A resource treatment method for copper-containing sludge

Abstract

The present invention discloses a method for resource treatment of copper-containing sludge, belonging to the technical field of resource recovery. The method for resource treatment of copper-containing sludge comprises the following steps: Step (1): Crushing, grinding and sieving the copper-containing sludge to obtain pretreated sludge; Step (2): Mixing the pretreated sludge, an organic leaching agent and water, heating and stirring to obtain a leaching solution and solid residues, washing the solid residues with distilled water, and mixing the washing solution and the leaching solution to obtain a mixed solution; Step (3): Performing chemical precipitation treatment on the mixed solution, using sodium hydroxide and lime milk as precipitants, stirring, separating solid from liquid, and drying to obtain copper salts; Step (4): Mixing a modified curing agent with the washed solid residues, stirring evenly, and performing curing to obtain a cured body. By this method, copper-containing sludge can be effectively treated and the recovery rate of copper can be improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of resource recovery, and particularly relates to a method for resource treatment of copper-containing sludge. Background Art

[0002] With the rapid development of industrial production, especially in industries such as metal processing, electroplating, and printed circuit board manufacturing, a large amount of copper-containing sludge has been generated. These sludges are solid wastes in the industrial production process, containing relatively high concentrations of copper and other heavy metal elements. If these heavy metals are not properly treated, they will not only seriously pollute the environment but also cause long-term harm to the ecosystem. At the same time, since copper is an important strategic resource with wide application value in industrial production, the treatment and resource utilization of copper-containing sludge have attracted wide attention.

[0003] Through refining technology, valuable metal elements such as copper in the sludge can be recycled, which can not only reduce environmental pollution but also effectively alleviate the problem of copper resource shortage. In the treatment of copper-containing sludge in printed circuit board enterprises, methods such as acid leaching, ammonia leaching, or biological leaching are usually used to leach copper from the sludge, and then chemical precipitation, ion exchange, electrolysis, solvent extraction, and microbial purification methods are used to recover elemental copper or copper salts. Among them, the solvent extraction method has quickly occupied an important position in the sludge treatment field due to its advantages such as environmental protection and rapidity.

[0004] Patent CN 117987648 A discloses a method for resource treatment of copper-containing sludge smelting slag. By weight parts on a dry basis, 60 - 70 parts of the copper-containing sludge smelting slag to be treated are mixed evenly with 20 - 30 parts of an acidic regulator and 20 - 30 parts of a basic regulator to obtain a compound material; the compound material and a reducing agent are added to a smelting furnace for smelting to obtain a melt and molten iron; the melt is fibrillated to obtain cotton fibers. This invention uses coal gangue, dolomite, etc. to synergistically melt with copper-containing sludge smelting slag to produce rock wool, realizing the high-value utilization of copper-containing sludge smelting slag. However, there is still room for improvement in the copper recovery rate. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for resource treatment of copper-containing sludge to solve the technical problem of poor copper recovery rate in the prior art.

[0006] To achieve the above purpose, the present invention adopts the following technical solutions:

[0007] The present invention provides a method for resource treatment of copper-containing sludge, comprising the following steps:

[0008] Step (1): Crushing, grinding, and sieving the copper-containing sludge to obtain pretreated sludge;

[0009] Step (2): Mix the pretreated sludge, the organic leaching agent and water, heat and stir to obtain a leachate and solid residues, wash the solid residues with distilled water, and mix the washing liquid and the leachate to obtain a mixed liquid;

[0010] Step (3): Perform chemical precipitation treatment on the mixed liquid, use sodium hydroxide and lime milk as precipitants, stir, separate the solid and liquid, and dry to obtain copper salts;

[0011] Step (4): Mix the modified curing agent with the washed solid residues, stir evenly, and then cure to obtain a cured body.

[0012] Preferably, in the said step (2), the preparation method of the organic leaching agent includes the following steps:

[0013] Q1: Add methyl methacrylate and divinylbenzene into a container, stir and mix, then add benzoyl peroxide. After dissolution, add paraffin and toluene, stir evenly. Subsequently, add the polyvinyl alcohol solution and calcium phosphate into the container. Under nitrogen protection, heat in a water bath, then add sodium chloride for accelerated stirring, heat and react. After the reaction ends, filter, perform Soxhlet extraction, soak, filter, and wash to obtain composite resin beads;

[0014] Q2: Add hydroxylamine hydrochloride and sodium hydroxide into a container filled with distilled water in sequence, react in an ice bath. After sufficient reaction, add L-glutamic acid dimethyl ester hydrochloride, heat and react. After the reaction ends, cool to room temperature, adjust the pH, and perform recrystallization to obtain modified hydroxamic acid;

[0015] Q3: Add the composite resin beads into ethanol for swelling. After swelling, pour them into a container containing ethanol, distilled water and sodium hydroxide. Under heating reaction conditions, add the modified hydroxamic acid into the container. After the reaction ends, filter, wash, and dry in vacuum to obtain the organic leaching agent.

[0016] In the above process, methyl methacrylate and divinylbenzene undergo a polymerization reaction under the condition of benzoyl peroxide as an initiator, and then under alkaline conditions, hydroxylamine hydrochloride and L-glutamic acid dimethyl ester hydrochloride undergo a hydroxylation reaction to obtain modified hydroxamic acid. Finally, an exchange reaction occurs between the ester group and the hydroxyl group to obtain the organic leaching agent.

[0017] Preferably, in Q1, the dosage ratios of methyl methacrylate, divinylbenzene, benzoyl peroxide, paraffin, toluene, polyvinyl alcohol solution, calcium phosphate and sodium chloride are (10 - 12) g : (2.4 - 2.88) g : (0.2 - 0.24) g : (0.1 - 0.12) g : (0.01 - 0.012) mL : (70 - 84) mL : (1 - 1.2) g : (2 - 2.4) g. The water bath heating temperature is 70 - 75 °C, the water bath heating time is 1 - 2 h, the heating reaction temperature is 80 - 85 °C, the time is 6 - 8 h. During the Soxhlet extraction process, petroleum ether is used for extraction for 6 - 8 h, ethanol is used for soaking, and distilled water is used for washing.

[0018] Preferably, in Q2, the dosage ratios of hydroxylamine hydrochloride, sodium hydroxide, distilled water and L-glutamate dimethyl ester hydrochloride are (27.8 - 30.58) g : (33.33 - 33.66) g : (100 - 110) mL : (21.16 - 23.28) g. The ice bath reaction time is 1 - 2 h, the heating reaction temperature is 50 - 55 °C, the time is 8 - 10 h, and 0.5 mol / L hydrochloric acid is used to adjust the pH to 4.8 - 5.2.

[0019] Preferably, in Q3, the dosage ratios of the composite resin beads, ethanol added after swelling, distilled water, sodium hydroxide and modified hydroxamic acid are (10 - 13) g : (80 - 104) mL : (20 - 26) mL : (8.8 - 11.44) g : (8.4 - 10.92) g. The swelling time is 20 - 24 h, the heating reaction temperature is 60 - 70 °C, the time is 10 - 12 h. It is washed with ethanol and distilled water until neutral, and the vacuum drying temperature is 50 - 60 °C, the time is 20 - 24 h.

[0020] Preferably, the preparation method of the modified curing agent includes the following steps:

[0021] S1: Add naringenin and p-aminobenzohydrazide into a container, add ethanol and acetic acid, stir and mix, then heat under reflux. After the reflux ends, elute and separate to obtain a derivative.

[0022] S2: Add the derivative and triethylamine into a container containing tetrahydrofuran, under nitrogen protection, transfer it to a container equipped with a reflux condenser and a magnetic stirrer. During low-temperature stirring, dropwise add chlorodiphenylphosphine. After the addition is completed, heat in an oil bath. After heating is completed, cool to room temperature, filter by suction, rotary evaporate, concentrate, dissolve in dichloromethane, wash, dry, rotary evaporate and concentrate, and vacuum dry to obtain a solid auxiliary agent.

[0023] S3: Dissolve the solid additive in dichloromethane, then mix it with novolac epoxy resin to obtain a mixture. After vacuum drying, mix the mixture with 4,4'-diaminodiphenylmethane, and perform degassing treatment to obtain a modified curing agent.

[0024] In the above process, the synthesis reaction formula of the solid additive is as follows:

[0025]

[0026] The results of mass spectrometry analysis of the derivative are: m / z: 405.13 (100.0%), 406.14 (24.2%), 407.14 (3.8%), 406.13 (1.1%); the results of mass spectrometry analysis of the solid additive are: m / z: 957.27 (100.0%), 958.27 (63.5%), 959.27 (21.5%), 960.28 (4.0%), 958.26 (1.1%).

[0027] Preferably, in the S1, the molar ratio of naringenin to p-aminobenzohydrazide is (1 - 2):(1.1 - 2.1), the heating reflux temperature is 110 - 120 °C, and the reflux time is 8 - 12 h.

[0028] Preferably, in the S2, the molar ratio of the derivative, triethylamine, and chlorodiphenylphosphine is (1 - 2):(3 - 6):(3 - 5.8), the low-temperature stirring temperature is 0 - 1 °C, the dropping time is 30 - 45 min, the oil bath heating temperature is 60 - 80 °C, the time is 6 - 8 h, wash with deionized water 3 - 5 times, dry with anhydrous magnesium sulfate, and the vacuum drying temperature is 60 - 80 °C, and the time is 20 - 24 h.

[0029] Preferably, in the S3, the dosage ratio of the solid additive, novolac epoxy resin, and 4,4'-diaminodiphenylmethane is (1 - 5) g:(100 - 120) g:(25 - 30) g, the vacuum drying temperature is 40 - 50 °C, and the time is 10 - 12 h.

[0030] Preferably, in the step (4), the curing process is: heat and cure at 120 °C and 150 °C for 2 - 3 h respectively.

[0031] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are:

[0032] 1. The present invention first uses methyl methacrylate, divinylbenzene, hydroxylamine hydrochloride, and L-glutamate dimethyl ester hydrochloride as raw materials to prepare an organic leaching agent, and then uses naringenin 、Using p-aminobenzoyl hydrazide and chlorodiphenylphosphine as raw materials, a modified curing agent is prepared. Adding an organic leaching agent to the pretreated sludge can effectively improve the recovery rate of copper. Adding the modified curing agent to the solid residue of the copper-containing sludge can make the obtained solidified body have excellent mechanical properties and flame retardancy, and improve the service life of the solidified body.

[0033] 2. In the present invention, methyl methacrylate, divinylbenzene, hydroxylamine hydrochloride and L-glutamic acid dimethyl ester hydrochloride are used as raw materials to prepare an organic leaching agent. The hydroxime group in the organic leaching agent can coordinate with copper ions in the sludge to form a stable complex. The strong coordination ability and selectivity of the hydroxime group enable the organic leaching agent to efficiently adsorb copper ions in the sludge, and the high specific surface area and porosity in the composite resin beads also significantly improve the adsorption and recovery rate of the organic leaching agent for copper ions.

[0034] 3. The present invention uses naringenin 、 Using p-aminobenzoyl hydrazide and chlorodiphenylphosphine as raw materials, a modified curing agent is prepared. The functional groups in the solid auxiliary react with phenolic epoxy resin and 4,4'-diaminodiphenylmethane to form a large number of crosslinking points, increasing the crosslinking density of the solidified body. The increase in crosslinking density makes the solidified body more dense and tough, improving its mechanical properties. Moreover, the introduction of derivatives and chlorodiphenylphosphine increases the rigidity of the molecular chain of the solidified body, making the solidified body less likely to deform and break when subjected to external forces. At the same time, the phosphorus element introduced in the solid auxiliary can form phosphate compounds with flame retardant effects during the combustion process, which can cover the combustion surface, isolate oxygen and heat, slow down the combustion speed and even extinguish the flame. Additionally, the phosphorus element of chlorodiphenylphosphine can also capture free radicals generated during the combustion process, interrupt the combustion chain reaction, and achieve the purpose of flame retardancy. Specific embodiments

[0035] The technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0036] Example 1: This example discloses a preparation method of an organic leaching agent, including the following steps:

[0037] Q1: Add 11 g of methyl methacrylate and 2.64 g of divinylbenzene into a container. After stirring and mixing, add 0.22 g of benzoyl peroxide. After dissolution, add 0.11 g of paraffin wax and 0.011 mL of toluene, and stir well. Subsequently, add 77 mL of polyvinyl alcohol solution and 1.1 g of calcium phosphate into the container. Under nitrogen protection, heat in a water bath at 75 °C for 2 h, then add 2.2 g of sodium chloride for accelerated stirring, and heat and react at 85 °C for 8 h. After the reaction is completed, filter, perform Soxhlet extraction with petroleum ether for 8 h, soak with ethanol, filter, and wash with distilled water to obtain composite resin microspheres;

[0038] Q2: Add 29.19 g of hydroxylamine hydrochloride and 33.5 g of sodium hydroxide successively into a container containing 105 mL of distilled water, and react in an ice bath for 2 h. After sufficient reaction, add 22.22 g of L-glutamic acid dimethyl ester hydrochloride, and heat and react at 55 °C for 10 h. After the reaction is completed, cool to room temperature, adjust the pH = 4.8 with 0.5 mol / L hydrochloric acid, and perform recrystallization to obtain modified hydroxamic acid;

[0039] Q3: Add 11.5 g of composite resin microspheres into ethanol for swelling for 24 h. After swelling, pour them into a container containing 92 mL of ethanol, 23 mL of distilled water, and 10.12 g of sodium hydroxide. Under the heating reaction condition of 70 °C, add 9.66 g of modified hydroxamic acid into the container. After reacting for 12 h, filter, wash with ethanol and distilled water until neutral, and dry in vacuum at 60 °C for 24 h to obtain an organic leaching agent.

[0040] This example discloses a preparation method of a modified curing agent, including the following steps:

[0041] S1: Add 2.46 g of naringenin and 1.45 g of p-aminobenzohydrazide into a container, add 20 mL of ethanol and 20 mL of acetic acid, stir and mix, then heat and reflux at 110 °C for 12 h. After the reflux is completed, perform elution and separation to obtain a derivative;

[0042] S2: Add 0.98 g of the derivative and 0.75 g of triethylamine into a container containing 100 mL of tetrahydrofuran. Under nitrogen protection, transfer it to a container equipped with a reflux condenser and a magnetic stirrer. During the low-temperature stirring at 0 °C, dropwise add 1.6 g of chlorodiphenylphosphine, and the dropping time is 30 min. After the dropping is completed, heat in an oil bath at 70 °C for 8 h. After the heating is completed, cool to room temperature, perform suction filtration, rotary evaporation, concentration, dissolve in dichloromethane, wash 5 times with deionized water, dry with anhydrous magnesium sulfate, rotary evaporate and concentrate, and dry in vacuum at 70 °C for 24 h to obtain a solid auxiliary agent;

[0043] S3: Dissolve 3 g of solid auxiliary agent in 20 mL of dichloromethane, then mix it with 110 g of phenolic epoxy resin to obtain a mixture. After vacuum drying the mixture at 50 °C for 12 h, mix the mixture with 27.5 g of 4,4'-diaminodiphenylmethane, and perform degassing treatment to obtain a modified curing agent.

[0044] This example discloses a resource treatment method for copper-containing sludge, including the following steps:

[0045] Step (1): Crush, grind, and screen the copper-containing sludge to obtain pretreated sludge.

[0046] Step (2): Mix the pretreated sludge, organic leaching agent, and water, heat and stir to obtain leachate and solid residue. Wash the solid residue with distilled water, and after mixing the washing liquid and the leachate, obtain a mixed liquid.

[0047] Step (3): Perform chemical precipitation treatment on the mixed liquid. Use sodium hydroxide and lime milk as precipitants, stir, separate the solid and liquid, and dry to obtain copper salt.

[0048] Step (4): Mix the modified curing agent with the washed solid residue, stir evenly, and then perform curing. The curing process is: heat and cure at 120 °C and 150 °C for 2 h respectively to obtain a cured body.

[0049] Example 2: This example discloses a preparation method for an organic leaching agent, including the following steps:

[0050] Q1: Add 10 g of methyl methacrylate and 2.88 g of divinylbenzene to a container, stir and mix, then add 0.24 g of benzoyl peroxide. After dissolution, add 0.1 g of paraffin wax and 0.01 mL of toluene, stir well. Subsequently, add 84 mL of polyvinyl alcohol solution and 1 g of calcium phosphate to the container. Under nitrogen protection, heat in a water bath at 75 °C for 2 h, then add 2 g of sodium chloride for accelerated stirring, and heat and react at 85 °C for 8 h. After the reaction ends, filter, perform Soxhlet extraction with petroleum ether for 8 h, soak with ethanol, filter, and wash with distilled water to obtain composite resin beads.

[0051] Q2: Add 27.8 g of hydroxylamine hydrochloride and 33.33 g of sodium hydroxide to a container containing 110 mL of distilled water in sequence, react in an ice bath for 2 h. After full reaction, add 23.28 g of L-glutamic acid dimethyl ester hydrochloride, heat and react at 55 °C for 10 h. After the reaction ends, cool to room temperature, adjust the pH = 4.8 with 0.5 mol / L hydrochloric acid, and perform recrystallization to obtain modified hydroxamic acid.

[0052] Q3: Add 13 g of composite resin balls to ethanol for swelling for 24 h. After swelling, pour them into a container containing 80 mL of ethanol, 26 mL of distilled water, and 8.8 g of sodium hydroxide. Under the heating reaction condition of 70 °C, add 10.92 g of modified hydroxamic acid to the container. After reacting for 12 h, filter, wash with ethanol and distilled water until neutral, and dry in vacuum at 60 °C for 24 h to obtain an organic leaching agent.

[0053] This example discloses a preparation method of a modified curing agent, which includes the following steps:

[0054] S1: Add 1.64 g of naringenin and 1.91 g of p-aminobenzohydrazide to a container, add 20 mL of ethanol and 20 mL of acetic acid, stir and mix, then heat under reflux at 110 °C for 12 h. After the reflux ends, elute and separate to obtain a derivative.

[0055] S2: Add 0.65 g of the derivative and 1 g of triethylamine to a container containing 100 mL of tetrahydrofuran. Under nitrogen protection, transfer it to a container equipped with a reflux condenser and a magnetic stirrer. During the low-temperature stirring at 0 °C, dropwise add 2.1 g of chlorodiphenylphosphine, and the dropping time is 30 min. After the dropping is completed, heat in an oil bath at 70 °C for 8 h. After the heating is completed, cool to room temperature, filter by suction, rotary evaporate, concentrate, dissolve in dichloromethane, wash 5 times with deionized water, dry with anhydrous magnesium sulfate, rotary evaporate and concentrate, and dry in vacuum at 70 °C for 24 h to obtain a solid auxiliary agent.

[0056] S3: Dissolve 1 g of the solid auxiliary agent in 20 mL of dichloromethane, then mix it with 100 g of phenolic epoxy resin to obtain a mixture. After vacuum drying at 50 °C for 12 h, mix the mixture with 25 g of 4,4'-diaminodiphenylmethane, and perform defoaming treatment to obtain a modified curing agent.

[0057] This example discloses a resource treatment method for copper-containing sludge, which includes the following steps:

[0058] Step (1): Crush, grind, and screen the copper-containing sludge to obtain pretreated sludge.

[0059] Step (2): Mix the pretreated sludge, the organic leaching agent, and water, heat and stir to obtain a leaching solution and solid residues. Wash the solid residues with distilled water, and mix the washing solution and the leaching solution to obtain a mixed solution.

[0060] Step (3): Perform chemical precipitation treatment on the mixed solution, use sodium hydroxide and lime milk as precipitants, stir, separate the solid and liquid, and dry to obtain copper salts.

[0061] Step (4): Mix the modified curing agent with the washed solid residue. After stirring evenly, carry out curing. The curing process is as follows: Heat and cure at 120°C and 150°C for 2 hours respectively to obtain a cured body.

[0062] Example 3: This example discloses a preparation method of an organic leaching agent, including the following steps:

[0063] Q1: Add 12 g of methyl methacrylate and 2.4 g of divinylbenzene into a container. After stirring and mixing, add 0.2 g of benzoyl peroxide. After dissolution, add 0.12 g of paraffin wax and 0.012 mL of toluene, and stir evenly. Subsequently, add 70 mL of polyvinyl alcohol solution and 1.2 g of calcium phosphate into the container. Under nitrogen protection, heat in a water bath at 75°C for 2 hours, then add 2.4 g of sodium chloride for accelerated stirring, and heat and react at 85°C for 8 hours. After the reaction is completed, filter, perform Soxhlet extraction with petroleum ether for 8 hours, soak with ethanol, filter, and wash with distilled water to obtain composite resin beads;

[0064] Q2: Add 30.58 g of hydroxylamine hydrochloride and 33.66 g of sodium hydroxide into a container containing 100 mL of distilled water in sequence. React in an ice bath for 2 hours. After sufficient reaction, add 21.16 g of L-glutamic acid dimethyl ester hydrochloride, and heat and react at 55°C for 10 hours. After the reaction is completed, cool to room temperature, adjust the pH = 4.8 with 0.5 mol / L hydrochloric acid, and perform recrystallization to obtain modified hydroxamic acid;

[0065] Q3: Add 10 g of composite resin beads into ethanol to swell for 24 hours. After swelling, pour them into a container containing 104 mL of ethanol, 20 mL of distilled water, and 11.44 g of sodium hydroxide. Under the heating reaction condition of 70°C, add 8.4 g of modified hydroxamic acid into the container. After reacting for 12 hours, filter, wash with ethanol and distilled water until neutral, and dry in vacuum at 60°C for 24 hours to obtain an organic leaching agent.

[0066] This example discloses a preparation method of a modified curing agent, including the following steps:

[0067] S1: Add 3.28 g of naringenin and 1 g of p-aminobenzohydrazide into a container, add 20 mL of ethanol and 20 mL of acetic acid, stir and mix, and heat under reflux at 110°C for 12 hours. After the reflux is completed, elute and separate to obtain a derivative;

[0068] S2: Add 1.3 g of the derivative and 0.5 g of triethylamine into a container filled with 100 mL of tetrahydrofuran. Under nitrogen protection, transfer it to a container equipped with a reflux condenser and a magnetic stirrer. During the low-temperature stirring at 0 °C, dropwise add 1.1 g of chlorodiphenylphosphine over 30 min. After the addition is completed, heat it in an oil bath at 70 °C for 8 h. After the heating is completed, cool it to room temperature, perform suction filtration, rotary evaporation, concentration, dissolve it in dichloromethane, wash it 5 times with deionized water, dry it with anhydrous magnesium sulfate, perform rotary evaporation and concentration, and vacuum dry it at 70 °C for 24 h to obtain a solid auxiliary agent;

[0069] S3: Dissolve 5 g of the solid auxiliary agent in 20 mL of dichloromethane and then mix it with 120 g of phenolic epoxy resin to obtain a mixture. After vacuum drying at 50 °C for 12 h, mix the mixture with 30 g of 4,4'-diaminodiphenylmethane and perform degassing treatment to obtain a modified curing agent.

[0070] This example discloses a resource treatment method for copper-containing sludge, including the following steps:

[0071] Step (1): Crush, grind, and screen the copper-containing sludge to obtain pretreated sludge;

[0072] Step (2): Mix the pretreated sludge, organic leaching agent, and water, heat and stir to obtain a leaching solution and solid residue. Wash the solid residue with distilled water, and after mixing the washing solution and the leaching solution, obtain a mixed solution;

[0073] Step (3): Perform chemical precipitation treatment on the mixed solution, use sodium hydroxide and lime milk as precipitants, stir, perform solid-liquid separation, and dry to obtain copper salts;

[0074] Step (4): Mix the modified curing agent with the washed solid residue, stir evenly, and then perform curing. The curing process is: heat and cure at 120 °C and 150 °C for 2 h respectively to obtain a cured body.

[0075] Example 4: This example discloses a preparation method for an organic leaching agent, including the following steps:

[0076] Q1: Add 10.5 g of methyl methacrylate and 2.52 g of divinylbenzene into a container. After stirring and mixing, add 0.23 g of benzoyl peroxide. After dissolution, add 0.105 g of paraffin and 0.011 mL of toluene, stir well. Subsequently, add 72 mL of polyvinyl alcohol solution and 1.05 g of calcium phosphate into the container. Under nitrogen protection, heat in a water bath at 75 °C for 2 h, then add 2.1 g of sodium chloride for accelerated stirring, heat and react at 85 °C for 8 h. After the reaction is completed, filter, perform Soxhlet extraction with petroleum ether for 8 h, soak with ethanol, filter, and wash with distilled water to obtain composite resin beads;

[0077] Q2: 28.57 g of hydroxylamine hydrochloride and 33.44 g of sodium hydroxide were added sequentially to a container containing 102 mL of distilled water, and the mixture was reacted in an ice bath for 2 h. After sufficient reaction, 22.07 g of L-glutamic acid dimethyl ester hydrochloride was added, and the mixture was heated at 55°C for 10 h. After the reaction was completed, the mixture was cooled to room temperature, and the pH was adjusted to 4.8 with 0.5 mol / L hydrochloric acid, and the mixture was recrystallized to obtain modified hydroxamic acid;

[0078] Q3: 11 g of composite resin beads were added to ethanol and swelled for 24 h. After swelling, the beads were poured into a container containing 85 mL of ethanol, 22 mL of distilled water, and 9.2 g of sodium hydroxide. Under heating reaction conditions at 70 °C, 9.2 g of modified hydroxamic acid was added to the container. After reacting for 12 h, the mixture was filtered, washed with ethanol and distilled water until neutral, and vacuum dried at 60 °C for 24 h to obtain an organic leachant.

[0079] This embodiment discloses a method for preparing a modified curing agent, comprising the following steps:

[0080] S1: 1.85 g of naringenin and 1.28 g of p-aminobenzoic acid hydrazide were added to a container, and 20 mL of ethanol and 20 mL of acetic acid were added. After stirring, the mixture was heated under reflux at 110°C for 12 h. After the reflux period, the mixture was eluted and separated to obtain a derivative.

[0081] S2: 0.83 g of the derivative and 0.58 g of triethylamine were added to a container containing 100 mL of tetrahydrofuran. Under nitrogen protection, the mixture was transferred to a container containing a reflux condenser and a magnetic stirrer. During the low-temperature stirring at 0°C, 1.3 g of chlorodiphenylphosphine was added dropwise for 30 min. After the addition was completed, the mixture was heated in an oil bath at 70°C for 8 h. After the heating was completed, the mixture was cooled to room temperature, filtered, rotary evaporated, concentrated, dissolved in dichloromethane, washed with deionized water 5 times, dried over anhydrous magnesium sulfate, rotary evaporated, and dried in vacuo at 70°C for 24 h to obtain a solid additive;

[0082] S3: 2 g of a solid additive was dissolved in 20 mL of dichloromethane and mixed with 105 g of a novolac epoxy resin to obtain a mixture. The mixture was vacuum dried at 50° C. for 12 h, and then mixed with 28 g of 4,4′-diaminodiphenylmethane and degassed to obtain a modified curing agent.

[0083] This embodiment discloses a method for resource recovery of copper-containing sludge, comprising the following steps:

[0084] Step (1): crushing, grinding and sieving the copper-containing sludge to obtain pretreated sludge;

[0085] Step (2): Mix the pretreated sludge, the organic leaching agent and water, heat and stir to obtain a leachate and solid residue. Wash the solid residue with distilled water, and after mixing the washing liquid and the leachate, obtain a mixed liquid;

[0086] Step (3): Perform chemical precipitation treatment on the mixed liquid. Use sodium hydroxide and lime milk as precipitants, stir, separate solid and liquid, and dry to obtain copper salts;

[0087] Step (4): Mix the modified curing agent with the washed solid residue, stir evenly, and then cure. The curing process is: heat and cure at 120 °C and 150 °C for 2 h respectively to obtain a cured body.

[0088] Example 5: This example discloses a preparation method of an organic leaching agent, including the following steps:

[0089] Q1: Add 11.5 g of methyl methacrylate and 2.71 g of divinylbenzene into a container, stir and mix, then add 0.21 g of benzoyl peroxide. After dissolution, add 0.115 g of paraffin and 0.012 mL of toluene, stir well. Subsequently, add 82 mL of polyvinyl alcohol solution and 1.15 g of calcium phosphate into the container. Under nitrogen protection, heat in a water bath at 75 °C for 2 h, then add 2.3 g of sodium chloride for accelerated stirring, and heat and react at 85 °C for 8 h. After the reaction, filter, perform Soxhlet extraction with petroleum ether for 8 h, soak with ethanol, filter, and wash with distilled water to obtain composite resin beads;

[0090] Q2: Add 29.85 g of hydroxylamine hydrochloride and 33.55 g of sodium hydroxide into a container containing 108 mL of distilled water in sequence, react in an ice bath for 2 h. After sufficient reaction, add 22.95 g of L-glutamic acid dimethyl ester hydrochloride, heat and react at 55 °C for 10 h. After the reaction, cool to room temperature, adjust the pH = 4.8 with 0.5 mol / L hydrochloric acid, and perform recrystallization to obtain modified hydroxamic acid;

[0091] Q3: Add 12 g of composite resin beads into ethanol to swell for 24 h. After swelling, pour them into a container containing 98 mL of ethanol, 24 mL of distilled water and 10.89 g of sodium hydroxide. Under the heating reaction condition of 70 °C, add 10.15 g of modified hydroxamic acid into the container. After reacting for 12 h, filter, wash with ethanol and distilled water until neutral, and dry in vacuum at 60 °C for 24 h to obtain the organic leaching agent.

[0092] This example discloses a preparation method of a modified curing agent, including the following steps:

[0093] S1: Add 2.84 g of naringenin and 1.77 g of p-aminobenzohydrazide into a container, add 20 mL of ethanol and 20 mL of acetic acid, stir and mix them, then heat under reflux at 110 °C for 12 h. After the reflux ends, elute and separate to obtain the derivative;

[0094] S2: Add 1.17 g of the derivative and 0.93 g of triethylamine into a container filled with 100 mL of tetrahydrofuran, under nitrogen protection, transfer it to a container equipped with a reflux condenser and a magnetic stirrer. During the low-temperature stirring at 0 °C, dropwise add 1.7 g of chlorodiphenylphosphine over 30 min. After the addition is completed, heat in an oil bath at 70 °C for 8 h. After heating is completed, cool to room temperature, filter by suction, rotary evaporate, concentrate, dissolve in dichloromethane, wash 5 times with deionized water, dry with anhydrous magnesium sulfate, rotary evaporate and concentrate, and vacuum dry at 70 °C for 24 h to obtain the solid auxiliary agent;

[0095] S3: Dissolve 4 g of the solid auxiliary agent in 20 mL of dichloromethane, then mix it with 115 g of phenolic epoxy resin to obtain a mixture. After vacuum drying at 50 °C for 12 h, mix the mixture with 26 g of 4,4'-diaminodiphenylmethane and perform degassing treatment to obtain the modified curing agent.

[0096] This example discloses a resource treatment method for copper-containing sludge, including the following steps:

[0097] Step (1): Crush, grind, and screen the copper-containing sludge to obtain the pretreated sludge;

[0098] Step (2): Mix the pretreated sludge, organic leaching agent, and water, heat and stir to obtain the leachate and solid residue. Wash the solid residue with distilled water, and after mixing the washing liquid and the leachate, obtain the mixed liquid;

[0099] Step (3): Perform chemical precipitation treatment on the mixed liquid, use sodium hydroxide and lime milk as precipitants, stir, separate the solid and liquid, and dry to obtain copper salts;

[0100] Step (4): Mix the modified curing agent with the washed solid residue, stir evenly, and then cure. The curing process is: heat and cure at 120 °C and 150 °C for 2 h respectively to obtain the cured body.

[0101] Comparative Example 1: Compared with Example 1, in the preparation process of the organic leaching agent in Comparative Example 1, hydroxylamine hydrochloride is not added, and other conditions remain unchanged.

[0102] Comparative Example 2: Compared with Example 1, in the preparation process of the modified curing agent in Comparative Example 2, naringenin is not added, and other conditions remain unchanged.

[0103] Comparative Example 3: Compared with Example 1, in the resource treatment process of copper-containing sludge in Comparative Example 3, the organic leaching agent was replaced with hydrochloric acid, and other conditions remained unchanged.

[0104] Comparative Example 4: Compared with Example 1, in the resource treatment process of copper-containing sludge in Comparative Example 4, the modified curing agent was replaced with asphalt, and other conditions remained unchanged.

[0105] The copper content in the copper salt and the copper content in the copper-containing sludge were measured by chemical analysis method and spectral analysis method. According to the copper recovery rate = [(total mass of copper salt × copper content in copper salt) / (total mass of copper-containing sludge × copper content in copper-containing sludge)]×100%, the hardness of the solidified body was tested according to GB / T 231.1-2018, and the combustion performance of the solidified body was tested according to GB 8624-2012. The test results are shown in Table 1:

[0106] Table 1

[0107]

[0108]

[0109] It can be seen from the test results in Table 1 that Examples 1-5 of the present invention have excellent recovery rates for copper in copper-containing sludge. By comparing Comparative Example 1 with Examples 1-5, it can be seen that adding hydroxylamine hydrochloride can improve the recovery rate of copper; by comparing Comparative Example 2 with Examples 1-5, it can be seen that adding naringenin can make the solidified body have excellent hardness and flame retardancy; by comparing Comparative Example 3 with Examples 1-5, it can be seen that the use of the organic leaching agent can improve the recovery rate of copper; by comparing Comparative Example 4 with Examples 1-5, it can be seen that the use of the modified curing agent can make the solidified body have excellent hardness and flame retardancy.

[0110] The above is only the preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

[0111] 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 present invention to only the specific embodiments. Obviously, many modifications and changes can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and utilize the present invention well. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A resource treatment method for copper-containing sludge, characterized in that, It includes the following steps: Step (1): Crush, grind and screen the copper-containing sludge to obtain pretreated sludge; Step (2): Mix the pretreated sludge, organic leaching agent and water, heat and stir to obtain leachate and solid residue. Wash the solid residue with distilled water, and after mixing the washing liquid and the leachate, obtain a mixed liquid; Step (3): Perform chemical precipitation treatment on the mixed liquid. Use sodium hydroxide and lime milk as precipitants, stir, separate solid and liquid, and dry to obtain copper salt; Step (4): Mix the modified curing agent with the washed solid residue, stir evenly, and then cure to obtain a cured body; Using methyl methacrylate, divinylbenzene, hydroxylamine hydrochloride and L-glutamic acid dimethyl ester hydrochloride as raw materials, prepare the organic leaching agent; Using naringenin, p-aminobenzohydrazide, chlorodiphenylphosphine, phenolic epoxy resin and 4,4'-diaminodiphenylmethane as raw materials, prepare the modified curing agent; In the said step (2), the preparation method of the organic leaching agent includes the following steps: Q1: Add methyl methacrylate and divinylbenzene into a container, stir and mix, then add benzoyl peroxide. After dissolution, add paraffin and toluene, stir well. Subsequently, add a polyvinyl alcohol solution and calcium phosphate into the container. Under nitrogen protection, heat in a water bath, then add sodium chloride for accelerated stirring, heat and react. After the reaction is completed, filter, perform Soxhlet extraction, soak, filter, and wash to obtain composite resin beads; Q2: Add hydroxylamine hydrochloride and sodium hydroxide into a container filled with distilled water in sequence, react in an ice bath. After sufficient reaction, add L-glutamic acid dimethyl ester hydrochloride, heat and react. After the reaction is completed, cool to room temperature, adjust the pH, and perform recrystallization to obtain modified hydroxamic acid; Q3: Add the composite resin beads into ethanol for swelling. After swelling, pour them into a container containing ethanol, distilled water and sodium hydroxide. Under heating reaction conditions, add the modified hydroxamic acid into the container. After the reaction is completed, filter, wash, and dry in vacuo to obtain the organic leaching agent; The preparation method of the modified curing agent includes the following steps: S1: Add naringenin and p-aminobenzohydrazide into a container, add ethanol and acetic acid, stir and mix, then heat under reflux. After the reflux is completed, elute and separate to obtain a derivative; S2: Add the derivative and triethylamine into a container filled with tetrahydrofuran. Under nitrogen protection, transfer it to a container equipped with a reflux condenser and a magnetic stirrer. During low-temperature stirring, dropwise add chlorodiphenylphosphine. After the addition is completed, heat in an oil bath. After heating is completed, cool to room temperature, perform suction filtration, rotary evaporation, concentration, dissolve in dichloromethane, wash, dry, rotary evaporate and concentrate, and dry in vacuo to obtain a solid auxiliary agent; S3: Dissolve the solid auxiliary agent in dichloromethane and then mix it with phenolic epoxy resin to obtain a mixture. After drying in vacuo, mix the mixture with 4,4'-diaminodiphenylmethane, and perform degassing treatment to obtain the modified curing agent.

2. The resource treatment method of copper-containing sludge according to claim 1, characterized in that, In Q1, the dosage ratio of methyl methacrylate, divinylbenzene, benzoyl peroxide, paraffin, toluene, polyvinyl alcohol solution, calcium phosphate and sodium chloride is (10 - 12) g : (2.4 - 2.88) g : (0.2 - 0.24) g : (0.1 - 0.12) g : (0.01 - 0.012) mL : (70 - 84) mL : (1 - 1.2) g : (2 - 2.4) g. The water bath heating temperature is 70 - 75 °C, the water bath heating time is 1 - 2 h, the heating reaction temperature is 80 - 85 °C, the time is 6 - 8 h. During the Soxhlet extraction process, petroleum ether is used for extraction for 6 - 8 h, ethanol is used for soaking, and distilled water is used for washing.

3. The resource treatment method of copper-containing sludge according to claim 1, characterized in that, In Q2, the dosage ratio of hydroxylamine hydrochloride, sodium hydroxide, distilled water and L-glutamate dimethyl ester hydrochloride is (27.8 - 30.58) g : (33.33 - 33.66) g : (100 - 110) mL : (21.16 - 23.28) g. The ice bath reaction time is 1 - 2 h, the heating reaction temperature is 50 - 55 °C, the time is 8 - 10 h, and 0.5 mol / L hydrochloric acid is used to adjust the pH to 4.8 - 5.

2.

4. The resource treatment method of copper-containing sludge according to claim 1, characterized in that In Q3, the dosage ratio of the composite resin beads, ethanol added after swelling, distilled water, sodium hydroxide and modified hydroxamic acid is (10 - 13) g : (80 - 104) mL : (20 - 26) mL : (8.8 - 11.44) g : (8.4 - 10.92) g. The swelling time is 20 - 24 h, the heating reaction temperature is 60 - 70 °C, the time is 10 - 12 h. It is washed with ethanol and distilled water until neutral, and the vacuum drying temperature is 50 - 60 °C, the time is 20 - 24 h.

5. The resource treatment method of copper-containing sludge according to claim 1, wherein In S1, the molar ratio of naringenin and p-aminobenzohydrazide is (1 - 2) : (1.1 - 2.1), the heating reflux temperature is 110 - 120 °C, and the reflux time is 8 - 12 h.

6. The resource treatment method of copper-containing sludge according to claim 1, characterized in that, In S2, the molar ratio of the derivative, triethylamine and chlorodiphenylphosphine is (1 - 2) : (3 - 6) : (3 - 5.8). The low-temperature stirring temperature is 0 - 1 °C, the dropping time is 30 - 45 min, the oil bath heating temperature is 60 - 80 °C, the time is 6 - 8 h. It is washed with deionized water 3 - 5 times, dried with anhydrous magnesium sulfate, and the vacuum drying temperature is 60 - 80 °C, the time is 20 - 24 h.

7. The resource treatment method of copper-containing sludge according to claim 1, characterized in that, In S3, the dosage ratio of the solid auxiliary, phenolic epoxy resin and 4,4'-diaminodiphenylmethane is (1 - 5) g : (100 - 120) g : (25 - 30) g. The vacuum drying temperature is 40 - 50 °C, the time is 10 - 12 h.

8. The resource treatment method of copper-containing sludge according to claim 1, characterized in that In step (4), the curing process is: heating and curing at 120 °C and 150 °C for 2 - 3 h respectively.

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