A system and method for extracting and recovering metals from etching waste liquid

Abstract

This invention relates to the field of resource recycling technology, specifically disclosing a system and method for extracting and recovering metals from etching waste liquid. The extractant combination of this invention can minimize the loss of etching aids, preserve the original composition of the etching liquid, and allow the etching liquid to be completely reused after reducing copper, molybdenum, and other metal ions. The extractant of this invention has a long effective life cycle of extraction-back-extraction, minimal loss of extractant aids in the extraction-back-extraction cycle, and no emulsification / flocculation of the extract phase during the extraction process. The extraction rate of copper and molybdenum in the etching liquid is high. By using a specific three-phase extractant combination, more than 98% of copper and molybdenum in the waste liquid can be recovered. The copper extraction process has a good retention effect on nitrogen azole etching aids, such as 5-aminotetrazole, thereby forming a closed loop in the extraction-back-extraction cycle of the etching liquid, reducing material input and pollution.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment and resource recycling technology, and discloses a system and method for extracting and recovering metals from etching waste liquid. Background Technology

[0002] Etching solutions are used for selective removal, cleaning, and pattern transfer on copper and copper alloy surfaces, and are applied in multiple industries such as PCB (printed circuit board) manufacturing, T-LCD display electrode substrate processing, and microelectronics processing.

[0003] After long-term operation, depending on the process, the concentration of copper and other etched free metal ions in the etching solution increases, leading to a decrease in etching rate, increased risk of crystallization and precipitation, uneven etching, and rough edges. Therefore, recycling copper and alloy ions from the etching solution is an indispensable part of the process. Existing copper recovery technologies include electrolysis, which uses an applied current to reduce copper ions to metallic copper, and membrane separation, which uses nanofiltration and reverse osmosis to retain copper ions. These methods focus on different scenarios, but all have certain drawbacks. Electrodeposition has a minimum concentration limit and low deposition efficiency. Below 10 g / L, the excessively low copper concentration makes electrolysis unsuitable for application and results in hydrogen evolution side reactions. The anode material often needs to be titanium, which also leads to high investment costs. Membrane separation is susceptible to organic contamination and suspended solids deposition, and its limited flux restricts its application to small to medium-sized processes, failing to meet the demands of large-scale rapid wastewater treatment. Solvent extraction effectively overcomes these shortcomings, effectively extracting copper ions at concentrations as low as 1 g / L, demonstrating a strong affinity for copper ions. However, this method also has drawbacks. Due to the diverse types of etching aids, some may be extracted into the organic phase along with copper ions, resulting in aid loss. Furthermore, in some processes, the etched metal composition is complex, not limited to a single metal, as illustrated in CN103924242A. In etching solutions for copper / molybdenum films or copper / molybdenum alloy films, it is necessary to extract copper and molybdenum ions simultaneously, and nitrazole compounds, which are etching aids, are present. However, some extractant formulations can only extract some metal ions, while their ability to extract other metal ions is poor. This results in the enrichment of some metal ions in the circulating system, or a significant reduction in the content of the aids during the cycle. Ultimately, this leads to unstable quality of the etched product and increased costs. Furthermore, the aids are carried into the extract phase during extraction, which shortens the number of extraction-back-extraction cycles of the extractant and reduces the lifespan of the product. Therefore, compared with electrowinning and membrane separation methods, solvent extraction requires the design of different extraction components for different etching processes. Summary of the Invention

[0004] To address the problems existing in the prior art, the first aspect of this invention proposes a system for extracting and recovering metals from etching waste liquid, comprising:

[0005] An extraction device is used to mix the etching solution to be treated and the extract phase. The etching solution to be treated and the extract phase are mixed, and metal ion transfer occurs to obtain a regenerated etching solution and a loaded extract phase containing metal ions. The extraction device outputs the loaded extract phase and the regenerated etching solution to a back-extraction device and a transfer tank, respectively.

[0006] The transfer tank receives the regenerated etching solution from the extraction device and outputs it to the mixing tank, which is used to adjust the content of each component in the regenerated etching solution. After adjustment, the regenerated etching solution is output to the regenerated sub-liquid tank and used as the etching solution in the etching machine.

[0007] The back-extraction device receives the loaded extract phase from the extraction device, and the loaded extract phase is mixed with the back-extraction acid solution to obtain a regenerated extract phase and a back-extraction acid solution loaded with metal ions.

[0008] The regenerated extract phase is output to the extraction device for the extraction of metal ions in the etching solution to be treated in the extraction device.

[0009] The back-extraction acid solution loaded with metal ions is output to the enrichment solution electrodeposition device, where it is electrolyzed to obtain the metal.

[0010] The extractant phase includes a diluent and a ternary mixture of extractant phases, wherein the ternary mixture of extractant phases includes butyl(1-styryl)phenylphosphonate, 1-(2-isobutylphenyl)ethyl ketone oxime, and 1-(2-dodecylphenyl)-1,3-butanedione.

[0011] In some specific embodiments of the system for extracting and recovering metals from etching wastewater in the first aspect, the molar ratio of butyl(1-styrene)phenylphosphonate to 1-(2-isobutylphenyl)ethyl ketone oxime in the extraction phase is (4~6):(3~5). In some specific embodiments of the system for extracting and recovering metals from etching wastewater in the first aspect, the molar ratio of butyl(1-styrene)phenylphosphonate to 1-(2-isobutylphenyl)ethyl ketone oxime in the extraction phase is optionally 4:3, 4:5, 5:3, or 5:3.

[0012] In some specific embodiments of the system for extracting and recovering metals from etching wastewater in the first aspect, the molar ratio of 1-(2-isobutylphenyl) ethyl ketone oxime to 1-(2-dodecylphenyl)-1,3-butanedione in the extraction phase is (6~10):(1~2). In some specific embodiments of the system for extracting and recovering metals from etching wastewater in the first aspect, the molar ratio of 1-(2-isobutylphenyl) ethyl ketone oxime to 1-(2-dodecylphenyl)-1,3-butanedione in the extraction phase is optionally 6:1, 8:1, or 10:1.

[0013] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the diluent is selected from non-polar solvents or polar solvents, wherein the non-polar solvent is selected from one or more of kerosene, diethyl ether, toluene, and cyclohexane.

[0014] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, 150-200g of a ternary mixture of the extractant phase is added to each 1L of the extractant phase. In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the ternary mixture of the extractant phase added to each 1L of the extractant phase is optionally 150g, 170g, or 190g.

[0015] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the volume ratio of the etching solution to be treated to the extractant phase in the extraction device is (1~3):1. In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the volume ratio of the etching solution to be treated to the extractant phase in the extraction device is optionally 1:1, 2:1, or 3:1.

[0016] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the etching solution to be treated and the extractant phase are mixed at 10~40°C in the extraction device. In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the etching solution to be treated and the extractant phase are optionally mixed at 15°C, 20°C, 25°C, 30°C, and 35°C in the extraction device.

[0017] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the etching solution to be treated and the extraction phase are mixed and stirred for 5 to 10 minutes in the extraction device. In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the etching solution to be treated and the extraction phase are mixed and stirred for 6, 7, 8, or 9 minutes in the extraction device.

[0018] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the back-extraction acid solution is selected from an aqueous solution of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the back-extraction acid solution is 3~5 mol / L. In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the back-extraction acid solution is selected from an aqueous solution of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the back-extraction acid solution is optionally 3 mol / L, 4 mol / L, or 5 mol / L.

[0019] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the mixing volume ratio of the back-extraction acid solution to the supported extraction phase is 1:(1~3). In some specific embodiments of the system for extracting and recovering metals from etching waste liquid in the first aspect, the mixing volume ratio of the back-extraction acid solution to the supported extraction phase is optionally 1:1, 1:2, or 1:3.

[0020] In specific embodiments of the system for extracting and recovering metals from etching wastewater in the first aspect, the electrolysis method involves adjusting the pH of the back-extraction acid solution loaded with metal ions to 2-4, using a titanium-coated iridium-tantalum anode as the anode and a copper plate as the cathode, and controlling the current density at 100-300 A / m. 2 Electrowinning is performed within a certain range to deposit a metal, the metal being selected from copper.

[0021] A second aspect of this invention provides a method for extracting and recovering metals from etching waste liquid, comprising the following steps:

[0022] S1: Butyl(1-styryl)phenylphosphonate, 1-(2-isobutylphenyl)ethyl ketone oxime, and 1-(2-dodecylphenyl)-1,3-butanedione are mixed to obtain a ternary mixture of the extract phase. The ternary mixture of the extract phase is then mixed with a diluent to obtain the extractant.

[0023] S2: The extractant is mixed with the etching solution to be treated, stirred, and separated to obtain a regenerated etching solution and a loaded extract phase;

[0024] S3: The loaded extract phase is mixed with the back-extraction acid solution to obtain a back-extraction acid solution loaded with metal ions and a regenerated extract phase;

[0025] S4: Electrowinning of the back-extraction acid solution yields the metal.

[0026] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the molar ratio of butyl(1-styrene)phenylphosphonate to 1-(2-isobutylphenyl)ethyl ketone oxime is (4~6):(3~5).

[0027] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the molar ratio of 1-(2-isobutylphenyl) ethyl ketone oxime to 1-(2-dodecylphenyl)-1,3-butanedione in the extraction phase is (6~10):(1~2).

[0028] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the diluent is selected from non-polar solvents or polar solvents, and the non-polar solvent is selected from one or more of kerosene, diethyl ether, toluene, and cyclohexane.

[0029] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, 150-200g of a ternary mixture of the extract phase is added to each 1L of extract phase.

[0030] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the volume ratio of the etching liquid to be treated to the extraction phase is (1~3):1.

[0031] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the etching solution to be treated and the extraction phase are mixed at 10~40°C.

[0032] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the etching solution to be treated is mixed and stirred with the extraction phase for 5 to 10 minutes.

[0033] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the back-extraction acid solution is selected from aqueous solutions of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the back-extraction acid solution is 3~5 mol / L.

[0034] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the mixing volume ratio of the back-extraction acid solution to the supported extraction phase is 1:(1~3).

[0035] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the pH of the back-extraction acid solution loaded with metal ions is adjusted to 2-4, a titanium-coated iridium-tantalum anode is used as the anode, a copper plate is used as the cathode, and the current density is controlled at 100-300 A / m. 2 Electrowinning is performed within a certain range to deposit a metal, the metal being selected from copper.

[0036] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the etching liquid to be treated includes copper ions, molybdenum ions, 5-aminotetrazole, iminodiacetic acid, sodium bisulfate, and water.

[0037] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid described in the second aspect, the etching liquid to be treated comprises 1~11wt% copper ions, 1.5~3.2wt% molybdenum ions, 1.0~2.0wt% 5-aminotetrazole, 0.5~1.0wt% iminodiacetic acid, 1.0~2.0wt% sodium bisulfate, and the remainder is water.

[0038] In Example 1 of this invention, the amount of hydrogen peroxide in the etching solution to be treated is 1.3 wt%, and in Example 2, the amount of hydrogen peroxide in the etching solution to be treated is 1.1 wt%.

[0039] In some embodiments, the room temperature is 5~45°C; in some embodiments, the room temperature is 10~40°C; in some embodiments, the room temperature is 15~35°C; in some embodiments, the room temperature is 20~30°C; and in some embodiments, the room temperature is 25°C.

[0040] The reagents used in this invention are all purchased from the open and legal market and have not undergone further purification.

[0041] In this invention, the titanium-coated iridium-tantalum anode is an iridium-tantalum-titanium anode;

[0042] In this invention, butyl(1-styryl)phenylphosphonate CAS: 31327-22-7; 1-(2-isobutylphenyl)ethyl ketone oxime CAS: 2728664-35-3; 1-(2-dodecylphenyl)-1,3-butanedione CAS: 59863-28-4

[0043] The waste etching solution in this invention consists of: 10~110 g / L Cu ions, 15~32 g / L Mo ions, 1.0~2.0 wt% 5-aminotetrazole (etching inhibitor, ATZ), 0.5~1.0 wt% iminodiacetic acid (chelating agent, IDA), and 1.0~2.0 wt% sodium bisulfate (SHS), with deionized water as the solvent.

[0044] Advantages of this invention:

[0045] The extractant combination of this invention does not damage the original composition of the etching solution, allowing the etching solution to be completely reused after reducing the levels of metal ions such as copper and molybdenum. The extractant of this invention has a long effective life cycle of extraction-back-extraction, with minimal loss of extractant aids during the extraction-back-extraction cycle. The extract phase does not produce emulsions / flocculations during the metal ion extraction process. During the extraction process, there is minimal loss of aids in the etching solution, and the extraction rate of copper and molybdenum in the etching solution is high. By using a specific three-phase extractant combination, more than 98% of copper and molybdenum in the waste liquid can be recovered. During the copper extraction process, azole-based etching aids, such as 5-aminotetrazole, have a good retention effect, thus requiring less material replenishment during the extraction process and forming a closed loop. The extractant and back-extraction solution are circulated in a closed loop, without generating new pollution. Attached Figure Description

[0046] Figure 1 The diagram shows the connection of the copper extraction and recovery system of the etching solution of the present invention. Detailed Implementation

[0047] To enable those skilled in the art to better understand the technical solutions of the present invention, some non-limiting embodiments are further disclosed below to provide a more detailed description of the present invention.

[0048] Extraction method:

[0049] Step 1: Preparation of the extraction solvent

[0050] A ternary mixture of extractant phases was obtained by mixing 40-60% by mass of butyl(1-styryl)phenylphosphonate, 30-50% by mass of 1-(2-isobutylphenyl)ethyl ketone oxime, and 5-10% by mass of 1-(2-dodecylphenyl)-1,3-butanedione.

[0051] The ternary mixture of the extract phase is dissolved in toluene or other inert organic solvents such as cyclohexane at a concentration of 150~200 g / L to prepare the extract phase.

[0052] Step 2: Extract metal ions from waste etching solution

[0053] The etching solution to be treated is mixed with the extractant prepared in step 1 at a volume ratio of 3:1 and stirred at 10~40℃ for 5~10 minutes to ensure full contact between the etching solution and the extractant. After mixing, the mixture is allowed to stand for phase separation. Copper and molybdenum metal ions are extracted into the extract phase, resulting in an upper layer of loaded extract phase containing copper and molybdenum metal ions. The lower layer of regenerated etching solution is placed in a transfer tank for standing. The content of each component in the regenerated etching solution in the transfer tank is measured, and then it is placed in a mixing tank to adjust the content of the additives. After mixing, the solution is collected in a regenerated sub-liquid tank, and hydrogen peroxide is added at a concentration of 10~25wt%. The solution is then recycled in the etching machine.

[0054] Step 3: Back-extract metal ions from the supported extraction phase

[0055] A loaded extract phase containing copper and molybdenum metal ions is mixed with a 3-5 mol / L sulfuric acid solution at a 1:1 volume ratio and stirred for 5-10 minutes to complete the back-extraction process. Metal ions are transferred from the metal-loaded extract phase to the back-extraction acid solution, resulting in a regenerated extract phase and a metal-loaded back-extraction acid solution. The back-extraction acid solution is recycled for extraction of each batch of metal-loaded extract phase. During the recycling process, the sulfuric acid concentration is maintained at 3-5 mol / L. When the copper metal ion concentration in the back-extraction acid solution exceeds 50 g / L, the acidic aqueous phase can be used as the raw solution for the copper electrowinning process.

[0056] Step 4: Copper recycling process in the electrowinning copper process.

[0057] The back-extraction acid solution was adjusted to pH 2-4. A titanium-coated iridium-tantalum anode was used as the anode, and a copper plate was used as the cathode. The current density was controlled at 100-300 A / m. 2 Electrowinning is performed within the specified range to deposit metallic copper.

[0058] Example 1

[0059] The etching solution prepared in this embodiment is: 50 g / L copper ions, 32 g / L molybdenum ions, 2.0 wt% 5-aminotetrazole, 1.0 wt% iminodiacetic acid, and 2.0 wt% sodium bisulfate.

[0060] Step 1: Preparation of the extraction solvent

[0061] A ternary mixture of extractant phases was obtained by mixing 40% by mass of butyl(1-styryl)phenylphosphonate, 50% by mass of 1-(2-isobutylphenyl)ethyl ketone oxime, and 10% by mass of 1-(2-dodecylphenyl)-1,3-butanedione.

[0062] The ternary mixture of the extract phase was dissolved in cyclohexane at a concentration of 150 g / L to prepare the extract phase.

[0063] Step 2: Extract metal ions from waste etching solution

[0064] In this embodiment, the etching solution and the extraction phase prepared in step 1 are mixed at a volume ratio of 3:1 and stirred at 20°C for 5 minutes to ensure sufficient contact between the etching solution and the extraction phase. After mixing, the mixture is allowed to stand and separate phases to obtain the upper layer of the copper and molybdenum ion-loaded extraction phase. The lower layer of regenerated etching solution is placed in a transfer tank and allowed to stand. The content of each component in the regenerated etching solution in the transfer tank is measured. Then, it is placed in a mixing tank to adjust the content of each auxiliary agent to 2.0 wt% 5-aminotetrazole, 1.0 wt% iminodiacetic acid, and 2.0 wt% sodium bisulfate. After mixing, the solution is collected in a regenerated sub-liquid tank and hydrogen peroxide is added to 15 wt% for recycling in the etching machine.

[0065] Step 3: Back-extract metal ions from the supported extraction phase

[0066] The loaded extract phase containing copper and molybdenum ions is mixed with a 3 mol / L sulfuric acid solution at a 1:1 volume ratio. The mixture is stirred for 5 minutes to complete the back-extraction process, during which copper and molybdenum ions are transferred from the loaded extract phase to the back-extraction acid solution, resulting in a regenerated extract phase and a back-extraction acid solution containing copper and molybdenum ions. The back-extraction acid solution is recycled to extract each batch of loaded extract phase containing copper and molybdenum ions. During the recycling process, the sulfuric acid concentration is maintained at 3 mol / L. The back-extraction acid solution is used as the raw solution for the copper electrowinning process.

[0067] Step 4: Copper recycling process in the electrowinning copper process.

[0068] The back-extraction acid solution was adjusted to pH 2-4. A titanium-coated iridium-tantalum anode was used as the anode, and a copper plate was used as the cathode. The current density was controlled at 100 A / m. 2 Electrowinning is performed within the specified range to deposit metallic copper.

[0069] Example 2

[0070] The waste etching solution in this invention consists of: 10 g / L copper ions, 15 g / L molybdenum ions, 2.0 wt% 5-aminotetrazole, 1.0 wt% iminodiacetic acid, and 1.0 wt% sodium bisulfate.

[0071] Step 1: Preparation of the extraction solvent

[0072] A ternary mixture of extractant phases was obtained by mixing 40% by mass of butyl(1-styryl)phenylphosphonate, 55% by mass of 1-(2-isobutylphenyl)ethyl ketone oxime, and 5% by mass of 1-(2-dodecylphenyl)-1,3-butanedione.

[0073] The ternary mixture of the extract phase was dissolved in cyclohexane at a concentration of 200 g / L to prepare the extract phase.

[0074] Step 2: Extract metal ions from waste etching solution

[0075] The etching solution to be treated is mixed with the extraction phase prepared in step 1 at a volume ratio of 3:1 and stirred at 40°C for 10 minutes to ensure full contact between the etching solution and the extraction phase. After mixing, the mixture is allowed to stand and separate phases to obtain the upper layer of copper and molybdenum ion-loaded extraction phase. The lower layer of regenerated etching solution is placed in a transfer tank and allowed to stand. The content of each component in the regenerated etching solution in the transfer tank is measured. Then, it is placed in a mixing tank to adjust the content of each auxiliary agent to 2.0 wt% 5-aminotetrazole, 1.0 wt% iminodiacetic acid, and 1.0 wt% sodium bisulfate. After mixing, the solution is collected in the regenerated sub-liquid tank and the hydrogen peroxide concentration is adjusted to 15 wt%. The solution is then recycled in the etching machine.

[0076] Step 3: Back-extract metal ions from the supported extraction phase

[0077] The copper- and molybdenum-loaded extract phase is mixed with a 5 mol / L sulfuric acid solution at a 1:1 volume ratio and stirred for 10 minutes to complete the back-extraction process. Metal ions are transferred from the copper- and molybdenum-loaded extract phase to the back-extraction acid solution, resulting in a regenerated extract phase and a copper- and molybdenum-loaded back-extraction acid solution. This back-extraction acid solution is recycled for extraction of each batch of copper- and molybdenum-loaded extract phase. During the recycling process, the sulfuric acid concentration is maintained at 5 mol / L. This back-extraction acid solution serves as the feed solution for the copper electrowinning process.

[0078] Step 4: Copper recycling process in the electrowinning copper process.

[0079] The back-extraction acid solution was adjusted to pH 2-4. A titanium-coated iridium-tantalum anode was used as the anode, and a copper plate was used as the cathode. The current density was controlled at 300 A / m. 2 Electrowinning is performed within the specified range to deposit metallic copper.

[0080] Comparative Example 1

[0081] The difference between Comparative Example 1 and Example 1 is that the butyl (1-styrene)phenylphosphonate in the step of preparing the ternary mixture of the extract phase in Comparative Example 1 is replaced with an equal mass fraction of tributyl phosphate (TBP). The remaining feed amounts and steps of Comparative Example 1 are the same as those of Example 1.

[0082] Comparative Example 2

[0083] The difference between Comparative Example 2 and Example 1 is that in Comparative Example 2, 1-(2-isobutylphenyl) acetone oxime was replaced with an equal mass fraction of 2-hydroxy-5-nonylacetone oxime (LIX84) in the step of preparing the ternary mixture of the extract phase. The remaining feed amounts and steps of Comparative Example 2 are the same as those of Example 1.

[0084] Comparative Example 3

[0085] The difference between Comparative Example 3 and Example 1 is that 1-(2-dodecylphenyl)-1,3-butanedione is not added in the step of preparing the ternary mixture of the extract phase in Comparative Example 3. The remaining feed amounts and steps are the same as those in Example 1.

[0086] Comparative Example 4

[0087] The difference between Comparative Example 4 and Example 1 is that butyl (1-styrene)phenylphosphonate is not added in the step of preparing the ternary mixture of the extract phase in Comparative Example 4. The remaining feed amounts and steps are the same as those in Example 1.

[0088] Comparative Example 5

[0089] The difference between Comparative Example 5 and Example 1 is that 1-(2-isobutylphenyl)ethyl ketone oxime was not added in the step of preparing the ternary mixture of the extract phase in Comparative Example 5. The remaining feed amounts and steps were the same as in Example 1.

[0090] Example 3

[0091] Examples 1 and 2, and Comparative Examples 1 to 5, were performed after the first extraction-back-extraction cycle. The values ​​of each component in the transfer tank were measured, as shown in Table 1.

[0092]

[0093] In Table 1, A1 represents the copper ion content (g / L) in the etching solution to be treated; A2 represents the copper ion content (g / L) in the transfer tank; B1 represents the molybdenum ion content (g / L) in the etching solution to be treated; B2 represents the molybdenum ion content (g / L) in the transfer tank; C% represents the copper ion extraction rate; D% represents the molybdenum ion extraction rate; E% represents the 5-aminotetrazole content (%) in the regenerated etching solution in the transfer tank; and F% represents the iminodiacetic acid content (%) in the transfer tank.

[0094] Comparative Example 6

[0095] The etching solution prepared in Example 1 was: 50 g / L Cu 2+ Ions, 32 g / L Mo 6+ Ions, 90 g / L Ni 2+ The etching solution, containing 2.0 wt% 5-aminotetrazole, 1.0 wt% iminodiacetic acid, and 2.0 wt% sodium bisulfate, was extracted using the same method as in Example 1. The etching solution in the transfer tank contained 0.21 g / L copper ions, 0.14 g / L molybdenum ions, 87.5 g / L nickel ions, 1.97 wt% 5-aminotetrazole, 1.98 wt% sodium bisulfate, and 0.98 wt% iminodiacetic acid. This indicates that even with a high concentration of competing nickel ions in the etching solution, the extraction of copper and molybdenum is not interfered with. The extractant combination of this invention can resist competitive extraction between metal ions, exhibits strong anti-interference capabilities, and effectively retains some of the auxiliary metal ions added to the etching solution.

[0096] Example 4

[0097] Examples 1 and 2, and Comparative Examples 1 to 5, were tested after the 30th extraction-back-extraction cycle, and the values ​​of each component in the transfer tank were measured, as shown in Table 2.

[0098]

[0099] In Table 2, A1 represents the copper ion content (g / L) in the etching solution to be treated; A2 represents the copper ion content (g / L) in the transfer tank; B1 represents the molybdenum ion content (g / L) in the etching solution to be treated; B2 represents the molybdenum ion content (g / L) in the transfer tank; C% represents the copper ion extraction rate; D% represents the molybdenum ion extraction rate; E% represents the 5-aminotetrazole content (%) in the regenerated etching solution in the transfer tank; F% represents the iminodiacetic acid content (%) in the transfer tank; △ represents emulsification of the loaded extraction phase in step 2; × represents no emulsification or flocculent matter in the loaded extraction phase in step 2; ≠ represents flocculent matter in the loaded extraction phase in step 2.

[0100] The extractant formulation of this invention does not produce emulsions or flocculents after running more than 30 cycles of extraction-back-extraction, and can effectively prevent the extraction of nitrogen-based etching aids 5-aminotetrazole and iminodiacetic acid. Compared with the extraction efficiency in the first extraction-back-extraction cycle, the extractant combination of this invention does not show a significant decrease in the extraction efficiency of metal ions copper and molybdenum after 30 cycles, and has a long service life.

[0101] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A system for extracting and recovering metals from etching waste liquid, comprising, An extraction device is used to mix etching waste liquid and extract phase. The etching waste liquid and extract phase are mixed, and metal ion transfer occurs to obtain regenerated etching liquid and loaded extract phase. The extraction device outputs the loaded extract phase and regenerated etching liquid to a back-extraction device and a transfer tank, respectively. The transfer tank receives the regenerated etching solution from the extraction device and outputs it to the mixing tank, which is used to adjust the content of each component in the regenerated etching solution. After adjustment, the regenerated etching solution is output to the regenerated sub-liquid tank and used as the etching solution in the etching machine. The back-extraction device receives the loaded extract phase from the extraction device, and the loaded extract phase is mixed with the back-extraction acid solution to obtain a regenerated extract phase and a back-extraction acid solution loaded with metal ions. The regenerated extract phase is output to the extraction device for the extraction of metal ions in the etching waste liquid. The back-extraction acid solution loaded with metal ions is output to the enrichment solution electrowinning device, where metal is obtained by electrowinning. The extract phase includes a diluent and a ternary mixture of extract phases, wherein the ternary mixture of extract phases comprises 40-60% by mass of butyl(1-styryl)phenylphosphonate, 30-50% by mass of 1-(2-isobutylphenyl)acetone oxime, and 5-10% by mass of 1-(2-dodecylphenyl)-1,3-butanedione. 150-200g of a ternary mixture of extract phase is added to each 1L of extract phase; The etching waste liquid consists of: 10~110 g / L Cu ions, 15~32 g / L Mo ions, 1.0~2.0 wt% 5-aminotetrazole, 0.5~1.0 wt% iminodiacetic acid, and 1.0~2.0 wt% sodium bisulfate, with deionized water as the solvent.

2. The system for extracting and recovering metals from etching waste liquid according to claim 1, characterized in that, The diluent is selected from non-polar solvents or polar solvents, and the non-polar solvent is selected from one or more of kerosene, diethyl ether, toluene, and cyclohexane.

3. The system for extracting and recovering metals from etching waste liquid according to claim 1, characterized in that, In the extraction device, the volume ratio of the etching waste liquid to the extract phase is (1~3):

1. In the extraction device, the etching waste liquid and the extract phase are mixed at 10~40℃. In the extraction device, the etching waste liquid and the extract phase are mixed and stirred for 5~10 minutes.

4. The system for extracting and recovering metals from etching waste liquid according to claim 1, characterized in that, The back-extraction acid solution is selected from aqueous solutions of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the back-extraction acid solution is 3-5 mol / L. The mixing volume ratio of the back-extraction acid solution to the supported extraction phase is 1:(1-3). The electrowinning method involves adjusting the pH of the metal ion-loaded back-extraction acid solution to 2-4, using a titanium-coated iridium-tantalum anode as the anode and a copper plate as the cathode, and controlling the current density at 100-300 A / m. 2 Electrowinning is performed within the specified range to deposit metallic copper.

5. A method for extracting and recovering metals from etching waste liquid, comprising the steps of: S1: Mix 40-60% by mass of butyl(1-styryl)phenylphosphonate, 30-50% by mass of 1-(2-isobutylphenyl) ethyl ketone oxime, and 5-10% by mass of 1-(2-dodecylphenyl)-1,3-butanedione to obtain a ternary mixture of extractable phases. Mix the ternary mixture of extractable phases with a diluent to obtain the extractable phase. S2: The extract phase is mixed with the etching waste liquid, stirred, and separated to obtain a regenerated etching solution and a loaded extract phase containing metal ions; S3: The loaded extract phase is mixed with the back-extraction acid solution to obtain a back-extraction acid solution loaded with metal ions and a regenerated extract phase; S4: Electrowinning is performed on the back-extraction acid solution loaded with metal ions to obtain the metal; 150-200g of a ternary mixture of extract phase is added to each 1L of extract phase; The etching waste liquid consists of: 10~110 g / L Cu ions, 15~32 g / L Mo ions, 1.0~2.0 wt% 5-aminotetrazole, 0.5~1.0 wt% iminodiacetic acid, and 1.0~2.0 wt% sodium bisulfate, with deionized water as the solvent.

6. The method for extracting and recovering metals from etching waste liquid according to claim 5, characterized in that, The diluent is selected from non-polar solvents or polar solvents. The non-polar solvent is selected from one or more of kerosene, diethyl ether, toluene, and cyclohexane. The volume ratio of the etching waste liquid to the extract phase is (1~3):

1. The etching waste liquid and the extract phase are mixed at 10~40℃ and stirred for 5~10 minutes.

7. The method for extracting and recovering metals from etching waste liquid according to claim 6, characterized in that, The back-extraction acid solution is selected from aqueous solutions of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the back-extraction acid solution is 3-5 mol / L. The mixing volume ratio of the back-extraction acid solution to the supported extraction phase is 1:(1-3). The electrowinning method involves adjusting the pH of the metal ion-loaded back-extraction acid solution to 2-4, using a titanium-coated iridium-tantalum anode as the anode and a copper plate as the cathode, and controlling the current density at 100-300 A / m. 2 Electrowinning is performed within the specified range to deposit metallic copper.

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