System and method for extracting and recovering metal from etching waste liquid

Abstract

The invention relates to the technical field of resource recovery, and particularly discloses a system and a method for extracting and recovering metal from waste etching liquid, an extraction agent combination can reduce the loss of an etching auxiliary agent as much as possible without damaging the original components of the etching liquid, so that the etching liquid is completely recycled after metal ions such as copper and molybdenum are reduced, and the cost is reduced. The effective life cycle of extraction-reverse extraction circulation of the extraction agent is long, loss of extraction liquid auxiliaries in the extraction-reverse extraction circulation is small, the extraction phase in the extraction process does not generate emulsification / floccules, the extraction rate of copper and molybdenum in the etching liquid is high, the specific three-phase extraction agent combination is adopted, more than 98% of copper and molybdenum in the waste liquid are recycled, the copper is extracted, and the extraction efficiency is high. According to the present invention, the liquid has the good retention effect on the azole etching auxiliary agent such as 5-aminotetrazole, such that the closed cycle is formed in the extraction-back extraction cycle process of the etching liquid, and the material input and the pollution are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater treatment and resource recovery, and discloses a system and method for extracting and recovering metals from etching waste liquid. Background Art

[0002] Etching liquid is used for selective removal, cleaning and pattern transfer of copper and copper alloy surfaces. It is used in many industries such as PCB (printed circuit board) manufacturing, T-LCD display electrode substrate processing, and microelectronics processing.

[0003] After long-term operation of the etching solution, depending on the process, the concentration of copper and other etched free metal ions in the etching solution increases, which will lead to a decrease in the etching rate, an increased risk of crystallization and precipitation, uneven etching, rough edges, etc. Therefore, recycling the etching solution to recover copper and alloy ions is an indispensable part of the process. The existing copper recovery technology stack includes electrolysis, which uses an external current to reduce copper ions to metallic copper, and membrane separation, which uses nanofiltration, reverse osmosis and other membranes to intercept copper ions. The above methods focus on different scenarios, but all have certain defects. The electrolytic method has a minimum concentration limit and low deposition efficiency. When the copper concentration is below 10g / L, the copper concentration is too low, resulting in poor application of the electrolytic method, and there is a hydrogen evolution side reaction. The anode material often needs to be titanium metal, which also leads to high investment costs. The membrane separation method is prone to organic contamination, suspended solids deposition, etc., and the membrane flux is limited. It is only suitable for small to medium-sized processing volumes and cannot meet the needs of large-scale rapid waste liquid treatment. The solvent extraction method can effectively overcome the shortcomings of the above methods. Copper ions can be effectively extracted at 1g / L and have good affinity for copper ions. However, this method also has certain defects. Due to the variety of etching aids, some etching aids and auxiliary metal ions may be extracted into the organic phase along with copper ions, resulting in the loss of the aid. Or in some processes, the metal components to be etched are often complex and not limited to one metal, such as CN103924242A The etching solution composition for copper / molybdenum film or copper / molybdenum alloy film needs to extract copper and molybdenum ions simultaneously, and there are etching auxiliary nitrogen azole compounds. However, some extractant formulations can only extract some metal ions, but have poor extraction ability for other metal ions, resulting in the enrichment of some metal ions in the circulation system, or significantly reducing the auxiliary agent content during the circulation, ultimately resulting in unstable quality of the etched product and increased costs. The auxiliary agent is extracted into the extraction phase, resulting in a shortened extraction-stripping cycle number of the extractant, reducing the number of life cycles of use. Therefore, compared with the electrolytic method and membrane separation method, the solvent extraction method needs to design different extraction components for different etching processes. Summary of the Invention

[0004] In view of the problems existing in the prior art, the first aspect of the present invention provides a system for extracting and recovering metals from etching waste liquid, comprising: An extraction device, the extraction device is used to mix the etching liquid to be treated and the extraction phase, the etching liquid to be treated and the extraction phase are mixed, metal ions are transferred, and regenerated etching liquid and a loaded extraction phase loaded with metal ions are obtained. The extraction device outputs the loaded extraction phase and the regenerated etching liquid to the back-extraction device and the transfer barrel respectively; The transfer barrel receives the regenerated etching liquid from the extraction device and outputs it to the mixing barrel. The mixing barrel is used to adjust the content of each component in the regenerated etching liquid. The adjusted regenerated etching liquid is output to the regenerated liquid sub-barrel and used as the etching liquid in the etching machine. The stripping device receives the loaded extraction phase from the extraction device, and the loaded extraction phase is mixed with the stripping acid solution to obtain a regenerated extraction phase and a stripping acid solution loaded with metal ions; The regenerated extraction phase is output to the extraction device for extracting metal ions in the etching solution to be processed in the extraction device; The stripping acid solution loaded with metal ions is output to the enriched liquid electrolysis device and electrolyzed to obtain metal; The extraction phase includes a diluent and a ternary mixture of the extraction phase, and the ternary mixture of the extraction phase includes butyl (1-phenylvinyl) phenyl phosphonate, 1-(2-isobutylphenyl) acetone oxime, and 1-(2-dodecylphenyl)-1,3-butanedione.

[0005] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the molar ratio of butyl (1-phenylvinyl) phenyl phosphonate to 1-(2-isobutylphenyl) acetone oxime in the extraction phase is (4~6):(3~5). In some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the molar ratio of butyl (1-phenylvinyl) phenyl phosphonate to 1-(2-isobutylphenyl) acetone oxime in the extraction phase is optionally 4:3, 4:5, 5:3, or 5:3.

[0006] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the molar ratio of 1-(2-isobutylphenyl)ethanone 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 waste liquid of the first aspect, the molar ratio of 1-(2-isobutylphenyl)ethanone oxime to 1-(2-dodecylphenyl)-1,3-butanedione in the extraction phase is optionally 6:1, 8:1, or 10:1.

[0007] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the diluent is selected from a non-polar solvent or a polar solvent, and the non-polar solvent is selected from one or more of kerosene, ether, toluene, and cyclohexane.

[0008] In some specific embodiments of the system for extracting and recovering metals from waste etching liquid of the first aspect, 150-200 g of the ternary mixture of the extraction phase is added to each 1 L of extraction phase. In some specific embodiments of the system for extracting and recovering metals from waste etching liquid of the first aspect, 150 g, 170 g, or 190 g of the ternary mixture of the extraction phase is added to each 1 L of extraction phase.

[0009] In some specific embodiments of the system for extracting and recovering metals from waste etching liquid of the first aspect, in the extraction device, the volume ratio of the etching liquid to be treated and the extraction phase is (1~3):1. In some specific embodiments of the system for extracting and recovering metals from waste etching liquid of the first aspect, in the extraction device, the volume ratio of the etching liquid to be treated and the extraction phase is optionally 1:1, 2:1, or 3:1.

[0010] In some specific embodiments of the system for extracting and recovering metals from waste etching liquid of the first aspect, in the extraction device, the etching liquid to be treated and the extraction phase are mixed at 10-40°C. In some specific embodiments of the system for extracting and recovering metals from waste etching liquid of the first aspect, in the extraction device, the etching liquid to be treated and the extraction phase are optionally mixed at 15°C, 20°C, 25°C, 30°C, or 35°C.

[0011] In some specific embodiments of the system for extracting and recovering metals from waste etching liquid of the first aspect, in the extraction device, the etching liquid to be treated and the extraction phase are mixed and stirred for 5 to 10 minutes. In some specific embodiments of the system for extracting and recovering metals from waste etching liquid of the first aspect, in the extraction device, the etching liquid to be treated and the extraction phase are mixed and stirred for 6, 7, 8, or 9 minutes.

[0012] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the stripping acid solution is selected from an aqueous solution of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the stripping acid solution is 3~5mol / L. In some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the stripping acid solution is selected from an aqueous solution of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the stripping acid solution is optionally 3mol / L, 4mol / L, or 5mol / L.

[0013] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the mixed volume ratio of the stripping acid solution to the loaded extraction phase is 1:(1~3); in some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the mixed volume ratio of the stripping acid solution to the loaded extraction phase is optionally 1:1, 1:2, or 1:3.

[0014] In some specific embodiments of the system for extracting and recovering metals from etching waste liquid of the first aspect, the electrolysis method is to adjust the pH of the stripping acid solution loaded with metal ions to 2-4, use a titanium-coated iridium-tantalum anode as an anode, a copper plate as a cathode, and control the current density at 100-300 A / m 2 Electrodeposition is performed within a range to deposit a metal, wherein the metal is selected from copper.

[0015] A second aspect of the present invention provides a method for extracting and recovering metals from etching waste liquid, comprising the steps of: S1: mixing butyl (1-phenylvinyl) phenylphosphonate, 1-(2-isobutylphenyl) acetone oxime, and 1-(2-dodecylphenyl)-1,3-butanedione to obtain a ternary mixture of the extract phase, and mixing the ternary mixture of the extract phase with a diluent to obtain an extractant; S2: The extractant is mixed with the etching solution to be treated, stirred, and separated into phases to obtain a regenerated etching solution and a loaded extraction phase; S3: The loaded extract phase is mixed with the stripping acid solution to obtain the stripping acid solution loaded with metal ions and the regenerated extract phase; S4: Electrolytically deposit the stripping acid solution to obtain metal.

[0016] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the molar ratio of butyl (1-phenylvinyl) phenyl phosphonate to 1-(2-isobutylphenyl) ethyl ketone oxime is (4-6): (3-5).

[0017] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the molar ratio of 1-(2-isobutylphenyl)ethanone oxime to 1-(2-dodecylphenyl)-1,3-butanedione in the extraction phase is (6~10):(1~2).

[0018] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the diluent is selected from a non-polar solvent or a polar solvent, and the non-polar solvent is selected from one or more of kerosene, ether, toluene, and cyclohexane.

[0019] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, 150-200 g of the ternary mixture of the extraction phase is added to each 1 L of the extraction phase.

[0020] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the volume ratio of the mixed etching liquid to be treated and the extraction phase is (1-3):1.

[0021] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the etching liquid to be treated and the extraction phase are mixed at a temperature of 10-40°C.

[0022] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the etching liquid to be treated is mixed and stirred with the extraction phase for 5 to 10 minutes.

[0023] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the stripping acid solution is selected from an aqueous solution of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the stripping acid solution is 3-5 mol / L.

[0024] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the mixed volume ratio of the stripping acid solution to the loaded extraction phase is 1:(1-3).

[0025] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the pH of the stripping 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 Electrodeposition is performed within a range to deposit a metal, wherein the metal is selected from copper.

[0026] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the etching liquid to be treated comprises copper ions, molybdenum ions, 5-aminotetrazole, iminodiacetic acid, sodium bisulfate, and water.

[0027] In some specific embodiments of the method for extracting and recovering metals from etching waste liquid according to the second aspect, the etching liquid to be treated comprises 1-11 wt% copper ions, 1.5-3.2 wt% molybdenum ions, 1.0-2.0 wt% 5-aminotetrazole, 0.5-1.0 wt% iminodiacetic acid, 1.0-2.0 wt% sodium bisulfate, and the remainder is water.

[0028] In the present invention, the amount of hydrogen peroxide in the etching solution to be treated in Example 1 is 1.3 wt %, and the amount of hydrogen peroxide in the etching solution to be treated in Example 2 is 1.1 wt %.

[0029] 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.

[0030] The drugs used in the present invention are all purchased from the open and legal market and have not been further purified.

[0031] The titanium-coated iridium-tantalum anode of the present invention is an iridium-tantalum-titanium anode; In the present invention, butyl (1-phenylvinyl) phenylphosphonate CAS: 31327-22-7; 1-(2-isobutylphenyl) acetone oxime CAS: 2728664-35-3; 1-(2-dodecylphenyl)-1,3-butanedione CAS: 59863-28-4 The waste etching solution of the present invention is composed 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), 1.0-2.0 wt% sodium bisulfate (SHS), and the solvent is deionized water.

[0032] Advantages of the present invention: The extractant combination of the present invention does not destroy the original components of the etching solution, and allows the etching solution to be completely reused after reducing metal ions such as copper and molybdenum. The extractant of the present invention has a long effective life cycle of the extraction-stripping cycle, reduces the loss of the extractant auxiliary agent in the extraction-stripping cycle, and does not produce emulsification or floccules in the extraction phase during the metal ion extraction process. During the extraction process, the extraction auxiliary agent in the etching solution is reduced, and the extraction rate of copper and molybdenum in the etching solution is high. The specific three-phase extractant combination is used to recover more than 98% of the copper and molybdenum in the waste liquid. During the copper extraction process, the extractant has a good retention effect on nitrogen azole etching auxiliary agents, such as 5-aminotetrazole, thereby reducing the need for material replenishment during the extraction process, forming a closed cycle, and the extractant and stripping solution circulate in a closed circuit without generating new pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The figure shows the connection diagram of the etching solution copper extraction and recovery system of the present invention. DETAILED DESCRIPTION

[0034] In order 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 further illustrate the present invention in detail.

[0035] Extraction method: Step 1: Preparation of the extraction solvent 40-60% by mass of butyl (1-phenylvinyl) phenylphosphonate, 30-50% by mass of 1-(2-isobutylphenyl) acetone oxime, and 5-10% by mass of 1-(2-dodecylphenyl)-1,3-butanedione are mixed to obtain a ternary mixture of the extract phase; The ternary mixture of the extraction phase is dissolved in toluene or other inert organic solvents such as cyclohexane at a concentration of 150-200 g / L to prepare the extraction phase.

[0036] Step 2: Extracting metal ions from waste etching solution The etching solution to be treated is mixed with the extractant configured in step 1 in a volume ratio of 3:1, stirred at 10-40°C for 5-10 minutes to fully contact the etching solution to be treated with the extractant, and allowed to stand for phase separation after mixing. Copper and molybdenum metal ions are extracted into the extraction phase to obtain an upper layer loaded with copper and molybdenum metal ions. The lower layer of regenerated etching liquid enters the transfer barrel and stands, and the content of each component in the regenerated etching liquid in the transfer barrel is detected. Then, the etching solution enters the mixing barrel, and the auxiliary agent content is adjusted. After adjustment, the solution is collected into the regenerated sub-liquid barrel, and hydrogen peroxide is added at a concentration of 10-25wt% before entering the etching machine for recycling.

[0037] Step 3: Stripping of metal ions from the loaded extract phase The loaded extraction phase loaded with copper and molybdenum metal ions is mixed with a stripping acid solution, which is a 3-5 mol / L sulfuric acid solution. The mixing ratio is 1:1 by volume and stirred for 5-10 minutes to complete the stripping process. The metal ions are transferred from the metal ion-loaded extraction phase to the stripping acid solution to obtain a regenerated extraction phase and a stripping acid solution loaded with metal ions. The stripping acid solution is recycled to extract each batch of metal ion-loaded extraction phase. The sulfuric acid concentration is maintained at 3-5 mol / L during the circulation process. When the copper metal ions in the stripping acid solution are greater than 50g / L, the acidic aqueous phase can be used as the stock solution for the electrolytic copper process.

[0038] Step 4: Electrolytic copper process for copper recovery Adjust the pH of the stripping acid solution to 2-4, use a titanium-coated iridium-tantalum anode as the anode, a copper plate as the cathode, and control the current density at 100-300 A / m 2 Electrodeposition is carried out within the range to deposit metallic copper.

[0039] Example 1 The etching solution used in this embodiment is formulated as follows: 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.

[0040] Step 1: Preparation of the extraction solvent 40% by mass of butyl (1-phenylvinyl) phenylphosphonate, 50% by mass of 1-(2-isobutylphenyl) acetone oxime, and 10% by mass of 1-(2-dodecylphenyl)-1,3-butanedione are mixed to obtain a ternary mixture of the extract phase; The ternary mixture of the extraction phase was dissolved in cyclohexane at a concentration of 150 g / L to prepare the extraction phase.

[0041] Step 2: Extracting metal ions from waste etching solution The etching solution treated in this embodiment was mixed with the extraction phase prepared in step 1 in a volume ratio of 3:1, stirred at 20° C. for 5 minutes to allow the etching solution to be treated to fully contact the extraction phase. After mixing, the mixture was allowed to stand for phase separation to obtain an upper layer of the extraction phase loaded with copper and molybdenum ions. The lower layer of regenerated etching solution entered the transfer barrel and was allowed to stand. The content of each component in the regenerated etching solution in the transfer barrel was detected, and then the mixture entered the mixing barrel. The content of each additive in the mixing barrel was adjusted to 2.0wt% 5-aminotetrazole, 1.0wt% iminodiacetic acid, and 2.0wt% sodium bisulfate. After mixing, the mixture was collected in the regenerated sub-liquid barrel to adjust the hydrogen peroxide to 15wt%, and then entered the etching machine for recycling.

[0042] Step 3: Stripping of metal ions from the loaded extract phase The loaded extraction phase loaded with copper and molybdenum ions is mixed with a stripping acid solution, which is a 3 mol / L sulfuric acid solution. The mixing ratio is 1:1 by volume and stirred for 5 minutes to complete the stripping process. The copper and molybdenum ions are transferred from the loaded extraction phase to the stripping acid solution to obtain a regenerated extraction phase and a stripping acid solution loaded with copper and molybdenum ions. The stripping acid solution is recycled to extract each batch of loaded extraction phase loaded with copper and molybdenum ions. The sulfuric acid concentration is maintained at 3 mol / L during the circulation process. The stripping acid solution is used as the stock solution for the electrolytic copper process.

[0043] Step 4: Electrolytic copper process for copper recovery The stripping acid solution was adjusted to pH 2-4, and 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 Electrodeposition is carried out within the range to deposit metallic copper.

[0044] Example 2 The waste etching solution of the present invention is composed of: 10g / L copper ions, 15g / L molybdenum ions, 2.0wt% 5-aminotetrazole, 1.0wt% iminodiacetic acid, and 1.0wt% sodium bisulfate.

[0045] Step 1: Preparation of the extraction solvent 40% by mass of butyl (1-phenylvinyl) phenylphosphonate, 55% by mass of 1-(2-isobutylphenyl) acetone oxime, and 5% by mass of 1-(2-dodecylphenyl)-1,3-butanedione were mixed to obtain a ternary mixture of the extract phase; The ternary mixture of the extraction phase was dissolved in cyclohexane at a concentration of 200 g / L to prepare the extraction phase.

[0046] Step 2: Extracting metal ions from waste etching solution The etching solution to be treated and the extraction phase configured in step 1 were mixed in a volume ratio of 3:1, stirred at 40°C for 10 minutes to fully contact the etching solution to be treated with the extraction phase, and allowed to stand for phase separation after mixing to obtain an upper layer of the extraction phase loaded with copper and molybdenum ions. The lower layer of regenerated etching liquid entered the transfer barrel and was allowed to stand. The content of each component in the regenerated etching liquid in the transfer barrel was detected, and then entered the mixing barrel. The content of each additive in the mixing barrel was adjusted to 2.0wt% 5-aminotetrazole, 1.0wt% iminodiacetic acid, and 1.0wt% sodium bisulfate. After mixing, the mixture was collected into the regenerated sub-liquid barrel, and the hydrogen peroxide concentration was adjusted to 15wt%. It was then recycled into the etching machine.

[0047] Step 3: Stripping of metal ions from the loaded extract phase The loaded extraction phase loaded with copper and molybdenum ions is mixed with a stripping acid solution, which is a 5 mol / L sulfuric acid solution. The mixing ratio is 1:1 by volume and stirred for 10 minutes to complete the stripping process. The metal ions are transferred from the loaded copper and molybdenum ion extraction phase to the stripping acid solution to obtain a regenerated extraction phase and a stripping acid solution loaded with copper and molybdenum ions. The stripping acid solution is recycled to extract each batch of loaded copper and molybdenum ion extraction phases. The sulfuric acid concentration is maintained at 5 mol / L during the circulation process. The stripping acid solution is used as the stock solution for the electrolytic copper process.

[0048] Step 4: Electrolytic copper process for copper recovery The stripping acid solution was adjusted to pH 2-4, and 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 Electrodeposition is carried out within the range to deposit metallic copper.

[0049] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that butyl (1-phenylvinyl) phenylphosphonate in the step of preparing the ternary mixture of the extraction phase in Comparative Example 1 is replaced by tributyl phosphate (TBP) with an equal mass fraction, and the remaining feed amounts and steps of Comparative Example 1 are the same as those of Example 1.

[0050] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that in the step of preparing the ternary mixture of the extraction phase in Comparative Example 2, 1-(2-isobutylphenyl)ethanone oxime is replaced by an equal mass fraction of 2-hydroxy-5-nonylacetophenone oxime (LIX84), and the remaining feeding amounts and steps of Comparative Example 2 are the same as those of Example 1.

[0051] Comparative Example 3 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 extraction phase in Comparative Example 3, and the remaining feeding amounts and steps of Comparative Example 3 are the same as those of Example 1.

[0052] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that butyl (1-phenylvinyl) phenylphosphonate is not added in the step of preparing the ternary mixture of the extraction phase in Comparative Example 4. The remaining feed amounts and steps of Comparative Example 4 are the same as those of Example 1.

[0053] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that 1-(2-isobutylphenyl)ethanone oxime is not added in the step of preparing the ternary mixture of the extraction phase in Comparative Example 5. The remaining feed amounts and steps of Comparative Example 5 are the same as those of Example 1.

[0054] Example 3 In Examples 1 and 2, and Comparative Examples 1 to 5, after the first extraction-stripping cycle, the values ​​of the components in the transfer barrel were detected, as shown in Table 1;

[0055] In Table 1, A1 represents the copper ion content in the etching solution to be treated (g / L); A2 represents the copper ion content in the transfer barrel (g / L); B1 represents the molybdenum ion content in the etching solution to be treated (g / L); B2 represents the molybdenum ion content in the transfer barrel (g / L); 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 barrel; F% represents the iminodiacetic acid content in the transfer barrel; Comparative Example 6 The etching solution prepared in Example 1 is: 50g / L Cu 2+ ions, 32g / L Mo 6+ ions, 90g / L Ni 2+ ions, 2.0wt% 5-aminotetrazole, 1.0wt% iminodiacetic acid, 2.0wt% sodium bisulfate, and the same method as Example 1 was used for extraction treatment. The etching solution in the transfer barrel was tested to contain 0.21g / L copper ions, 0.14g / L molybdenum ions, 87.5g / L nickel ions, 1.97wt% 5-aminotetrazole, 1.98wt% sodium bisulfate, and 0.98wt% iminodiacetic acid. It can be seen that when the etching solution has a high concentration of competitive nickel metal ions, it does not interfere with the extraction of copper and molybdenum. The extractant combination of the present invention can resist competitive extraction between metal ions, has strong anti-interference ability, and can well retain the auxiliary metal ions added to some etching solutions.

[0056] Example 4 For Examples 1 and 2 and Comparative Examples 1 to 5, after the 30th extraction-stripping cycle, the values ​​of the components in the transfer barrel were detected, as shown in Table 2;

[0057] In Table 2, A1 represents the copper ion content in the etching solution to be treated in g / L; A2 represents the copper ion content in the transfer barrel in g / L; B1 represents the molybdenum ion content in the etching solution to be treated in g / L; B2 represents the molybdenum ion content in the transfer barrel in g / L; C% represents the copper ion extraction rate; D% represents the molybdenum ion extraction rate; E% is the 5-aminotetrazole content of the regenerated etching solution in the transfer barrel; F% is the iminodiacetic acid content in the transfer barrel; △ represents the emulsification of the loaded extraction phase in step 2; × represents that no emulsification or floccules appear in the loaded extraction phase in step 2; ≠ represents the presence of floccules in the loaded extraction phase in step 2.

[0058] The extractant formula of the present invention does not produce emulsification or floccules after running 30 extraction-back extraction cycles or more, and can effectively prevent the extraction of azole etching aids 5-aminotetrazole and iminodiacetic acid. Compared with the extraction efficiency in the first extraction-back extraction cycle, the extraction efficiency of the extractant combination of the present invention for the metal ions copper and molybdenum does not decrease significantly after 30 cycles, and has a long service life.

[0059] 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 in the scope of protection of the present invention.

Claims

1. A system for extracting and recovering metals from etching waste liquid, comprising: An extraction device, the extraction device is used to mix the etching liquid to be treated and the extraction phase, the etching liquid to be treated and the extraction phase are mixed, metal ions are transferred, and regenerated etching liquid and a loaded extraction phase are obtained. The extraction device outputs the loaded extraction phase and the regenerated etching liquid to the back-extraction device and the transfer barrel respectively; The transfer barrel receives the regenerated etching liquid from the extraction device and outputs it to the mixing barrel. The mixing barrel is used to adjust the content of each component in the regenerated etching liquid. The adjusted regenerated etching liquid is output to the regenerated liquid sub-barrel and used as the etching liquid in the etching machine. The stripping device receives the loaded extraction phase from the extraction device, and the loaded extraction phase is mixed with the stripping acid solution to obtain a regenerated extraction phase and a stripping acid solution loaded with metal ions; The regenerated extraction phase is output to the extraction device for extracting metal ions in the etching solution to be processed in the extraction device; The stripping acid solution loaded with metal ions is output to the enriched liquid electrolysis device and electrolyzed to obtain metal; The extraction phase includes a diluent and a ternary mixture of the extraction phase, and the ternary mixture of the extraction phase includes butyl (1-phenylvinyl) phenyl phosphonate, 1-(2-isobutylphenyl) acetone oxime, and 1-(2-dodecylphenyl)-1,3-butanedione.

2. The system for extracting and recovering metals from etching waste liquid according to claim 1, characterized in that: The molar ratio of butyl (1-phenylvinyl) phenylphosphonate to 1-(2-isobutylphenyl) ethanone oxime in the extract phase is (4-6):(3-5); and / or the molar ratio of 1-(2-isobutylphenyl) ethanone oxime to 1-(2-dodecylphenyl)-1,3-butanedione in the extract phase is (6-10):(1-2).

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

4. The system for extracting and recovering metals from etching waste liquid according to any one of claims 1 to 3, characterized in that: 150-200 g of the ternary mixture of the extraction phase is added to each 1 L of the extraction phase; and / or, in the extraction device, the volume ratio of the etching solution to be treated and the extraction phase is (1-3):1; and / or, in the extraction device, the etching solution to be treated and the extraction phase are mixed at 10-40° C.; and / or, in the extraction device, the etching solution to be treated and the extraction phase are mixed and stirred for 5-10 minutes.

5. The system for extracting and recovering metals from etching waste liquid according to any one of claims 1 to 4, characterized in that: The stripping acid solution is selected from an aqueous solution of sulfuric acid or hydrochloric acid, and the hydrogen ion concentration in the stripping acid solution is 3-5 mol / L; and / or the mixed volume ratio of the stripping acid solution to the loaded extraction phase is 1:(1-3); the electrolysis method is to adjust the pH of the stripping acid solution loaded with metal ions to 2-4, use a titanium-coated iridium-tantalum anode as the anode, a copper plate as the cathode, and control the current density at 100-300 A / m 2 Electrodeposition is performed within a range to deposit a metal, wherein the metal is selected from copper.

6. A method for extracting and recovering metal from etching waste liquid, comprising the steps of: S1: mixing butyl (1-phenylvinyl) phenylphosphonate, 1-(2-isobutylphenyl) acetonoxime, and 1-(2-dodecylphenyl)-1,3-butanedione to obtain a ternary mixture of the extract phase, and mixing the ternary mixture of the extract phase with a diluent to obtain an extract phase; S2: The extraction phase is mixed with the etching solution to be treated, stirred, and separated to obtain a regenerated etching solution and a loaded extraction phase loaded with metal ions; S3: The loaded extract phase is mixed with the stripping acid solution to obtain the stripping acid solution loaded with metal ions and the regenerated extract phase; S4: Electrolysis is performed on the stripping acid solution loaded with metal ions to obtain metal.

7. The method for extracting and recovering metal from etching waste liquid according to claim 6, characterized in that: The molar ratio of butyl (1-phenylvinyl) phenylphosphonate to 1-(2-isobutylphenyl) ethanone oxime is (4-6):(3-5); and / or the molar ratio of 1-(2-isobutylphenyl) ethanone oxime to 1-(2-dodecylphenyl)-1,3-butanedione in the extract phase is (6-10):(1-2).

8. The method for extracting and recovering metal from etching waste liquid according to any one of claims 6 or 7, characterized in that: The diluent is selected from a non-polar solvent or a polar solvent, and the non-polar solvent is selected from one or more of kerosene, ether, toluene, and cyclohexane; and / or, 150-200 g of the ternary mixture of the extraction phase is added to each 1 L of the extraction phase; and / or, the volume ratio of the etching solution to be treated and the extraction phase is (1-3):1; and / or, the etching solution to be treated and the extraction phase are mixed at 10-40° C.; and / or, the etching solution to be treated and the extraction phase are mixed and stirred for 5-10 minutes.

9. The method for extracting and recovering metal from etching waste liquid according to any one of claims 6 to 8, characterized in that: The stripping acid solution is selected from an aqueous solution of sulfuric acid or hydrochloric acid; and / or, the hydrogen ion concentration in the stripping acid solution is 3-5 mol / L; and / or, the mixed volume ratio of the stripping acid solution to the loaded extraction phase is 1:(1-3); and / or, the electrolysis method is to adjust the pH of the stripping acid solution loaded with metal ions to 2-4, use a titanium-coated iridium-tantalum anode as the anode, a copper plate as the cathode, and control the current density to be 100-300 A / m 2 Electrodeposition is performed within a range to deposit a metal, wherein the metal is selected from copper.

10. The method for extracting and recovering metal from etching waste liquid according to any one of claims 6 to 9, characterized in that: The etching solution to be treated includes copper ions, platinum ions, 5-aminotetrazole, iminodiacetic acid, sodium bisulfate, and water; and / or, the etching solution to be treated includes 1-11 wt% copper ions, 1.5-3.2 wt% platinum ions, 1.0-2.0 wt% 5-aminotetrazole, 0.5-1.0 wt% iminodiacetic acid, 1.0-2.0 wt% sodium bisulfate, and the remainder is water.

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