Acid-resistant extractant and method for purifying copper-containing wastewater in integrated circuit industry

Abstract

The invention provides an acid-resistant extraction agent and a method for purifying copper-containing wastewater in the integrated circuit industry, and belongs to the field of wastewater purification. Tromethamine serves as a raw material of the extraction agent, selective chelation of target metal ions is achieved through esterification reaction derivatization and molecular structure space tension regulation, and by controlling the length of an aliphatic chain, the copper-containing wastewater in the integrated circuit industry is purified. The surface hydrophobic capacity of the extraction agent is directionally regulated and controlled, carboxyl at the tail end in the molecular structure can be hydrolyzed in a specific environment to generate free hydrogen ions, and a buffer effect on a pH solution window of the environment is achieved. The specific molecular structure and high-density carboxyl jointly guarantee the stability of the extracting agent under the acidic condition, so that when the pH value of copper-containing wastewater is adjusted, the extracting agent activated into anions shows excellent competitive complexing chemical reaction activity, copper ions are prevented from precipitating to form sludge, and efficient selective extraction of copper is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of purification of copper-containing wastewater and resource recycling in the integrated circuit industry, and in particular to an acid-resistant extractant and a method for purifying copper-containing wastewater in the integrated circuit industry. Background Art

[0002] The copper-containing waste liquid / wastewater generated by the integrated circuit industry has the characteristics of complex components, difficult to control ingredients, unstable physical and chemical properties, and large concentration differences in each process. These factors constitute the technical difficulties of harmless treatment of copper-containing wastewater. The sources of copper-containing waste liquid / wastewater can be traced back mainly to etching, electroplating and cleaning processes. The copper-containing waste liquid generated in the etching and electroplating processes has a high concentration and is accompanied by a large number of other types of pollutants. At present, coagulation and sedimentation technology is generally used for the resource treatment of such high-concentration copper-containing waste liquid, but the economic value of the products prepared by this method is low. The copper-containing waste liquid generated by the cleaning process has a low concentration, and some copper ions exist in the form of stable complexes. Neutralization precipitation technology is used for treatment. This technology mainly focuses on making the wastewater meet the discharge standards, but it will produce a large amount of hazardous waste sludge that needs to be outsourced for treatment, which is difficult to meet the needs of deep purification.

[0003] At present, the mainstream enrichment process for high-concentration copper-containing wastewater is extraction. The extraction method has been widely used in the field of remediation of heavy metal-contaminated water bodies due to its simple operation and strong applicability. However, existing extractants have certain limitations, such as poor selectivity, difficulty in achieving selective extraction of copper in multi-metal waste liquid, and easy co-extraction of other metal ions in the chelating extraction stage. In addition, since high-concentration copper-containing wastewater is usually highly acidic, it is easy to cause the decomposition of the effective ingredients of the extractant. It is usually necessary to adjust the pH of the copper-containing wastewater to alkaline before introducing the extractant. The above process often causes a large amount of copper ions to generate copper hydroxide precipitation, resulting in the generation of a large amount of copper-containing sludge. The copper-containing sludge needs to be outsourced for hazardous waste treatment, which increases the environmental protection cost of the enterprise.

[0004] In view of this, it is necessary to design an improved acid-resistant extractant and a method for purifying copper-containing wastewater in the integrated circuit industry to solve the above problems. Summary of the invention

[0005] In view of the technical problems existing in the background technology, the present application provides an acid-resistant extractant and a method for purifying copper-containing wastewater in the integrated circuit industry, aiming to solve the technical problems of poor selectivity of the extractant, easy decomposition in highly acidic copper-containing wastewater, and difficulty in extracting copper alone from multi-metal waste liquid.

[0006] In a first aspect, the present application provides an acid-resistant extractant, the general structural formula of which is: Among them, 1≤x≤4.

[0007] In a second aspect, the present application provides a method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant, wherein the acid-resistant extractant described in the first aspect is used for extraction, and the method comprises the following steps: Mixing the acid-resistant extractant with a diluent to obtain a diluent; Adding the diluent to the copper-containing wastewater, and then adding a pH adjuster to adjust the pH value of the solution to a predetermined range, and selectively extracting copper in the solution; The organic phase is separated, the concentration of copper in the inorganic liquid phase solution is detected, and the extraction rate of the acid-resistant extractant is calculated using the following formula: Extraction rate (%) = ×100%; Wherein, C0 is the initial concentration of copper in copper-containing wastewater before extraction; C1 is the residual concentration of copper in the inorganic liquid phase solution after extraction.

[0008] As a further improvement of the present invention, the anions in the copper-containing wastewater are one or more of sulfate anions, chloride ions, nitrate anions, citrate anions, and tartaric acid anions.

[0009] As a further improvement of the present invention, the pH regulator is sodium hydroxide.

[0010] Furthermore, the predetermined range of the pH value is 7-14.

[0011] As a further improvement of the present invention, the diluent is sulfonated kerosene.

[0012] Furthermore, the volume ratio of the acid-resistant extractant to the sulfonated kerosene is 1:(10-100). The volume ratio of the copper-containing wastewater to the diluent is 1:(1-2).

[0013] As a further improvement of the present invention, the copper-containing wastewater is one or more of catalyst waste liquid, metallurgical waste liquid, electronic waste leaching solution, photovoltaic module etching liquid, and waste circuit board electroplating liquid.

[0014] The beneficial effects of the present invention are: The acid-resistant extractant provided by the present invention can effectively bind to copper ions, and by changing the type of derivatized functional groups, the length of functional group segments, the molecular main chain structure and the regulation of steric hindrance, efficient and selective extraction of copper can be achieved. By using the acid-resistant extractant to treat copper-containing wastewater in the integrated circuit industry and recover copper ions, the pollution of heavy metals to the environment is reduced, which meets environmental protection requirements. The method is easy to operate and can adapt to different types of copper-containing wastewater.

[0015] The acid-resistant extractant provided by the present invention uses tromethamine as a raw material, and through its unique spatial tetrahedral structure and chemical activity, it undergoes an esterification reaction with an aliphatic dibasic acid, and through precise regulation of the molecular structure, selective chelation of specific metal ions is achieved, and the stability under acidic conditions is improved through the design of surface hydrophobicity and pH buffering capacity. When used, the extractant can be directly added in an acidic environment, and then in the process of adjusting the pH value of copper-containing wastewater, the extractant is activated into anions, and its special molecular structure gives it excellent competitive complexation chemical reaction activity, avoiding the precipitation of copper ions under alkaline conditions to form copper-containing sludge, and finally achieving efficient selective extraction of copper by the extractant.

[0016] The method of the present invention optimizes the purification process of copper-containing wastewater in the integrated circuit industry, and avoids the problem that the traditional extractant extraction process needs to first adjust the pH of the copper-containing wastewater to alkaline, and then introduce the extractant, which causes a large amount of copper ions to generate copper hydroxide precipitation and produce a large amount of copper-containing sludge.

[0017] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0019] Figure 1 A schematic diagram of the chemical structure of the acid-resistant extractant A-1 provided in Example 1 of the present application; Figure 2 A schematic diagram of the chemical structure of the acid-resistant extractant A-2 provided in Example 17 of the present application; Figure 3 A physical picture of the acid-resistant extractant A-1 prepared in Example 37 of the present application; Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of the acid-resistant extractant A-1 prepared in Example 37 of the present application. DETAILED DESCRIPTION

[0020] The following embodiments of the technical solution of the present application will be described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

[0022] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is more than two, unless otherwise clearly and specifically defined.

[0023] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0024] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple pieces" refers to more than two pieces (including two pieces).

[0025] At present, the mainstream enrichment process for high-concentration copper-containing wastewater is extraction. The extraction method has been widely used in the field of remediation of heavy metal-contaminated water bodies due to its simple operation and strong applicability. However, existing extractants have certain limitations, such as poor selectivity, difficulty in achieving selective extraction of copper in multi-metal waste liquids, and the easy extraction of other metal ions during the chelating extraction stage. In addition, since high-concentration copper-containing wastewater is usually highly acidic, direct use can easily lead to the decomposition of the effective ingredients of the extractant. It is usually necessary to adjust the pH value of the copper-containing wastewater to alkaline before introducing the extractant. The above process often causes a large amount of copper ions to generate copper hydroxide precipitation, resulting in the production of a large amount of copper-containing sludge.

[0026] In order to solve the technical problems of poor selectivity of extractants, easy decomposition in highly acidic copper-containing wastewater, and difficulty in extracting copper alone from multi-metal waste liquid, the present application provides an acid-resistant extractant and a method for purifying copper-containing wastewater in the integrated circuit industry, wherein an acid-resistant extractant is synthesized, the extractant has good stability under acidic conditions and is not easy to decompose, so that the extractant can be added to a strong acid, and the pH value of the solution can be adjusted to activate the extractant, thereby avoiding the generation of a large amount of copper-containing sludge and achieving the technical effect of efficient and selective extraction of copper.

[0027] In a first aspect, the present invention provides an acid-resistant extractant, the general structural formula of which is: Among them, 1≤x≤4.

[0028] In the technical scheme of the embodiment of the present application, the extractant uses tromethamine as a raw material. Tromethamine belongs to a spatial tetrahedron, and the cone angle is a triol. At the same time, the triol of the cone angle exists in the form of a primary alcohol, has high chemical activity, and is easy to derivatize. The primary alcohol of the cone angle is esterified with an aliphatic dibasic acid. After derivatization, the bond angle of the tetrahedral NCO can be changed, thereby controlling the spatial tension of the entire molecular structure, and achieving selective chelation of the target metal ions. By controlling the length of the aliphatic chain (the value of x), the directional regulation of the surface hydrophobicity of the extractant is achieved. The carboxyl group at the tail end of the molecular structure can be hydrolyzed under a specific environment to produce free hydrogen ions, which has a buffering effect on the pH solution window of the environment, ensuring the stability of the extractant under acidic conditions. By changing the type of derivatized functional groups, the length of the functional group chain segment, the molecular main chain structure and its steric hindrance, the extractant can achieve efficient and selective extraction of copper.

[0029] The preparation method of the acid-resistant extractant provided in the present application comprises the following steps: S1. Add tromethamine to the dimethyl sulfoxide solution to prepare a tromethamine solution with a concentration of 0.05-0.1 mol / L, maintain the temperature of the system in the range of 50-70°C, and stir for 10-30 minutes.

[0030] S2. Dissolve the aliphatic dibasic acid in dimethyl sulfoxide to prepare a dibasic acid solution with a concentration of 1-2 mol / L, add it dropwise to the system obtained in step S1, add an appropriate amount of dilute sulfuric acid, the concentration of sulfuric acid is 0.5-2 mmol / L. Maintain the temperature of the system in the range of 50-100°C, and reflux for 6-24 hours.

[0031] S3. After the reaction is completed, the dimethyl sulfoxide solution and excess dibasic acid are removed, deionized water is added, ultrasonically dissolved, filtered, and inorganic impurities are removed. Subsequently, tetrahydrofuran and deionized water are added, extracted, and the organic phase is collected. After drying and filtering, the liquid phase is collected, and the solvent is removed by rotary evaporation to obtain an acid-resistant extractant.

[0032] In a second aspect, an embodiment of the present application provides a method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant, wherein the acid-resistant extractant described in the first aspect is used for extraction, and the method comprises the following steps: mixing an acid-resistant extractant with a diluent to obtain a diluent; Adding a diluent to the copper-containing wastewater, and then adding a pH adjuster to adjust the pH value of the solution to a predetermined range, and selectively extracting copper in the solution; Separate the organic phase, detect the concentration of copper in the inorganic liquid phase solution, and calculate the extraction rate of the acid-resistant extractant. The calculation formula is: Extraction rate (%) = ×100%; Wherein, C0 is the initial concentration of copper in copper-containing wastewater before extraction; C1 is the residual concentration of copper in the inorganic liquid phase solution after extraction.

[0033] In the technical scheme of the embodiment of the present application, by using a specific acid-resistant extractant, copper ions can be selectively and efficiently extracted from copper-containing wastewater, thereby realizing copper recovery and wastewater purification; the method optimizes the extraction conditions by adjusting the pH value, making the extraction process more efficient and improving the efficiency of wastewater treatment; by effectively removing copper ions in wastewater, the pollution of copper-containing wastewater to the environment is reduced, meeting environmental protection requirements; the acid-resistant extractant used can maintain stability in an acidic environment and is not easily destroyed by acid, thereby ensuring the stability of the extraction process and the reusability of the extractant; by detecting the residual concentration of copper in the inorganic liquid phase, the extraction rate can be conveniently calculated, thereby evaluating the extraction effect, and facilitating process control and optimization; by recovering copper ions, not only can environmental pollution be reduced, but also valuable metals can be recovered, which has certain economic benefits; the method is simple to operate and easy to realize large-scale application in industry, and is suitable for the treatment of copper-containing wastewater in the integrated circuit industry, and also has good applicability to copper-containing wastewater generated in other industries.

[0034] Further, in some embodiments, the anions in the copper-containing wastewater are one or more of sulfate anions, chloride anions, nitrate anions, citrate anions, and tartaric acid anions.

[0035] In the technical solution of the embodiment of the present application, the acid-resistant extractant can adapt to complex wastewater systems containing different anions and has good versatility. Different anions will affect the existence form and extraction efficiency of copper ions. By adjusting the type or proportion of the extractant, the extraction effect of copper ions in wastewater containing different anions can be improved. In wastewater containing multiple anions, the acid-resistant extractant can selectively extract copper ions and reduce the interference of other anions on the extraction process.

[0036] Further, in some embodiments, the pH adjuster is sodium hydroxide, and the predetermined range of pH value is 7-14.

[0037] In the technical solution of the embodiment of the present application, the acid-resistant extractant has a higher extraction efficiency for copper ions under specific conditions. By adjusting the pH value to 7-14, the reaction between the extractant and copper ions can be optimized and the extraction efficiency can be improved.

[0038] Further, in some embodiments, the diluent is sulfonated kerosene. The volume ratio of the acid-resistant extractant to the sulfonated kerosene is 1:(10-100). The volume ratio of the copper-containing wastewater to the diluent is 1:(1-2).

[0039] In the technical solution of the embodiment of the present application, the acid-resistant extractant is diluted by sulfonated kerosene to reduce its concentration, improve the extraction efficiency, and reduce the amount of the extractant to reduce the cost. Sulfonated kerosene has high chemical stability and is not easy to react with acids and bases. A higher dilution ratio helps to increase the contact area between the extractant and the copper-containing wastewater, thereby improving the extraction efficiency. The volume of the diluent is equivalent to or slightly more than the volume of the copper-containing wastewater, which ensures that there is enough extractant to contact the copper ions in the wastewater to achieve effective extraction. An appropriate volume ratio can reduce the excessive use of the extractant, avoid unnecessary waste, and also reduce the burden in subsequent processing steps.

[0040] In some embodiments, the extraction efficiency can also be improved by water bath oscillation or stirring. The mixed solution is placed in a water bath oscillator at 25-30°C for extraction. Water bath oscillation helps maintain a constant temperature, and oscillation can promote contact and mixing between the two phases. The oscillation time is 5-10 minutes, and the extractant and copper ions are fully in contact and reacted to achieve efficient extraction of copper ions.

[0041] Furthermore, in some embodiments, the copper-containing wastewater is one or more of catalyst waste liquid, metallurgical waste liquid, electronic waste leaching solution, photovoltaic module etching liquid, and waste circuit board electroplating liquid.

[0042] In the technical solution of the embodiment of the present application, the source of copper-containing wastewater includes waste liquid generated in various industrial production processes, which contains a relatively high concentration of copper ions. By adopting the treatment method of the present application to recover copper, environmental pollution is reduced.

[0043] Some specific embodiments are listed below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be obtained commercially.

[0044] Example 1 This embodiment provides an acid-resistant extractant A-1, the molecular structure of which is , the structural diagram is as follows Figure 1 The acid-resistant extractant A-1 is used to purify copper-containing wastewater in the integrated circuit industry, including the following steps: S1. Mix the acid-resistant extractant A-1 and sulfonated kerosene in a volume ratio of 1:10 and dissolve them by ultrasonication.

[0045] S2. At room temperature, take 100 ml of the diluted solution of the above-mentioned acid-resistant extractant A-1, put it into 50 ml of the copper-containing wastewater solution, adjust the pH value of the copper-containing wastewater solution to 9 with sodium hydroxide, shake it in a water bath oscillator at 25°C for 5 minutes, separate the organic phase, and use ICP-OES (inductively coupled plasma emission spectrometer) to detect the concentration of copper in the inorganic liquid phase solution, thereby calculating the extraction rate of the acid-resistant extractant A-1, wherein the detection error of ICP-OES is ±2%.

[0046] Examples 2-8 and Comparative Example 1 Examples 2-8 and Comparative Example 1 respectively provide a method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant. Acid-resistant extractant A-1 is used for extraction. Compared with Example 1, the only difference is that sodium hydroxide is added to adjust the pH value of the solution, as shown in Table 1. Other experimental parameters and conditions are basically the same as those in Example 1 and will not be repeated here.

[0047] As can be seen from Table 1, the acid-resistant extractant A-1 provided in Example 1 has a high efficiency in extracting copper, and the extraction effect is more than 98% in the pH range (7-14), indicating that the acid-resistant extractant A-1 has a wide window of use under specific conditions. At the same time, the acid-resistant extractant A-1 has good stability under acidic conditions and does not decompose, which will not affect the subsequent extraction process. In Comparative Example 1, when the pH value of the solution is 6, the extraction rate of copper ions is low, only 52%. The main reason is that the acid-resistant extractant A-1 is difficult to hydrolyze to form anions under acidic conditions, and the activation degree of the chelating ability of the extractant is limited, which makes it difficult to achieve efficient extraction of copper ions.

[0048] Example 9 Example 9 provides a method for purifying copper-containing wastewater from the integrated circuit industry using an acid-resistant extractant. Acid-resistant extractant A-1 is used for extraction. Compared with Example 1, the only difference is that the type of copper-containing wastewater is different, and it contains an acidic mixed solution with a volume ratio of citric acid: sulfuric acid: water of 30:5:65. Other experimental parameters and conditions are basically the same as those in Example 1 and will not be repeated here.

[0049] Examples 10-16 Examples 10-16 respectively provide a method for purifying copper-containing wastewater from the integrated circuit industry using an acid-resistant extractant, and acid-resistant extractant A-1 is used for extraction. Compared with Example 9, the only difference is that sodium hydroxide is added to adjust the pH value of the solution, as shown in Table 2. Other experimental parameters and conditions are basically the same as those in Example 9 and will not be repeated here.

[0050] As shown in Table 2, the acid-resistant extractant A-1 has a high efficiency in extracting copper and is suitable for complex solution systems containing a variety of anion species.

[0051] Embodiment 17 This embodiment provides an acid-resistant extractant A-2, the molecular structure of which is , the structural diagram is as follows Figure 2 The acid-resistant extractant A-2 is used to purify copper-containing wastewater in the integrated circuit industry, including the following steps: S1. Mix the acid-resistant extractant A-2 and sulfonated kerosene in a volume ratio of 1:10 and dissolve them by ultrasonication.

[0052] S2. At room temperature, take 100 ml of the diluted solution of the above-mentioned acid-resistant extractant A-2, put it into 50 ml of the copper-containing wastewater solution, adjust the pH value of the solution to 9 with sodium hydroxide, shake it in a water bath oscillator at 25°C for 5 minutes, separate the organic phase, and use ICP-OES to detect the concentration of copper in the inorganic liquid phase solution, thereby calculating the extraction rate of the acid-resistant extractant A-2, wherein the detection error of ICP-OES is ±2%.

[0053] Examples 18-24 and Comparative Example 2 Examples 18-24 and Comparative Example 2 respectively provide a method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant. Acid-resistant extractant A-2 is used for extraction. Compared with Example 17, the only difference is that the pH value of the copper-containing wastewater is different, as shown in Table 2. Other experimental parameters and conditions are basically the same as those in Example 17 and will not be repeated here.

[0054] As shown in Table 3, the acid-resistant extractant A-2 provided in Example 17 has a high efficiency in extracting copper, and the extraction effect is more than 98% in the pH range (7-14). The acid-resistant extractant A-2 has a wide window of use under specific conditions. At the same time, the acid-resistant extractant A-2 has good stability under acidic conditions and does not decompose, which will not affect the subsequent extraction process. When the pH is 6, the extraction rate of copper ions is low, only 26%. The main reason is that the acid-resistant extractant A-2 is difficult to hydrolyze to form an anion form under acidic conditions, and the activation degree of the chelating ability of the extractant is limited, which makes it difficult to achieve efficient extraction of copper ions.

[0055] Examples 25-30 Examples 25-30 respectively provide a method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant, wherein the acid-resistant extractant A-1 provided in Example 1 is used to extract and separate copper from a variety of coexisting ion solutions, and the specific operation steps are as follows: A series of blended solutions containing copper and tungsten, molybdenum, rhenium and antimony in different concentration ratios were prepared, and 100 ml of the diluted acid-resistant extractant A-1 provided in Example 1 was added to 500 ml of the blended solution, respectively. After shaking for 5 minutes, the inorganic liquid phase was taken, and the concentration of each metal ion in the solution was detected by ICP-OES to calculate the extraction rate, wherein the detection error of ICP-OES was ±2%. The results are shown in Table 4. It can be seen from Table 4 that the acid-resistant extractant A-1 has a selective extraction effect on copper, but basically does not extract other metal ions, such as tungsten, molybdenum, rhenium, and antimony. The main reason is attributed to the unique molecular structure and spatial structure of the acid-resistant extractant A-1, and the coordinated effect between the functional groups, which achieves the effect of efficient selective chelating extraction of copper ions.

[0056] Examples 31-36 Examples 31-36 respectively provide a method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant, wherein the acid-resistant extractant A-2 provided in Example 17 is used to extract and separate copper from a variety of coexisting ion solutions, and the specific operation steps are as follows: A series of blended solutions containing copper and tungsten, molybdenum, rhenium and antimony in different concentration ratios were prepared, and 100 ml of the diluted acid-resistant extractant A-2 provided in Example 17 was added to 500 ml of the blended solution, respectively. After shaking for 5 minutes, the inorganic liquid phase was taken, and the concentration of each metal ion in the solution was detected by ICP-OES to calculate the extraction rate, wherein the detection error of ICP-OES was ±2%. The results are shown in Table 5. It can be seen from Table 5 that the acid-resistant extractant A-2 has a selective extraction effect on copper, but basically does not extract other metal ions, such as tungsten, molybdenum, rhenium, and antimony. The main reason is attributed to the unique molecular structure and spatial structure of the acid-resistant extractant A-2, and the coordinated effect between the functional groups, which achieves the effect of efficient selective chelating extraction of copper ions.

[0057] Embodiment 37 Example 37 provides a method for preparing the acid-resistant extractant A-1 in Example 1, which specifically comprises the following steps: S1. Add 0.1 mol of tromethamine to a sufficient amount of dimethyl sulfoxide solution, so that the concentration of tromethamine is 0.05 mol / L. Maintain the temperature of the system within the range of 60±5°C and stir for 30 minutes.

[0058] S2. Dissolve 1 mol of malonic acid in dimethyl sulfoxide, at which the concentration of malonic acid is 1 mol / L, and add it dropwise to the system in step S1, and then add an appropriate amount of dilute sulfuric acid, at a concentration of 1 mmol / L. Maintain the temperature of the system within the range of 80±5°C, and reflux for 6 to 24 hours.

[0059] S3. After the reaction is completed, the dimethyl sulfoxide solution and excess malonic acid are removed by rotary evaporation under reduced pressure, the brown oil is collected, deionized water is added, ultrasonic dissolution is performed, and inorganic impurities are removed by filtration. Subsequently, tetrahydrofuran and deionized water are added in a volume ratio of 1:1, and the organic phase is collected and dried over anhydrous magnesium sulfate, filtered, the liquid phase is collected, and the solvent is removed by rotary evaporation to obtain a yellow product, such as Figure 3 As shown, the yield was 63%.

[0060] The product (acid-resistant extractant A-1) was tested by nuclear magnetic resonance hydrogen spectrum, 1 H NMR (deuterated reagent D2O, 300MHz), the spectrum is as follows Figure 4 shown.

[0061] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. An acid-resistant extractant, characterized in that: The general structural formula of the acid-resistant extractant is: , where 1≤x≤4.

2. A method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant, wherein the acid-resistant extractant according to claim 1 is used for extraction, characterized in that: The following steps are involved: Mixing the acid-resistant extractant with a diluent to obtain a diluent; Adding the diluent to the copper-containing wastewater, and then adding a pH adjuster to adjust the pH value of the solution to a predetermined range, and selectively extracting copper in the solution; The organic phase is separated, the concentration of copper in the inorganic liquid phase solution is detected, and the extraction rate of the acid-resistant extractant is calculated using the following formula: Extraction rate (%) = ×100%; Wherein, C0 is the initial concentration of copper in copper-containing wastewater before extraction; C1 is the residual concentration of copper in the inorganic liquid phase solution after extraction.

3. The method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant according to claim 2, characterized in that: The anions in the copper-containing wastewater are one or more of sulfate anions, chloride anions, nitrate anions, citrate anions, and tartaric acid anions.

4. The method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant according to claim 2, characterized in that: The pH regulator is sodium hydroxide.

5. The method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant according to claim 4, characterized in that: The predetermined range of the pH value is 7 to 14.

6. The method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant according to claim 2, characterized in that: The diluent is sulfonated kerosene.

7. The method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant according to claim 6, characterized in that: The volume ratio of the acid-resistant extractant to the sulfonated kerosene is 1:(10-100).

8. The method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant according to claim 2, characterized in that: The volume ratio of the copper-containing wastewater to the diluent is 1:(1-2).

9. The method for purifying copper-containing wastewater in the integrated circuit industry using an acid-resistant extractant according to claim 2, characterized in that: The copper-containing wastewater is one or more of catalyst waste liquid, metallurgical waste liquid, electronic waste leaching solution, photovoltaic module etching liquid, and waste circuit board electroplating liquid.

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