Method for preparing copper oxide by utilizing copper etching waste liquid

Abstract

The invention belongs to the technical field of etching liquid treatment, and particularly discloses a method for preparing copper oxide by utilizing copper etching waste liquid, which comprises the following steps: step (1): mixing the copper etching waste liquid with cyclodextrin-ionic liquid microemulsion, performing intermittent ultrasonic extraction, and performing centrifugal separation to obtain a water phase rich in ionic liquid; and (2) firstly dropwise adding a sodium hydroxide solution into the aqueous phase rich in the ionic liquid, stirring for reaction, then dropwise adding a cinnamic acid solution, heating, stirring for reaction, filtering, washing and sintering to obtain copper oxide. The invention provides a method for preparing copper oxide by using copper etching waste liquid, which comprises the following steps: extracting copper ions by using cyclodextrin-ionic liquid microemulsion, and promoting the formation of copper oxide in cooperation with cinnamic acid, thereby achieving the purposes of cleaning treatment and clean utilization of the copper etching waste liquid.

Description

Technical Field

[0001] The invention belongs to the technical field of etching liquid treatment, and in particular relates to a method for preparing copper oxide by utilizing copper etching waste liquid. Background Art

[0002] With the rapid development of my country's electronics industry, printed circuit boards are an irreplaceable part of the production of various electronic products, and the demand for production is strong. A large amount of waste etching solution is generated in the process of circuit board production, and its main components are copper chloride, ammonium chloride and hydrochloric acid. Since the waste etching solution contains a high concentration of copper ions, it is a typical secondary resource and has a high recycling value. Electrolysis is a common technical means for copper recovery, and there have been relevant reports on the direct electrolytic recycling of acidic copper chloride etching solution. Although electrolysis can achieve the purpose of copper recovery, it is difficult to overcome the negative impact of high chloride ion concentration in the solution, because a large amount of chlorine gas will be precipitated during the electrolysis process, which will cause serious environmental pollution. The discharge of a large amount of chlorine-containing residual liquid will cause serious environmental pollution, making it difficult to achieve green environmental protection and clean utilization.

[0003] At present, the invention patent CN118084039A discloses a method for preparing copper oxide nanopowder by using copper-containing etching waste liquid, comprising the following steps: (1) concentrating the copper-containing etching waste liquid to obtain a copper-containing etching waste liquid concentrate; (2) mixing the copper-containing etching waste liquid concentrate obtained in step (1) with landfill leachate, stirring, and obtaining a copper etching leachate mixed solution; (3) mixing the copper etching leachate mixed solution obtained in step (3) with straw powder, standing, and obtaining a straw-absorbed copper etching leachate slurry; (4) drying the straw-absorbed copper etching leachate slurry obtained in step (3) to obtain a copper etching precursor powder; (5) carbonizing the copper etching precursor powder obtained in step (4) to obtain a carbon copper powder; (6) incinerating the carbon copper powder obtained in step (5) to obtain a copper oxide powder residue; (7) mixing water and the copper oxide powder residue obtained in step (6), separating the solid from the liquid, and drying the obtained solid powder to obtain a copper oxide nanopowder. The steps of this preparation method are too complicated, and pollutants such as waste gas and waste residue will still be generated during the incineration process. Summary of the invention

[0004] The purpose of the present invention is to overcome the above problems existing in the prior art and provide a method for preparing copper oxide by using copper etching waste liquid, wherein cyclodextrin-ionic liquid microemulsion is used to extract copper ions and cinnamic acid is used to promote the formation of copper oxide, thereby achieving the purpose of clean treatment and clean utilization of copper etching waste liquid.

[0005] In order to achieve the above technical objectives and the above technical effects, the present invention is implemented through the following technical solutions:

[0006] A method for preparing copper oxide using copper etching waste liquid comprises the following steps:

[0007] Step (1): mixing the copper etching waste liquid with the cyclodextrin-ionic liquid microemulsion, extracting by intermittent ultrasonication, and centrifuging to obtain an ionic liquid-rich aqueous phase;

[0008] Step (2): firstly drop a sodium hydroxide solution into the ion liquid-rich aqueous phase, stir to react, then drop a cinnamic acid solution, heat up, stir to react, filter, wash, and sinter to obtain copper oxide.

[0009] Furthermore, the preparation method of the cyclodextrin-ionic liquid microemulsion comprises the following steps:

[0010] Cyclodextrin-ionic liquid, nonionic surfactant, organic solvent, potassium carbonate and water are ultrasonically mixed in a mass ratio of 5:(10-20):(40-60):(3-6):(20-40) to obtain a cyclodextrin-ionic liquid microemulsion.

[0011] Furthermore, the preparation method of the cyclodextrin-ionic liquid comprises the following steps:

[0012] S1. Add benzotriazole and n-octane bromide to acetone, heat to 45-50°C, react for 8-10 hours, then remove acetone by rotary evaporation, wash with ethyl acetate, and rotary evaporate to obtain [C8BTA]Br;

[0013] S2. Add [C8BTA]Br to the aqueous solution of sodium sulfobutyl-β-cyclodextrin, stir thoroughly at 60-70°C for 2 hours, then freeze at 4-10°C for 18-24 hours, and finally filter, wash, and dry to obtain cyclodextrin-ionic liquid.

[0014] Furthermore, the molar ratio of the benzotriazole, n-octane bromide and sodium sulfobutyl-β-cyclodextrin is 1:(1-1.2):1;

[0015] The concentration of the aqueous solution of sodium sulfobutyl-β-cyclodextrin is 0.25 mol / L.

[0016] Furthermore, the nonionic surfactant is one or more of Triton, Tween, Span, Sophorolipid, Rhamnolipid, and polyethylene glycol mixed in any proportion;

[0017] The organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of 10:1.

[0018] Furthermore, in the step (1), the volume ratio of the copper etching waste liquid to the cyclodextrin-ionic liquid microemulsion is 1:(2-6);

[0019] The copper ion concentration in the copper etching waste liquid is 1.5-3 mol / L.

[0020] Furthermore, in step (1), intermittent ultrasonic extraction means that each ultrasonic extraction is performed for 10 seconds, followed by a 5-second interval, and each ultrasonic extraction and intermittent process is collectively referred to as a cycle;

[0021] During the intermittent ultrasonic extraction process, the ultrasonic power is 300-400W and the extraction temperature is 35-45°C;

[0022] The time of the intermittent ultrasonic extraction is 30 minutes.

[0023] Furthermore, in the step (2), the volume ratio of the ionic liquid-rich water phase, the sodium hydroxide solution and the cinnamic acid solution is 1:(3-6):(2-5);

[0024] The concentration of the sodium hydroxide solution is 0.5-2 mol / L;

[0025] The concentration of the cinnamic acid solution is 0.1-0.5 mol / L.

[0026] Furthermore, in the step (2), the dropping speeds of the sodium hydroxide solution and the cinnamic acid solution are independently 0.5-1 mL / min;

[0027] The said heating refers to the temperature rising to 70-80°C;

[0028] During the two stirring reactions, the stirring speeds were independently 400-800 r / min, and the stirring reaction times were independently 1-3 h.

[0029] Furthermore, in the step (2), the specific operation of sintering is: heating to 400-600°C at a heating rate of 5-10°C / h, maintaining for 2-5h, and then naturally cooling to room temperature.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1. In the present invention, the cyclodextrin-ionic liquid uses the cyclodextrin molecule as the skeleton to modify the ionic liquid. The cavity structure of the cyclodextrin provides a good microenvironment for benzotriazole, which is conducive to the coordination reaction between benzotriazole and copper ions, thereby improving the selectivity of the extraction process for copper ions.

[0032] 2. When the cyclodextrin-ionic liquid microemulsion of the present invention interacts with a nonionic surfactant, a larger polar core is formed inside the ionic liquid, which is more conducive to the stable migration of copper ions into the ionic liquid microemulsion; at the same time, the addition of inorganic salt potassium carbonate helps to form a two-phase aqueous system, so that the prepared cyclodextrin-ionic liquid microemulsion can significantly improve the extraction rate of copper ions.

[0033] 3. In the present invention, in the process of preparing copper oxide, cyclodextrin-ionic liquid can also be used as a template to jointly regulate the morphology of copper oxide with cinnamic acid to obtain spherical copper oxide with high purity, high surface activity, large specific surface area and high crystallinity. It has good hydrophilic properties and is widely used in catalysis, gas sensing and antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of this application. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0035] Figure 1 This is a photograph of the static contact angle of copper oxide prepared in Example 1 of the present invention to water in air;

[0036] Figure 2 is a scanning electron microscope image of the copper oxide prepared in Example 1 of the present invention;

[0037] Figure 3 This is the X-ray diffraction pattern of the copper oxide prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0038] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] The present invention provides a method for preparing copper oxide by using copper etching waste liquid, the method comprising the following steps:

[0040] Step (1): mixing the copper etching waste liquid and the cyclodextrin-ionic liquid microemulsion in a volume ratio of 1:(2-6), performing intermittent ultrasonic extraction, and then centrifuging to obtain an ionic liquid-rich aqueous phase;

[0041] Wherein, in step (1), the copper ion concentration in the copper etching waste liquid is 1.5-3 mol / L;

[0042] In step (1), intermittent ultrasonic extraction means that each ultrasonic extraction is performed for 10 seconds, followed by a 5-second pause; during the intermittent ultrasonic extraction, the ultrasonic power is 300-400W, and the extraction temperature is 35-45°C;

[0043] The time of intermittent ultrasonic extraction is 10-40 minutes, specifically, the time of intermittent ultrasonic extraction is 30 minutes;

[0044] In step (1), the method for preparing the cyclodextrin-ionic liquid microemulsion comprises the following steps:

[0045] Ultrasonic mixing of cyclodextrin-ionic liquid, nonionic surfactant, organic solvent, potassium carbonate and water in a mass ratio of 5:(10-20):(40-60):(3-6):(20-40) was performed to obtain a cyclodextrin-ionic liquid microemulsion;

[0046] Wherein, the nonionic surfactant is one or more of Triton, Tween, Span, Sophorolipid, Rhamnolipid, and Polyethylene Glycol mixed in any proportion;

[0047] The organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of (6-15):1. Specifically, the organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of 10:1.

[0048] In the preparation method of cyclodextrin-ionic liquid microemulsion, the preparation method of cyclodextrin-ionic liquid comprises the following steps:

[0049] S1. Add benzotriazole and n-octane bromide to acetone, heat to 45-50°C, react for 8-10 hours, then remove acetone by rotary evaporation, wash with ethyl acetate, and rotary evaporate to obtain [C8BTA]Br;

[0050] In step S1, the molar ratio of benzotriazole, n-octane bromide and sodium sulfobutyl-β-cyclodextrin is 1:(1-1.2):1;

[0051] The concentration of the aqueous solution of sodium sulfobutyl-β-cyclodextrin is 0.10-0.50 mol / L, specifically, the concentration of the aqueous solution of sodium sulfobutyl-β-cyclodextrin is 0.25 mol / L;

[0052] S2, adding [C8BTA]Br to an aqueous solution of sodium sulfobutyl-β-cyclodextrin, stirring at 60-70°C for 2h, then freezing at 4-10°C for 18-24h, and finally filtering, washing, and drying to obtain a cyclodextrin-ionic liquid;

[0053] Step (2): firstly adding a sodium hydroxide solution with a concentration of 0.5-2 mol / L to the aqueous phase rich in ionic liquid at a dropping speed of 0.5-1 mL / min, stirring at a speed of 400-800 r / min, stirring for reaction for 1-3 h, then adding a cinnamic acid solution with a concentration of 0.1-0.5 mol / L at a dropping speed of 0.5-1 mL / min, heating to 70-80° C., stirring at a speed of 400-800 r / min, stirring for reaction for 1-3 h, filtering, washing, and sintering to obtain copper oxide;

[0054] In step (2), the volume ratio of the ionic liquid-rich aqueous phase, the sodium hydroxide solution and the cinnamic acid solution is 1:(3-6):(2-5);

[0055] In step (2), the specific operation of sintering is: heating to 400-600°C at a heating rate of 5-10°C / h, maintaining for 2-5h, and then naturally cooling to room temperature.

[0056] Preparation Example 1

[0057] This preparation example provides a cyclodextrin-ionic liquid microemulsion, which is prepared by the following method:

[0058] S1. Take 0.01 mol of benzotriazole and 0.01 mol of n-octane bromide respectively, add them to 60 mL of acetone, heat to 45 °C, react for 8 hours, then remove acetone by rotary evaporation, wash with ethyl acetate, and rotary evaporate to obtain [C8BTA]Br;

[0059] S2, adding the [C8BTA]Br obtained in step S1 to 40 mL of an aqueous solution of 0.25 mol / L sodium sulfobutyl-β-cyclodextrin, stirring at 60° C. for 2 h, then freezing at 4° C. for 18 h, and finally filtering, washing, and drying to obtain a cyclodextrin-ionic liquid;

[0060] S3, ultrasonically mixing the cyclodextrin-ionic liquid, nonionic surfactant, organic solvent, potassium carbonate, and water obtained in step S2 at a mass ratio of 5:10:40:3:20 to obtain a cyclodextrin-ionic liquid microemulsion;

[0061] The nonionic surfactant is Triton X-100; and the organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of 10:1.

[0062] Preparation Example 2

[0063] This preparation example provides a cyclodextrin-ionic liquid microemulsion, which is prepared by the following method:

[0064] S1. Take 0.01 mol of benzotriazole and 0.011 mol of n-octane bromide respectively, add them to 60 mL of acetone, heat to 48 °C, react for 9 hours, then remove acetone by rotary evaporation, wash with ethyl acetate, and rotary evaporate to obtain [C8BTA]Br;

[0065] S2, adding the [C8BTA]Br obtained in step S1 to 40 mL of an aqueous solution of 0.25 mol / L sodium sulfobutyl-β-cyclodextrin, stirring at 65° C. for 2 h, then freezing at 7° C. for 20 h, and finally filtering, washing, and drying to obtain a cyclodextrin-ionic liquid;

[0066] S3, ultrasonically mixing the cyclodextrin-ionic liquid, nonionic surfactant, organic solvent, potassium carbonate and water obtained in step S2 at a mass ratio of 5:15:50:4:30 to obtain a cyclodextrin-ionic liquid microemulsion;

[0067] The nonionic surfactant is sophorolipid; and the organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of 10:1.

[0068] Preparation Example 3

[0069] This preparation example provides a cyclodextrin-ionic liquid microemulsion, which is prepared by the following method:

[0070] S1. Take 0.01 mol of benzotriazole and 0.012 mol of n-octane bromide respectively, add them into 60 mL of acetone, heat to 50°C, react for 10 hours, then remove acetone by rotary evaporation, wash with ethyl acetate, and rotary evaporate to obtain [C8BTA]Br;

[0071] S2, adding the [C8BTA]Br obtained in step S1 to 40 mL of an aqueous solution of 0.25 mol / L sodium sulfobutyl-β-cyclodextrin, stirring at 70° C. for 2 h, then freezing at 10° C. for 24 h, and finally filtering, washing, and drying to obtain a cyclodextrin-ionic liquid;

[0072] S3, ultrasonically mixing the cyclodextrin-ionic liquid, nonionic surfactant, organic solvent, potassium carbonate, and water obtained in step S2 at a mass ratio of 5:20:60:6:40 to obtain a cyclodextrin-ionic liquid microemulsion;

[0073] The nonionic surfactant is Tween 80; and the organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of 10:1.

[0074] Preparation Example 4

[0075] This preparation example provides a cyclodextrin-ionic liquid microemulsion, which is different from Preparation Example 1 only in that an equimolar amount of tri-n-butylphosphine is used to replace benzotriazole, as follows:

[0076] Cyclodextrin-ionic liquid microemulsion is prepared by the following method:

[0077] S1. Take 0.01 mol tri-n-butylphosphine and 0.01 mol n-octane bromide respectively, add them to 60 mL acetone, heat to 45°C, react for 8 hours, then remove acetone by rotary evaporation, wash with ethyl acetate, and rotary evaporate to obtain [P4448]Br;

[0078] S2, adding the [P4448]Br obtained in step S1 to 40 mL of an aqueous solution of 0.25 mol / L sodium sulfobutyl-β-cyclodextrin, stirring at 60° C. for 2 h, then freezing at 4° C. for 18 h, and finally filtering, washing, and drying to obtain a cyclodextrin-ionic liquid;

[0079] S3, ultrasonically mixing the cyclodextrin-ionic liquid, nonionic surfactant, organic solvent, potassium carbonate, and water obtained in step S2 at a mass ratio of 5:10:40:3:20 to obtain a cyclodextrin-ionic liquid microemulsion;

[0080] The nonionic surfactant is Triton X-100; and the organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of 10:1.

[0081] Preparation Example 5

[0082] This preparation example provides an ionic liquid microemulsion, which is prepared by the following method:

[0083] S1. Take 0.01 mol of benzotriazole and 0.01 mol of n-octane bromide respectively, add them to 60 mL of acetone, heat to 45 °C, react for 8 hours, then remove acetone by rotary evaporation, wash with ethyl acetate, and rotary evaporate to obtain [C8BTA]Br;

[0084] S2, ultrasonically mixing the [C8BTA]Br obtained in step S1, a nonionic surfactant, an organic solvent, potassium carbonate, and water in a mass ratio of 5:10:40:3:20 to obtain an ionic liquid microemulsion;

[0085] The nonionic surfactant is Triton X-100; and the organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of 10:1.

[0086] Preparation Example 6

[0087] This preparation example provides an ionic liquid aqueous solution, which is prepared by the following method:

[0088] N-hexylpyridinium chloride, potassium phosphate and water are ultrasonically mixed in a mass ratio of 1:10:25 to obtain an ionic liquid aqueous solution.

[0089] The following Examples 1-3 and Comparative Examples 1-4 provide a method for preparing copper oxide using copper etching waste liquid. In the following Examples and Comparative Examples, unless otherwise specified, all raw materials can be obtained commercially.

[0090] Example 1

[0091] This embodiment provides a method for preparing copper oxide using copper etching waste liquid, comprising the following steps:

[0092] Step (1): mixing copper etching waste liquid (copper ion concentration of 1.5 mol / L) with cyclodextrin-ionic liquid microemulsion in a volume ratio of 1:2, performing intermittent ultrasonic extraction, ultrasonicating for 10 s each time, resting for 5 s, the ultrasonic power is 400 W, the intermittent ultrasonic extraction time is 30 min, the extraction temperature is 35° C., and then centrifuging at a speed of 2000 r / min to obtain an ionic liquid-rich aqueous phase;

[0093] Wherein, the cyclodextrin-ionic liquid microemulsion is prepared by Preparation Example 1;

[0094] Step (2): firstly, 120 mL of 0.5 mol / L sodium hydroxide solution was added dropwise at a rate of 1 mL / min to 20 mL of the ion-rich liquid aqueous phase obtained in step (1). After the addition was completed, the mixture was reacted at a speed of 400 r / min for 1 h. Then, 40 mL of 0.5 mol / L cinnamic acid solution was added dropwise at a rate of 0.5 mL / min. After the addition was completed, the mixture was heated to 70° C., reacted at a speed of 400 r / min for 1 h, filtered, washed, heated to 400° C. at a heating rate of 5° C. / h for sintering, maintained for 5 h, and then naturally cooled to room temperature to obtain copper oxide.

[0095] Example 2

[0096] This embodiment provides a method for preparing copper oxide using copper etching waste liquid, comprising the following steps:

[0097] Step (1): mixing copper etching waste liquid (copper ion concentration of 2.5 mol / L) with cyclodextrin-ionic liquid microemulsion in a volume ratio of 1:4, performing intermittent ultrasonic extraction, ultrasonicating for 10 s each time, resting for 5 s, the ultrasonic power is 350 W, the intermittent ultrasonic extraction time is 30 min, the extraction temperature is 40° C., and then centrifuging at a speed of 4000 r / min to obtain an ionic liquid-rich aqueous phase;

[0098] Wherein, the cyclodextrin-ionic liquid microemulsion is prepared by Preparation Example 2;

[0099] Step (2): firstly add 100 mL of 1 mol / L sodium hydroxide solution at a speed of 0.8 mL / min to 20 mL of the ion-rich liquid aqueous phase obtained in step (1), and then react at a speed of 600 r / min for 2 h. Then, add 60 mL of 0.3 mol / L cinnamic acid solution at a speed of 0.8 mL / min. After the addition is completed, the temperature is raised to 75° C., reacted at a speed of 600 r / min for 2 h, filtered, washed, and then heated to 500° C. at a heating rate of 8° C. / h for sintering, and maintained for 4 h to obtain copper oxide.

[0100] Example 3

[0101] This embodiment provides a method for preparing copper oxide using copper etching waste liquid, comprising the following steps:

[0102] Step (1): mixing copper etching waste liquid (copper ion concentration of 3 mol / L) with cyclodextrin-ionic liquid microemulsion in a volume ratio of 1:6, performing intermittent ultrasonic extraction, ultrasonicating for 10 s each time, resting for 5 s, the ultrasonic power is 300 W, the intermittent ultrasonic extraction time is 30 min, the extraction temperature is 45° C., and then centrifuging at a speed of 6000 r / min to obtain an ionic liquid-rich aqueous phase;

[0103] Wherein, the cyclodextrin-ionic liquid microemulsion is prepared by Preparation Example 3;

[0104] Step (2): Take 20 mL of the ion-rich liquid aqueous phase obtained in step (1), first add 60 mL of a 2 mol / L sodium hydroxide solution at a rate of 0.5 mL / min, after the addition is completed, react at a speed of 800 r / min for 3 hours, then add 100 mL of a 0.1 mol / L cinnamic acid solution at a rate of 1 mL / min, after the addition is completed, heat to 80°C, react at a speed of 800 r / min for 3 hours, filter, wash, heat to 600°C at a heating rate of 10°C / h for sintering, and maintain for 2 hours to obtain copper oxide.

[0105] Comparative Example 1

[0106] This comparative example provides a method for preparing copper oxide using copper etching waste liquid, comprising the following steps:

[0107] Step (1): mixing copper etching waste liquid (copper ion concentration of 1.5 mol / L) with cyclodextrin-ionic liquid microemulsion in a volume ratio of 1:2, performing intermittent ultrasonic extraction, ultrasonicating for 10 s each time, resting for 5 s, the ultrasonic power is 400 W, the intermittent ultrasonic extraction time is 30 min, the extraction temperature is 35° C., and then centrifuging at a speed of 2000 r / min to obtain an ionic liquid-rich aqueous phase;

[0108] Wherein, the cyclodextrin-ionic liquid microemulsion is prepared by Preparation Example 4;

[0109] Step (2): firstly, 120 mL of 0.5 mol / L sodium hydroxide solution was added dropwise at a rate of 1 mL / min to 20 mL of the ion-rich liquid aqueous phase obtained in step (1). After the addition was completed, the mixture was reacted at a speed of 400 r / min for 1 h. Then, 40 mL of 0.5 mol / L cinnamic acid solution was added dropwise at a rate of 0.5 mL / min. After the addition was completed, the mixture was heated to 70° C., reacted at a speed of 400 r / min for 1 h, filtered, washed, heated to 400° C. at a heating rate of 5° C. / h for sintering, maintained for 5 h, and then naturally cooled to room temperature to obtain copper oxide.

[0110] Comparative Example 2

[0111] This comparative example provides a method for preparing copper oxide using copper etching waste liquid, comprising the following steps:

[0112] Step (1): mixing copper etching waste liquid (copper ion concentration of 1.5 mol / L) with ionic liquid microemulsion in a volume ratio of 1:2, performing intermittent ultrasonic extraction, ultrasonicating for 10 s each time, resting for 5 s, the ultrasonic power is 400 W, the intermittent ultrasonic extraction time is 30 min, the extraction temperature is 35° C., and then centrifuging at a speed of 2000 r / min to obtain an ionic liquid-rich aqueous phase;

[0113] Wherein, the ionic liquid microemulsion is prepared by Preparation Example 5;

[0114] Step (2): firstly, 120 mL of 0.5 mol / L sodium hydroxide solution was added dropwise at a rate of 1 mL / min to 20 mL of the ion-rich liquid aqueous phase obtained in step (1). After the addition was completed, the mixture was reacted at a speed of 400 r / min for 1 h. Then, 40 mL of 0.5 mol / L cinnamic acid solution was added dropwise at a rate of 0.5 mL / min. After the addition was completed, the mixture was heated to 70° C., reacted at a speed of 400 r / min for 1 h, filtered, washed, heated to 400° C. at a heating rate of 5° C. / h for sintering, maintained for 5 h, and then naturally cooled to room temperature to obtain copper oxide.

[0115] Comparative Example 3

[0116] This comparative example provides a method for preparing copper oxide using copper etching waste liquid, comprising the following steps:

[0117] Step (1): mixing copper etching waste liquid (copper ion concentration of 1.5 mol / L) with an ionic liquid aqueous solution in a volume ratio of 1:2, performing intermittent ultrasonic extraction, ultrasonicating for 10 s each time, resting for 5 s, the ultrasonic power is 400 W, the intermittent ultrasonic extraction time is 30 min, the extraction temperature is 35° C., and then centrifuging at a speed of 2000 r / min to obtain an ionic liquid-rich aqueous phase;

[0118] Wherein, the ionic liquid aqueous solution is prepared by Preparation Example 6;

[0119] Step (2): firstly, 120 mL of 0.5 mol / L sodium hydroxide solution was added dropwise at a rate of 1 mL / min to 20 mL of the ion-rich liquid aqueous phase obtained in step (1). After the addition was completed, the mixture was reacted at a speed of 400 r / min for 1 h. Then, 40 mL of 0.5 mol / L cinnamic acid solution was added dropwise at a rate of 0.5 mL / min. After the addition was completed, the mixture was heated to 70° C., reacted at a speed of 400 r / min for 1 h, filtered, washed, heated to 400° C. at a heating rate of 5° C. / h for sintering, maintained for 5 h, and then naturally cooled to room temperature to obtain copper oxide.

[0120] Comparative Example 4

[0121] This comparative example provides a method for preparing copper oxide using copper etching waste liquid, comprising the following steps:

[0122] Step (1): mixing copper etching waste liquid (copper ion concentration of 1.5 mol / L) with cyclodextrin-ionic liquid microemulsion in a volume ratio of 1:2, performing intermittent ultrasonic extraction, ultrasonicating for 10 s each time, resting for 5 s, the ultrasonic power is 400 W, the intermittent ultrasonic extraction time is 30 min, the extraction temperature is 35° C., and then centrifuging at a speed of 2000 r / min to obtain an ionic liquid-rich aqueous phase;

[0123] Wherein, the cyclodextrin-ionic liquid microemulsion is prepared by Preparation Example 1;

[0124] Step (2): Take 20 mL of the ion-rich liquid aqueous phase obtained in step (1), first add 120 mL of a 0.5 mol / L sodium hydroxide solution at a rate of 1 mL / min. After the addition is completed, the temperature is raised to 70°C, and the reaction is carried out at a speed of 400 r / min for 1 hour. After filtering and washing, the temperature is raised to 400°C at a heating rate of 5°C / h for sintering, and the temperature is maintained for 5 hours. Then, it is naturally cooled to room temperature to obtain copper oxide.

[0125] Performance Testing

[0126] The copper etching waste liquid and the prepared copper oxide provided in Examples 1-3 and Comparative Examples 1-4 were tested, and the relevant test items were as follows:

[0127] Extraction rate of copper ions: Atomic absorption spectrometer was used to measure the content of copper ions in the solution, that is, the content of copper ions in the solution before and after intermittent ultrasonic extraction. The extraction rate of copper ions was obtained by the concentration difference of copper ions in the solution before and after extraction. The specific calculation formula is: Extraction rate = C t(Cu 2+ ) / C 0(Cu 2+) × 100%, where C 0(Cu 2+ ) is the copper ion concentration in copper etching waste liquid, mol / L; C t(Cu 2+) is the copper ion concentration in the aqueous phase rich in ionic liquid after extraction, mol / L, and the specific results are shown in Table 1;

[0128] Purity of copper oxide: The purity of the obtained copper oxide was tested by iodine titration. The specific test steps were carried out according to GB / T26046-2010. The specific results are shown in Table 1.

[0129] Hydrophilicity of copper oxide: At room temperature, drop 5 μL of water on the glass slide coated with the sample and test the static contact angle of copper oxide using a contact angle meter;

[0130] The static contact angle of the copper oxide prepared in Example 1 to water in air is shown in the following figure: Figure 1 As shown;

[0131] Microscopic morphology of copper oxide: The microscopic morphology of the copper oxide prepared in Example 1 was observed using a scanning electron microscope. Figure 2 As shown;

[0132] Crystallinity of copper oxide: The crystallinity of the copper oxide obtained in Example 1 was characterized by an X-ray diffractometer. Figure 3 As shown;

[0133] Table 1

[0134] Extraction rate / % Purity A / % Contact angle / ° Example 1 96.1 98.4 21.13 Example 2 98.3 99.1 20.34 Example 3 97.6 99.5 19.18 Comparative Example 1 90.3 91.2 27.24 Comparative Example 2 87.9 93.6 33.56 Comparative Example 3 82.4 88.3 45.29 Comparative Example 4 95.9 93.7 30.35

[0135] It can be seen from the data in Table 1 that in the process of preparing copper oxide in Examples 1-3, the extraction rate of copper ions obtained in step (1) is high, and the purity of copper oxide obtained in step (2) is high, the contact angle is between 19-22°, and it has good hydrophilicity; compared with Comparative Examples 1-4, it is fully demonstrated that the cyclodextrin-ionic liquid microemulsion of the present invention has excellent extraction ability for copper ions, and at the same time, synergistically with cinnamic acid, it helps to promote the formation of copper oxide, and has the positive significance of green environmental protection and sustainable development;

[0136] also, Figure 2 is a scanning electron microscope image of the copper oxide prepared in Example 1 of the present invention, Figure 2 It can be seen that the microscopic morphology of the copper oxide prepared by the present invention is spherical particles with uniform particle size and smooth surface; Figure 3 is the X-ray diffraction pattern of the copper oxide prepared in Example 1 of the present invention, Figure 3 It can be seen that Figure 3The characteristic diffraction peaks shown confirm that the material prepared in Example 1 has a copper oxide crystal structure, and the diffraction peak intensity is relatively high, indicating that the prepared nano copper oxide has high crystallinity.

[0137] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0138] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A method for preparing copper oxide using copper etching waste liquid, characterized in that: The following steps are involved: Step (1): mixing the copper etching waste liquid with the cyclodextrin-ionic liquid microemulsion, extracting by intermittent ultrasonication, and centrifuging to obtain an ionic liquid-rich aqueous phase; Step (2): firstly drop a sodium hydroxide solution into the ion liquid-rich aqueous phase, stir to react, then drop a cinnamic acid solution, heat up, stir to react, filter, wash, and sinter to obtain copper oxide.

2. A method for preparing copper oxide using copper etching waste liquid according to claim 1, characterized in that: The preparation method of the cyclodextrin-ionic liquid microemulsion comprises the following steps: Cyclodextrin-ionic liquid, nonionic surfactant, organic solvent, potassium carbonate and water are ultrasonically mixed in a mass ratio of 5:(10-20):(40-60):(3-6):(20-40) to obtain a cyclodextrin-ionic liquid microemulsion.

3. A method for preparing copper oxide using copper etching waste liquid according to claim 2, characterized in that: The preparation method of the cyclodextrin-ionic liquid comprises the following steps: S1. Add benzotriazole and n-octane bromide to acetone, heat to 45-50°C, react for 8-10 hours, then remove acetone by rotary evaporation, wash with ethyl acetate, and rotary evaporate to obtain [C8BTA]Br; S2. Add [C8BTA]Br to the aqueous solution of sodium sulfobutyl-β-cyclodextrin, stir thoroughly at 60-70°C for 2 hours, then freeze at 4-10°C for 18-24 hours, and finally filter, wash, and dry to obtain cyclodextrin-ionic liquid.

4. A method for preparing copper oxide using copper etching waste liquid according to claim 3, characterized in that: The molar ratio of the benzotriazole, n-octane bromide and sodium sulfobutyl-β-cyclodextrin is 1:(1-1.2):1; The concentration of the aqueous solution of sodium sulfobutyl-β-cyclodextrin is 0.25 mol / L.

5. A method for preparing copper oxide using copper etching waste liquid according to claim 2, characterized in that: The nonionic surfactant is one or more of Triton, Tween, Span, sophorolipid, rhamnolipid, and polyethylene glycol mixed in any proportion; The organic solvent is obtained by mixing isooctyl alcohol and cyclohexane in a mass ratio of 10:

1.

6. The method for preparing copper oxide using copper etching waste liquid according to claim 1, characterized in that: In the step (1), the volume ratio of the copper etching waste liquid to the cyclodextrin-ionic liquid microemulsion is 1:(2-6); The copper etching waste liquid has a copper ion concentration of 1.5-3 mol / L.

7. The method for preparing copper oxide using copper etching waste liquid according to claim 1, characterized in that: In the step (1), intermittent ultrasonic extraction means that each ultrasonic extraction is performed for 10 seconds, followed by a 5-second break; During the intermittent ultrasonic extraction process, the ultrasonic power is 300-400W and the extraction temperature is 35-45°C; The time of the intermittent ultrasonic extraction is 30 minutes.

8. The method for preparing copper oxide using copper etching waste liquid according to claim 1, characterized in that: In the step (2), the volume ratio of the ionic liquid-rich aqueous phase, the sodium hydroxide solution and the cinnamic acid solution is 1:(3-6):(2-5); The concentration of the sodium hydroxide solution is 0.5-2 mol / L; The concentration of the cinnamic acid solution is 0.1-0.5 mol / L.

9. The method for preparing copper oxide using copper etching waste liquid according to claim 1, characterized in that: In the step (2), the dropping speeds of the sodium hydroxide solution and the cinnamic acid solution are independently 0.5-1 mL / min; The said heating refers to the temperature rising to 70-80°C; During the two stirring reactions, the stirring speeds were independently 400-800 r / min, and the stirring reaction times were independently 1-3 h.

10. The method for preparing copper oxide using copper etching waste liquid according to claim 1, characterized in that: In the step (2), the specific operation of sintering is: heating to 400-600°C at a heating rate of 5-10°C / h, maintaining for 2-5h, and then naturally cooling to room temperature.

Images