Recycling treatment method of copper-containing sludge

Abstract

The invention discloses a resourceful treatment method for copper-containing sludge, and belongs to the technical field of resource recovery. The resourceful treatment method of the copper-containing sludge comprises the following steps: (1) crushing, grinding and sieving the copper-containing sludge to obtain pretreated sludge; (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 by using distilled water, and mixing a washing solution and the leaching solution to obtain a mixed solution; (3) carrying out chemical precipitation treatment on the mixed solution, stirring by using sodium hydroxide and lime milk as precipitants, carrying out solid-liquid separation, and drying to obtain copper salt; and (4) mixing a modified curing agent with the washed solid residues, uniformly stirring, and curing to obtain a cured body. The method can be used for effectively treating the copper-containing sludge and improving the recovery rate of copper.

Description

Technical Field

[0001] The invention belongs to the technical field of resource recovery, and in particular relates to a resource treatment method for 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 is generated. These sludges are solid wastes from the industrial production process, which contain high concentrations of copper and other heavy metal elements. If these heavy metals are not properly handled, they will not only seriously pollute the environment, but also cause long-term harm to the ecosystem. At the same time, since copper, as an important strategic resource, has a wide range of application value in industrial production, the treatment and resource utilization of copper-containing sludge has attracted widespread attention.

[0003] Through refining technology, valuable metal elements such as copper in 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, 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 are used to recover elemental copper or copper salts. Among them, solvent extraction has quickly occupied an important position in the field of sludge treatment due to its advantages of environmental protection and rapidity.

[0004] Patent CN 117987648 A discloses a resource treatment method for copper-containing sludge smelting slag, wherein 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 an alkaline regulator by dry weight to obtain a batch material; the batch material and a reducing agent are added to a smelting furnace for smelting to obtain a melt and molten iron; the melt is fiberized to obtain cotton fibers. This invention utilizes coal gangue, dolomite, etc. to synergistically melt and produce rock wool with copper-containing sludge smelting slag, thereby realizing the high-value utilization of copper-containing sludge smelting slag. However, there is still room for improvement in the recovery rate of copper. Summary of the invention

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

[0006] In order to achieve the above object, 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): mixing the pretreated sludge, the organic leaching agent and water, heating and stirring to obtain a leachate and a solid residue, washing the solid residue with distilled water, and mixing the washing liquid and the leachate to obtain a mixed liquid;

[0010] Step (3): subjecting the mixed solution to chemical precipitation treatment, using sodium hydroxide and lime milk as precipitants, stirring, solid-liquid separation, and drying to obtain copper salt;

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

[0012] Preferably, in step (2), the method for preparing the organic leaching agent comprises the following steps:

[0013] Q1: Add methyl methacrylate and divinylbenzene to a container, stir and mix, then add benzoyl peroxide, after dissolving, add paraffin and toluene, stir thoroughly, then add polyvinyl alcohol solution and calcium phosphate to the container, heat in a water bath under nitrogen protection, then add sodium chloride to accelerate stirring, heat to react, filter after the reaction is completed, extract with Soxhlet, soak, filter, wash, and obtain composite resin beads;

[0014] Q2: Hydroxylamine hydrochloride and sodium hydroxide are added to a container filled with distilled water in sequence, reacted in an ice bath, and after sufficient reaction, L-glutamic acid dimethyl ester hydrochloride is added, heated to react, and after the reaction is completed, cooled to room temperature, the pH is adjusted, and recrystallized to obtain modified hydroxamic acid;

[0015] Q3: Add the composite resin beads into ethanol for swelling, and then 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 vacuum dry to obtain an organic leachant.

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

[0017] Preferably, 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, and petroleum ether is used for extraction for 6-8 h during Soxhlet extraction, ethanol is used for soaking, and distilled water is used for washing.

[0018] Preferably, 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 the pH is adjusted to 4.8-5.2 with 0.5 mol / L hydrochloric acid.

[0019] Preferably, in Q3, the ratio of the amount of the composite resin beads, the ethanol added after swelling, the distilled water, the sodium hydroxide and the 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, the mixture is washed with ethanol and distilled water until it is neutral, and the vacuum drying temperature is 50-60°C, and the time is 20-24 h.

[0020] Preferably, the method for preparing the modified curing agent comprises the following steps:

[0021] S1: adding naringenin and p-aminobenzoic acid hydrazide into a container, adding ethanol and acetic acid, stirring and mixing, heating to reflux, and eluting and separating after the reflux to obtain a derivative;

[0022] S2: Add the derivative and triethylamine to a container containing tetrahydrofuran, transfer to a container containing a reflux condenser and a magnetic stirrer under nitrogen protection, add chlorodiphenylphosphine dropwise during low-temperature stirring, heat in an oil bath after the addition is complete, cool to room temperature, filter, rotary evaporate, concentrate, dissolve in dichloromethane, wash, dry, rotary evaporate and concentrate, and vacuum dry to obtain a solid auxiliary agent;

[0023] S3: dissolving a solid auxiliary agent in dichloromethane and mixing the mixture with a phenolic epoxy resin to obtain a mixture, vacuum drying the mixture and mixing it with 4,4'-diaminodiphenylmethane, performing a degassing treatment, and obtaining a modified curing agent.

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

[0025]

[0026] The results of mass spectrometry analysis of the derivatives were: 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 auxiliary agent were: 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 S1, the molar ratio of naringenin to p-aminobenzoic acid hydrazide 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 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 dropwise addition time is 30-45min, the oil bath heating temperature is 60-80°C, the time is 6-8h, washed with deionized water 3-5 times, dried with anhydrous magnesium sulfate, and the vacuum drying temperature is 60-80°C for 20-24h.

[0029] Preferably, in S3, the usage ratio of the solid auxiliary agent, the 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, and the time is 10-12 h.

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

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

[0032] 1. The present invention first uses methyl methacrylate, divinylbenzene, hydroxylamine hydrochloride and L-glutamic acid dimethyl ester hydrochloride as raw materials to prepare an organic leaching agent, and then uses naringenin 、The modified curing agent is prepared by using p-aminobenzoic acid hydrazide and chlorodiphenylphosphine as raw materials. The recovery rate of copper can be effectively improved by adding an organic leaching agent to the pretreated sludge. The modified curing agent is added to the solid residue of the copper-containing sludge, so that the obtained solidified body has excellent mechanical properties and flame retardant properties, thereby improving the service life of the solidified body.

[0033] 2. The present invention uses methyl methacrylate, divinylbenzene, hydroxylamine hydrochloride and L-glutamic acid dimethyl ester hydrochloride as raw materials to prepare an organic leaching agent. The hydroxylamine group in the organic leaching agent can coordinate with the copper ions in the sludge to form a stable complex. The strong coordination ability and selectivity of the hydroxylamine group enable the organic leaching agent to efficiently adsorb the 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 、 The modified curing agent is prepared by using p-aminobenzoyl hydrazide and chlorodiphenylphosphine as raw materials. The functional groups in the solid auxiliary agent react with the phenolic epoxy resin and 4,4'-diaminodiphenylmethane to form a large number of cross-linking points, thereby increasing the cross-linking density of the cured body. The increase in the cross-linking density makes the cured body denser and tougher, and improves its mechanical properties. The introduction of the derivatives and chlorodiphenylphosphine increases the rigidity of the molecular chain of the cured body, making the cured body less likely to deform and break when subjected to external forces. At the same time, the phosphorus element introduced into the solid auxiliary agent can form a phosphate compound with a flame retardant effect during the combustion process, which can cover the combustion surface, isolate oxygen and heat, slow down the combustion speed, and even extinguish the flame. The phosphorus element of chlorodiphenylphosphine can also capture the free radicals generated during the combustion process, interrupt the combustion chain reaction, and achieve the purpose of flame retardancy. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present invention are described clearly and completely below. 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.

[0036] Example 1: This example discloses a method for preparing an organic leaching agent, comprising the following steps:

[0037] Q1: 11g methyl methacrylate and 2.64g divinylbenzene were added to a container, stirred and mixed, and then 0.22g benzoyl peroxide was added. After dissolving, 0.11g paraffin and 0.011mL toluene were added, and the mixture was thoroughly stirred. Then 77mL polyvinyl alcohol solution and 1.1g calcium phosphate were added to the container, and heated in a 75°C water bath for 2h under nitrogen protection, and then 2.2g sodium chloride was added for accelerated stirring, and the mixture was heated at 85°C for 8h. After the reaction was completed, the mixture was filtered, extracted with petroleum ether for 8h, soaked with ethanol, filtered, and washed with distilled water to obtain composite resin beads;

[0038] Q2: 29.19 g of hydroxylamine hydrochloride and 33.5 g of sodium hydroxide were added to a container containing 105 mL of distilled water in sequence, and the mixture was reacted in an ice bath for 2 h. After sufficient reaction, 22.22 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;

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

[0040] This embodiment discloses a method for preparing a modified curing agent, comprising the following steps:

[0041] S1: 2.46 g of naringenin and 1.45 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 and mixing, the mixture was heated to reflux at 110° C. for 12 h. After the reflux was completed, the mixture was eluted and separated to obtain a derivative;

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

[0043] S3: 3 g of a solid auxiliary agent was dissolved in 20 mL of dichloromethane and mixed with 110 g of a phenolic epoxy resin to obtain a mixture. The mixture was vacuum dried at 50° C. for 12 h and then mixed with 27.5 g of 4,4′-diaminodiphenylmethane and subjected to degassing to obtain a modified curing agent.

[0044] This embodiment discloses a method for recycling copper-containing sludge, comprising the following steps:

[0045] Step (1): crushing, grinding and sieving the copper-containing sludge to obtain pretreated sludge;

[0046] Step (2): mixing the pretreated sludge, the organic leaching agent and water, heating and stirring to obtain a leachate and a solid residue, washing the solid residue with distilled water, and mixing the washing liquid and the leachate to obtain a mixed liquid;

[0047] Step (3): subjecting the mixed solution to chemical precipitation treatment, using sodium hydroxide and lime milk as precipitants, stirring, solid-liquid separation, and drying to obtain copper salt;

[0048] 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 hours respectively to obtain a cured product.

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

[0050] Q1: 10g methyl methacrylate and 2.88g divinylbenzene were added to a container, stirred and mixed, and then 0.24g benzoyl peroxide was added. After dissolving, 0.1g paraffin and 0.01mL toluene were added, and the mixture was thoroughly stirred. Then 84mL polyvinyl alcohol solution and 1g calcium phosphate were added to the container, and heated in a 75°C water bath for 2h under nitrogen protection, and then 2g sodium chloride was added to accelerate stirring, and the mixture was heated at 85°C for 8h. After the reaction was completed, the mixture was filtered, extracted with petroleum ether for 8h, soaked with ethanol, filtered, and washed with distilled water to obtain composite resin beads;

[0051] Q2: 27.8 g of hydroxylamine hydrochloride and 33.33 g of sodium hydroxide were added to a container containing 110 mL of distilled water in sequence, and reacted in an ice bath for 2 h. After sufficient reaction, 23.28 g of L-glutamic acid dimethyl ester hydrochloride was added, and the reaction was heated at 55 ° C for 10 h. After the reaction was completed, it was cooled to room temperature, and the pH was adjusted to 4.8 with 0.5 mol / L hydrochloric acid, and recrystallized to obtain modified hydroxamic acid;

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

[0053] This embodiment discloses a method for preparing a modified curing agent, comprising the following steps:

[0054] S1: 1.64 g of naringenin and 1.91 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 and mixing, the mixture was heated to reflux at 110° C. for 12 h. After the reflux was completed, the mixture was eluted and separated to obtain a derivative;

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

[0056] S3: 1 g of a solid auxiliary agent was dissolved in 20 mL of dichloromethane and mixed with 100 g of a phenolic epoxy resin to obtain a mixture. The mixture was vacuum dried at 50° C. for 12 h and then mixed with 25 g of 4,4′-diaminodiphenylmethane and subjected to a degassing treatment to obtain a modified curing agent.

[0057] This embodiment discloses a method for recycling copper-containing sludge, comprising the following steps:

[0058] Step (1): crushing, grinding and sieving the copper-containing sludge to obtain pretreated sludge;

[0059] Step (2): mixing the pretreated sludge, the organic leaching agent and water, heating and stirring to obtain a leachate and a solid residue, washing the solid residue with distilled water, and mixing the washing liquid and the leachate to obtain a mixed liquid;

[0060] Step (3): subjecting the mixed solution to chemical precipitation treatment, using sodium hydroxide and lime milk as precipitants, stirring, solid-liquid separation, and drying to obtain copper salt;

[0061] 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 hours respectively to obtain a cured product.

[0062] Example 3: This example discloses a method for preparing an organic leaching agent, comprising the following steps:

[0063] Q1: 12g of methyl methacrylate and 2.4g of divinylbenzene were added to a container, stirred and mixed, and then 0.2g of benzoyl peroxide was added. After dissolving, 0.12g of paraffin and 0.012mL of toluene were added, and the mixture was thoroughly stirred. Subsequently, 70mL of polyvinyl alcohol solution and 1.2g of calcium phosphate were added to the container, and heated in a 75°C water bath for 2h under nitrogen protection, and then 2.4g of sodium chloride was added for accelerated stirring, and the mixture was heated at 85°C for 8h. After the reaction was completed, the mixture was filtered, extracted with petroleum ether for 8h, soaked with ethanol, filtered, and washed with distilled water to obtain composite resin beads;

[0064] Q2: 30.58 g of hydroxylamine hydrochloride and 33.66 g of sodium hydroxide were added to a container containing 100 mL of distilled water in sequence, and reacted in an ice bath for 2 h. After sufficient reaction, 21.16 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;

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

[0066] This embodiment discloses a method for preparing a modified curing agent, comprising the following steps:

[0067] S1: 3.28 g of naringenin and 1 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 and mixing, the mixture was heated to reflux at 110° C. for 12 h. After the reflux was completed, the mixture was eluted and separated to obtain a derivative;

[0068] S2: Add 1.3 g of the derivative and 0.5 g of triethylamine to a container containing 100 mL of tetrahydrofuran, transfer to a container containing a reflux condenser and a magnetic stirrer under nitrogen protection, and dropwise add 1.1 g of chlorodiphenylphosphine during stirring at 0°C for 30 min. After the dropwise addition is completed, heat in an oil bath at 70°C for 8 h. After the heating is completed, cool to room temperature, filter, rotary evaporate, concentrate, dissolve in dichloromethane, wash with deionized water 5 times, dry with anhydrous magnesium sulfate, rotary evaporate and concentrate, and vacuum dry at 70°C for 24 h to obtain a solid auxiliary agent;

[0069] S3: 5 g of a solid auxiliary agent was dissolved in 20 mL of dichloromethane and mixed with 120 g of a phenolic epoxy resin to obtain a mixture. The mixture was vacuum dried at 50° C. for 12 h and then mixed with 30 g of 4,4′-diaminodiphenylmethane and subjected to a degassing treatment to obtain a modified curing agent.

[0070] This embodiment discloses a method for recycling copper-containing sludge, comprising the following steps:

[0071] Step (1): crushing, grinding and sieving the copper-containing sludge to obtain pretreated sludge;

[0072] Step (2): mixing the pretreated sludge, the organic leaching agent and water, heating and stirring to obtain a leachate and a solid residue, washing the solid residue with distilled water, and mixing the washing liquid and the leachate to obtain a mixed liquid;

[0073] Step (3): subjecting the mixed solution to chemical precipitation treatment, using sodium hydroxide and lime milk as precipitants, stirring, solid-liquid separation, and drying to obtain copper salt;

[0074] 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 hours respectively to obtain a cured product.

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

[0076] Q1: 10.5g of methyl methacrylate and 2.52g of divinylbenzene were added to a container, stirred and mixed, and then 0.23g of benzoyl peroxide was added. After dissolving, 0.105g of paraffin and 0.011mL of toluene were added, and the mixture was thoroughly stirred. Subsequently, 72mL of polyvinyl alcohol solution and 1.05g of calcium phosphate were added to the container, and heated in a 75°C water bath for 2h under nitrogen protection, and then 2.1g of sodium chloride was added for accelerated stirring, and the mixture was heated at 85°C for 8h. After the reaction was completed, the mixture was filtered, extracted with petroleum ether for 8h, soaked with ethanol, filtered, and washed 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 to a container containing 102 mL of distilled water in sequence, and 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 reaction 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: Add 11g of composite resin beads to ethanol and swell for 24h. After swelling, pour into a container containing 85mL of ethanol, 22mL of distilled water and 9.2g of sodium hydroxide. Under heating reaction conditions at 70℃, add 9.2g of modified hydroxamic acid to the container. After reacting for 12h, filter, wash with ethanol and distilled water until neutral, and dry in vacuum at 60℃ for 24h 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 and mixing, the mixture was heated to reflux at 110° C. for 12 h. After the reflux was completed, the mixture was eluted and separated to obtain a derivative;

[0081] S2: Add 0.83g of the derivative and 0.58g of triethylamine to a container containing 100mL of tetrahydrofuran, transfer to a container containing a reflux condenser and a magnetic stirrer under nitrogen protection, and dropwise add 1.3g of chlorodiphenylphosphine during stirring at 0°C for 30min. After the dropwise addition is completed, heat in an oil bath at 70°C for 8h. After the heating is completed, cool to room temperature, filter, rotary evaporate, concentrate, dissolve in dichloromethane, wash with deionized water 5 times, dry with anhydrous magnesium sulfate, rotary evaporate and concentrate, and vacuum dry at 70°C for 24h to obtain a solid auxiliary agent;

[0082] S3: 2 g of a solid auxiliary agent was dissolved in 20 mL of dichloromethane and mixed with 105 g of a phenolic 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 subjected to a degassing treatment to obtain a modified curing agent.

[0083] This embodiment discloses a method for recycling 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): mixing the pretreated sludge, the organic leaching agent and water, heating and stirring to obtain a leachate and a solid residue, washing the solid residue with distilled water, and mixing the washing liquid and the leachate to obtain a mixed liquid;

[0086] Step (3): subjecting the mixed solution to chemical precipitation treatment, using sodium hydroxide and lime milk as precipitants, stirring, solid-liquid separation, and drying to obtain copper salt;

[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 hours respectively to obtain a cured product.

[0088] Example 5: This example discloses a method for preparing an organic leaching agent, comprising the following steps:

[0089] Q1: 11.5g of methyl methacrylate and 2.71g of divinylbenzene were added to a container, stirred and mixed, and then 0.21g of benzoyl peroxide was added. After dissolving, 0.115g of paraffin and 0.012mL of toluene were added, and the mixture was thoroughly stirred. Subsequently, 82mL of polyvinyl alcohol solution and 1.15g of calcium phosphate were added to the container, and heated in a 75°C water bath for 2h under nitrogen protection, and then 2.3g of sodium chloride was added for accelerated stirring, and the mixture was heated at 85°C for 8h. After the reaction was completed, the mixture was filtered, extracted with petroleum ether for 8h, soaked with ethanol, filtered, and washed with distilled water to obtain composite resin beads;

[0090] Q2: 29.85 g of hydroxylamine hydrochloride and 33.55 g of sodium hydroxide were added to a container containing 108 mL of distilled water in sequence, and the mixture was reacted in an ice bath for 2 h. After sufficient reaction, 22.95 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;

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

[0092] This embodiment discloses a method for preparing a modified curing agent, comprising the following steps:

[0093] S1: 2.84 g of naringenin and 1.77 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 and mixing, the mixture was heated to reflux at 110° C. for 12 h. After the reflux was completed, the mixture was eluted and separated to obtain a derivative;

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

[0095] S3: 4 g of a solid auxiliary agent was dissolved in 20 mL of dichloromethane and mixed with 115 g of a phenolic epoxy resin to obtain a mixture. The mixture was vacuum dried at 50° C. for 12 h and then mixed with 26 g of 4,4′-diaminodiphenylmethane and subjected to a degassing treatment to obtain a modified curing agent.

[0096] This embodiment discloses a method for recycling copper-containing sludge, comprising the following steps:

[0097] Step (1): crushing, grinding and sieving the copper-containing sludge to obtain pretreated sludge;

[0098] Step (2): mixing the pretreated sludge, the organic leaching agent and water, heating and stirring to obtain a leachate and a solid residue, washing the solid residue with distilled water, and mixing the washing liquid and the leachate to obtain a mixed liquid;

[0099] Step (3): subjecting the mixed solution to chemical precipitation treatment, using sodium hydroxide and lime milk as precipitants, stirring, solid-liquid separation, and drying to obtain copper salt;

[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 hours respectively to obtain a cured product.

[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 was not added, and other conditions remained unchanged.

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

[0104] Comparative Example 4: Compared with Example 1, in Comparative Example 4, during the resource recovery process of copper-containing sludge, the modified curing agent is replaced by asphalt, and other conditions remain unchanged.

[0105] The copper content in the copper salt and the copper content in the copper-containing sludge were measured by chemical analysis and spectral analysis. 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] From the test results in Table 1, it can be seen that Examples 1-5 of the present invention have excellent recovery rates for copper in copper-containing sludge. From the comparison between Comparative Example 1 and Examples 1-5, it can be seen that the addition of hydroxylamine hydrochloride can improve the recovery rate of copper; from the comparison between Comparative Example 2 and Examples 1-5, it can be seen that the addition of naringenin can make the solidified body have excellent hardness and flame retardancy; from the comparison between Comparative Example 3 and Examples 1-5, it can be seen that the use of an organic leaching agent can improve the recovery rate of copper; from the comparison between Comparative Example 4 and Examples 1-5, it can be seen that the use of a modified curing agent can make the solidified body have excellent hardness and flame retardancy.

[0110] 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.

[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 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 recycling copper-containing sludge, characterized in that: The following steps are involved: Step (1): crushing, grinding and sieving the copper-containing sludge to obtain pretreated sludge; Step (2): mixing the pretreated sludge, the organic leaching agent and water, heating and stirring to obtain a leachate and a solid residue, washing the solid residue with distilled water, and mixing the washing liquid and the leachate to obtain a mixed liquid; Step (3): subjecting the mixed solution to chemical precipitation treatment, using sodium hydroxide and lime milk as precipitants, stirring, solid-liquid separation, and drying to obtain copper salt; Step (4): mixing the modified curing agent with the washed solid residue, stirring them evenly, and curing them to obtain a cured product; The organic leaching agent is prepared using methyl methacrylate, divinylbenzene, hydroxylamine hydrochloride and L-glutamic acid dimethyl ester hydrochloride as raw materials; Naringenin 、 The modified curing agent is prepared by taking p-aminobenzoic acid hydrazide, chlorodiphenylphosphine, phenolic epoxy resin and 4,4'-diaminodiphenylmethane as raw materials.

2. The method for recycling copper-containing sludge according to claim 1, characterized in that: In the step (2), the method for preparing the organic leaching agent comprises the following steps: Q1: Add methyl methacrylate and divinylbenzene to a container, stir and mix, then add benzoyl peroxide, after dissolving, add paraffin and toluene, stir thoroughly, then add polyvinyl alcohol solution and calcium phosphate to the container, heat in a water bath under nitrogen protection, then add sodium chloride to accelerate stirring, heat to react, filter after the reaction is completed, extract with Soxhlet, soak, filter, wash, and obtain composite resin beads; Q2: Hydroxylamine hydrochloride and sodium hydroxide are added to a container filled with distilled water in sequence, reacted in an ice bath, and after sufficient reaction, L-glutamic acid dimethyl ester hydrochloride is added, heated to react, and after the reaction is completed, cooled to room temperature, the pH is adjusted, and recrystallized to obtain modified hydroxamic acid; Q3: Add the composite resin beads into ethanol for swelling, and then 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 vacuum dry to obtain an organic leachant.

3. The method for recycling copper-containing sludge according to claim 2, characterized in that: In the 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, petroleum ether is used for extraction for 6-8 h during Soxhlet extraction, ethanol is used for soaking, and distilled water is used for washing.

4. The method for recycling copper-containing sludge according to claim 2, characterized in that: In the Q2, the dosage ratio of hydroxylamine hydrochloride, sodium hydroxide, distilled water and L-glutamic acid 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 the pH is adjusted to 4.8-5.2 with 0.5 mol / L hydrochloric acid.

5. The method for recycling copper-containing sludge according to claim 2, characterized in that: In the Q3, the amount 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, and the product is washed with ethanol and distilled water until it is neutral. The vacuum drying temperature is 50-60°C, and the time is 20-24 h.

6. The method for recycling copper-containing sludge according to claim 1, characterized in that: The preparation method of the modified curing agent comprises the following steps: S1: adding naringenin and p-aminobenzoic acid hydrazide into a container, adding ethanol and acetic acid, stirring and mixing, heating to reflux, and eluting and separating after the reflux to obtain a derivative; S2: Add the derivative and triethylamine to a container containing tetrahydrofuran, transfer to a container containing a reflux condenser and a magnetic stirrer under nitrogen protection, add chlorodiphenylphosphine dropwise during low-temperature stirring, heat in an oil bath after the addition is complete, cool to room temperature, filter, rotary evaporate, concentrate, dissolve in dichloromethane, wash, dry, rotary evaporate and concentrate, and vacuum dry to obtain a solid auxiliary agent; S3: dissolving a solid auxiliary agent in dichloromethane and mixing the mixture with a phenolic epoxy resin to obtain a mixture, vacuum drying the mixture and mixing it with 4,4'-diaminodiphenylmethane, performing a degassing treatment, and obtaining a modified curing agent.

7. The method for recycling copper-containing sludge according to claim 6, characterized in that: In the S1, the molar ratio of naringenin to p-aminobenzoic acid hydrazide is (1-2): (1.1-2.1), the heating reflux temperature is 110-120° C., and the reflux time is 8-12 h.

8. The method for recycling copper-containing sludge according to claim 6, characterized in that: 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 dropwise addition time is 30-45min, the oil bath heating temperature is 60-80°C, the time is 6-8h, washed with deionized water 3-5 times, dried with anhydrous magnesium sulfate, and the vacuum drying temperature is 60-80°C for 20-24h.

9. The method for recycling copper-containing sludge according to claim 6, characterized in that: In S3, the usage ratio of the solid auxiliary agent, the 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., and the time is 10-12 h.

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

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