Multistage treatment method for resource utilization of copper-containing solid waste

Abstract

The application discloses a multi-stage treatment method for copper-containing solid waste, and belongs to the technical field of copper-containing solid waste resource treatment. The multi-stage treatment method for copper-containing solid waste comprises the following steps: step (1): crushing the copper-containing solid waste to obtain pretreated copper-containing solid waste; step (2): adding the pretreated copper-containing solid waste into a leaching agent, stirring, and separating the leaching liquid from the solid residue through a filter press; step (3): adding an organic complexing agent into the leaching liquid, stirring, and solid-liquid separation to obtain a precipitate and a first waste liquid, washing the precipitate, filter pressing, drying, obtaining a copper-containing substance, extracting the copper-containing substance, refining, and obtaining metallic copper and a second waste liquid; step (4): mixing the first waste liquid and the second waste liquid, filtering, and obtaining dischargeable water; and step (5): adding a stabilizer into the solid residue, heating, and stirring to obtain a solidified body. The method can effectively improve the copper recovery rate and reduce environmental pollution.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of copper-containing solid waste resource utilization, and particularly relates to a multi-stage processing method for copper-containing solid waste. BACKGROUND

[0002] With the acceleration of global industrialization, a large amount of solid waste containing copper elements is continuously generated in the fields of metal smelting, electronic manufacturing, chemical production, etc. The complexity and diversity of copper-containing solid waste increase the difficulty of its processing. These wastes not only contain copper elements, but also may be accompanied by harmful elements such as lead, zinc, cadmium, mercury, etc. If these elements are directly discharged into the environment, they will accumulate through the food chain, causing long-term harm to the ecological system and human health. In addition, copper-containing solid waste has different physical and chemical properties, such as copper sulfide minerals such as chalcopyrite, bornite, and chalcocite, as well as gangue minerals such as quartz, feldspar, and mica, which make it necessary to consider multiple factors in the processing process.

[0003] Under this background, the multi-stage processing method for copper-containing solid waste is particularly important. This method aims to convert copper-containing solid waste into reusable resources through scientific, efficient, and environmentally friendly means, reducing environmental pollution and achieving sustainable utilization of resources. This research not only conforms to the current global environmental protection and sustainable development trend, but also is an important way to solve the problem of copper-containing solid waste processing.

[0004] Patent CN 116282716 A discloses a copper-containing waste residue resource utilization method. This method adds copper-containing waste residue to mine acid water, and after slurry mixing, flocculation and thickening treatment, an iron-removed underflow and an iron-removed overflow are obtained. After mixing and washing the iron-removed underflow with the neutralization overflow, pressure filtration dewatering is performed to obtain a first pressure filtrate and a first pressure filtration residue that meets the general industrial solid waste requirements. Then, the first pressure filtrate and the iron-removed overflow are subjected to copper recovery treatment by sulfidation to obtain a sulfidation overflow, a second pressure filtrate, and a second pressure filtration residue that can be collected as copper residue. Then, the sulfidation overflow and the second pressure filtrate are subjected to neutralization treatment to obtain a neutralization overflow that meets the emission standard and a third pressure filtrate, as well as a third pressure filtration residue that meets the general industrial solid waste requirements. This method can utilize mine acid water to treat copper-containing waste residue to achieve deep purification of mine acid water. However, this method does not process and collect copper-containing substances, and the treatment of wastewater still has room for improvement. SUMMARY

[0005] The purpose of the present application is to provide a multi-stage processing method for copper-containing solid waste resource utilization, which solves the technical problems of low recovery rate of copper-containing substances in copper-containing solid waste and poor treatment effect of wastewater generated during the processing in the prior art.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] The application provides a multi-stage processing method for resource utilization of copper-containing solid waste, comprising the following steps:

[0008] Step (1): crushing the copper-containing solid waste into small particles, removing large impurities through screening, removing ferromagnetic substances through magnetic separation, and removing light substances through air separation to obtain pretreated copper-containing solid waste;

[0009] Step (2): adding the pretreated copper-containing solid waste into a leaching agent, stirring, and separating the leaching liquid from the solid residue through a filter press;

[0010] Step (3): adding an organic complexing agent into the leaching liquid, stirring, and separating the solid and liquid to obtain a precipitate and a first waste liquid, washing, filtering and drying the precipitate to obtain a copper-containing substance, and extracting, refining the copper-containing substance to obtain metallic copper and a second waste liquid;

[0011] Step (4): mixing the first waste liquid and the second waste liquid to obtain a mixed waste liquid, and filtering to obtain dischargeable water;

[0012] Step (5): adding a stabilizer into the solid residue, heating and stirring to obtain a solidified body.

[0013] Preferably, in step (2), the leaching agent is composed of one or more of sulfuric acid, nitric acid, hydrochloric acid, ammonia, sodium carbonate, sodium hydroxide and sodium chloride.

[0014] Preferably, the preparation method of the organic complexing agent comprises the following steps:

[0015] Q1: adding toluene into a container containing carbon tetrachloride, then adding N-bromosuccinimide and benzoyl peroxide, heating and refluxing, cooling and filtering, washing and drying, rotary evaporation to obtain intermediate 1;

[0016] Q2: adding sodium bicarbonate, dichloromethane, distilled water, tetrabutylammonium iodide and intermediate 1 into a container, heating and refluxing, adding N-hydroxy peptide imide into the container, cooling after refluxing, separating the liquid, extracting the water layer, combining the organic phase, washing, drying, filtering to obtain intermediate 2;

[0017] Q3: adding intermediate 2 and concentrated hydrochloric acid into a container, heating and refluxing, cooling to room temperature and filtering to obtain white solid and filtrate, reducing pressure to concentrate the filtrate to obtain white solid, washing the white solid, distilling to obtain intermediate 3;

[0018] Q4: under nitrogen protection, adding lithium diisopropylamide into a round-bottom flask, adding 3-methylpyridine under low temperature conditions, stirring to obtain a mixed solution, then adding 1-adamantane ethyl carboxylate, continuing to stir, washing, extraction, washing the organic phase, drying, distilling, purifying to obtain organic matter 1;

[0019] Q5: adding intermediate 3 to pyridine containing organic matter 1, refluxing reaction, after the reaction is completed, adding distilled water to the reaction mixture, extracting, washing the organic phase, drying, distilling under reduced pressure, purifying to obtain the organic complexing agent.

[0020] In the above process, benzoyl peroxide is decomposed by heating, the generated free radicals attack the methyl hydrogen of toluene to generate methyl radicals and hydrogen bromide, then the toluene radicals react with N-bromosuccinimide to generate intermediate 1; then, under the condition of tetrabutylammonium iodide as a phase transfer catalyst, N-hydroxyl peptide imide reacts with intermediate 1 to generate intermediate 2; intermediate 2 is hydrolyzed under the action of concentrated hydrochloric acid to obtain intermediate 3; under nitrogen protection, lithium diisopropylamide reacts with 3-methylpyridine under low temperature conditions, then continues to react with 1-adamantyl hexanoic acid ethyl ester to obtain organic matter 1; then, organic matter 1 reacts with intermediate 3 to prepare the organic complexing agent.

[0021] As preferred, in the Q1, the molar ratio of toluene, N-bromosuccinimide and benzoyl peroxide is (6-12):(7-14):(0.2-0.4), the heating reflux temperature is 70-80℃, the reflux time is 3-5h, the washing is performed with 5wt% sodium bicarbonate solution and ice water, and the drying is performed with anhydrous magnesium sulfate; in the Q2, the amount ratio of sodium bicarbonate, dichloromethane, distilled water, tetrabutylammonium iodide, intermediate 1 and N-hydroxyl peptide imide is (6-9)g:(30-45)mL:(50-75)mL:(3-4.5)g:(6-9)g:(5-7.5)g, the heating reflux temperature is 55-65℃, the time of adding N-hydroxyl peptide imide is 30-45min, the reflux time is 2-4h, the extraction is performed with dichloromethane, the washing is performed with 5wt% sodium bicarbonate solution and distilled water, and the drying is performed with anhydrous magnesium sulfate.

[0022] As preferred, in the Q3, the amount ratio of intermediate 2 and concentrated hydrochloric acid is (3-6)g:(20-40)mL, the heating reflux temperature is 70-90℃, the time is 3-5h, and the white solid is washed with acetonitrile.

[0023] As preferred, in the Q4, the molar ratio of lithium diisopropylamide, 3-methylpyridine and 1-adamantane carboxylic acid ethyl ester is (1.7-2.2):(1.8-2.4):(1-1.3), the low temperature is 0-1℃, the stirring time is 1-2h, the continuous stirring time is 3-5h, the washing is performed with saturated sodium chloride, the extraction is performed with ethyl acetate, the organic phase is washed with distilled water for 3-5 times, dried with anhydrous sodium sulfate, and the purification is performed with a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 5:1 as eluent; in the Q5, the ratio of the use amount of organic matter 1, intermediate 3 and distilled water is (3-6)mL:(0.65-1.3)g:(10-20)mL, the reflux time is 3-4h, the extraction is performed with dichloromethane, the organic phase is washed with distilled water, dried with anhydrous sodium sulfate, and the purification is performed with a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 7:1 as eluent.

[0024] As preferred, in the step (4), the mixed waste liquid is filtered using a chitosan composite film, and the preparation method of the chitosan composite film comprises the following steps:

[0025] S1: chitosan is added into glacial acetic acid for dissolution, then diluted with anhydrous ethanol and placed in an ultrasonic cleaner, then benzaldehyde is added, heated and shaken for reaction, and a mixed chitosan solution is obtained;

[0026] S2: carbon disulfide and sodium hydroxide solution are added into the mixed chitosan solution, stirred at room temperature, then heated for reaction, then hydrochloric acid is added for pH adjustment, and heated for reaction, and a modified chitosan is obtained;

[0027] S3: the glutaraldehyde solution and ethanol are mixed uniformly and then added into a polytetrafluoroethylene reaction kettle, heated for reaction, cooled, rotary evaporated, and a viscous liquid is obtained; the viscous liquid and the modified chitosan are mixed and stirred, then transferred into a mold, quickly frozen under liquid nitrogen, placed in a freeze dryer, then heated for reaction, and a chitosan composite film is obtained.

[0028] In the above process, the chitosan is first reacted with benzaldehyde to obtain a mixed chitosan solution, then a xanthate group is introduced to the hydroxyl group at C6 position of the product, then the imine is converted into a primary amine by acid hydrolysis with hydrochloric acid, and a modified chitosan is prepared; then the glutaraldehyde solution and ethanol are used as raw materials to obtain a viscous liquid by solvothermal method, and the viscous liquid is mixed with the modified chitosan to prepare a chitosan composite film.

[0029] As preferred, in the S1, the ratio of the use amount of chitosan, glacial acetic acid, anhydrous ethanol and benzaldehyde is (1-1.5)g:(20-30)mL:(20-30)mL:(0.013-0.019)mL, the volume fraction of glacial acetic acid is 3vt%, the heating and shaking temperature is 70-80℃, and the time is 4-6h.

[0030] Preferably, in S2, the volume ratio of the mixed chitosan solution, carbon disulfide and sodium hydroxide solution is (10-15) mL:(2-3) mL:(50-75) mL, the mass fraction of the sodium hydroxide solution is 5 wt%, the stirring time is 30-45 min, the temperature of the reaction is 40-50℃, the time is 3-4 h, the concentration of the hydrochloric acid is 1 mol / L, and the pH is adjusted to 9-10.

[0031] Preferably, in S3, the volume ratio of the glutaraldehyde solution and ethanol is (15-30):(30-60), the volume fraction of the glutaraldehyde solution is 5 vt%, the heating reaction temperature is 150-160℃, the time is 2-3 h, the rotary evaporation temperature is 40-50℃, the time is 4-6 h, the volume ratio of the viscous liquid and modified chitosan is (10-12) mL:(8-10) g, the mixing and stirring time is 10-15 min, the sample is placed in a freeze dryer for 10-12 h, the heating reaction temperature is 60-70℃, and the reaction time is 4-6 h.

[0032] In summary, due to the adoption of the above technical solutions, the present application has the following advantages:

[0033] 1. The present application first uses toluene, N-bromosuccinimide, N-hydroxyphthalimide, 3-methylpyridine and 1-adamantane ethyl carbonate as raw materials to prepare an organic complex, adds the substance to the leaching solution, can effectively adsorb copper ions in the leaching solution, and obtains metal copper, and then uses chitosan, benzaldehyde, carbon disulfide, sodium hydroxide, glutaraldehyde and ethanol as raw materials to prepare a chitosan composite film, which is applied to the filtration process of mixed waste liquid, can effectively adsorb heavy metal ions in the mixed waste liquid, so that the waste liquid reaches the discharge standard, and the generation of polluted wastewater is reduced.

[0034] 2. The present application uses toluene, N-bromosuccinimide, N-hydroxyphthalimide, 3-methylpyridine and 1-adamantane ethyl carbonate as raw materials to prepare an organic complex, and the organic complex and copper ions in the leaching solution undergo complexation reaction, in the complexation reaction, the nitrogen atom and oxygen atom in the pyridine oxime group of the organic complex have lone pair electrons, which can form a coordination bond with the empty orbital of the copper ion, and with the formation of the coordination bond, the copper ion is firmly fixed in the complexing agent molecule, and a precipitate is obtained, so that the copper-containing substance is extracted from the leaching solution, and through extraction and refining, metal copper is obtained, and the copper recovery rate is improved.

[0035] 3.The chitosan composite membrane is prepared by using chitosan, benzaldehyde, carbon disulfide, sodium hydroxide, glutaraldehyde and ethanol as raw materials, and contains rich active groups, such as amino groups, hydroxyl groups and xanthic acid groups, which can have strong coordination or electrostatic adsorption with heavy metal ions in mixed waste liquid, effectively removing the heavy metal ions in the waste liquid, and the porous structure and high specific surface area of the chitosan composite membrane can further enhance the adsorption capacity, so that more heavy metal ions can be intercepted in the membrane and on the membrane surface, so that the tail water can reach the discharge standard. BRIEF DESCRIPTION OF DRAWINGS

[0036] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings described below are only some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained without creative labor on the basis of these drawings.

[0037] Figure 1 is a flow chart of the resourceful multi-stage treatment method of the copper-containing solid waste of the present application. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0039] Embodiment 1: The present embodiment discloses a preparation method of an organic complexing agent, comprising the following steps:

[0040] Q1: 15.72 mL of toluene is added to a container containing 40 mL of carbon tetrachloride, then 30.89 g of N-bromosuccinimide and 1.2 g of benzoyl peroxide are added, heated to reflux at 75℃ for 5 h, then cooled and filtered, washed with 5 wt% sodium bicarbonate solution and ice water, dried with anhydrous magnesium sulfate, and rotary evaporated to obtain intermediate 1;

[0041] Q2: 7.5 g of sodium bicarbonate, 37.5 mL of dichloromethane, 62.5 mL of distilled water, 3.75 g of tetrabutylammonium iodide and 7.5 g of intermediate 1 are added to a container, heated to reflux at 60℃, 6.25 g of N-hydroxyl peptide imide is added to the container within 30 min, refluxed for 3 h, then cooled, separated, the water layer is extracted with dichloromethane, the organic phases are combined, washed with 5 wt% sodium bicarbonate solution and distilled water, dried with anhydrous magnesium sulfate, filtered to obtain intermediate 2;

[0042] Q3: 4.5 g of intermediate 2 and 30 mL of concentrated hydrochloric acid were added to a container, heated to reflux at 80°C for 4 h, then cooled to room temperature and filtered to obtain a white solid and a filtrate, the filtrate was concentrated under reduced pressure to obtain a white solid, which was washed with acetonitrile and distilled to obtain intermediate 3;

[0043] Q4: 1.22 g of lithium diisopropylamide was added to a round-bottom flask under nitrogen protection, 1.16 mL of 3-methylpyridine was added at 0°C, and the mixture was stirred for 1 h to obtain a solution, then 1.37 g of ethyl 1-adamantane carboxylate was added, and the stirring was continued for 5 h, then the mixture was washed with saturated sodium chloride, extracted with ethyl acetate, washed with distilled water 5 times, dried over anhydrous sodium sulfate, distilled, and purified with a mixture of petroleum ether and ethyl acetate (5:1 by volume) as eluent to obtain organic matter 1;

[0044] Q5: 0.93 g of intermediate 3 was added to 5 mL of pyridine containing 4.5 mL of organic matter 1, and the mixture was refluxed for 4 h, then 15 mL of distilled water was added to the reaction mixture, extracted with dichloromethane, the organic phase was washed with distilled water, dried over anhydrous sodium sulfate, and distilled under reduced pressure, and purified with a mixture of petroleum ether and ethyl acetate (7:1 by volume) as eluent to obtain an organic complexing agent.

[0045] The present embodiment discloses a preparation method of a chitosan composite film, comprising the following steps:

[0046] S1: 1.25 g of chitosan was dissolved in 25 mL of 3% (v / v) glacial acetic acid, then diluted with 25 mL of anhydrous ethanol and placed in an ultrasonic cleaner, and then 0.016 mL of benzaldehyde was added, and the mixture was heated and shaken at 75°C for 4 h to obtain a mixed chitosan solution;

[0047] S2: 2 mL of carbon disulfide and 62.5 mL of 5% (w / w) sodium hydroxide solution were added to 12.5 mL of the mixed chitosan solution, stirred at room temperature for 45 min, then reacted at 50°C for 4 h, then adjusted to pH = 9 with 1 mol / L hydrochloric acid, and reacted at 35°C for 1.5 h to obtain modified chitosan;

[0048] S3: 27.5 mL of 5% (v / v) glutaraldehyde solution and 45 mL of ethanol were mixed and added to a polytetrafluoroethylene reaction kettle, heated and reacted at 155°C for 3 h, then cooled, and rotary evaporated at 45°C for 6 h to obtain a viscous liquid; 11 mL of the viscous liquid and 9 g of the modified chitosan were mixed and stirred for 15 min, then transferred to a mold, quickly frozen under liquid nitrogen, then placed in a freeze dryer for 12 h, and then heated and reacted at 70°C for 6 h to obtain a chitosan composite film.

[0049] Referring to Figure 1 The embodiment discloses a multi-stage treatment method for resource utilization of copper-containing solid waste, comprising the following steps:

[0050] Step (1): crushing the copper-containing solid waste into small particles, removing large impurities by screening, removing ferromagnetic substances by magnetic separation, and removing light substances by air separation to obtain pretreated copper-containing solid waste;

[0051] Step (2): adding the pretreated copper-containing solid waste into sulfuric acid, stirring, and separating the leaching liquid from the solid residue by a filter press;

[0052] Step (3): adding an organic complexing agent to the leaching liquid, stirring, and solid-liquid separation to obtain a precipitate and a first waste liquid, washing and filtering the precipitate, and drying to obtain a copper-containing substance, and extracting and refining the copper-containing substance to obtain metallic copper and a second waste liquid;

[0053] Step (4): mixing the first waste liquid and the second waste liquid to obtain a mixed waste liquid, filtering the mixed waste liquid using a chitosan composite membrane to obtain dischargeable water;

[0054] Step (5): adding a stabilizer to the solid residue, heating and stirring to obtain a solidified body.

[0055] Embodiment 2: The embodiment discloses a preparation method of an organic complexing agent, comprising the following steps:

[0056] Q1: 10.48 mL of toluene is added to a container containing 40 mL of carbon tetrachloride, followed by adding 41.18 g of N-bromosuccinimide and 0.8 g of benzoyl peroxide, heating and refluxing at 75°C for 5 h, cooling and filtering, washing with 5 wt% sodium bicarbonate solution and ice water, drying with anhydrous magnesium sulfate, and rotary evaporation to obtain intermediate 1;

[0057] Q2: 9 g of sodium bicarbonate, 45 mL of dichloromethane, 50 mL of distilled water, 4.5 g of tetrabutylammonium iodide, and 6 g of intermediate 1 are added to a container, 5 g of N-hydroxyl succinimide is added to the container within 30 min at 60°C, refluxing for 3 h, cooling, separating the layers, extracting the water layer with dichloromethane, washing the combined organic phase with 5 wt% sodium bicarbonate solution and distilled water, drying with anhydrous magnesium sulfate, filtering to obtain intermediate 2;

[0058] Q3: 3 g of intermediate 2 and 40 mL of concentrated hydrochloric acid are added to a container, heating and refluxing at 80°C for 4 h, cooling to room temperature and filtering to obtain a white solid and a filtrate, the filtrate is concentrated under reduced pressure to obtain a white solid, the white solid is washed with acetonitrile and distilled to obtain intermediate 3;

[0059] Q4: Under the protection of nitrogen, 1.38 g of lithium diisopropylamide was added to a round-bottom flask, 1.33 mL of 3-methylpyridine was added at 0°C, and the mixture was stirred for 1 h to obtain a mixed solution, then 1.19 g of 1-adamantane ethyl carboxylate was added, and the stirring was continued for 5 h. The mixture was washed with saturated sodium chloride, extracted with ethyl acetate, washed with distilled water 5 times, dried over anhydrous sodium sulfate, distilled, and purified with a mixture of petroleum ether and ethyl acetate (5:1 by volume) as the eluent to obtain organic matter 1;

[0060] Q5: 0.65 g of intermediate 3 was added to 6.5 mL of pyridine containing 6 mL of organic matter 1, and the mixture was refluxed for 4 h. After the reaction was completed, 20 mL of distilled water was added to the reaction mixture, extracted with dichloromethane, washed with distilled water, dried over anhydrous sodium sulfate, and distilled under reduced pressure. The mixture was purified with a mixture of petroleum ether and ethyl acetate (7:1 by volume) as the eluent to obtain an organic complexing agent.

[0061] The present embodiment discloses a preparation method of a chitosan composite film, comprising the following steps:

[0062] S1: 1.5 g of chitosan was dissolved in 30 mL of 3 vt% glacial acetic acid, then diluted with 28 mL of anhydrous ethanol and placed in an ultrasonic cleaner, and then 0.013 mL of benzaldehyde was added. After being heated and shaken at 75°C for 4 h, a mixed chitosan solution was obtained;

[0063] S2: 2.5 mL of carbon disulfide and 50 mL of 5 wt% sodium hydroxide solution were added to 10 mL of the mixed chitosan solution, and stirred at room temperature for 45 min. After being reacted at 50°C for 4 h, 1 mol / L hydrochloric acid was added to adjust the pH to 9, and then reacted at 35°C for 1.5 h to obtain modified chitosan;

[0064] S3: 15 mL of 5 vt% glutaraldehyde solution and 30 mL of ethanol were mixed and added to a polytetrafluoroethylene reaction kettle. After being heated and reacted at 155°C for 3 h, the mixture was cooled and rotary evaporated at 45°C for 6 h to obtain a viscous liquid. After 10 mL of the viscous liquid and 8 g of the modified chitosan were mixed and stirred for 15 min, the mixture was transferred to a mold, quickly frozen under liquid nitrogen, and then placed in a freeze dryer for 12 h. After being heated and reacted at 70°C for 6 h, a chitosan composite film was obtained.

[0065] Referring to Figure 1 The present embodiment discloses a multi-stage treatment method for resource utilization of copper-containing solid waste, comprising the following steps:

[0066] Step (1): The copper-containing solid waste was crushed into small particles, and large impurities were removed by screening. Ferromagnetic substances were removed by magnetic separation, and light substances were removed by air separation to obtain pretreated copper-containing solid waste.

[0067] Step (2): The pretreated copper-containing solid waste is added to sulfuric acid, stirred, and the leaching solution is separated from the solid residue by a filter press;

[0068] Step (3): An organic complexing agent is added to the leaching solution, stirred, and solid-liquid separation is performed to obtain a precipitate and a first waste liquid. The precipitate is washed, filtered, and dried to obtain a copper-containing substance. The copper-containing substance is subjected to extraction and refining to obtain metallic copper and a second waste liquid;

[0069] Step (4): The first waste liquid and the second waste liquid are mixed to obtain a mixed waste liquid. The mixed waste liquid is filtered using a chitosan composite membrane to obtain dischargeable water;

[0070] Step (5): A stabilizer is added to the solid residue, heated, and stirred to obtain a solidified body.

[0071] Example 3: This example discloses a preparation method of an organic complexing agent, comprising the following steps:

[0072] Q1: 20.96 mL of toluene is added to a container containing 40 mL of carbon tetrachloride, followed by the addition of 20.59 g of N-bromosuccinimide and 1.6 g of benzoyl peroxide. After heating and refluxing at 75°C for 5 h, the mixture is cooled and filtered, washed with a 5 wt% sodium bicarbonate solution and ice water, dried with anhydrous magnesium sulfate, and rotary evaporated to obtain an intermediate 1;

[0073] Q2: 6 g of sodium bicarbonate, 30 mL of dichloromethane, 75 mL of distilled water, 3 g of tetrabutylammonium iodide, and 9 g of the intermediate 1 are added to a container. 7.5 g of N-hydroxyl succinimide is added to the container within 30 min at 60°C. After refluxing for 3 h, the mixture is cooled, separated, and the aqueous layer is extracted with dichloromethane. The combined organic phases are washed with a 5 wt% sodium bicarbonate solution and distilled water, dried with anhydrous magnesium sulfate, filtered, and an intermediate 2 is obtained;

[0074] Q3: 6 g of the intermediate 2 and 20 mL of concentrated hydrochloric acid are added to a container. After heating and refluxing at 80°C for 4 h, the mixture is cooled to room temperature and filtered to obtain a white solid and a filtrate. The filtrate is concentrated under reduced pressure to obtain a white solid, which is washed with acetonitrile and distilled to obtain an intermediate 3;

[0075] Q4: Under the protection of nitrogen, 1.06 g of lithium diisopropylamide was added to a round-bottom flask, 1.01 mL of 3-methylpyridine was added at 0°C, and the mixture was stirred for 1 h to obtain a mixed solution, then 1.55 g of 1-adamantane ethyl carboxylate was added, and the stirring was continued for 5 h. The mixture was washed with saturated sodium chloride, extracted with ethyl acetate, washed with distilled water 5 times, dried with anhydrous sodium sulfate, distilled, and purified with a mixture of petroleum ether and ethyl acetate (5:1 by volume) as the eluent to obtain organic matter 1;

[0076] Q5: 1.3 g of intermediate 3 was added to 3.5 mL of pyridine containing 3 mL of organic matter 1, and the mixture was refluxed for 4 h. After the reaction was completed, 10 mL of distilled water was added to the reaction mixture, extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, and distilled under reduced pressure. The mixture was purified with a mixture of petroleum ether and ethyl acetate (7:1 by volume) as the eluent to obtain an organic complexing agent.

[0077] The present embodiment discloses a preparation method of a chitosan composite film, comprising the following steps:

[0078] S1: 1 g of chitosan was dissolved in 20 mL of 3 vt% glacial acetic acid, then diluted with 22 mL of anhydrous ethanol and placed in an ultrasonic cleaner, and then 0.019 mL of benzaldehyde was added. After being heated and shaken at 75°C for 4 h, a mixed chitosan solution was obtained;

[0079] S2: 3 mL of carbon disulfide and 75 mL of 5 wt% sodium hydroxide solution were added to 15 mL of the mixed chitosan solution, and stirred at room temperature for 45 min. After being reacted at 50°C for 4 h, 1 mol / L hydrochloric acid was added to adjust the pH to 9, and then reacted at 35°C for 1.5 h to obtain modified chitosan;

[0080] S3: 30 mL of 5 vt% glutaraldehyde solution and 60 mL of ethanol were mixed and added to a polytetrafluoroethylene reaction kettle. After being heated and reacted at 155°C for 3 h, the mixture was cooled and rotary evaporated at 45°C for 6 h to obtain a viscous liquid. After being mixed and stirred for 15 min, 12 mL of the viscous liquid and 10 g of the modified chitosan were transferred to a mold, quickly frozen under liquid nitrogen, and then placed in a freeze dryer for 12 h. After being heated and reacted at 70°C for 6 h, a chitosan composite film was obtained.

[0081] Referring to Figure 1 The present embodiment discloses a multi-stage treatment method for resource utilization of copper-containing solid waste, comprising the following steps:

[0082] Step (1): The copper-containing solid waste was crushed into small particles, and large impurities were removed by screening. Ferromagnetic substances were removed by magnetic separation, and light substances were removed by air separation to obtain pretreated copper-containing solid waste.

[0083] Step (2): the pretreated copper-containing solid waste is added into sulfuric acid, stirred, and the leaching solution is separated from the solid residue by a filter press;

[0084] Step (3): an organic complexing agent is added into the leaching solution, stirred, and solid-liquid separation is performed to obtain a precipitate and a first waste liquid, the precipitate is washed, filtered, and dried to obtain a copper-containing substance, the copper-containing substance is extracted and refined to obtain metallic copper and a second waste liquid;

[0085] Step (4): the first waste liquid and the second waste liquid are mixed to obtain a mixed waste liquid, the mixed waste liquid is filtered using a chitosan composite membrane to obtain dischargeable water;

[0086] Step (5): a stabilizer is added into the solid residue, heated, and stirred to obtain a solidified body.

[0087] Comparative Example 1: Comparative Example 1 is compared with Example 1, and in the process of treating copper-containing solid waste, ethylenediaminetetraacetic acid is used instead of an organic complexing agent, and other conditions are unchanged.

[0088] Comparative Example 2: Comparative Example 2 is compared with Example 1, and in the process of treating copper-containing solid waste, a common filter membrane is used instead of a chitosan composite membrane, and other conditions are unchanged.

[0089] Experimental Example: According to GB 25467-2010 and GB 8978-1996, the dischargeable water is judged to determine whether it meets the discharge standard, the copper content in the metallic copper and the copper content in the copper-containing solid waste are measured according to the chemical analysis method and the spectral analysis method, and the copper recovery rate is calculated according to the formula: copper recovery rate = [(total mass of metallic copper × copper content in metallic copper) / (total mass of copper-containing solid waste × copper content in copper-containing solid waste)] × 100%, and the test results are shown in Table 1:

[0090] Table 1

[0091]

[0092]

[0093] According to the test results in Table 1, the method according to Examples 1-3 of the present application can effectively treat copper-containing solid waste, and has excellent copper recovery rate and low environmental pollution. According to the comparison between Comparative Example 1 and Examples 1-3, the use of an organic complexing agent can effectively improve the copper recovery rate; according to the comparison between Comparative Example 2 and Examples 1-3, the use of a chitosan composite membrane can reduce the heavy metal content in tail water to meet the discharge standard.

[0094] The above merely describes preferred embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, within the technical scope disclosed by the present application, can make equivalent replacements or changes according to the technical scheme and inventive concept of the present application, which should be covered within the protection scope of the present application.

[0095] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details and do not limit the application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The present application selects and describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application. The present application is limited only by the claims and their full scope and equivalents.

Claims

1. A multi-stage resource recovery method for copper-containing solid waste, characterized in that, Includes the following steps: Step (1): Crush copper-containing solid waste into small particles, remove large impurities by screening, remove ferromagnetic substances by magnetic separation, and remove light substances by air separation to obtain pretreated copper-containing solid waste. Step (2): Add the pretreated copper-containing solid waste to the leaching agent, stir, and separate the leaching solution from the solid residue using a filter press; Step (3): Add an organic complexing agent to the leachate, stir, separate solid and liquid to obtain precipitate and first waste liquid, wash the precipitate, filter and dry to obtain copper-containing substances, extract and refine the copper-containing substances to obtain metallic copper and second waste liquid. Step (4): Mix the first waste liquid and the second waste liquid to obtain a mixed waste liquid, filter it, and obtain water that can be discharged; Step (5): Add stabilizer to solid residue, heat and stir to obtain solidified body; The method for preparing the organic complexing agent includes the following steps: Q1: Toluene was added to a container containing carbon tetrachloride, followed by N-bromosuccinimide and benzoyl peroxide. After heating to reflux, the mixture was cooled, filtered, washed, dried, and rotary evaporated to obtain intermediate 1. Q2: Add sodium bicarbonate, dichloromethane, distilled water, tetrabutylammonium iodide and intermediate 1 to a container, heat to reflux, add N-hydroxypeptidyl imide to the container, after reflux, cool, separate the layers, extract the aqueous layer, combine the organic phases, wash, dry, filter, and obtain intermediate 2. Q3: Add intermediate 2 and concentrated hydrochloric acid to a container, heat to reflux, cool to room temperature and filter to obtain a white solid and filtrate. Concentrate the filtrate under reduced pressure to obtain a white solid. Wash the white solid and distill to obtain intermediate 3. Q4: Under nitrogen protection, lithium diisopropylamine was added to a round-bottom flask. Under low temperature conditions, 3-methylpyridine was added and stirred to obtain a mixed solution. Then, ethyl 1-adamantane carboxylate was added and stirred, washed, extracted, and the organic phase was washed, dried, distilled, and purified to obtain organic compound 1. Q5: Add intermediate 3 to pyridine containing organic compound 1, reflux the reaction, add distilled water to the reaction mixture, extract, wash the organic phase, dry, distill under reduced pressure, and purify to obtain the organic complexing agent; In step (4), the mixed waste liquid is filtered using a chitosan composite membrane. The preparation method of the chitosan composite membrane includes the following steps: S1: Chitosan is dissolved in glacial acetic acid, then diluted with anhydrous ethanol and placed in an ultrasonic cleaner. Benzaldehyde is then added, and the mixture is heated and shaken to react, resulting in a mixed chitosan solution. S2: Add carbon disulfide and sodium hydroxide solution to the mixed chitosan solution, stir at room temperature, heat to react, then add hydrochloric acid to adjust the pH, heat to react and obtain modified chitosan. S3: After mixing glutaraldehyde solution and ethanol evenly, add them to a polytetrafluoroethylene reactor, heat and react, then cool and rotary evaporate to obtain a viscous liquid; mix the viscous liquid and modified chitosan, transfer it to a mold, freeze it rapidly under liquid nitrogen, place it in a freeze dryer, and then heat and react to obtain a chitosan composite film.

2. The multi-stage resource recovery method for copper-containing solid waste according to claim 1, characterized in that, In step (2), the leaching agent is composed of one or more combinations of sulfuric acid, nitric acid, hydrochloric acid, ammonia, sodium carbonate, and sodium hydroxide.

3. The multi-stage resource recovery method for copper-containing solid waste according to claim 1, characterized in that, In Q1, the molar ratio of toluene, N-bromosuccinimide, and benzoyl peroxide is (6-12):(7-14):(0.2-0.4). The heating temperature is refluxed at 70-80℃ for 3-5 hours. The mixture is washed with a 5wt% sodium bicarbonate solution and ice water, and dried with anhydrous magnesium sulfate. In Q2, sodium bicarbonate, dichloromethane, distilled water, tetrabutylammonium iodide, intermediate 1, and N-hydroxypeptidyl... The ratio of imine used was (6-9) g: (30-45) mL: (50-75) mL: (3-4.5) g: (6-9) g: (5-7.5) g. The heating and reflux temperature was 55-65℃. The time for adding N-hydroxypeptidyl imine was 30-45 min. The reflux time was 2-4 h. The mixture was extracted with dichloromethane, washed with 5 wt% sodium bicarbonate solution and distilled water, and dried with anhydrous magnesium sulfate.

4. The multi-stage resource recovery method for copper-containing solid waste according to claim 1, characterized in that, In Q3, the ratio of intermediate 2 to concentrated hydrochloric acid is (3-6) g: (20-40) mL, the heating reflux temperature is 70-90℃, the time is 3-5 h, and the white solid is washed with acetonitrile.

5. The multi-stage resource recovery treatment method for copper-containing solid waste according to claim 1, characterized in that, In Q4, the molar ratio of lithium diisopropylamine, 3-methylpyridine, and ethyl 1-adamantane carboxylate is (1.7-2.2):(1.8-2.4):(1-1.3), the low temperature is 0-1℃, the stirring time is 1-2h, the stirring time is continued for 3-5h, the product is washed with saturated sodium chloride, extracted with ethyl acetate, washed with distilled water 3-5 times, dried with anhydrous sodium sulfate, and purified using a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 5:1 as the eluent; In Q5, the volume ratio of organic matter 1, intermediate 3, and distilled water is (3-6)mL:(0.65-1.3)g:(10-20)mL, the reflux time is 3-4h, the product is extracted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, and purified using a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 7:1 as the eluent.

6. The multi-stage resource recovery method for copper-containing solid waste according to claim 1, characterized in that, In S1, the ratio of chitosan, glacial acetic acid, anhydrous ethanol and benzaldehyde is (1-1.5) g: (20-30) mL: (20-30) mL: (0.013-0.019) mL, the volume fraction of glacial acetic acid is 3 wt%, the heating and shaking temperature is 70-80℃, and the time is 4-6 h.

7. The multi-stage resource recovery method for copper-containing solid waste according to claim 1, characterized in that, In S2, the ratio of the mixed chitosan solution, carbon disulfide and sodium hydroxide solution is (10-15) mL: (2-3) mL: (50-75) mL, the mass fraction of sodium hydroxide solution is 5 wt%, the stirring time is 30-45 min, the reaction temperature is 40-50℃, the time is 3-4 h, the concentration of hydrochloric acid is 1 mol / L, and the pH is adjusted to 9-10.

8. The multi-stage resource recovery method for copper-containing solid waste according to claim 1, characterized in that, In S3, the volume ratio of glutaraldehyde solution to ethanol is (15-30):(30-60), the volume fraction of glutaraldehyde solution is 5 wt%, the heating reaction temperature is 150-160℃, the time is 2-3 h, the rotary evaporation temperature is 40-50℃, the time is 4-6 h, the ratio of viscous liquid to modified chitosan is (10-12) mL:(8-10) g, the mixing and stirring time is 10-15 min, the mixture is placed in a freeze dryer for 10-12 h, the heating reaction temperature is 60-70℃, and the reaction time is 4-6 h.

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