Method for improving copper recovery rate through regeneration smelting of copper-containing dangerous waste copper

Abstract

The invention discloses a method for improving the copper recovery rate through regeneration smelting of copper-containing dangerous waste copper, and belongs to the technical field of copper smelting. The method for improving the copper recovery rate through regeneration smelting of the copper-containing hazardous waste copper comprises the following steps that 1, after collected copper-containing hazardous waste copper is subjected to cleaning, crushing and impurity removal treatment, the copper-containing hazardous waste copper is mixed with an organic fluxing agent, and a pretreated raw material is obtained; 2, the pretreated raw materials are put into a smelting furnace to be heated and smelted, and anode copper is obtained; and step 3, casting the anode copper into an anode plate, adding the anode plate into the electrolyte, electrifying and carrying out electrolytic refining to obtain electrolytic copper. The copper obtained by the method has excellent purity and recovery rate.

Description

Technical Field

[0001] The invention belongs to the technical field of copper smelting, and in particular relates to a method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate. Background Art

[0002] The importance of copper is self-evident. However, my country's copper reserves per capita are small, and mainly poor copper. Large copper mines are scarce. This situation poses a severe challenge to the supply of copper resources. With the deepening of mining, mineral resources gradually show the characteristics of poor, fine and mixed, and the difficulty of sorting operations is increasing. At the same time, the rapid development of the national economy continues to increase the demand for high-quality mineral raw materials and metals, and the contradiction between supply and demand becomes more prominent.

[0003] Therefore, improving the comprehensive utilization rate of copper mineral resources, especially the recycling of low-grade, difficult-to-handle copper mineral resources and copper-containing hazardous waste, has become a key way to alleviate the contradiction between supply and demand and ensure the sustainable development of the national economy. Copper-containing hazardous waste, such as waste wires and cables, motors, transformers, etc., has become an important source of recycled copper resources because it contains a large amount of copper and has a high recycling value. However, due to the complex composition of raw materials, containing a variety of impurities and harmful substances, traditional smelting methods are often difficult to extract copper elements efficiently and environmentally friendly. In addition, energy consumption, emissions and other problems in the smelting process also need to be solved urgently. Therefore, the development of an efficient and environmentally friendly method for the recycling and smelting of copper-containing hazardous waste to improve the copper recovery rate is of great significance to promoting the sustainable development of the copper industry.

[0004] Patent CN117512372A discloses a method for preparing copper-iron alloy by deep depletion of copper-iron nonferrous metal solid waste. The invention uses carbon-containing waste as a reducing agent and part of the white mud as a slag-making agent, and uses trace amounts of TiO2 and Na2O in the white mud to strengthen the copper slag melting and smelting process. The invention achieves a copper and iron recovery rate of more than 90% during the deep depletion process, and the residual copper and iron in the slag are reduced to less than 0.1wt% and 0.4wt% respectively, thereby improving resource utilization efficiency. However, there is still room for improvement in the copper recovery rate through this method. Summary of the invention

[0005] The purpose of the present invention is to provide a method for regenerating and smelting copper-containing hazardous waste to improve the copper recovery rate, which is used to solve the technical problems in the prior art regarding the poor copper recovery rate and purity of copper-containing hazardous waste.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention provides a method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate, comprising the following steps:

[0008] Step (1): washing, crushing and removing impurities from the collected copper-containing hazardous waste copper, and then mixing it with an organic flux to obtain a pretreated raw material;

[0009] Step (2): placing the pretreated raw material into a smelting furnace, heating and smelting to obtain anode copper;

[0010] Step (3): Cast the anode copper into an anode plate, add it into an electrolyte, and apply electricity for electrolytic refining to obtain electrolytic copper.

[0011] Preferably, the method for preparing the organic flux comprises the following steps:

[0012] Q1: Add 1,2-diphenylethylenediamine, triethylamine and N-ethoxycarbonylphthalimide to a container filled with chloroform, react at room temperature, add hydrochloric acid solution under ice bath condition after the reaction, stir, distill under reduced pressure, adjust pH, extract, wash the organic phase, dry, and vacuum spin dry to obtain an intermediate;

[0013] Q2: The intermediate is added to a container filled with dichloromethane, and then 2-formylphenylboronic acid and anhydrous sodium sulfate are added, nitrogen is introduced, vacuum is evacuated, and stirred at room temperature. Sodium triacetoxyborohydride is added during the stirring process, and the reaction is continued after the addition, and then distilled water is added to quench the reaction, extract, wash the organic phase, dry, vacuum spin dry, purify, and recrystallize to obtain an organic flux.

[0014] In the above process, the synthesis reaction formula of the organic flux is as follows:

[0015]

[0016] The results of mass spectrometry analysis were: m / z: 476.19 (100.0%), 477.19 (32.3%), 475.19 (24.8%), 476.20 (7.9%), 478.20 (5.1%), 477.20 (1.7%), 478.19 (1.1%).

[0017] Preferably, in Q1, the molar ratio of 1,2-diphenylethylenediamine, triethylamine and N-ethoxycarbonylphthalimide is (1-2): (1.1-2.2): (1-2), the reaction time at room temperature is 10-12h, the concentration of the hydrochloric acid solution is 1mol / L, the pH is adjusted to 8-10 with 1mol / L sodium hydroxide solution, extraction is carried out with carbon trichloride, the organic phase is washed with saturated sodium chloride, and dried with anhydrous sodium sulfate.

[0018] Preferably, in Q2, the molar ratio of the intermediate, 2-formylphenylboric acid, anhydrous sodium sulfate and sodium triacetoxyborohydride is (1-1.5): (1.2-1.8): (7-10.5): (3-4.5), the stirring time at room temperature is 3-5 hours, the continued reaction time is 8-10 hours, carbon trichloride is used for extraction, saturated sodium chloride is used for washing, and anhydrous sodium sulfate is used for drying. During the purification process, a mixed solution of dichloromethane and glacial acetic acid with a volume ratio of 20:1 is used as the eluent.

[0019] Preferably, the electrolyte in step (3) contains a composite auxiliary agent, and the preparation method of the composite auxiliary agent comprises the following steps:

[0020] S1: Mix oxalic acid dihydrate and o-phenylenediamine and grind them. Add the ground mixture into a container, add polyphosphoric acid and ethylene glycol, stir and mix, heat and reflux under nitrogen protection, cool after the reaction, pour into distilled water, stir, let stand, filter by suction to obtain a filter cake, add the filter cake into an ethanol solution, stir and disperse, filter by suction, and dry to obtain a crude product. Transfer the crude product into glacial acetic acid, heat to dissolve, and cool to obtain compound 1;

[0021] S2: Compound 1 is added to a container, and N,N-dimethylformamide and ethyl methacrylate are added. After stirring, potassium phosphate is added, and polyethylene glycol 400 is added at the same time. The mixture is heated under reflux and stirred, cooled and filtered, decompressed, rotary evaporated, washed, dried, and recrystallized to obtain compound 2.

[0022] S3: adding compound 2 and hydrazine hydrate to methanol, heating and stirring under reflux, and after the reflux is completed, rotating to dryness and recrystallizing to obtain compound 3;

[0023] S4: Add 3-hydroxybenzaldehyde, potassium iodide, potassium carbonate and 1-bromopropane to N,N-dimethylformamide, heat and stir under reflux under nitrogen protection, filter, concentrate and purify to obtain compound A;

[0024] S5: Add compound 3 and compound A into methanol, stir to dissolve, heat to reflux, and after reflux, spin dry and recrystallize to obtain a composite auxiliary agent.

[0025] In the above process, the synthetic reaction formula of the composite additive is as follows:

[0026]

[0027] The results of mass spectrometry analysis were: m / z: 698.33 (100.0%), 699.34 (43.9%), 700.34 (10.2%), 699.33 (3.0%), 701.34 (1.9%), 700.33 (1.3%).

[0028] Preferably, in S1, the dosage ratio of oxalic acid dihydrate, o-phenylenediamine, polyphosphoric acid and ethylene glycol is (4.2-5.04) g: (7.2-8.64) g: (12-14.4) mL: (20-24) mL, the reflux temperature is 150-170°C, the time is 1-2h, the cooling temperature is 70-75°C, and the volume fraction of the ethanol solution is 20vt%.

[0029] Preferably, in S2, the dosage ratio of compound 1, N,N-dimethylformamide, ethyl methacrylate, potassium phosphate and polyethylene glycol 400 is (1-1.2) g: (30-36) mL: (0.064-0.077) g: (1.33-1.6) g: (0.02-0.024) g, the heating reflux temperature is 80-85°C, and the stirring time is 10-12 h.

[0030] Preferably, in S3, the amount ratio of compound 2, hydrazine hydrate and methanol is (0.41-0.49) g: (0.19-0.23) g: (5-6) mL, the heating and stirring temperature is 60-70°C, and the time is 16-18 h; in S4, the amount ratio of 3-hydroxybenzaldehyde, potassium iodide, potassium carbonate, 1-bromopropane and N,N-dimethylformamide is (2.44-3.17) g: (0.33-0.43) g: (5.56-7.23) g: (2.95-3.84) g: (10-13) mL, the heating and stirring temperature is 80-85°C, and the time is 20-24 h. During the purification process, a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 30:1 is used as the eluent.

[0031] Preferably, in S5, the usage ratio of compound 3, compound A and methanol is (0.18-0.22) g: (0.45-54) g: (25-30) mL, the heating reflux temperature is 60-70° C., and the time is 28-30 h.

[0032] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0033] The invention firstly uses 1,2-diphenylethylenediamine, triethylamine, N-ethoxycarbonylphthalimide and 2-formylphenylboric acid as raw materials to prepare an organic flux, and then uses oxalic acid dihydrate, o-phenylenediamine, ethyl methacrylate, hydrazine hydrate, 3-hydroxybenzaldehyde and 1-bromopropane as raw materials to prepare a composite auxiliary agent. When copper is recovered by regenerating and smelting copper, the organic flux and the composite auxiliary agent are applied to the reaction process, which can effectively improve the recovery rate of copper. DETAILED DESCRIPTION

[0034] The following will be described clearly and completely in conjunction with 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.

[0035] Embodiment 1: This embodiment discloses a method for preparing an organic flux, comprising the following steps:

[0036] Q1: 7.77 g of 1,2-diphenylethylenediamine, 4.08 g of triethylamine and 8.02 g of N-ethoxycarbonylphthalimide were added to a container containing 20 mL of chloroform, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, 1 mol / L hydrochloric acid solution was added under ice bath conditions, stirred, and distilled under reduced pressure. The pH was adjusted to 9 with 1 mol / L sodium hydroxide solution, extracted with carbon trichloride, and the organic phase was washed with saturated sodium chloride, dried with anhydrous sodium sulfate, and vacuum-dried to obtain an intermediate;

[0037] Q2: 1.25 g of the intermediate was added to a container containing 15 mL of dichloromethane, and then 0.66 g of 2-formylphenylboronic acid and 3.75 g of anhydrous sodium sulfate were added, nitrogen was introduced, vacuum was evacuated, and stirred at room temperature for 5 h. 2.33 g of sodium triacetoxyborohydride was added during the stirring process. The reaction was continued for 10 h after the addition, and then distilled water was added to quench the reaction. Carbon trichloride was used for extraction, and the organic phase was washed with saturated sodium chloride, dried with anhydrous sodium sulfate, and vacuum dried. A mixed solution of dichloromethane and glacial acetic acid with a volume ratio of 20:1 was used as an eluent for purification and recrystallization to obtain an organic flux.

[0038] This embodiment discloses a method for preparing a composite auxiliary agent, comprising the following steps:

[0039] S1: 4.62 g of oxalic acid dihydrate and 7.92 g of o-phenylenediamine were mixed and ground, and then added to a container. 13.7 mL of polyphosphoric acid and 22 mL of ethylene glycol were added, and the mixture was stirred and mixed. Under nitrogen protection, the mixture was heated to 170° C. and refluxed for 2 h. After the reaction was completed, the mixture was cooled to 70° C. and poured into 500 mL of distilled water. The mixture was stirred, allowed to stand, and filtered to obtain a filter cake. The filter cake was added to an ethanol solution with a volume fraction of 20 vt%, and the mixture was stirred and dispersed, and then filtered and dried to obtain a crude product. The crude product was transferred to 500 mL of glacial acetic acid, heated to dissolve, and cooled to obtain compound 1.

[0040] S2: Add 1.1 g of compound 1 to a container, add 33 mL of N,N-dimethylformamide and 0.072 g of ethyl methacrylate, stir, then add 1.48 g of potassium phosphate and 0.023 g of polyethylene glycol 400, heat under reflux at 85°C and stir for 12 h, cool and filter, reduce pressure, rotary evaporate, wash, dry, and recrystallize to obtain compound 2;

[0041] S3: Add 0.45 g of compound 2 and 0.20 g of hydrazine hydrate to 5.5 mL of methanol, heat and stir under reflux at 65° C. for 18 h, spin dry, and recrystallize to obtain compound 3;

[0042] S4: 2.66 g of 3-hydroxybenzaldehyde, 0.38 g of potassium iodide, 6.34 g of potassium carbonate and 3.65 g of 1-bromopropane were added to 11.5 mL of N,N-dimethylformamide, heated at 85° C. with stirring and reflux for 24 h under nitrogen protection, filtered, concentrated and purified. During the purification process, a mixture of petroleum ether and ethyl acetate in a volume ratio of 30:1 was used as an eluent to obtain compound A;

[0043] S5: Add 0.2 g of compound 3 and 0.5 g of compound A into 28 mL of methanol, stir to dissolve, heat to reflux at 65° C. for 28 h, spin dry, and recrystallize to obtain a composite auxiliary agent.

[0044] This embodiment discloses a method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate, comprising the following steps:

[0045] Step (1): washing, crushing and removing impurities from the collected copper-containing hazardous waste copper, and then mixing it with an organic flux to obtain a pretreated raw material;

[0046] Step (2): placing the pretreated raw material into a smelting furnace, heating and smelting to obtain anode copper;

[0047] Step (3): Cast the anode copper into an anode plate, add it into an electrolyte (the electrolyte contains a composite additive), and apply electricity for electrolytic refining to obtain electrolytic copper.

[0048] Embodiment 2: This embodiment discloses a method for preparing an organic flux, comprising the following steps:

[0049] Q1: 5.18 g of 1,2-diphenylethylenediamine, 2.72 g of triethylamine and 5.35 g of N-ethoxycarbonylphthalimide were added to a container containing 20 mL of chloroform, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, 1 mol / L hydrochloric acid solution was added under ice bath conditions, stirred, and distilled under reduced pressure. The pH was adjusted to 9 with 1 mol / L sodium hydroxide solution, extracted with carbon trichloride, and the organic phase was washed with saturated sodium chloride, dried with anhydrous sodium sulfate, and vacuum-dried to obtain an intermediate;

[0050] Q2: 1.5 g of the intermediate was added to a container containing 15 mL of dichloromethane, and then 0.53 g of 2-formylphenylboronic acid and 4.5 g of anhydrous sodium sulfate were added, nitrogen was introduced, vacuum was evacuated, and stirred at room temperature for 5 h. 1.86 g of sodium triacetoxyborohydride was added during the stirring process. The reaction was continued for 10 h after the addition, and then distilled water was added to quench the reaction. Carbon trichloride was used for extraction, and the organic phase was washed with saturated sodium chloride, dried with anhydrous sodium sulfate, and vacuum dried. A mixed solution of dichloromethane and glacial acetic acid with a volume ratio of 20:1 was used as an eluent for purification and recrystallization to obtain an organic flux.

[0051] This embodiment discloses a method for preparing a composite auxiliary agent, comprising the following steps:

[0052] S1: 4.2 g of oxalic acid dihydrate and 7.2 g of o-phenylenediamine were mixed and ground, and then added to a container. 12 mL of polyphosphoric acid and 20 mL of ethylene glycol were added, and the mixture was stirred and mixed. Under nitrogen protection, the mixture was heated to 170° C. and refluxed for 2 h. After the reaction was completed, the mixture was cooled to 70° C. and poured into 500 mL of distilled water. The mixture was stirred, allowed to stand, and filtered to obtain a filter cake. The filter cake was added to an ethanol solution with a volume fraction of 20 vt%, and the mixture was stirred and dispersed, and then filtered and dried to obtain a crude product. The crude product was transferred to 500 mL of glacial acetic acid, heated to dissolve, and cooled to obtain compound 1.

[0053] S2: Add 1.2 g of compound 1 to a container, add 36 mL of N,N-dimethylformamide and 0.064 g of ethyl methacrylate, stir, then add 1.33 g of potassium phosphate and 0.02 g of polyethylene glycol 400, heat under reflux at 85°C and stir for 12 h, cool and filter, reduce pressure, rotary evaporate, wash, dry, and recrystallize to obtain compound 2;

[0054] S3: Add 0.41 g of compound 2 and 0.19 g of hydrazine hydrate to 5 mL of methanol, heat and stir under reflux at 65° C. for 18 h, spin dry, and recrystallize to obtain compound 3;

[0055] S4: 2.44 g of 3-hydroxybenzaldehyde, 0.33 g of potassium iodide, 5.56 g of potassium carbonate and 2.95 g of 1-bromopropane were added to 10 mL of N,N-dimethylformamide, heated at 85°C with stirring and reflux for 24 h under nitrogen protection, filtered, concentrated and purified. During the purification process, a mixture of petroleum ether and ethyl acetate in a volume ratio of 30:1 was used as an eluent to obtain compound A;

[0056] S5: Add 0.18 g of compound 3 and 0.45 g of compound A into 25 mL of methanol, stir to dissolve, heat to reflux at 65° C. for 28 h, spin dry, and recrystallize to obtain a composite auxiliary agent.

[0057] This embodiment discloses a method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate, comprising the following steps:

[0058] Step (1): washing, crushing and removing impurities from the collected copper-containing hazardous waste copper, and then mixing it with an organic flux to obtain a pretreated raw material;

[0059] Step (2): placing the pretreated raw material into a smelting furnace, heating and smelting to obtain anode copper;

[0060] Step (3): Cast the anode copper into an anode plate, add it into an electrolyte (the electrolyte contains a composite additive), and apply electricity for electrolytic refining to obtain electrolytic copper.

[0061] Embodiment 3: This embodiment discloses a method for preparing an organic flux, comprising the following steps:

[0062] Q1: 10.36 g of 1,2-diphenylethylenediamine, 5.44 g of triethylamine and 10.7 g of N-ethoxycarbonylphthalimide were added to a container containing 20 mL of chloroform, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, 1 mol / L hydrochloric acid solution was added under ice bath conditions, stirred, and distilled under reduced pressure. The pH was adjusted to 9 with 1 mol / L sodium hydroxide solution, extracted with carbon trichloride, and the organic phase was washed with saturated sodium chloride, dried with anhydrous sodium sulfate, and vacuum-dried to obtain an intermediate;

[0063] Q2: 1 g of the intermediate was added to a container containing 15 mL of dichloromethane, and then 0.79 g of 2-formylphenylboronic acid and 3 g of anhydrous sodium sulfate were added, nitrogen was introduced, vacuum was evacuated, and stirred at room temperature for 5 h. During the stirring process, 2.79 g of sodium triacetoxyborohydride was added, and the reaction was continued for 10 h after the addition. Then distilled water was added to quench the reaction, and carbon trichloride was used for extraction. The organic phase was washed with saturated sodium chloride, dried with anhydrous sodium sulfate, and vacuum dried. A mixed solution of dichloromethane and glacial acetic acid with a volume ratio of 20:1 was used as an eluent for purification and recrystallization to obtain an organic flux.

[0064] This embodiment discloses a method for preparing a composite auxiliary agent, comprising the following steps:

[0065] S1: 5.04 g of oxalic acid dihydrate and 8.64 g of o-phenylenediamine were mixed and ground, and then added to a container. 14.4 mL of polyphosphoric acid and 24 mL of ethylene glycol were added, and the mixture was stirred and mixed. Under nitrogen protection, the mixture was heated to 170° C. and refluxed for 2 h. After the reaction was completed, the mixture was cooled to 70° C. and poured into 500 mL of distilled water. The mixture was stirred, allowed to stand, and filtered to obtain a filter cake. The filter cake was added to an ethanol solution with a volume fraction of 20 vt%, and the mixture was stirred and dispersed, and then filtered and dried to obtain a crude product. The crude product was transferred to 500 mL of glacial acetic acid, heated to dissolve, and cooled to obtain compound 1.

[0066] S2: Add 1 g of compound 1 to a container, add 30 mL of N,N-dimethylformamide and 0.077 g of ethyl methacrylate, stir, then add 1.6 g of potassium phosphate and 0.024 g of polyethylene glycol 400, heat under reflux at 85°C and stir for 12 h, cool and filter, reduce pressure, rotary evaporate, wash, dry, and recrystallize to obtain compound 2;

[0067] S3: 0.49 g of compound 2 and 0.23 g of hydrazine hydrate were added to 6 mL of methanol, heated and stirred at 65° C. for 18 h, and after the reflux, the mixture was spin-dried and recrystallized to obtain compound 3;

[0068] S4: 3.17 g of 3-hydroxybenzaldehyde, 0.43 g of potassium iodide, 7.23 g of potassium carbonate and 3.84 g of 1-bromopropane were added to 11 mL of N,N-dimethylformamide, heated at 85°C with stirring and reflux for 24 h under nitrogen protection, filtered, concentrated and purified. During the purification process, a mixture of petroleum ether and ethyl acetate in a volume ratio of 30:1 was used as an eluent to obtain compound A;

[0069] S5: Add 0.22 g of compound 3 and 0.54 g of compound A into 30 mL of methanol, stir to dissolve, heat to reflux at 65° C. for 28 h, spin dry, and recrystallize to obtain a composite auxiliary agent.

[0070] This embodiment discloses a method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate, comprising the following steps:

[0071] Step (1): washing, crushing and removing impurities from the collected copper-containing hazardous waste copper, and then mixing it with an organic flux to obtain a pretreated raw material;

[0072] Step (2): placing the pretreated raw material into a smelting furnace, heating and smelting to obtain anode copper;

[0073] Step (3): Cast the anode copper into an anode plate, add it into an electrolyte (the electrolyte contains a composite additive), and apply electricity for electrolytic refining to obtain electrolytic copper.

[0074] Embodiment 4: This embodiment discloses a method for preparing an organic flux, comprising the following steps:

[0075] Q1: 6.47 g of 1,2-diphenylethylenediamine, 3.4 g of triethylamine and 6.87 g of N-ethoxycarbonylphthalimide were added to a container containing 20 mL of chloroform, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, 1 mol / L hydrochloric acid solution was added under ice bath conditions, stirred, and distilled under reduced pressure. The pH was adjusted to 9 with 1 mol / L sodium hydroxide solution, extracted with carbon trichloride, and the organic phase was washed with saturated sodium chloride, dried with anhydrous sodium sulfate, and vacuum-dried to obtain an intermediate;

[0076] Q2: 1.2 g of the intermediate was added to a container containing 15 mL of dichloromethane, and then 0.58 g of 2-formylphenylboronic acid and 3.15 g of anhydrous sodium sulfate were added, nitrogen was introduced, vacuum was evacuated, and stirred at room temperature for 5 h. 2.05 g of sodium triacetoxyborohydride was added during the stirring process. The reaction was continued for 10 h after the addition, and then distilled water was added to quench the reaction. Carbon trichloride was used for extraction, and the organic phase was washed with saturated sodium chloride, dried with anhydrous sodium sulfate, and vacuum dried. A mixed solution of dichloromethane and glacial acetic acid with a volume ratio of 20:1 was used as an eluent for purification and recrystallization to obtain an organic flux.

[0077] This embodiment discloses a method for preparing a composite auxiliary agent, comprising the following steps:

[0078] S1: 4.41 g of oxalic acid dihydrate and 7.61 g of o-phenylenediamine were mixed and ground, and then added to a container. 12.8 mL of polyphosphoric acid and 21 mL of ethylene glycol were added, and the mixture was stirred and mixed. Under nitrogen protection, the mixture was heated to 170°C and refluxed for 2 h. After the reaction was completed, the mixture was cooled to 70°C, poured into 500 mL of distilled water, stirred, allowed to stand, and filtered to obtain a filter cake. The filter cake was added to an ethanol solution with a volume fraction of 20 vt%, and then filtered after stirring and dispersion, and dried to obtain a crude product. The crude product was transferred to 500 mL of glacial acetic acid, heated to dissolve, and cooled to obtain compound 1;

[0079] S2: Add 1.05 g of compound 1 to a container, add 31 mL of N,N-dimethylformamide and 0.068 g of ethyl methacrylate, stir, then add 1.41 g of potassium phosphate and 0.021 g of polyethylene glycol 400, heat under reflux at 85°C and stir for 12 h, cool and filter, reduce pressure, rotary evaporate, wash, dry, and recrystallize to obtain compound 2;

[0080] S3: Add 0.43 g of compound 2 and 0.21 g of hydrazine hydrate to 5.2 mL of methanol, heat and stir under reflux at 65° C. for 18 h, spin dry, and recrystallize to obtain compound 3;

[0081] S4: 2.32 g of 3-hydroxybenzaldehyde, 0.34 g of potassium iodide, 6.12 g of potassium carbonate and 2.8 g of 1-bromopropane were added to 12 mL of N,N-dimethylformamide, heated at 85°C with stirring and reflux for 24 h under nitrogen protection, filtered, concentrated and purified. During the purification process, a mixture of petroleum ether and ethyl acetate in a volume ratio of 30:1 was used as an eluent to obtain compound A;

[0082] S5: Add 0.19 g of compound 3 and 0.48 g of compound A into 27 mL of methanol, stir to dissolve, heat to reflux at 65° C. for 28 h, spin dry, and recrystallize to obtain a composite auxiliary agent.

[0083] This embodiment discloses a method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate, comprising the following steps:

[0084] Step (1): washing, crushing and removing impurities from the collected copper-containing hazardous waste copper, and then mixing it with an organic flux to obtain a pretreated raw material;

[0085] Step (2): placing the pretreated raw material into a smelting furnace, heating and smelting to obtain anode copper;

[0086] Step (3): Cast the anode copper into an anode plate, add it into an electrolyte (the electrolyte contains a composite additive), and apply electricity for electrolytic refining to obtain electrolytic copper.

[0087] Comparative Example 1: Compared with Example 1, in the preparation process of the organic flux in Comparative Example 1, no 2-formylphenylboric acid is added, and other conditions remain unchanged.

[0088] Comparative Example 2: Compared with Example 1, in the preparation process of the composite auxiliary agent in Comparative Example 2, o-phenylenediamine was not added, and other conditions remained unchanged.

[0089] Comparative Example 3: Compared with Example 1, in Comparative Example 3, no organic flux is added during the treatment process, and other conditions remain unchanged.

[0090] Comparative Example 4: Compared with Example 1, in Comparative Example 4, no composite auxiliary agent is added during the treatment process, and other conditions remain unchanged.

[0091] Experimental Example: The copper content of the samples obtained by the methods of Examples 1-4 and Comparative Examples 1-4 was determined according to GB / T 5121.1-2008, and the recovery rate of the samples was determined according to GB / T 38470-2019. The test results are shown in Table 1:

[0092] Table 1

[0093] project Recovery rate / % purity / % Example 1 90.1 99.66 Example 2 89.9 99.62 Example 3 90.0 99.62 Example 4 89.8 99.61 Comparative Example 1 82.5 98.14 Comparative Example 2 82.3 98.19 Comparative Example 3 78.1 97.18 Comparative Example 4 78.0 97.21

[0094] It can be seen from the test results in Table 1 that the treatment methods of Examples 1-4 of the present invention can effectively improve the recovery rate and purity of copper. By comparing Comparative Example 1 with Examples 1-4, it can be seen that adding 2-formylphenylboric acid can effectively improve the recovery rate and purity of copper; by comparing Comparative Example 2 with Examples 1-4, it can be seen that adding o-phenylenediamine can effectively improve the recovery rate and purity of copper; by comparing Comparative Example 3 with Examples 1-4, it can be seen that adding an organic flux can effectively improve the recovery rate and purity of copper; by comparing Comparative Example 4 with Examples 1-4, it can be seen that adding a composite additive can effectively improve the recovery rate and purity of copper.

[0095] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0096] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for regenerating and smelting copper containing hazardous waste to improve copper recovery rate, characterized in that: The following steps are involved: Step (1): washing, crushing and removing impurities from the collected copper-containing hazardous waste copper, and then mixing it with an organic flux to obtain a pretreated raw material; Step (2): placing the pretreated raw material into a smelting furnace, heating and smelting to obtain anode copper; Step (3): Cast the anode copper into an anode plate, add it into an electrolyte, and apply electricity for electrolytic refining to obtain electrolytic copper.

2. The method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate according to claim 1, characterized in that: The preparation method of the organic flux, The following steps are involved: Q1: Add 1,2-diphenylethylenediamine, triethylamine and N-ethoxycarbonylphthalimide to a container filled with chloroform, react at room temperature, add hydrochloric acid solution under ice bath condition after the reaction, stir, distill under reduced pressure, adjust pH, extract, wash the organic phase, dry, and vacuum spin dry to obtain an intermediate; Q2: The intermediate is added to a container filled with dichloromethane, and then 2-formylphenylboronic acid and anhydrous sodium sulfate are added, nitrogen is introduced, vacuum is evacuated, and stirred at room temperature. Sodium triacetoxyborohydride is added during the stirring process, and the reaction is continued after the addition, and then distilled water is added to quench the reaction, extract, wash the organic phase, dry, vacuum spin dry, purify, and recrystallize to obtain an organic flux.

3. The method for improving copper recovery rate by regenerating and smelting copper-containing hazardous waste according to claim 2, characterized in that: In Q1, the molar ratio of 1,2-diphenylethylenediamine, triethylamine and N-ethoxycarbonylphthalimide is (1-2): (1.1-2.2): (1-2), the reaction time at room temperature is 10-12h, the concentration of the hydrochloric acid solution is 1mol / L, the pH is adjusted to 8-10 with 1mol / L sodium hydroxide solution, extraction is performed with carbon trichloride, the organic phase is washed with saturated sodium chloride, and dried with anhydrous sodium sulfate.

4. The method for improving copper recovery rate by regenerating and smelting copper-containing hazardous waste according to claim 2, characterized in that: In Q2, the molar ratio of the intermediate, 2-formylphenylboric acid, anhydrous sodium sulfate and sodium triacetoxyborohydride is (1-1.5): (1.2-1.8): (7-10.5): (3-4.5), the stirring time at room temperature is 3-5 hours, the continued reaction time is 8-10 hours, carbon trichloride is used for extraction, saturated sodium chloride is used for washing, and anhydrous sodium sulfate is used for drying. During the purification process, a mixed solution of dichloromethane and glacial acetic acid with a volume ratio of 20:1 is used as the eluent.

5. The method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate according to claim 1, characterized in that: The electrolyte in step (3) contains a composite auxiliary agent, and the preparation method of the composite auxiliary agent comprises the following steps: S1: Mix oxalic acid dihydrate and o-phenylenediamine and grind them. Add the ground mixture into a container, add polyphosphoric acid and ethylene glycol, stir and mix, heat and reflux under nitrogen protection, cool after the reaction, pour into distilled water, stir, let stand, filter by suction to obtain a filter cake, add the filter cake into an ethanol solution, stir and disperse, filter by suction, and dry to obtain a crude product. Transfer the crude product into glacial acetic acid, heat to dissolve, and cool to obtain compound 1; S2: Compound 1 is added to a container, and N,N-dimethylformamide and ethyl methacrylate are added. After stirring, potassium phosphate is added, and polyethylene glycol 400 is added at the same time. The mixture is heated under reflux and stirred, cooled and filtered, decompressed, rotary evaporated, washed, dried, and recrystallized to obtain compound 2. S3: adding compound 2 and hydrazine hydrate to methanol, heating and stirring under reflux, and after the reflux is completed, rotating to dryness and recrystallizing to obtain compound 3; S4: Add 3-hydroxybenzaldehyde, potassium iodide, potassium carbonate and 1-bromopropane to N,N-dimethylformamide, heat and stir under reflux under nitrogen protection, filter, concentrate and purify to obtain compound A; S5: Add compound 3 and compound A into methanol, stir to dissolve, heat to reflux, spin dry, and recrystallize to obtain a composite auxiliary agent.

6. The method for improving copper recovery rate by regenerating and smelting copper-containing hazardous waste according to claim 5, characterized in that: In S1, the dosage ratio of oxalic acid dihydrate, o-phenylenediamine, polyphosphoric acid and ethylene glycol is (4.2-5.04) g: (7.2-8.64) g: (12-14.4) mL: (20-24) mL, the reflux temperature is 150-170° C., the time is 1-2 h, the cooling temperature is 70-75° C., and the volume fraction of the ethanol solution is 20 vt%.

7. The method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate according to claim 5, characterized in that: In S2, the dosage ratio of compound 1, N,N-dimethylformamide, ethyl methacrylate, potassium phosphate and polyethylene glycol 400 is (1-1.2) g: (30-36) mL: (0.064-0.077) g: (1.33-1.6) g: (0.02-0.024) g, the heating reflux temperature is 80-85° C., and the stirring time is 10-12 h.

8. The method for regenerating and smelting copper-containing hazardous waste to improve copper recovery rate according to claim 5, characterized in that: In the S3, the dosage ratio of compound 2, hydrazine hydrate and methanol is (0.41-0.49) g: (0.19-0.23) g: (5-6) mL, the heating and stirring temperature is 60-70°C, and the time is 16-18 h; in the S4, the dosage ratio of 3-hydroxybenzaldehyde, potassium iodide, potassium carbonate, 1-bromopropane and N,N-dimethylformamide is (2.44-3.17) g: (0.33-0.43) g: (5.56-7.23) g: (2.95-3.84) g: (10-13) mL, the heating and stirring temperature is 80-85°C, and the time is 20-24 h. During the purification process, a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 30:1 is used as the eluent.

9. The method for improving copper recovery rate by regenerating and smelting copper-containing hazardous waste according to claim 5, characterized in that: In the S5, the usage ratio of compound 3, compound A and methanol is (0.18-0.22) g: (0.45-54) g: (25-30) mL, the heating reflux temperature is 60-70° C., and the time is 28-30 h.

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