Process system for surface treatment, waste liquid regeneration apparatus, and waste liquid regeneration method

Abstract

A wastewater regeneration device includes an electrolytic cell, multiple cation exchange membranes, and at least one anion exchange membrane. The cation exchange membranes and anion exchange membranes are alternately and spaced apart within the electrolytic cell to divide the cell into two electrode chambers, at least one first compartment, and at least one second compartment. Each first compartment is configured to receive anion-containing wastewater and regenerate it into a chemical reagent. Each second compartment is configured to receive anions from the anion-containing wastewater via the anion exchange membrane and cations from the anion-containing wastewater or electrolyte via the cation exchange membrane, and to synthesize an acid solution using the anions and cations. A surface treatment process system incorporating the wastewater regeneration device is also proposed, as well as a wastewater regeneration method utilizing the wastewater regeneration device.

Description

Technical Field

[0001] This invention relates to a process technology for surface modification of substrates, and in particular to a surface treatment process system, waste liquid regeneration equipment, and waste liquid regeneration method. Background Technology

[0002] Aluminum foil etching typically involves multiple processes, including alkaline washing, acid washing, electro-etching, coating treatment, and chemical cleaning. These processes require large quantities of acid and alkali solutions. The coating treatment chemicals are often contaminated by chemicals from the electro-etching process adhering to the aluminum foil surface, containing trace amounts of anions, which gradually reduces the effectiveness of the coating treatment. Furthermore, when the anions in the chemicals accumulate to a certain concentration, the coating treatment chemicals need to be replaced, resulting in a large amount of anion-containing acidic wastewater being discharged into the wastewater treatment system. This anion-containing acidic wastewater requires the addition of large amounts of alkali to adjust its pH to neutral before treatment. Therefore, the sludge and chemical costs generated by the entire aluminum foil etching process increase the overall cost of the process. Consequently, some manufacturers utilize regeneration processes to recover and regenerate the acidic wastewater.

[0003] Common methods for recycling or regenerating acidic waste liquids include ion exchange resins, precipitation, and distillation. These methods remove impurities from the acidic waste liquid and regenerate treatment agents, which can then be returned to the process that generated the acidic waste liquid. Summary of the Invention

[0004] However, common methods for recycling or regenerating acidic waste liquids suffer from high water consumption, high reagent usage, and high energy consumption. Therefore, this paper provides a surface treatment process system, waste liquid regeneration equipment, and waste liquid regeneration method to solve the aforementioned problems. This provides a low-energy-consumption and low-waste-emission technology for recycling or regenerating anionic waste liquids, thereby effectively reducing carbon emissions and operating costs in surface treatment processes.

[0005] In some embodiments, a surface treatment process system for a substrate includes a film treatment device and a wastewater regeneration device. The film treatment device is used to surface-modify the substrate and includes an acid pickling unit, a formation unit, and a feeding unit. The acid pickling unit receives acid. The formation unit receives a formation agent and produces an anion-containing wastewater. The feeding unit transports the substrate so that it sequentially passes through the acid pickling unit and the formation unit. The wastewater regeneration device is connected to the film treatment device and includes an electrolytic cell, a plurality of cation exchange membranes, and at least one anion exchange membrane. The cation exchange membranes and anion exchange membranes are alternately and spaced apart within the electrolytic cell to divide the electrolytic cell into two electrode chambers, at least one first intermediate chamber, and at least one second intermediate chamber. The first intermediate chamber and at least one second intermediate chamber are alternately located between the two electrode chambers. Each first intermediate chamber is configured to regenerate the anion-containing wastewater into a formation agent. Each of the second intermediate compartments is configured to receive anions from anion-containing waste liquid via anion exchange membranes and cations from anion-containing waste liquid or electrolyte via cation exchange membranes, and to synthesize acid solution with anions and cations.

[0006] In some embodiments, the aforementioned formation unit is a film processing tank.

[0007] In some embodiments, the aforementioned pickling unit is a pickling tank suitable for containing acid solution.

[0008] In some embodiments, the aforementioned acid solution is hydrochloric acid or sulfuric acid.

[0009] In some embodiments, the aforementioned anionic waste liquid includes phosphate-containing chemical reagents and anions.

[0010] In some embodiments, the waste liquid regeneration equipment further includes a temporary storage tank. The temporary storage tank is coupled between the formation unit and the waste liquid regeneration equipment and is used to temporarily store anionic waste liquid.

[0011] In some embodiments, the anion concentration of the anion-containing waste liquid discharged by the aforementioned formation unit is less than the anion concentration of the anion-containing waste liquid received by the first intermediate compartment.

[0012] In some embodiments, the coating treatment apparatus further includes a dosing tank. The dosing tank is coupled between the formation unit and the waste liquid regeneration equipment and is used to provide formation agents to the pickling unit. The waste liquid regeneration equipment is configured to provide the regenerated formation agents from each of the first intermediate compartments to the dosing tank.

[0013] In some embodiments, the aforementioned waste liquid regeneration equipment is also coupled to an acid washing unit and configured to provide the acid synthesized in each of the second intermediate compartments to the acid washing unit.

[0014] In some embodiments, the aforementioned cation exchange membrane is a hydrogen ion selective membrane.

[0015] In some embodiments, a wastewater regeneration apparatus includes an electrolytic cell, a plurality of cation exchange membranes, and at least one anion exchange membrane. The cation exchange membranes and anion exchange membranes are alternately and spaced apart within the electrolytic cell to divide the cell into two electrode chambers, at least one first compartment, and at least one second compartment. The at least one first compartment and at least one second compartment are alternately located between the two electrode chambers. Each first compartment is configured to receive anion-containing wastewater and regenerate it into a chemical reagent. Each second compartment is configured to receive anions from the anion-containing wastewater via the anion exchange membrane, receive cations from the anion-containing wastewater or electrolyte via the cation exchange membrane, and synthesize an acid solution using the anions and cations.

[0016] In some embodiments, a waste liquid regeneration method includes injecting anion-containing waste liquid into at least one first compartment of an electrolytic cell, injecting a first electrolyte into at least one second compartment of the electrolytic cell, injecting a second electrolyte into a two-electrode compartment of the electrolytic cell, and applying a voltage to two electrodes in the two-electrode compartment to perform an electrodialysis procedure. The two-electrode compartment, the at least one first compartment, and the at least one second compartment are separated by a plurality of cation exchange membranes and at least one anion exchange membrane alternately arranged within the electrolytic cell, and the at least one first compartment and the at least one second compartment are alternately located between the two-electrode compartments. The steps of performing the electrodialysis procedure include: electrolyzing the anion-containing waste liquid and the second electrolyte to form anion, cation, and a forming agent in the first compartment and forming a cation in the electrode compartment; introducing anion into the second compartment via an anion exchange membrane; introducing cation into the second compartment via a cation exchange membrane; and synthesizing an acid solution with anion and cation in the second compartment.

[0017] In some embodiments, the concentration of the aforementioned anion-containing waste liquid is less than or equal to 10%.

[0018] In some embodiments, the concentration of acid in the second compartment is less than or equal to 0.5%.

[0019] In summary, the surface treatment process system, waste liquid regeneration equipment, or waste liquid regeneration method of any embodiment utilizes electrodialysis technology to remove anions from the anion-containing waste liquid during the waste liquid regeneration process to regenerate the chemical forming agent, and simultaneously produces acid. Therefore, the waste liquid regeneration process does not require the addition of additional agents or the consumption of additional heat energy, thereby effectively reducing the carbon emissions and operating costs of the surface treatment process. In some embodiments, the surface treatment process system, waste liquid regeneration equipment, or waste liquid regeneration method can also guide the simultaneously generated chemical forming agent and acid back to the film treatment equipment for reuse in the surface treatment process, thereby achieving full recycling. Attached Figure Description

[0020] Figure 1This is a schematic diagram of a surface treatment process system according to one embodiment;

[0021] Figure 2 for Figure 1 A schematic diagram of the main body of a waste liquid regeneration equipment;

[0022] Figure 3 for Figure 1 A schematic diagram of another exemplary example of the main body of a waste liquid regeneration device;

[0023] Figure 4 This is a flowchart of a waste liquid regeneration method according to one embodiment;

[0024] Figure 5 for Figure 4 A flowchart of an example of step S04; and

[0025] Figure 6 This is a graph showing the changes in conductivity and chloride ion concentration of the relevant liquid during the application of a surface treatment process system according to one embodiment.

[0026] [Symbol Explanation]

[0027] 1: Process System

[0028] 10: Skin coating treatment equipment

[0029] 110: Feeding Unit

[0030] 130: Pickling Unit

[0031] 140: Drug mixing tank

[0032] 150: First Electrolytic Erosion Unit

[0033] 170: Unit of transformation

[0034] 190: Second Electro-erosion Unit

[0035] 20: Waste liquid regeneration equipment

[0036] 210: Temporary storage slot

[0037] 230: Main Body

[0038] 231: Electrolytic cell

[0039] 233: Cation exchange membrane

[0040] 235: Anion exchange membrane

[0041] 237, 239: Electrodes

[0042] 281: Detection Unit

[0043] 30: Substrate

[0044] Ia: Anion

[0045] Ic: Cation

[0046] La,La': acid solution

[0047] Le1: First electrolyte

[0048] Le2: Second electrolyte

[0049] Lr,Lr': Chemical agents

[0050] Lw,Lw': Waste liquid containing anions

[0051] RE1, RE2: Electrode chambers

[0052] RM1, RM2: Interval room

[0053] S01~S04: Steps

[0054] S41~S44: Steps Detailed Implementation

[0055] Reference Figure 1 The surface treatment process system 1 includes a coating treatment device 10 and a waste liquid regeneration device 20. The coating treatment device 10 is suitable for surface modification of a substrate 30. In some embodiments, the substrate 30 may be aluminum foil. For example, the coating treatment device 10 may form an aluminum oxide coating on the surface of the aluminum foil as an insulating protective layer for the aluminum foil. The waste liquid regeneration device 20 is suitable for regenerating the anionic waste liquid Lw generated by the coating treatment device 10 to produce reusable forming agent Lr' and acid La'.

[0056] The coating treatment equipment 10 includes a feeding unit 110 and multiple processing units that perform various processing procedures on the substrate 30. The feeding unit 110 defines a feeding path that sequentially passes through each processing unit. The feeding unit 110 is used to transport the substrate 30 so that the substrate 30 sequentially passes through each processing unit. In some embodiments, these processing procedures may be one or more alkaline washes, one or more acid washes, one or more electro-erosions, one or more chemical formations (also known as coating treatments), one or more chemical cleanings, one or more water washes, and drying, among others. That is, each processing unit performs one processing procedure on the substrate 30. Specifically, the processing unit may be a processing tank (e.g., a water bath, reaction bath, reaction tank, or rinsing tank) containing a corresponding processing solution. When the substrate 30 passes through any processing tank, the substrate 30 is immersed in the corresponding processing solution, so that the processing solution chemically reacts with the surface of the substrate 30 or cleans the surface of the substrate 30, thereby completing the corresponding processing procedure.

[0057] Herein, these processing units include at least an acid pickling unit 130 and a formation unit 170. A feeding unit 110 defines a feeding path that sequentially passes through the acid pickling unit 130 and the formation unit 170, and is used to transport the substrate 30 along this feeding path so that the substrate 30 sequentially passes through the acid pickling unit 130 and the formation unit 170. The acid pickling unit 130 receives acid solution La and acid-treats the substrate 30 accordingly. The formation unit 170 receives formation agent Lr and performs a coating treatment on the substrate 30 accordingly. Herein, the formation unit 170 also outputs the used formation agent Lr (i.e., anion-containing waste liquid Lw) to the waste liquid regeneration equipment 20. In some embodiments, the acid pickling unit 130 is an acid pickling tank suitable for containing acid solution La, and the formation unit 170 is a coating treatment tank suitable for containing formation agent Lr. Specifically, when the substrate 30 passes through the film treatment tank (i.e., through the formation unit 170), the substrate 30 is immersed in the formation agent Lr, so that the formation agent Lr reacts chemically with the surface of the substrate 30 to form an insulating protective film on the surface of the substrate 30. This insulating protective film can be aluminum oxide (Al2O3).

[0058] Reference Figure 1 and Figure 2 The waste liquid regeneration equipment 20 utilizes electrodialysis technology to remove the anions Ia contained in the anion-containing waste liquid Lw' and regenerate the chemical conversion agent Lr', while simultaneously producing acidic liquid La'. Specifically, the main body 230 of the waste liquid regeneration equipment 20 includes an electrolytic cell 231, multiple cation exchange membranes 233, and at least one anion exchange membrane 235. The cation exchange membranes 233 and anion exchange membranes 235 are alternately and intermittently arranged within the electrolytic cell 231, such that the cation exchange membranes 233 and anion exchange membranes 235 divide the internal space of the electrolytic cell 231 into two-electrode chambers RE1 and RE2 and multiple intermediate chambers RM1 and RM2. Among them, these intermediate chambers RM1 and RM2 include at least one first intermediate chamber RM1 and at least one second intermediate chamber RM2, and the first intermediate chamber RM1 and the second intermediate chamber RM2 are alternately located between the two-electrode chambers RE1 and RE2.

[0059] Therefore, the main body 230 of the waste liquid regeneration equipment 20 also includes two electrodes 237 and 239, and these two electrodes 237 and 239 are respectively inserted into the two electrode chambers RE1 and RE2.

[0060] Reference Figures 1 to 4During the regeneration process, firstly, anion-containing waste liquid Lw' is injected into the first intermediate chamber RM1 of the electrolytic cell 231 (step S01), first electrolyte Le1 is injected into the second intermediate chamber RM2 of the electrolytic cell 231 (step S02), and second electrolyte Le2 is injected into the two electrode chambers RE1 and RE2 of the electrolytic cell 231 (step S03). After injecting the corresponding solutions into electrode chambers RE1 and RE2 and intermediate chambers RM1 and RM2 respectively (steps S01 to S03), voltage is applied to the two electrodes 237 and 239 in the two electrode chambers RE1 and RE2 to perform an electrodialysis process (step S04). The anion-containing waste liquid Lw' originates from the formation unit 170.

[0061] In some embodiments, the first electrolyte Le1 may be water or a very low concentration acid solution. The very low concentration acid solution may be, for example, hydrochloric acid, sulfuric acid, or phosphoric acid. In some embodiments, the very low concentration acid solution is an acid solution with a concentration of less than or equal to 0.1%.

[0062] In some embodiments, the second electrolyte Le2 may be a conductive liquid. The conductive liquid may be, for example, sodium sulfate, sodium chloride, or the aforementioned anion-containing waste liquids Lw, Lw', etc.

[0063] Reference Figures 1 to 5 In step S04, the main body 230 of the waste liquid regeneration device 20 electrolyzes the anion-containing waste liquid Lw' in the first intermediate compartment RM1 and the second electrolyte Le2 in the electrode compartments RE1 and RE2 to form (i.e., separated by electric field force) anions Ia, cations Ic and forming agent Lr' in the first intermediate compartment RM1, and to form (i.e., separated by electric field force) cations Ic in the electrode compartment RE1 (step S41). Then, each second intermediate compartment RM2 introduces anions Ia from the intermediate compartment (i.e., the first intermediate compartment RM1) adjacent to it on one side via anion exchange membrane 235 (step S42), and introduces cations Ic from the electrode compartment RE1 or intermediate compartment (i.e., the first intermediate compartment RM1) adjacent to it on the other side via cation exchange membrane 233 (step S43). Furthermore, the main body 230 of the waste liquid regeneration device 20 synthesizes acid solution La' in each of the second intermediate compartments RM2 using anions Ia and cations Ic (step S44). In some embodiments, acid solution La' is, for example, hydrochloric acid or sulfuric acid. In some embodiments, anion Ia is, for example, chloride ion or sulfate ion.

[0064] In some embodiments, the anion-containing waste liquid Lw' is an acidic aqueous solution containing anion Ia. Specifically, the anion-containing waste liquid Lw' includes a phosphate-containing forming agent Lr' and anion Ia. In step S41, during electrolysis, the anion Ia in the anion-containing waste liquid Lw' will form a free state. In some embodiments, the anion-containing waste liquid Lw' may also include a solvent. The solvent is water. In other words, the concentration of the phosphate-containing forming agent Lr' is greater than 0% and less than 100%. In step S41, during electrolysis, in addition to the anion Ia in the anion-containing waste liquid Lw' forming a free state, the water in the anion-containing waste liquid Lw' will be decomposed to obtain hydrogen ions (i.e., cation Ic).

[0065] In some embodiments, the anion-containing waste liquid Lw' may be a chloride-containing waste liquid. The second electrolyte Le2 includes water. In step S41, during electrolysis, free chloride ions (Cl) are generated. - (i.e., anion Ia) and hydrogen ions (H) + (i.e., cation Ic). In steps S42 to S44, free chloride ions (i.e., anions Ia) and hydrogen ions (i.e., cations Ic) can enter the second compartment RM2 through anion exchange membrane 235 and cation exchange membrane 233 respectively, and combine in the second compartment RM2 to form hydrochloric acid (HCl) (i.e., acid La').

[0066] In some embodiments, the cation exchange membrane 233 may be a hydrogen ion selective membrane, thereby more effectively introducing hydrogen ions into the second intermediate compartment RM2.

[0067] In some embodiments, the main body 230 of the wastewater regeneration device 20 is also coupled to the pickling unit 130. Specifically, the second intermediate chamber RM2 is controllably connected to the pickling unit 130. After the electrodialysis procedure is completed (step S04), the main body 230 of the wastewater regeneration device 20 can provide the acid solution La' synthesized in the second intermediate chamber RM2 to the pickling unit 130. That is, in addition to receiving the externally supplied acid solution La, the pickling unit 130 also receives the acid solution La' from the second intermediate chamber RM2. In some embodiments, after the electrodialysis procedure is completed (step S04), the acid solution La' in the second intermediate chamber RM2 is the same as the acid solution La required by the pickling unit 130 during the pickling procedure (e.g., both are hydrochloric acid), but its concentration is lower than the concentration of the acid solution La required during the pickling procedure. The acid solution La' synthesized in the second intermediate chamber RM2 in the pickling unit 130 is mixed with the externally supplied acid solution La, thus forming the concentration of the acid solution La required during the pickling procedure. In some embodiments, the first electrolyte Le1 may be a low-concentration acid solution similar to the acid solution La' synthesized in the second compartment RM2, i.e., its concentration is lower than the concentration of the acid solution La' in the second compartment RM2 after the completion of the electrodialysis procedure (step S04). For example, the acid solution La' synthesized in the second compartment RM2 after the completion of the electrodialysis procedure (step S04) is 0.5% hydrochloric acid, while the first electrolyte Le1 is 0.1% hydrochloric acid.

[0068] In some embodiments, the waste regeneration device 20 maintains the concentration of acid La' in the second compartment RM2 at less than or equal to 0.5%. In other words, when the concentration of acid La' in the second compartment RM2 is equal to or greater than 0.5%, the waste regeneration device 20 discharges the liquid (i.e., acid La') from the second compartment RM2 and provides it to the pickling unit 130. Then, during the next electrodialysis procedure, the waste regeneration device 20 re-injects the first electrolyte Le1 into the second compartment RM2. In some embodiments, the first electrolyte Le1 may be provided externally or prepared (diluted) from the acid La' generated in the previous electrodialysis procedure. In some embodiments, the concentration of acid La' in the second compartment RM2 may be maintained at less than 0.5%.

[0069] In some embodiments, electrode chamber RE1 is an anode chamber, and electrode chamber RE2 is a cathode chamber. In some exemplary embodiments, refer to... Figure 2Taking two cation exchange membranes 233 and one anion exchange membrane 235 interleaved and separated into a first compartment RM1 and a second compartment RM2 as an example, one side of the first compartment RM1 is adjacent to the electrode chamber RE2 via the cation exchange membrane 233, and the other side of the first compartment RM1 is adjacent to one side of the second compartment RM2 via the anion exchange membrane 235. The other side of the second compartment RM2 is adjacent to the electrode chamber RE1 via the cation exchange membrane 233. In steps S42-S43, the second compartment RM2 receives anions Ia from the first compartment RM1 via the anion exchange membrane 235 and receives cations Ic from the electrode chamber RE1 via the cation exchange membrane 233.

[0070] In other examples, refer to Figure 3 Taking a different configuration, with three cation exchange membranes 233 and two anion exchange membranes 235 interleaved and separated to form two first compartments RM1 (hereinafter referred to as the left first compartment RM1 and the right first compartment RM1) and two second compartments RM2 (hereinafter referred to as the left second compartment RM2 and the right second compartment RM2), one side (left side) of the left first compartment RM1 is adjacent to the electrode chamber RE2 by a cation exchange membrane 233, and the other side (right side) of the left first compartment RM1 is adjacent to one side (left side) of the left second compartment RM2 by anion exchange membrane 235. Similarly, the other side (right side) of the left second compartment RM2 is adjacent to one side (left side) of the right first compartment RM1 by a cation exchange membrane 233. The other side (right side) of the right first compartment RM1 is adjacent to one side (left side) of the right second compartment RM2 by anion exchange membrane 235. And the other side (right side) of the right second compartment RM2 is adjacent to the electrode chamber RE1 by a cation exchange membrane 233. At this time, in steps S42 to S43, the left second compartment RM2 receives anion Ia from the left first compartment RM1 via anion exchange membrane 235 and receives cation Ic from the right first compartment RM1 via cation exchange membrane 233, and the right second compartment RM2 receives anion Ia from the right first compartment RM1 via anion exchange membrane 235 and receives cation Ic from electrode chamber RE1 via cation exchange membrane 233.

[0071] Therefore, in other embodiments, the number of cation exchange membranes 233 and anion exchange membranes 235 can be adjusted as needed, thereby adjusting the number of intermediate compartments RM1 and RM2, without being limited to the aforementioned embodiments.

[0072] In some embodiments, in step S01, the injected anionic waste liquid Lw' can be directly discharged from the formation unit 170 and injected into the first intermediate compartment RM1.

[0073] In other embodiments, in step S01, the injected anion-containing waste liquid Lw' may be discharged from the formation unit 170, accumulated to a predetermined concentration, and then injected into the first intermediate chamber RM1. In other words, the waste liquid regeneration device 20 may also include a temporary storage tank 210 for temporarily storing the anion-containing waste liquid Lw'. The temporary storage tank 210 is coupled between the formation unit 170 and the first intermediate chamber RM1 of the main body 230, and controllably connects the formation unit 170 and the first intermediate chamber RM1. The anion concentration of the anion-containing waste liquid Lw output by the formation unit 170 is greater than the anion concentration of the anion-containing waste liquid Lw' received by the first intermediate chamber RM1.

[0074] After each membrane treatment, the formation unit 170 can first discharge the anion-containing waste liquid Lw' into the temporary storage tank 210. Only when the anion-containing waste liquid Lw' in the temporary storage tank 210 accumulates to a predetermined anion concentration will it be introduced into the first intermediate compartment RM1. This avoids the chloride ion concentration in the anion-containing waste liquid Lw' being too low, which could affect the effectiveness of electrodialysis, and also prevents uneven concentration distribution of the formation reagent Lr in the formation unit 170. In some embodiments, the concentration of the anion-containing waste liquid Lw output from the temporary storage tank 210 is less than or equal to 10%.

[0075] In some embodiments, the waste liquid regeneration equipment 20 can directly measure the anion concentration of the liquid (i.e., anion-containing waste liquid Lw') in the temporary storage tank 210 using the detection unit 281. In other words, the detection unit 281 includes anion measuring instruments. For example, when the anion Ia in the anion-containing waste liquid Lw' is chloride ions, the detection unit 281 includes chloride ion measuring instruments. In other embodiments, considering equipment cost, the waste liquid regeneration equipment 20 can also indirectly determine the chloride ion concentration by measuring the conductivity of the liquid (i.e., anion-containing waste liquid Lw') in the temporary storage tank 210 using the detection unit 281. In other words, the detection unit 281 includes a conductivity meter. When the measured chloride ion concentration or conductivity reaches a predetermined value, the detection unit 281 then opens the pump or valve to introduce the anion-containing waste liquid Lw' in the temporary storage tank 210 into the first intermediate compartment RM1.

[0076] In some embodiments, the coating treatment apparatus 10 may further include a dosing tank 140. The dosing tank 140 is coupled between the formation unit 170 and the first intermediate chamber RM1 of the main body 230. In addition to receiving externally supplied formation agent Lr, the dosing tank 140 also receives regenerated formation agent Lr' from the first intermediate chamber RM1. In other words, the coating treatment apparatus 10 supplies (outputs) the regenerated formation agent Lr' from the first intermediate chamber RM1 to the dosing tank 140. The dosing tank 140 adjusts the concentration of the formation agent Lr' and provides the formation unit 170 with the required concentration of formation agent Lr for coating treatment. For example, in an aluminum foil process, the formation agent Lr may be dipotassium hydrogen phosphate (K2HPO4), and the concentration required for coating treatment may be 10%. If the regenerated formation agent Lr' in the first intermediate compartment RM1 is less than 10%, the new formation agent Lr input from the outside into the dosing tank 140 will be greater than 10%. The regenerated formation agent Lr' and the new formation agent Lr are input into the dosing tank 140 together to adjust the concentration, so that the dosing tank 140 can provide 10% dipotassium hydrogen phosphate to the formation unit 170 for film treatment.

[0077] For example, taking aluminum foil processing as an example, when using... Figure 1 and Figure 3In the illustrated architecture, the substrate 30 is aluminum foil, the forming agent Lr is dipotassium hydrogen phosphate, and the anion in the anion-containing waste liquid Lw is chloride ion. Here, the coating treatment equipment 10 has four consecutively operating processing units: an acid pickling unit 130, a first electro-erosion unit 150, a forming unit 170, and a second electro-erosion unit 190. In other words, the first electro-erosion unit 150 is executed between the acid pickling unit 130 and the forming unit 170, and the forming unit 170 is executed between the first electro-erosion unit 150 and the second electro-erosion unit 190. The feeding unit 110 controls the substrate 30 (aluminum foil) to sequentially pass through the pickling unit 130, the first electro-etching unit 150, the formation unit 170, and the second electro-etching unit 190. The substrate 30 (aluminum foil) first undergoes a pickling process in hydrochloric acid in the pickling unit 130, then undergoes a first electro-etching process in the first electro-etching unit 150, followed by a film treatment with the formation agent Lr (dipotassium hydrogen phosphate) in the formation unit 170 to form an aluminum oxide film on its surface, and then undergoes a second electro-etching process in the second electro-etching unit 190. After each aluminum foil process is completed, the chloride-containing waste liquid in the formation unit 170 is discharged into the temporary storage tank 210. Then, at two different time points, the chloride-containing waste liquid in the temporary storage tank 210 is introduced into the waste liquid regeneration equipment 20 for a regeneration process. Furthermore, during the electrodialysis regeneration process in the waste liquid regeneration equipment 20, the conductivity of the liquid in the second intermediate compartment RM2 (i.e., the first electrolyte Le1, acid La' or a mixture thereof) and the changes in the chloride ion removal efficiency of the liquid in the first intermediate compartment RM1 (i.e., chloride-containing waste liquid) were observed.

[0078] Reference Figure 6 When the first batch of chloride-containing waste liquid was introduced, the initial conductivity of the liquid in the second compartment RM2 was 10.86 mS / cm. After 20 minutes of electrodialysis, the conductivity of the liquid in the second compartment RM2 was 15.96 mS / cm. At this point, the chloride ion removal rate of the chloride-containing waste liquid in the first compartment RM1 reached 88%. - =150 mg / L). After 40 minutes of electrodialysis, the conductivity of the liquid in the second compartment RM2 was 13.25 mS / cm, and the chloride ion removal rate of the chloride-containing waste liquid in the first compartment RM1 was 96% (Cl... - =52 mg / L). When the second batch of chloride-containing waste liquid was introduced, the initial conductivity of the liquid in the second compartment RM2 was 16.42 mS / cm. After 20 minutes of electrodialysis, the conductivity of the liquid in the second compartment RM2 was 20.30 mS / cm. At this point, the chloride ion removal rate of the chloride-containing waste liquid in the first compartment RM1 reached 80% (Cl... -=256 mg / L). After 40 minutes of electrodialysis, the conductivity of the liquid in the second compartment RM2 was 16.60 mS / cm. At this point, the chloride ion removal rate of the chloride-containing waste liquid in the first compartment RM1 was 95% (Cl...). - =64mg / L). Therefore, the chloride ion removal rate of both the first and second batches of chloride-containing wastewater entering the influent reached 90% within 30 minutes (Cl...). - <300mg / L). The conductivity of the liquid in the second compartment RM2 gradually increases with the accumulation of hydrogen and chloride ions (i.e., the HCl concentration gradually increases). During the 20-minute electrodialysis period after the introduction of the chloride-containing waste liquid, the conductivity of the liquid in the first compartment RM1 decreases slightly and the pH value increases as the chloride ion concentration of the chloride-containing waste liquid in the first compartment RM1 decreases and hydrogen ions in the water are removed.

[0079] It should be understood that although the steps are described sequentially above, this is not the only possible approach. Under reasonable circumstances, the execution order of some steps may be performed simultaneously or interchanged. For example, steps S01 to S03 may be executed sequentially or simultaneously, or in the order of S01, S03, and S02; S02, S03, and S01; S02, S01, and S03; S03, S01, and S02; or S03, S02, and S01. Step S04 is executed only after steps S01 to S03 are completed. In another example, besides... Figure 4 The sequence shown can be either simultaneous or in reverse order, with steps S42 to S43 occurring after step S41 and before step S44.

[0080] In summary, the surface treatment process system 1, waste liquid regeneration equipment 20, or waste liquid regeneration method of any embodiment utilizes electrodialysis technology to remove the anions Ia contained in the anion-containing waste liquid Lw' during the waste liquid regeneration process, thereby regenerating the formation agent Lr' and simultaneously producing acid La'. Therefore, the waste liquid regeneration process does not require the addition of additional agents or the consumption of additional heat energy, thus effectively reducing the carbon emissions and operating costs of the surface treatment process. In some embodiments, the surface treatment process system 1, waste liquid regeneration equipment 20, or waste liquid regeneration method can also guide the simultaneously generated formation agent Lr' and acid La' back to the film treatment equipment 10 for reuse in the surface treatment process, thereby achieving full recycling.

Claims

1. A surface treatment process system, characterized in that, Applied to a substrate, including: A coating treatment apparatus for surface modification of the substrate, comprising: Pickling unit, used to receive acid solution; A formation unit is used to receive formation reagents and output anion-containing waste liquid; and A feeding unit is used to convey the substrate so that it sequentially passes through the pickling unit and the formation unit; and Waste liquid regeneration equipment, connected to the membrane treatment equipment, includes: Electrolytic cell; Multiple cation exchange membranes are spaced apart within the electrolyzer; and At least one anion exchange membrane is disposed at intervals within the electrolytic cell; The plurality of cation exchange membranes and the at least one anion exchange membrane are alternately arranged to divide the electrolytic cell into two electrode chambers, at least one first intermediate chamber and at least one second intermediate chamber. The at least one first intermediate chamber and the at least one second intermediate chamber are alternately located between the two electrode chambers. Each first intermediate chamber is configured to regenerate the anion-containing waste liquid into the chemical reagent. Each second intermediate chamber is configured to receive anions from the anion-containing waste liquid via the anion exchange membrane and cations from the anion-containing waste liquid or electrolyte via the cation exchange membrane, and to synthesize the acid solution with the anions and the cations.

2. The surface treatment process system as described in claim 1, characterized in that, The formation unit is a film treatment tank.

3. The surface treatment process system as described in claim 2, characterized in that, The pickling unit is a pickling tank suitable for containing the acid solution.

4. The surface treatment process system as described in claim 3, characterized in that, The acid solution is hydrochloric acid or sulfuric acid.

5. The surface treatment process system as described in claim 2, characterized in that, The anion-containing waste liquid includes the chemical reagent containing phosphate and the anion.

6. The surface treatment process system as described in claim 1, characterized in that, The waste liquid regeneration equipment further includes a temporary storage tank, coupled between the formation unit and the waste liquid regeneration equipment, for temporarily storing the anion-containing waste liquid.

7. The surface treatment process system as described in claim 6, characterized in that, The concentration of anions in the anion-containing waste liquid output by the formation unit is less than the concentration of anions in the anion-containing waste liquid received by the first intermediate compartment.

8. The surface treatment process system as described in claim 1, characterized in that, The film treatment equipment further includes a dosing tank coupled between the formation unit and the waste liquid regeneration equipment for providing the formation agent to the pickling unit, wherein the waste liquid regeneration equipment is configured to provide the formation agent regenerated in each of the first intermediate compartments to the dosing tank.

9. The surface treatment process system as described in claim 1, characterized in that, The waste liquid regeneration equipment is coupled to the pickling unit and configured to provide the acid liquid synthesized in each of the second intermediate compartments to the pickling unit.

10. The surface treatment process system as described in claim 1, characterized in that, The cation exchange membrane is a hydrogen ion selective membrane.

11. A waste liquid regeneration device, characterized in that, include: Electrolytic cell; Multiple cation exchange membranes are located within the electrolytic cell; as well as At least one anion exchange membrane is located within the electrolytic cell; The plurality of cation exchange membranes and the at least one anion exchange membrane are alternately and spaced apart to divide the electrolytic cell into two electrode chambers, at least one first intermediate chamber and at least one second intermediate chamber. The at least one first intermediate chamber and the at least one second intermediate chamber are alternately located between the two electrode chambers. Each first intermediate chamber is configured to receive anion-containing waste liquid and regenerate the anion-containing waste liquid into a chemical reagent. Each second intermediate chamber is configured to receive anions from the anion-containing waste liquid via the anion exchange membrane, receive cations from the anion-containing waste liquid or electrolyte via the cation exchange membrane, and synthesize an acid solution with the anions and the cations.

12. A method for regenerating waste liquid, characterized in that, include: Injecting anion-containing waste liquid into at least one of the first intermediate compartments of the electrolytic cell; Injecting a first electrolyte into at least one second compartment of the electrolytic cell; A second electrolyte is injected into the two electrode chambers of the electrolytic cell, wherein the two electrode chambers, the at least one first compartment and the at least one second compartment are separated by a plurality of cation exchange membranes and at least one anion exchange membrane alternately arranged in the electrolytic cell, and the at least one first compartment and the at least one second compartment are alternately located between the two electrode chambers; as well as Applying a voltage to the two electrodes in the two-electrode chamber to perform an electrodialysis procedure, wherein the steps of performing the electrodialysis procedure include: The anion-containing waste liquid and the second electrolyte are electrolyzed to form anions, cations and a chemical reagent in the first intermediate compartment, and the cations are formed in the electrode compartment; The anions are introduced into the second compartment via the anion exchange membrane; The cations are introduced into the second compartment via the cation exchange membrane; and An acid solution is synthesized by combining the anion and the cation in the second compartment.

13. The waste liquid regeneration method as described in claim 12, characterized in that, The concentration of the anion-containing waste liquid is less than or equal to 10%.

14. The waste liquid regeneration method as described in claim 12, characterized in that, The concentration of the acid in the second compartment is less than or equal to 0.5%.

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