CN111672487B - Selective heavy metal ion adsorption material and preparation method and application thereof - Google Patents

Selective heavy metal ion adsorption material and preparation method and application thereof Download PDF

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CN111672487B
CN111672487B CN202010574444.1A CN202010574444A CN111672487B CN 111672487 B CN111672487 B CN 111672487B CN 202010574444 A CN202010574444 A CN 202010574444A CN 111672487 B CN111672487 B CN 111672487B
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sulfur
polyacrylonitrile
copper
metal ion
heavy metal
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CN111672487A (en
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李鹏
王立章
徐桂银
蒋海斌
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China University of Mining and Technology CUMT
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
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    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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    • Y02P10/00—Technologies related to metal processing
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Abstract

The invention discloses a polyacrylonitrile-sulfur @ melamine sponge as a selective heavy metal ion adsorbing material, which is prepared by forming a polyacrylonitrile-sulfur polymer through high-temperature polymerization reaction of polyacrylonitrile and sulfur and fixing the polyacrylonitrile-sulfur in a framework structure of the melamine sponge through a hot solvent bonding method. The polyacrylonitrile-sulfur @ melamine sponge has selective adsorption, the copper removal rate of the copper-containing wastewater is high, the copper-containing wastewater, a cathode and an anode and an electrolyte solution form an electrolytic cell, copper-sulfur high-efficiency separation is carried out through electrochemical anodic oxidation reaction, an adsorption material is regenerated, and copper is deposited and recovered through cathodic reduction reaction. The method realizes green, efficient and low-cost standard treatment and resource recovery of copper in the copper-containing wastewater, and has the advantages of wide sources of preparation raw materials, low price, easy obtainment, simple preparation process and convenient large-scale production.

Description

Selective heavy metal ion adsorption material and preparation method and application thereof
Technical Field
The invention relates to a heavy metal ion adsorbing material, in particular to a selective heavy metal ion adsorbing material and a preparation method and application thereof.
Background
With the rapid development of economic society and industry, more and more heavy metals enter the environment along with industrial wastewater, and the wastewater has serious threats to ecological environment and human health. Copper-containing wastewater is one of the most important heavy metal wastewater, mainly comes from copper ore mining and dressing and smelting processes, and in China, the mining amount of copper is increased from 890000t in 2009 to 1600000t in 2019, while the hydrometallurgical process inevitably causes the problems of surface and underground water pollution at the periphery of the copper ore location and the like. In addition, copper-containing wastewater is also generated in the industries of electroplating, spraying, electronic device processing, battery manufacturing and treatment, electronic waste treatment, and the like. The treatment of various copper-containing waste water is always a research hotspot in the field of environmental protection.
Take copper-containing waste water generated in copper mining and dressing and smelting of copper mines as an example. The copper-containing wastewater is mainly from pit wastewater generated by copper mining and tailing wastewater generated by copper tailing heap leaching, the copper content of the tailing wastewater is low, the pH of the wastewater is neutral (6.5-7.5) due to dilution of surface water and environmental intervention, copper is precipitated, and the copper content in the wastewater can easily reach the surface water discharge limit (1.0 mg/L) after chemical precipitation or adsorption treatment. The pit wastewater has the characteristics of high copper content (30-80 mg/L) and low wastewater pH (2.0-5.0), and the removal and resource recovery of copper have obvious significance for environmental protection and resource recovery. Therefore, the treatment of copper-containing wastewater is aimed at not only the copper removal efficiency but also the resource recovery of copper.
At present, the treatment method of copper-containing wastewater mainly comprises a chemical precipitation method, an electrolysis method, an ion exchange method, an adsorption method and a biological treatment method. The sulfide precipitation method utilizes the characteristics of easy-to-change chemical state and easy-to-oxidize S2-group of sulfur-containing compound, and Cu with large ionic radius and small outer layer electron binding force 2+ 、Hg 2+ 、Pb 2+ Better affinity of plasma metal ions and is used for Cu 2+ 、Hg 2+ 、Pb 2+ And selectively removing the metal ions. However, inorganic sulfur-containing compounds (FeS or FeS) are now widely used x CeS) waste water metal ionStrong acid water environment is needed during the process of the seed adsorption, and H is generated 2 S, great potential safety hazards are brought to process operators; and the metal-containing sludge has high yield and strong metal-sulfur polarization coordination, so that the recovery of metals in the later period is very difficult. The polymer material adsorption method is widely used as a heavy metal ion adsorption material by taking advantage of the advantages of high porosity, large specific surface area and the like of a polymer material, but has problems of low adsorption capacity, difficulty in recycling adsorbed ions, preparation cost of the adsorption material and the like. The electrolytic method is a method of separating metal ions from a solution by causing a redox reaction in the vicinity of an electrode by an electrochemical method. The electrolytic method can reduce the use of chemical reagents and directly recover metallic copper, but the separated metallic ions are limited, and the electrode needs to be improved to improve the current efficiency and the recovery capability.
The organic sulfur-containing compound has high sulfur content and wide pH adaptation range, is easy to realize metal analysis and adsorption material regeneration, can be used for surface modification of a polymer adsorption material to increase adsorption capacity, and is combined with an electrolytic method to realize copper recovery. The precipitation method, the adsorption method and the electrolysis method are combined in a multi-element way, the defects of the precipitation method, the adsorption method and the electrolysis method are compensated by the advantages of various processes, the optimal combination is achieved, and the method has great scientific research and practical significance for realizing green, efficient and low-cost standard treatment, resource recovery and industrial application of the copper-containing wastewater.
Disclosure of Invention
The invention aims to provide a selective heavy metal ion adsorption material and a preparation method and application thereof. The adsorption material for adsorbing copper ions, the cathode and the anode and the electrolyte solution form an electrolytic cell, copper-sulfur high-efficiency separation is carried out through electrochemical anodic oxidation reaction, the adsorption material is regenerated, copper deposition is carried out through cathode reduction reaction, and green, high-efficiency and low-cost standard treatment and resource recovery of copper in the copper-containing wastewater are realized.
The purpose of the invention can be realized by the following technical scheme:
a selective heavy metal ion adsorption material takes MF with porous characteristics as a framework structure, and PAN with S surface modification is fixed on the framework structure to form PAN-S @ MF with adsorption active sites and micro-fine pore channels.
Wherein, the porous MF with large specific surface area is used as a skeleton structure to provide attachment sites for PAN-S, so that the attachment sites are fully dispersed to increase the contact area, and pore channels are provided for wastewater water flow to pass through so that the wastewater water flow is fully contacted with PAN-S to complete adsorption; PAN-S is immobilized on the framework structure as an adsorption active site.
Preferably, the content of the S element on the surface of PAN-S @ MF is 65-75%.
A preparation method of the selective heavy metal ion adsorption material comprises the following steps:
(1) PAN powder was mixed with S powder and thoroughly ground with a mortar to thoroughly mix them.
(2) And placing the ground mixed powder in a magnetic boat, and transferring the magnetic boat to an argon atmosphere furnace for high-temperature treatment.
(3) The PAN-S particles obtained were sufficiently ground with a mortar to be sufficiently dispersed.
(4) Mixing 1-methyl-2-pyrrolidone (NMP) and polyvinylidene fluoride (PVDF), and stirring at constant temperature.
(5) PAN-S powder was added to the above solution, and the mixture was stirred at room temperature.
(6) And soaking the dried MF in the obtained solution system, taking out the solution system, and drying the solution system in a forced air drying oven to obtain the PAN-S @ MF.
Preferably, the mass ratio of the PAN powder to the S powder in the step (1) is (3.5-4.5): 1.
preferably, the heat treatment procedure of the high-temperature treatment in the step (2) is 25-300 ℃, and the heating rate is 3 ℃/min; keeping the temperature at 300 ℃ for 10h; the temperature is reduced at a rate of 3 ℃/min to 25 ℃.
Preferably, in the step (5), the mass of the added PAN-S is 0.08-0.12 times of that of the NMP, and the stirring treatment time is 24h.
Preferably, the MF soaking time in the step (6) is 2min, the drying temperature is 80 ℃, and the drying time is 24h.
The application of the selective heavy metal ion adsorbing material comprises the following steps:
(1) And (2) placing the PAN-S @ MF in a reaction device, allowing the copper-containing wastewater to enter from the lower part of the reaction device, performing contact reaction with the PAN-S @ MF to complete adsorption of copper ions, and then allowing the copper-containing wastewater to flow out from the upper part of the reaction device.
(2) And (3) taking out the PAN-S @ MF which adsorbs the copper ions, and forming an electrolytic cell with the cathode and the anode and an electrolyte solution for regeneration of the adsorption material and recovery of copper.
Preferably, the reaction conditions in the step (1) are that the pH value of the solution is 3.0-5.0, and the reaction time is 40-320 s.
Preferably, in the step (2), the anode of the electrolytic cell is a graphite electrode, the cathode is a titanium plate, and the electrolyte is a nitric acid solution.
Compared with the prior art, the invention has the following beneficial effects:
1) Compared with a direct sulfide chemical precipitation method and an adsorption method, the selective heavy metal ion adsorption material PAN-S @ MF has strong selectivity and high copper removal efficiency. PAN-S selective adsorption of Cd 2+ 、Pd 2+ 、Hg 2+ 、Cu 2+ Especially for Cu 2+ Has obvious selective adsorption. After the PAN-S is fixed on the MF, the dispersibility and the surface contact area are increased, and the adsorption capacity of the PAN-S @ MF on copper can reach 5.1% of the surface element content. The copper-containing wastewater treated by PAN-S @ MF can reach a copper removal rate of more than 95%, and the concentration of copper ions in the treated solution is lower than 1.0mg/mL, so that the emission limit of drinking water is reached.
2) The selective heavy metal ion adsorption material PAN-S @ MF is applied to an electrolysis method, and meanwhile, in-situ regeneration of the adsorption material and recovery of elemental copper are realized. The content of copper element on the surface of PAN-S @ MF is only 0.1% after electrochemical analysis treatment, and copper deposition appears on the negative plate.
3) The selective heavy metal ion adsorbing material PAN-S @ MF has the advantages of wide sources of preparation raw materials, low price, easy obtainment, simple preparation process and convenience for large-scale production.
Drawings
FIG. 1 (a) shows the copper adsorption removal rate of PAN-S powder obtained in example 1 for copper-containing wastewater at different liquid phase pH.
FIG. 1 (b) shows the saturated adsorption capacity of PAN-S powder obtained in example 1 for copper in copper-containing wastewater at a liquid phase pH of 5.0.
FIG. 2 is a graph showing the copper selective adsorption of PAN-S powder obtained in example 1 in multi-metal ion wastewater.
FIG. 3 (a) is a photograph of PAN-S @ MF obtained in example 5.
FIG. 3 (b) is a scanning electron micrograph of PAN-S @ MF obtained in example 5.
FIG. 3 (c) is a partially enlarged scanning electron micrograph of PAN-S @ MF obtained in example 5.
FIG. 4 is a Mapping plot of the sulfur content of PAN-S @ MF obtained in example 5.
FIG. 5 (a) shows the copper adsorption removal rate of PAN-S @ MF obtained in example 5 on copper-containing wastewater under different liquid phase pH and different adsorption equilibrium time.
FIG. 5 (b) is the effluent Cu of PAN-S @ MF obtained in example 5 after treating copper-containing wastewater at different liquid phase pH values 2+ And (4) concentration.
FIG. 6 is the EDS photograph and copper content of the copper-containing wastewater treated by PAN-S @ MF in example 9.
FIG. 7 is an EDS photograph and copper content of PAN-S @ MF having adsorbed copper ions in example 9 after electrochemical analysis.
FIG. 8 (a) shows a titanium cathode plate before electrochemical analysis in example 9.
FIG. 8 (b) shows a titanium cathode plate after electrochemical desorption in example 9.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and examples, but the scope of the present invention is not limited thereto.
Examples 1-3 were PAN-S polymers prepared at different mass ratios of PAN to S.
High temperature polymerization to prepare PAN-S polymer: the white PAN powder and the yellow S powder are mixed and fully ground for 2 hours by using a mortar, so that the white PAN powder and the yellow S powder are fully mixed, and the full contact reaction of PAN and S in the high-temperature treatment process is guaranteed. And placing the ground mixed powder in a magnetic boat, and transferring the magnetic boat to an argon atmosphere furnace for high-temperature treatment. And (3) heat treatment procedure: the temperature is 25 to 300 ℃, and the heating rate is 3 ℃/min; keeping the temperature at 300 ℃ for 10h; 300-25 ℃, and the heating rate is 3 ℃/min. The PAN-S obtained after the heat treatment is black powder. Fully grinding for 30min by adopting a mortar to fully disperse the particles.
Examples 1 2 3
Mass ratio of PAN to S 4:1 3.5:1 4.5:1
Example 4
Adsorption characteristics of PAN-S to copper were tested. Simulated copper-containing wastewater is taken as a treatment object, and PAN-S obtained in example 1 is used for evaluating the adsorption characteristic of the simulated copper-containing wastewater on copper in the wastewater. 50mL of copper-containing wastewater was placed in a 250mL Erlenmeyer flask at room temperature (. About.20 ℃) in a water bath shaker, the amount of PAN-S added was 30.0mg, and the adsorption equilibrium time was 4h.
FIG. 1 (a) shows initial Cu 2+ The copper removal rate of PAN-S was found to be 50.0mg/L, and the pH of the liquid phase was 3.0,4.0, and 5.0, respectively. As the pH of the liquid phase is increased, the adsorption capacity of the PAN-S on copper in the wastewater is enhanced.
FIG. 1 (b) shows initial Cu 2+ Concentration of 0,1.0,2.0,4.0,5.0,10.0,20.0,50.0,100.0mg/L, liquid phase pH 5.0, copper removal of PAN-S. When the pH value of the liquid phase is 5.0, the saturated adsorption capacity of PAN-S on copper in the wastewater can reach 44.85mg/g, and the copper adsorption capacity is stronger.
Fig. 2 shows the removal rate of PAN-S for each metal when the initial concentration of each metal ion was 0.1mg/L and the pH of the liquid phase = 5.0. PAN-S vs. Fe 3+ 、Al 3+ 、Mg 2+ 、Ca 2+ Poor isoaffinity but for Cd 2+ 、Pd 2+ 、Hg 2+ And Cu 2+ The removal efficiency of (A) is 70.20%,97.36%,98.42% and 99.56% in this order, especially for Cu 2+ Has remarkable selective adsorption property.
Examples 5-7 PAN-S @ MF was prepared for different PAN-S loadings.
Preparation of PAN-S @ MF by hot solvent bonding: NMP and PVDF are mixed according to the mass ratio of 10 to 1, stirred at the constant temperature of 60 ℃ for 2.0h, added with PAN-S powder obtained in the embodiments 1-3, and stirred at room temperature for 24.0h for later use. Soaking the dried sponge in the obtained solution system for 2.0 min, and taking out. And (3) placing the sponge material in a drying box with air drying at 80 ℃ for drying treatment for 24.0h to obtain PAN-S @ MF.
Figure GDA0003746259250000051
Figure GDA0003746259250000061
FIG. 3 (a) is a photograph, FIG. 3 (b) is a scanning electron micrograph of PAN-S @ MF obtained in example 5, and FIG. 3 (c) is a partial enlarged view of the scanning electron micrograph of PAN-S @ MF obtained in example 5. The material maintains the porous characteristic of the sponge and provides a pore channel for the permeation of water flow. In addition, PVDF in the material bonds PAN-S into a porous block material which is fixed on a skeleton structure, and a large number of tiny PAN-S particles and tiny pore canals are formed. The abundant PAN-S polymer is Cu in water body 2+ Provides the active site.
FIG. 4 shows the sulfur content M of PAN-S @ MF obtained in example 5and (4) an apping element analysis diagram. The S element content on the surface of the alloy reaches up to 74 percent. Higher sulfur content can ensure Cu 2+ High-efficiency adsorption removal.
Example 8
Adsorption characteristics of PAN-S @ MF on copper were tested. Simulated copper-containing wastewater is taken as a treatment object, and PAN-S @ MF obtained in example 5 is used for evaluating the adsorption property of the copper-containing wastewater on copper in the wastewater. Adopting a self-made organic glass reaction device (with the size of 60.0mm, width of 20.0mm and height of 120.0 mm), carrying out copper-containing wastewater treatment under the condition of room temperature by adopting a circulating operation mode of lower water inlet and upper water outlet, and carrying out initial Cu 2+ Concentration 50.0mg/L, liquid phase pH =3.0,4.0,5.0, treated water amount 500.0mL.
FIG. 5 (a) shows the copper removal rate for different adsorption equilibrium times for copper-containing wastewater treatment. PAN-S @ MF has higher copper removal efficiency under different liquid phase pH conditions, and the copper removal efficiency is gradually increased along with the increase of pH. When the pH of the liquid phase is =3.0,4.0 and 5.0, the removal efficiency of copper in the wastewater is 95.22%,98.68% and 99.88% in sequence, the reaction time is short, and when the pH is 5.0, the copper can be removed by adsorption within 120 s.
FIG. 5 (b) shows Cu in the effluent after the copper-containing wastewater is treated at different liquid phase pH values 2+ And (4) concentration. When the pH of the liquid phase is =3.0,4.0 and 5.0, the concentration of copper ions in the treated effluent is less than 1.0mg/L, and the discharge limit of drinking water is reached.
Example 9
PAN-S @ MF is used for treating the copper-containing wastewater. The self-made organic glass reaction device (size: 60.0mm wide 20.0mm high 120.0 mm) is adopted, the PAN-S @ MF obtained in the example 5 is placed in the reaction device, the treatment of the copper-containing wastewater is carried out under the condition of room temperature in a circulating operation mode of lower water inlet and upper water outlet, and the initial Cu is obtained 2+ Concentration 50.0mg/L, pH =5.0 of the liquid phase, and treated water amount 500.0mL.
Taking a graphite electrode as an anode, a titanium plate as a cathode, electrolyte as 0.5mol/L nitric acid, and the size of the electrolytic cell is as follows: length 55.0mm, width 30.0mm, height 50.0mm; wherein the distance between the polar plates is 30.0mm, the PAN-S @ ML processed by the copper-containing wastewater is placed in the polar plates, the operating voltage is 5.0V, the time is 30min, and the adsorption material and the elemental copper are recovered.
FIG. 6 shows EDS photographs and copper contents of 500.0mL of copper-containing wastewater at a concentration of 50.0mg/L when PAN-S @ MF was at pH = 5.0. After the copper wastewater is treated, a large amount of copper is adsorbed and fixed on the sponge material and accounts for 5.1 percent of the surface element content.
FIG. 7 shows the EDS photograph and copper content of the copper ion-adsorbed PAN-S @ MF after electrochemical analysis. The surface copper content of the PAN-S @ ML after the copper adsorption treatment is extremely low (only 0.1 percent) after the electrochemical analysis treatment, and almost no copper exists, which indicates that the anodic oxidation mode can break S-Cu bonds formed by adsorption, and the analysis of the adsorbed copper on the PAN-S @ ML and the regeneration of the adsorption material are realized.
Fig. 8 (a) shows a titanium cathode plate before electrochemical analysis, and fig. 8 (b) shows a titanium cathode plate after electrochemical analysis. The cathode titanium plate is covered with a layer of yellow elemental copper, which shows that the copper ions resolved from PAN-S @ ML are reduced and deposited at the cathode and can be recycled.

Claims (10)

1. The selective heavy metal ion adsorption material is characterized in that melamine sponge with porous characteristic is used as a framework structure, polyacrylonitrile with sulfur surface modification is fixed on the framework structure, polyacrylonitrile-sulfur polymer is formed by utilizing high-temperature polymerization reaction of the polyacrylonitrile and sulfur, and the polyacrylonitrile-sulfur polymer is fixed in the framework structure of the melamine sponge through a hot solvent bonding method, so that the polyacrylonitrile-sulfur @ melamine sponge with adsorption active sites and micro-fine pores is formed.
2. The selective heavy metal ion adsorbing material as claimed in claim 1, wherein the sulfur element content on the surface of the polyacrylonitrile-sulfur @ melamine sponge is 65-75%.
3. The preparation method of the selective heavy metal ion adsorbing material as claimed in claim 1, characterized by comprising the following steps:
(1) Mixing polyacrylonitrile powder and sulfur powder, and fully grinding with a mortar to fully mix the polyacrylonitrile powder and the sulfur powder;
(2) Placing the ground mixed powder in a magnetic boat, and transferring the magnetic boat to an argon atmosphere furnace for high-temperature treatment;
(3) Fully grinding the obtained polyacrylonitrile-sulfur particles by using a mortar to fully disperse the polyacrylonitrile-sulfur particles;
(4) Mixing 1-methyl-2-pyrrolidone with polyvinylidene fluoride, and stirring at constant temperature;
(5) Adding polyacrylonitrile-sulfur powder into the solution, and stirring at room temperature;
(6) And soaking the dried melamine sponge in the obtained solution system, taking out the melamine sponge, and then placing the melamine sponge in a forced air drying oven for drying treatment to obtain the polyacrylonitrile-sulfur @ melamine sponge.
4. The preparation method of the selective heavy metal ion adsorbing material as claimed in claim 3, wherein the mass ratio of the polyacrylonitrile powder to the sulfur powder in the step (1) is (3.5-4.5): 1.
5. the preparation method of the selective heavy metal ion adsorbing material according to claim 3, wherein the heat treatment procedure of the high-temperature treatment in the step (2) is 25-300 ℃, and the temperature rise rate is 3 ℃/min; keeping the temperature at 300 ℃ for 10h; the temperature is 300-25 ℃, and the cooling rate is 3 ℃/min.
6. The preparation method of the selective heavy metal ion adsorbing material as claimed in claim 3, wherein the mass of polyacrylonitrile-sulfur added in the step (5) is 0.08-0.12 times of the mass of 1-methyl-2-pyrrolidone, and the stirring treatment time is 24h.
7. The preparation method of the selective heavy metal ion adsorbing material as claimed in claim 3, wherein the soaking time of the melamine sponge in the step (6) is 2min, the drying temperature is 80 ℃, and the drying time is 24h.
8. The use of a selective heavy metal ion adsorbent material according to claim 1, comprising the steps of:
(1) Placing polyacrylonitrile-sulfur @ melamine sponge in a reaction device, wherein copper-containing wastewater enters from the lower part of the reaction device, is in contact reaction with the polyacrylonitrile-sulfur @ melamine sponge to complete the adsorption of copper ions, and then flows out from the upper part of the reaction device;
(2) And (3) taking out the polyacrylonitrile-sulfur @ melamine sponge which adsorbs copper ions, and forming an electrolytic cell with a cathode and an anode and an electrolyte solution for regeneration of an adsorption material and recovery of copper.
9. The use of a selective heavy metal ion adsorbent according to claim 8, wherein in step (1), the reaction conditions are a solution pH of 3.0-5.0 and a reaction time of 40-320 s.
10. The application of the selective heavy metal ion adsorbing material as claimed in claim 8, wherein in the step (2), the anode of the electrolytic cell is a graphite electrode, the cathode of the electrolytic cell is a titanium plate, and the electrolyte is a nitric acid solution.
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