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

Abstract

The present application provides an acid-resistant extractant and a method for purifying copper-containing wastewater in the integrated circuit industry, belonging to the field of wastewater purification. The extractant uses tromethamine as a raw material, and is derivatized through an esterification reaction to regulate the spatial tension of the molecular structure to achieve selective chelation of the target metal ions. By controlling the length of the aliphatic chain, the surface hydrophobicity of the extractant is directionally regulated. The carboxyl group at the tail end of the molecular structure can be hydrolyzed under specific conditions to produce free hydrogen ions, which has a buffering effect on the pH solution window of the environment. The unique molecular structure and high-density carboxyl groups jointly ensure the stability of the extractant under acidic conditions. Therefore, when adjusting the pH value of the copper-containing wastewater, the extractant activated into anions exhibits excellent competitive complexation chemical reaction activity, avoiding the precipitation of copper ions to form sludge, and achieving efficient and selective extraction of copper.

Description

Technical Field

[0001] The present 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 using the same. 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 differences in concentration 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 to the 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 precipitation 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 relatively 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 wastewater, and easy co-extraction of other metal ions during the chelation 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 precipitates, resulting in the production of a large amount of copper-containing sludge. The copper-containing sludge needs to be outsourced for hazardous waste treatment, which increases the company's environmental protection costs.

[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 having the general structural formula:

[0007]

[0008] Among them, 1≤x≤4.

[0009] In a second aspect, the present application provides a method for purifying copper-containing wastewater from the integrated circuit industry using an acid-resistant extractant, wherein the extraction is performed using the acid-resistant extractant described in the first aspect, comprising the following steps:

[0010] mixing the acid-resistant extractant with a diluent to obtain a diluent;

[0011] adding the diluent to the copper-containing wastewater, and then adding a pH regulator to adjust the pH value of the solution to a predetermined range, thereby selectively extracting the copper in the solution;

[0012] The organic phase was separated, the concentration of copper in the inorganic liquid phase solution was detected, and the extraction rate of the acid-resistant extractant was calculated using the following formula:

[0013] Extraction rate (%) = ×100%;

[0014] Wherein, C0 is the initial concentration of copper in copper-containing wastewater before extraction;

[0015] C1 is the residual concentration of copper in the inorganic liquid solution after extraction.

[0016] 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, citric acid anions, and tartaric acid anions.

[0017] As a further improvement of the present invention, the pH regulator is sodium hydroxide.

[0018] Furthermore, the predetermined range of the pH value is 7-14.

[0019] As a further improvement of the present invention, the diluent is sulfonated kerosene.

[0020] 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).

[0021] 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 solution, and waste circuit board electroplating solution.

[0022] The beneficial effects of the present invention are:

[0023] The acid-resistant extractant provided by the present invention can effectively bind to copper ions. By varying the type of derivatized functional groups, the length of the functional group segments, the molecular backbone structure, and its steric hindrance, efficient and selective copper extraction can be achieved. By using the acid-resistant extractant to treat copper-containing wastewater from the integrated circuit industry and recover copper ions, heavy metal pollution is reduced, meeting environmental protection requirements. The method is easy to operate and can be adapted to different types of copper-containing wastewater.

[0024] The acid-resistant extractant provided by the present invention uses tromethamine as a raw material. Through its unique spatial tetrahedral structure and chemical activity, it undergoes an esterification reaction with an aliphatic dibasic acid. Through precise control of the molecular structure, it achieves selective chelation of specific metal ions. Furthermore, through the design of surface hydrophobicity and pH buffering capacity, it improves stability under acidic conditions. During use, the extractant can be directly added to an acidic environment. Subsequently, during the process of adjusting the pH value of copper-containing wastewater, the extractant is activated into anions. Its unique molecular structure gives it excellent competitive complexation chemical reaction activity, preventing copper ions from precipitating under alkaline conditions to form copper-containing sludge, ultimately achieving efficient and selective extraction of copper by the extractant.

[0025] The method of the present invention optimizes the purification process of copper-containing wastewater in the integrated circuit industry, avoiding the problem that the traditional extraction process requires first adjusting the pH of the copper-containing wastewater to alkaline and then introducing the extractant, which causes a large amount of copper ions to generate copper hydroxide precipitation and produce a large amount of copper-containing sludge.

[0026] 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

[0027] To more clearly illustrate the technical solution of this application, the following is a brief introduction to the drawings used in this application. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be derived from these drawings without inventive effort.

[0028] Figure 1 A schematic diagram of the chemical structure of the acid-resistant extractant A-1 provided in Example 1 of the present application;

[0029] Figure 2 A schematic diagram of the chemical structure of the acid-resistant extractant A-2 provided in Example 17 of the present application;

[0030] Figure 3 A physical image of the acid-resistant extractant A-1 prepared in Example 37 of the present application;

[0031] 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

[0032] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art 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" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0034] In the description of the embodiments of this application, the technical terms "first" and "second" are used only to distinguish different objects and should not be understood to indicate or imply relative importance or implicitly specify the quantity, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, the meaning of "plurality" is more than two, unless otherwise clearly and specifically defined.

[0035] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0036] 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).

[0037] At present, the mainstream enrichment process for high-concentration copper-containing wastewater is extraction. Due to its simple operation and strong applicability, the extraction method has been widely used in the field of remediation of heavy metal-contaminated water bodies. However, existing extractants have certain limitations, such as poor selectivity, difficulty in achieving selective extraction of copper in multi-metal wastewater, and easy co-extraction of other metal ions during the chelation 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 precipitates, resulting in the production of a large amount of copper-containing sludge.

[0038] 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. The acid-resistant extractant is synthesized, and the extractant has good stability under acidic conditions and is not easy to decompose. Therefore, 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.

[0039] In a first aspect, the present invention provides an acid-resistant extractant having the general structural formula:

[0040]

[0041] Among them, 1≤x≤4.

[0042] In the technical solution of the present embodiment, the extractant is made from tromethamine. Tromethamine is a tetrahedral triol with a cone angle. The cone angle triol exists as a primary alcohol, which is highly chemically active and easily derivatized. The cone angle primary alcohol undergoes an esterification reaction with an aliphatic dibasic acid. Derivatization modifies the tetrahedral NCO bond angle, thereby controlling the steric tension of the entire molecular structure and achieving selective chelation of the target metal ion. By controlling the length of the aliphatic chain (the value of x), the surface hydrophobicity of the extractant is controlled. The carboxyl group at the end of the molecular structure can hydrolyze under specific conditions to produce free hydrogen ions, which acts as a buffer within the pH window of the environment and ensures the extractant's stability under acidic conditions. By varying the type of derivatized functional group, the length of the functional group chain, the molecular backbone structure, and its steric hindrance, efficient and selective copper extraction can be achieved.

[0043] The preparation method of the acid-resistant extractant provided in the present application comprises the following steps:

[0044] 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.

[0045] S2. Dissolve an aliphatic dibasic acid in dimethyl sulfoxide to prepare a dibasic acid solution with a concentration of 1-2 mol / L. Add the solution dropwise to the system obtained in step S1. Add an appropriate amount of dilute sulfuric acid to a concentration of 0.5-2 mmol / L. Maintain the system temperature between 50-100°C and reflux for 6-24 hours.

[0046] 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.

[0047] In a second aspect, an embodiment of the present application provides a method for purifying copper-containing wastewater from the integrated circuit industry using an acid-resistant extractant, wherein the extraction is performed using the acid-resistant extractant described in the first aspect, comprising the following steps:

[0048] mixing an acid-resistant extractant with a diluent to obtain a diluent;

[0049] Adding a diluent to the copper-containing wastewater, and then adding a pH regulator to adjust the pH value of the solution to a predetermined range, thereby selectively extracting copper from the solution;

[0050] Separate the organic phase, detect the copper concentration in the inorganic liquid phase solution, and calculate the extraction rate of the acid-resistant extractant. The calculation formula is:

[0051] Extraction rate (%) = ×100%;

[0052] Wherein, C0 is the initial concentration of copper in copper-containing wastewater before extraction;

[0053] C1 is the residual concentration of copper in the inorganic liquid solution after extraction.

[0054] In the technical solution 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; this 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, facilitating process control and optimization; by recovering copper ions, not only can environmental pollution be reduced, but also the recovery of valuable metals can be achieved, which has certain economic benefits; this method is simple to operate and easy to implement large-scale application in industry. It 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.

[0055] Furthermore, 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.

[0056] In the technical solutions of the embodiments of the present application, the acid-resistant extractant is adaptable to complex wastewater systems containing different anions and has good versatility. Different anions affect the existence form and extraction efficiency of copper ions. By adjusting the type or ratio 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, reducing the interference of other anions in the extraction process.

[0057] Furthermore, in some embodiments, the pH adjuster is sodium hydroxide, and the predetermined pH range is 7-14.

[0058] 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, thereby improving the extraction efficiency.

[0059] Furthermore, in some embodiments, the diluent is sulfonated kerosene, the volume ratio of the acid-resistant extractant to the sulfonated kerosene is 1:(10-100), and the volume ratio of the copper-containing wastewater to the diluent is 1:(1-2).

[0060] 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 at the same time reduce the amount of extractant used, thereby reducing costs. Sulfonated kerosene has high chemical stability and is not easy to react with acids and alkalis. 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 larger 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.

[0061] 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.

[0062] 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 solution, and waste circuit board electroplating solution.

[0063] 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.

[0064] Some specific examples are listed below. It should be noted that the examples described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in this area or the product specifications are used. Reagents or instruments used without manufacturer's indication are all commercially available conventional products.

[0065] Example 1

[0066] This embodiment provides an acid-resistant extractant A-1, the molecular structure of which is

[0067] , the structural diagram is as follows Figure 1 The acid-resistant extractant A-1 is used to purify copper-containing wastewater from the integrated circuit industry, including the following steps:

[0068] S1. Mix acid-resistant extractant A-1 and sulfonated kerosene at a volume ratio of 1:10 and dissolve them by ultrasonication.

[0069] S2. At room temperature, take 100 ml of the diluted solution of the above-mentioned acid-resistant extractant A-1 and add it to 50 mL of the copper-containing wastewater solution. Adjust the pH value of the copper-containing wastewater solution to 9 with sodium hydroxide. After shaking in a water bath oscillator at 25°C for 5 minutes, separate the organic phase and use ICP-OES (inductively coupled plasma optical emission spectrometry) to detect the copper concentration in the inorganic liquid phase solution, thereby calculating the extraction rate of the acid-resistant extractant A-1. The detection error of ICP-OES is ±2%.

[0070] Examples 2-8 and Comparative Example 1

[0071] Examples 2-8 and Comparative Example 1 each provide 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 sodium hydroxide is added to adjust the pH value of the solution, as shown in Table 1. Other experimental parameters and conditions are essentially the same as those in Example 1 and are not further described here.

[0072]

[0073] As shown in Table 1, the acid-resistant extractant A-1 provided in Example 1 exhibits highly efficient copper extraction, achieving an extraction efficiency exceeding 98% within the pH range of 7–14. This demonstrates that the acid-resistant extractant A-1 has a wide window of application under specific conditions. Furthermore, the acid-resistant extractant A-1 exhibits excellent stability under acidic conditions and does not decompose, thus preventing subsequent extraction. In contrast, the copper ion extraction rate in Comparative Example 1 was low, at only 52%, at a solution pH of 6. This is primarily due to the difficulty of acid-resistant extractant A-1 in hydrolyzing to anionic form under acidic conditions, resulting in limited activation of the extractant's chelating ability and, consequently, difficulty in achieving efficient copper ion extraction.

[0074] Example 9

[0075] 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. It contains an acidic mixture 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 are not repeated here.

[0076] Examples 10-16

[0077] Examples 10-16 respectively provide 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 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 are not further described here.

[0078]

[0079] As shown in Table 2, the acid-resistant extractant A-1 has a high extraction capacity for copper and is suitable for complex solution systems containing multiple anion species.

[0080] Example 17

[0081] This embodiment provides an acid-resistant extractant A-2, the molecular structure of which is

[0082] , the structural diagram is as follows Figure 2 The acid-resistant extractant A-2 is used to purify copper-containing wastewater from the integrated circuit industry, including the following steps:

[0083] S1. Mix the acid-resistant extractant A-2 and sulfonated kerosene at a volume ratio of 1:10 and dissolve them by ultrasonication.

[0084] S2. At room temperature, 100 ml of the diluted solution of the acid-resistant extractant A-2 was added to 50 ml of the copper-containing wastewater solution. The pH of the solution was adjusted to 9 with sodium hydroxide. After shaking in a water bath oscillator at 25°C for 5 minutes, the organic phase was separated and the copper concentration in the inorganic liquid phase solution was detected by ICP-OES to calculate the extraction rate of the acid-resistant extractant A-2. The detection error of the ICP-OES was ±2%.

[0085] Examples 18-24 and Comparative Example 2

[0086] Examples 18-24 and Comparative Example 2 each provide a method for purifying copper-containing wastewater from 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 the pH value of the copper-containing wastewater, as shown in Table 2. Other experimental parameters and conditions are basically the same as those in Example 17 and are not further described here.

[0087]

[0088] Table 3 shows that the acid-resistant extractant A-2 provided in Example 17 exhibits highly efficient copper extraction, achieving extraction efficiency exceeding 98% within the pH range of 7–14. This indicates that the acid-resistant extractant A-2 has a wide window of application under specific environmental conditions. Furthermore, under acidic conditions, the acid-resistant extractant A-2 exhibits excellent stability and does not decompose, thereby preventing subsequent extraction. However, at a pH of 6, the copper ion extraction rate is low, at only 26%. This is primarily due to the difficulty of acid-resistant extractant A-2 in hydrolyzing to anionic form under acidic conditions, resulting in limited activation of the extractant's chelating ability and, consequently, difficulty in achieving efficient copper ion extraction.

[0089] Examples 25-30

[0090] Examples 25-30 provide methods for purifying copper-containing wastewater from the integrated circuit industry using an acid-resistant extractant. The acid-resistant extractant A-1 provided in Example 1 is used to extract and separate copper from various coexisting ion solutions. The specific steps are as follows:

[0091] A series of blend solutions containing copper and tungsten, molybdenum, rhenium, and antimony at different concentration ratios were prepared. 100 ml of the diluted acid-resistant extractant A-1 provided in Example 1 was added to 500 ml of the blend solution. 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. The detection error of ICP-OES was ±2%. The results are shown in Table 4.

[0092]

[0093] As shown in Table 4, the acid-resistant extractant A-1 has a selective extraction effect on copper, while 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.

[0094] Examples 31-36

[0095] Examples 31-36 provide methods for purifying copper-containing wastewater from the integrated circuit industry using an acid-resistant extractant. The acid-resistant extractant A-2 provided in Example 17 is used to extract and separate copper from various coexisting ion solutions. The specific steps are as follows:

[0096] A series of blended solutions containing copper and tungsten, molybdenum, rhenium, and antimony at different concentration ratios were prepared. 100 ml of the diluted acid-resistant extractant A-2 provided in Example 17 was added to 500 ml of the blended solution. 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. The detection error of ICP-OES was ±2%. The results are shown in Table 5.

[0097]

[0098] As shown in Table 5, the acid-resistant extractant A-2 has a selective extraction effect on copper, while basically does not extract other metal ions, such as tungsten, molybdenum, rhenium, and antimony. The main reason is that the acid-resistant extractant A-2 has a unique molecular structure and spatial structure, and the functional groups coordinate with each other, which achieves the effect of efficient selective chelating extraction of copper ions.

[0099] Example 37

[0100] Example 37 provides a method for preparing the acid-resistant extractant A-1 in Example 1, which specifically comprises the following steps:

[0101] S1. Add 0.1 mol of tromethamine to a sufficient amount of dimethyl sulfoxide solution to obtain a tromethamine concentration of 0.05 mol / L. Maintain the system temperature at 60 ± 5°C and stir for 30 minutes.

[0102] S2. Dissolve 1 mol of malonic acid in dimethyl sulfoxide (DMSO) to a concentration of 1 mol / L and add it dropwise to the reaction mixture in step S1. Then, add an appropriate amount of dilute sulfuric acid to a concentration of 1 mmol / L. Maintain the temperature of the reaction mixture at 80 ± 5°C and reflux for 6–24 hours.

[0103] S3. After the reaction is completed, the dimethyl sulfoxide solution and excess malonic acid are removed by rotary evaporation under reduced pressure, and the brown oil is collected. Deionized water is added, and the oil is dissolved by ultrasonication. The oil is filtered to remove inorganic impurities. 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. The organic phase is filtered, and 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%.

[0104] The product (acid-resistant extractant A-1) was subjected to nuclear magnetic resonance hydrogen spectrum test, 1 H NMR (deuterated reagent D2O, 300MHz), the spectrum is as follows Figure 4 shown.

[0105] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same structure and effect as the technical concept within the scope of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the present application, any other embodiments that can be conceived by those skilled in the art and that combine 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 from 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 regulator to adjust the pH value of the solution to a predetermined range, thereby selectively extracting the copper in the solution; The organic phase was separated, the concentration of copper in the inorganic liquid phase solution was detected, and the extraction rate of the acid-resistant extractant was 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 solution after extraction.

3. The method for purifying copper-containing wastewater from 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, citric acid anions, and tartaric acid anions.

4. The method for purifying copper-containing wastewater from 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 from 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 from 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 from 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 from 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 from 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 solution, and waste circuit board electroplating solution.

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