directional enrichment of TMAH from the first water chamber 113 to the second water chamber 114.

[0110] After multiple batches of feed developing waste liquid and maintaining circulation, the TMAH concentration in the first water chamber 113 gradually decreased to 50 ppm, and the TMAH concentration in the second water chamber 114 gradually increased to 2.38 wt%, so as to carry out separate treatment through two circulation components.

[0111] Reference Figure 5 As shown, in some embodiments of the developer waste liquid fractionation and recovery device of the present invention, the first circulation component 20 includes a first water tank 21, a first diverter 22 and a first concentration detector 23.

[0112] The first water tank 21 is used to receive developer waste liquid, and the outlet of the first water tank 21 is connected to the inlet of the first water chamber 113 in the electrodialysis assembly 10. By setting up the first water tank 21, a buffer can be achieved to enable batch feeding of developer waste liquid.

[0113] The first diverter 22 has an inlet and two outlets. For example, the first diverter 22 can be configured as a two-position three-way valve, preferably an electromagnetic two-position three-way valve.

[0114] The inlet of the first diverter 22 is connected to the outlet of the first concentration detector 23 to receive the first circulating liquid after being detected by the first concentration detector 23. The first outlet of the first diverter 22 is connected to the freshwater inlet of the oxidation component 30, and the second outlet of the first diverter 22 is connected to the inlet of the first water tank 21.

[0115] The inlet of the first concentration detector 23 is connected to the outlet of the first water chamber 113 in the electrodialysis assembly 10 so as to receive the first circulating liquid output from the first water chamber 113. The first concentration detector 23 is used to detect the TMAH concentration of the first circulating liquid, and the first concentration detector 23 is signal-connected to the first shunt 22.

[0116] When the TMAH concentration of the first circulating liquid is higher than the first preset range, the inlet of the first distributor 22 is isolated from the first outlet of the first distributor 22, and the inlet of the first distributor 22 is connected to the second outlet of the first distributor 22.

[0117] In the initial stage of electrodialysis, the TMAH concentration of the first circulating solution is relatively high. Thus, the first circulating solution with a TMAH concentration higher than the first preset range is transported back to the first water tank 21 through the first distributor 22, and then enters the electrodialysis module 10 for circulation and removal.

[0118] When the TMAH concentration of the first circulating liquid meets the first preset range, the inlet of the first distributor 22 is connected to the first outlet of the first distributor 22, and the inlet of the first distributor 22 is disconnected from the second outlet of the first distributor 22.

[0119] After a certain period of time, the TMAH concentration of the first circulating liquid drops to 50 ppm. Then, the first circulating liquid with a TMAH concentration within the first preset range is output to the oxidation assembly 30 via the first distributor 22 for subsequent ozone catalytic oxidation.

[0120] In actual operation, the first water tank 21 can receive batches of developer waste liquid. After electrodialysis circulation removes the TMAH, reducing the concentration of the first circulating liquid to 50 ppm, all of the first circulating liquid is sent to the oxidation component 30. After the first water tank 21 is emptied, it receives the next batch of developer waste liquid. For example, a level sensor can be installed in the first water tank 21 to detect the liquid level. Preferably, the electrodialysis component 10 remains energized during batch switching intervals.

[0121] Considering that the developing waste liquid generated in the developing process usually contains impurities such as photoresist, colloidal particles, macromolecular organic matter, surfactants and metal ions in addition to TMAH, it needs to be pretreated before electrodialysis.

[0122] Therefore, refer to Figure 5 As shown, in some embodiments of the developer waste liquid separation and recovery device of the present invention, a nanofiltration unit 70 is further included. The nanofiltration unit 70 is used to receive and retain the developer waste liquid. The outlet of the nanofiltration unit 70 is connected to the inlet of the first water tank 21 so as to input the retained developer waste liquid into the first water tank 21.

[0123] In this way, at least some of the impurities such as photoresist, colloidal particles, macromolecular organic matter, surfactants and metal ions in the developing waste liquid can be intercepted by nanofiltration 70, avoiding organic pollution in subsequent electrodialysis.

[0124] Preferably, the TMAH concentration of the developing waste liquid entering the first water tank 21 and the electrodialysis assembly 10 is 300 ppm to 1000 ppm.

[0125] Preferably, the nanofiltration unit 70 includes a polypiperazine amide composite nanofiltration membrane with a molecular weight cutoff of 250 Da to 350 Da and an operating pressure of 0.6 MPa to 1.0 MPa. This effectively meets the requirements for retaining impurities in the developing wastewater, minimizing impurity retention and preventing organic pollution during subsequent electrodialysis.

[0126] Reference Figure 6 As shown, in some embodiments of the developer waste liquid fractionation and recovery device of the present invention, the second circulation component 40 includes a second diverter 41, a second concentration detector 42, and a second water tank 43.

[0127] The second diverter 41 has an inlet and two outlets. For example, the second diverter 41 can be configured as a two-position three-way valve, preferably a solenoid-type two-position three-way valve.

[0128] The inlet of the second diverter 41 is connected to the outlet of the second concentration detector 42 to receive the first circulating liquid after it has been detected by the second concentration detector 42. The first outlet of the second diverter 41 is connected to the inlet of the second water tank 43, and the second outlet of the second diverter 41 is used to output the second target liquid.

[0129] The inlet of the second concentration detector 42 is connected to the outlet of the second water chamber 114 in the electrodialysis assembly 10 to receive the second circulating liquid output from the second water chamber 114. The second concentration detector 42 is used to detect the TMAH concentration of the second circulating liquid and is signal-connected to the second shunt 41. The outlet of the second water tank 43 is connected to the inlet of the second water chamber 114 in the electrodialysis assembly 10.

[0130] When the TMAH concentration of the second circulating liquid is lower than the second preset range, the inlet of the second distributor 41 is connected to the first outlet of the second distributor 41, and the inlet of the second distributor 41 is disconnected from the second outlet of the second distributor 41.

[0131] In the initial stage of electrodialysis, the TMAH concentration of the second circulating solution is low. Thus, the second circulating solution with a TMAH concentration below the second preset range is transported back to the second water tank 43 via the second distributor 41, and then enters the electrodialysis assembly 10 for circulation and accumulation.

[0132] When the TMAH concentration of the second circulating liquid meets the second preset range, the inlet of the second distributor 41 is isolated from the first outlet of the second distributor 41, and the inlet of the second distributor 41 is connected to the second outlet of the second distributor 41.

[0133] After a certain period of time, the TMAH concentration of the second circulating liquid increases to 2.38 wt%. Thus, the second target liquid with a TMAH concentration that meets the second preset range is output through the second distributor 41.

[0134] In actual operation, the initial second circulating fluid can be added to the second water tank 43. After the electrodialysis cycle accumulates and the TMAH concentration of the second circulating fluid rises to 2.38 wt%, all of the second circulating fluid is output. After the second water tank 43 is emptied, new, initial second circulating fluid is added. For example, a level sensor can be installed in the second water tank 43 to realize level detection.

[0135] It should be noted that while TMAH in the primary target liquid has been thoroughly removed through oxidation, residual organic matter and trace amounts of iron ions may still remain despite nanofiltration. Therefore, referring to... Figure 7 As shown, the developer waste liquid fractionation and recovery device of the present invention, in some embodiments, further includes a first purifier 80.

[0136] The inlet of the first purifier 80 is connected to the outlet of the oxidation component 30 to receive the first target liquid and purify it with metal ions, thereby achieving purification and outputting pure water. The first purifier 80 can employ a mixed bed or independent cation exchange resin to purify the first target liquid after catalytic oxidation.

[0137] Considering that the TMAH concentration of the first target liquid is extremely low, less than 0.5 ppm, and the ionic strength is significantly lower than that of the second target liquid, the resin exchange driving force is weakened. At the same time, trace amounts of iron ions may be dissolved during the oxidation process. Preferably, an additional iron ion detector can be set to detect the effluent from the first purifier 80 to avoid iron ion leakage.

[0138] Similarly, the TMAH concentration in the second target liquid is approximately 2.38 wt%, and it is strongly alkaline, potentially containing metal ion impurities such as sodium and potassium ions, although the concentrations of these impurities are relatively low. Therefore, referring to... Figure 7 As shown, in some embodiments of the developer waste liquid fractionation and recovery device of the present invention, a second purifier 90 is also included.

[0139] The inlet of the second purifier 90 is connected to the second outlet of the second circulation assembly 40 to receive the second target liquid and purify it with metal ions, outputting a TMAH solution. The second purifier 90 may employ a strong acid cation exchange resin to purify the TMAH-enriched second target liquid. The resin exchanges cations, removing metal impurity ions through displacement.

[0140] By independently setting up two purification units, cross-contamination and conflicting resin regeneration conditions can be effectively avoided. Furthermore, the resin treating the second target liquid can operate stably under high ionic strength, while the resin treating the first target liquid is susceptible to contamination by trace impurities and organic matter at low concentrations, resulting in a relatively shorter lifespan. Setting them up independently facilitates monitoring and replacement of the first purification unit 80.

[0141] On the other hand, refer to Figure 8 As shown, this embodiment of the invention also provides a method for the fractional recovery of developer waste liquid, applied to the developer waste liquid fractional recovery device described in any of the above embodiments. The developer waste liquid fractional recovery method includes steps S10, S20, S30, and S40.

[0142] In step S10, the electrodialysis unit 10 is controlled to receive the developing waste liquid and perform cyclic electrodialysis treatment to obtain a first circulating liquid and a second circulating liquid. The TMAH concentration in the first circulating liquid is lower than that in the second circulating liquid.

[0143] In step S20, the first circulation component 20 is controlled to receive the first circulation liquid and the TMAH concentration is detected.

[0144] Specifically, if the TMAH concentration in the first circulating solution is higher than a first preset range, the first circulating solution is fed into the electrodialysis unit 10 for cyclic removal. If the TMAH concentration in the first circulating solution meets the first preset range, the target fresh water is output.

[0145] In step S30, the oxidation component 30 is controlled to receive the target fresh water and perform oxidative degradation of TMAH treatment to output the first target liquid.

[0146] In step S40, the second circulation component 40 is controlled to receive the second circulating liquid and the TMAH concentration is detected. If the TMAH concentration of the second circulating liquid is lower than a second preset range, the second circulating liquid is fed to the electrodialysis component 10 for circulation and accumulation. If the TMAH concentration of the second circulating liquid meets the second preset range, the second target liquid is output. Steps S20 and S40 can be performed simultaneously or sequentially, without restriction.

[0147] The effectiveness of the present invention is verified below using Examples 1, 2, and 3. The object of treatment is developing wastewater from a 12-inch wafer fab. The developing wastewater contains a TMAH concentration of 800 ppm and approximately 0.3 wt% photoresist residue and Na. + Approximately 15 ppm, K + Approximately 8 ppm.

[0148] In Example 1, nanofiltration unit 70 uses a polypiperazine amide composite nanofiltration membrane with a molecular weight cutoff of approximately 300 Da, an operating pressure of 0.8 MPa, and an operating temperature of 25°C. After nanofiltration treatment, the photoresist removal rate is greater than 98%, effectively reducing the risk of organic contamination in the subsequent electrodialysis module 10.

[0149] The electrodialysis module 10 uses ten pairs of ion exchange membranes, with each membrane having an effective area of ​​0.5 m². 2 The membrane spacing is 0.5 mm. The operating parameters of the electrodialysis module 10 are set as follows: current density 30 A / m³. 2 The operating voltage is approximately 22V. The electrode water uses a 0.1mol / L sodium sulfate solution. The electrode water tank 14 has a volume of 500L and a circulation flow rate of 50L / min. The effective volume of the first water chamber 113 is 2500L, and the amount of nanofiltration-processed developer wastewater treated in a single batch is approximately 2000L. The second water tank 43 has a volume of 100L, an initial liquid level of 60L, and an initial TMAH concentration of approximately 800ppm. The circulation flow rate of the first circulating liquid is 100L / min, and the circulation flow rate of the second circulating liquid is 10L / min.

[0150] During electrodialysis, the TMAH concentration of the first circulating solution is monitored in real time. When the concentration is higher than 50 ppm, the first circulating solution is returned to the first water chamber 113 for continued circulation and removal. When the concentration is lower than 50 ppm, the target desalinated water is introduced into the oxidation unit 30.

[0151] The conditioning component 60 includes a gas-liquid separator 61, a dryer 62, and a filter 63, which are connected in series to achieve conditioning. The ozone generator 50 uses the oxygen output from the conditioning component 60 as a gas source to supply an ozone-containing gas stream with an ozone concentration of approximately 500 mg / L to the oxidation component 30. The oxidation component 30 is a fixed-bed design, internally packed with 500 g of ferric oxide-supported activated carbon catalyst, of which the iron loading is 5 wt% and the activated carbon specific surface area is 1000 m². 2 / g, with a catalyst particle size of 3mm to 5mm.

[0152] The target freshwater, carrying sensible heat of approximately 35°C, enters the oxidation unit 30 and resides for approximately 10 minutes. After catalytic oxidation treatment, the TMAH concentration in the output target liquid is below 0.3 ppm, and the TMAH removal rate is greater than 99.3%. The chemical oxygen demand (COD) of the effluent is approximately 5 mg / L, the total nitrogen is approximately 3 mg / L, and the pH value is approximately 7.2, indicating that the residual TMAH and organic pollutants have been efficiently mineralized.

[0153] The first target liquid is output to the first purifier 80, which adopts a mixed-bed structure. A cation exchange resin (type 001×7) and anion exchange resin (type 201×7) are mixed and filled at a volume ratio of 1:1.5, with a total filling volume of 30L. The first target liquid after catalytic oxidation flows through the mixed bed at a contact time of 5 minutes, ensuring that the concentration of various cations in the output pure water meets the SEMI Grade 2 ultrapure water standard. This allows for direct reuse in production processes, achieving net-zero discharge.

[0154] On the other hand, after approximately 18 minutes of electrodialysis operation, the total dissolved solids concentration of the second circulating liquid reached 2.38 ± 0.1 wt%, and the volume of the second circulating liquid was approximately 60 L. At this point, the second target liquid was output to the second purification unit 90, which uses a strong acid cation exchange resin with a resin loading of 20 L. The second target liquid passed through the resin bed at a flow rate of 10 min contact time, and the effluent Na... + Concentration below 5 ppb, K + With a concentration below 5 ppb, residual metal cations were effectively removed.

[0155] In Example 2, the difference from Example 1 is that the first circulation component 20 and the oxidation component 30 are removed, and instead continuous electrodialysis concentration is performed until the TMAH concentration of the first circulation solution is lower than 0.5 ppm.

[0156] In the initial stage of electrodialysis operation, when the TMAH concentration of the first circulating solution decreased from 800 ppm to 200 ppm, the unit energy consumption was approximately 6 kWh / m³. As the concentration continued to decrease to below 50 ppm, the current efficiency dropped significantly due to a substantial decrease in the conductivity of the first circulating solution, and the unit energy consumption increased to approximately 18 kWh / m³. 3 .

[0157] When the concentration of TMAH is further concentrated to below 0.5 ppm, the energy consumption per unit increases sharply to approximately 35 kWh / m³. 3 Furthermore, the current density fluctuates drastically, significantly deteriorating the operational stability of the membrane stack. In addition, to maintain the electromigration rate under low concentration conditions, the operating voltage needs to be continuously increased, leading to a significant increase in heat generation of the membrane stack, necessitating additional cooling measures.

[0158] The comparison between Example 2 and Example 1 shows that continuing to use electrodialysis for deep concentration of the first circulating fluid is not feasible in terms of both economy and operational stability.

[0159] In Example 3, the difference from Example 1 is that the target freshwater temperature is reduced to 25°C by a cooler before being fed into the oxidation component 30.

[0160] To achieve the same TMAH removal rate (greater than 99%) as in Example 1 at 25°C, the ozone dosage needs to be increased to approximately 1000 mg / L, an increase of about 30% compared to the 35°C condition in Example 1. Alternatively, the residence time can be extended to approximately 35 minutes. These adjustments mean that the ozone generator 50 needs to operate at higher power, resulting in a significant increase in energy consumption.

[0161] The comparison between Example 3 and Example 1 shows that directly using the sensible heat of electrodialysis desalinated water to maintain the temperature of the catalytic oxidation reaction can significantly reduce the ozone dosage and system energy consumption.

[0162] For ease of description, spatial relative terms such as "above," "on top of," "on the upper surface of," "above," etc., are used herein to describe the spatial positional relationship of a device or feature as shown in the figures to other devices or features. It should be understood that spatial relative terms are intended to encompass different orientations in use or operation beyond the orientation of the device as described in the figures. For example, if the device in the figures were inverted, a device described as "above" or "on top of" other devices or structures would subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein will be interpreted accordingly.

[0163] Furthermore, it should be noted that the use of terms such as "first" and "second" to define components is merely for the purpose of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore should not be construed as limiting the scope of protection of this invention.

[0164] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A device for the fractional recovery of developer waste liquid, characterized in that, include: An electrodialysis unit is used to receive developer waste liquid and perform cyclic electrodialysis treatment to obtain a first circulating liquid and a second circulating liquid; the TMAH concentration of the first circulating liquid is lower than that of the second circulating liquid. A first circulation component is used to receive the first circulation liquid and detect the TMAH concentration; if the TMAH concentration of the first circulation liquid is higher than a first preset range, the first circulation liquid is sent to the electrodialysis component for circulation and removal; if the TMAH concentration of the first circulation liquid meets the first preset range, the target fresh water is output. An oxidation component is used to receive the target fresh water and perform oxidative degradation of TMAH to output the first target liquid; The second circulation component is used to receive the second circulation liquid and detect the TMAH concentration; when the TMAH concentration of the second circulation liquid is lower than a second preset range, the second circulation liquid is sent to the electrodialysis component for circulation accumulation. If the TMAH concentration of the second circulating liquid meets the second preset range, the second target liquid is output.

2. The developing waste liquid fractionation and recovery device according to claim 1, characterized in that: The freshwater inlet of the oxidation component is connected to the first outlet of the first circulation component to receive the target freshwater; the target freshwater carries sensible heat within the target temperature range, which is generated by the electrodialysis component during cyclic electrodialysis; the ozone inlet of the oxidation component is used to receive ozone. The oxidation component contains a heterogeneous iron-based catalyst. The surface catalysis of the heterogeneous iron-based catalyst synergistically with the strong oxidation of ozone to oxidize and degrade TMAH in the target fresh water. The sensible heat maintains the oxidation reaction temperature to obtain the first target liquid.

3. The developing waste liquid fractionation and recovery device according to claim 2, characterized in that: It also includes an ozone generator for receiving oxygen and producing ozone; the ozone inlet of the oxidation component is connected to the ozone outlet of the ozone generator to receive the ozone.

4. The developing waste liquid fractionation and recovery device according to claim 3, characterized in that: It also includes a conditioning component; the inlet of the conditioning component is connected to the gas outlet of the electrodialysis component to receive oxygen-containing gas for conditioning and to obtain the oxygen; the outlet of the conditioning component is connected to the oxygen inlet of the ozone generator to output the oxygen; wherein the oxygen-containing gas is produced by the oxidation reaction of the electrodialysis component.

5. The developing waste liquid fractionation and recovery device according to claim 4, characterized in that: The conditioning component includes a gas-liquid separator, a dryer, and a filter; the inlet of the gas-liquid separator is connected to the gas outlet of the electrodialysis component to receive the oxygen-containing gas and perform gas-liquid separation, outputting moist oxygen; the inlet of the dryer is connected to the gas outlet of the gas-liquid separator to receive the moist oxygen and perform drying, outputting impurity-containing oxygen; the inlet of the filter is connected to the outlet of the dryer to receive the impurity-containing oxygen and perform filtration, outputting the oxygen. The oxygen inlet of the ozone generator is connected to the outlet of the filter.

6. The developing waste liquid fractionation and recovery device according to claim 5, characterized in that: The electrodialysis unit includes a circulation sub-unit, an anode sub-unit, and a cathode sub-unit; the circulation sub-unit is used to receive the developing waste liquid, the first circulating liquid with a TMAH concentration higher than the first preset range, and the second circulating liquid with a TMAH concentration lower than the second preset range; The anode sub-assembly and the cathode sub-assembly are respectively disposed on both sides of the circulation sub-assembly; the anode sub-assembly is used to conduct electricity and undergo an oxidation reaction to generate the oxygen-containing gas; The cathode sub-assembly is used to conduct an energization and a reduction reaction, in conjunction with the anode sub-assembly, to cause the tetramethylammonium cations in the circulation sub-assembly to migrate toward the cathode sub-assembly, and the hydroxide anions to migrate toward the anode sub-assembly, thereby generating heat and obtaining the first circulation liquid and the second circulation liquid.

7. The developing waste liquid fractionation and recovery device according to claim 6, characterized in that: The circulation sub-assembly includes multiple cation exchange membranes and multiple anion exchange membranes; along the arrangement direction of the anode sub-assembly and the cathode sub-assembly, the multiple cation exchange membranes and the multiple anion exchange membranes are arranged alternately, and a first water chamber or a second water chamber is provided between two adjacent exchange membranes; The first water chamber is used to receive the developing waste liquid and the first circulating liquid with a TMAH concentration higher than the first preset range, and the outlet of the first water chamber is connected to the inlet of the first circulating component. The second water chamber is used to receive the second circulating liquid with a TMAH concentration lower than the second preset range, and the outlet of the second water chamber is connected to the inlet of the second circulation component.

8. The developing waste liquid fractionation and recovery device according to claim 2, characterized in that, Includes at least one of the following features: The heterogeneous iron-based catalyst is a catalyst in which ferric oxide or ferric oxide is supported on activated carbon. The iron loading in the heterogeneous iron-based catalyst is 1 wt% to 10 wt%. The heterogeneous iron-based catalyst has a particle size of 0.1 mm to 10 mm; The heterogeneous iron-based catalyst is configured as a fixed bed or fluidized bed structure. The target temperature range is 30°C to 40°C.

9. The developing waste liquid fractionation and recovery device according to claim 1, characterized in that: The first circulation assembly includes a first water tank, a first distributor, and a first concentration detector; the first water tank is used to receive the developing waste liquid, and the outlet of the first water tank is connected to the inlet of the first water chamber in the electrodialysis assembly; The inlet of the first diverter is connected to the outlet of the first concentration detector, the first outlet of the first diverter is connected to the freshwater inlet of the oxidation component, and the second outlet of the first diverter is connected to the inlet of the first water tank; the inlet of the first concentration detector is connected to the outlet of the first water chamber, and the first concentration detector is used to detect the TMAH concentration of the first circulating liquid. The first concentration detector is signal-connected to the first shunt. When the TMAH concentration of the first circulating liquid is higher than the first preset range, the inlet of the first shunt is disconnected from the first outlet of the first shunt, and the inlet of the first shunt is connected to the second outlet of the first shunt. When the TMAH concentration of the first circulating liquid meets the first preset range, the inlet of the first shunt is connected to the first outlet of the first shunt, and the inlet of the first shunt is disconnected from the second outlet of the first shunt.

10. The developing waste liquid fractionation and recovery device according to claim 9, characterized in that: It also includes a nanofiltration unit for receiving and retaining developer waste liquid; the outlet of the nanofiltration unit is connected to the inlet of the first water tank so as to input the retained developer waste liquid into the first water tank.

11. The developing waste liquid fractionation and recovery device according to claim 10, characterized in that: The nanofiltration device includes a polypiperazine amide composite nanofiltration membrane with a molecular weight cutoff of 250 Da to 350 Da and an operating pressure of 0.6 MPa to 1.0 MPa.

12. The developing waste liquid fractionation and recovery device according to claim 1 or 9, characterized in that: The first preset range is 45ppm to 55ppm.

13. The developing waste liquid fractionation and recovery device according to claim 1, characterized in that: The second circulation assembly includes a second diverter, a second concentration detector, and a second water tank; the inlet of the second diverter is connected to the outlet of the second concentration detector, the first outlet of the second diverter is connected to the inlet of the second water tank, and the second outlet of the second diverter is used to output the second target liquid; the outlet of the second water tank is connected to the inlet of the second water chamber in the electrodialysis assembly. The inlet of the second concentration detector is connected to the outlet of the second water chamber, and the second concentration detector is used to detect the TMAH concentration of the second circulating liquid; The second concentration detector is connected to the second shunt. When the TMAH concentration of the second circulating liquid is lower than the second preset range, the inlet of the second shunt is connected to the first outlet of the second shunt, and the inlet of the second shunt is disconnected from the second outlet of the second shunt. When the TMAH concentration of the second circulating liquid meets the second preset range, the inlet of the second distributor is isolated from the first outlet of the second distributor, and the inlet of the second distributor is connected to the second outlet of the second distributor.

14. The developing waste liquid fractionation and recovery device according to claim 1 or 13, characterized in that: The second preset range is 2.37wt% to 2.39wt%.

15. The developing waste liquid fractionation and recovery device according to claim 1, characterized in that: It also includes a first purifier, the inlet of which is connected to the outlet of the oxidation component to receive the first target liquid and purify it with metal ions to output pure water.

16. The developer waste liquid fractionation and recovery device according to claim 1, characterized in that: It also includes a second purifier, the inlet of which is connected to the second outlet of the second circulation component to receive the second target liquid and purify it with metal ions, and output TMAH solution.

17. A method for the fractional recovery of developer waste liquid, applied to the developer waste liquid fractional recovery apparatus as described in any one of claims 1 to 16, characterized in that, Including the following steps: The electrodialysis unit is controlled to receive the developing waste liquid and perform cyclic electrodialysis treatment to obtain a first circulating liquid and a second circulating liquid; the TMAH concentration of the first circulating liquid is lower than that of the second circulating liquid. The system controls the first circulation component to receive the first circulation liquid and detects the TMAH concentration; if the TMAH concentration of the first circulation liquid is higher than a first preset range, the first circulation liquid is sent to the electrodialysis component for circulation and removal; if the TMAH concentration of the first circulation liquid meets the first preset range, the target fresh water is output. The control oxidation component receives the target fresh water and performs oxidative degradation of TMAH to output the first target liquid; The second circulation component receives the second circulation liquid and detects the TMAH concentration; if the TMAH concentration of the second circulation liquid is lower than a second preset range, the second circulation liquid is sent to the electrodialysis component for circulation accumulation. If the TMAH concentration of the second circulating liquid meets the second preset range, the second target liquid is output.

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