A method for the selective recovery of copper, lead and arsenic from acid mine drainage

Abstract

This invention discloses a method for selectively recovering copper, lead, and arsenic from acidic mining wastewater, comprising the following steps: 1) preparing iron-manganese oxides with strong stability under acidic conditions; 2) converting acidic mining wastewater containing copper, cadmium, lead, arsenic, and zinc into copper-cadmium-zinc enriched wastewater and lead-arsenic enriched iron-manganese oxides; 3) converting the lead-arsenic enriched iron-manganese oxides into a lead-containing solution and arsenic-enriched iron-manganese oxides; 4) converting the arsenic-enriched iron-manganese oxides into an arsenic-containing solution and arsenic-loaded iron-manganese oxides; 5) converting copper-cadmium-zinc enriched wastewater into cadmium-zinc enriched wastewater and copper-enriched iron-manganese oxides; 6) desorbing copper from the copper-enriched iron-manganese oxides to obtain a copper-containing solution. This invention can separately enrich and recover copper, lead, and arsenic from acidic mining wastewater, achieving the recovery and utilization of heavy metal resources while treating heavy metal-polluted wastewater, and has a very broad application prospect.

Description

Technical Field

[0001] This invention relates to the field of heavy metal polluted wastewater treatment technology, specifically to a method for selectively recovering copper, lead, and arsenic from acidic mining wastewater. Background Technology

[0002] During mining operations, large quantities of heavy metal-polluted wastewater containing toxic and harmful heavy metal ions such as copper, cadmium, lead, arsenic, and zinc are generated, making its treatment and disposal crucial. Currently, the commonly used method for treating heavy metal-polluted wastewater is adsorption, which effectively removes heavy metal ions from the wastewater and is simple to operate with low treatment costs. It is worth noting that the heavy metal ions in the wastewater are also a resource with significant application value. However, ordinary adsorption methods can only selectively separate one or a class of heavy metal ions in the wastewater and cannot simultaneously and selectively recover multiple heavy metal ions (anions and cations). This results in very limited recovery and utilization of heavy metal resources, leading to serious resource waste.

[0003] Therefore, developing a method for selectively recovering copper, lead, and arsenic from heavy metal-contaminated wastewater is of great significance. Summary of the Invention

[0004] The purpose of this invention is to provide a method for selectively recovering copper, lead and arsenic from acidic mine wastewater.

[0005] The technical solution adopted in this invention is:

[0006] A method for selectively recovering copper, lead, and arsenic from acidic mine wastewater includes the following steps:

[0007] 1) Disperse soluble permanganate in water, then add strong acid solution for acidification, then add ferrous salt solution for redox reaction, then add alkaline solution to adjust the pH of the system to 7-8 and stir to obtain stabilized iron-manganese oxide.

[0008] 2) Stabilized iron-manganese oxides were added to acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc for adsorption reaction, followed by solid-liquid separation to obtain wastewater enriched with copper-cadmium-zinc and iron-manganese oxides enriched with lead-arsenic, respectively.

[0009] 3) The lead- and arsenic-enriched iron-manganese oxides were added to an acid solution for desorption reaction, followed by solid-liquid separation to obtain a lead-containing solution and arsenic-enriched iron-manganese oxides, respectively.

[0010] 4) The arsenic-enriched iron-manganese oxides were added to an alkaline solution for desorption reaction, followed by solid-liquid separation to obtain an arsenic-containing solution and arsenic-loaded iron-manganese oxides, respectively.

[0011] 5) Arsenic-loaded iron-manganese oxides were added to copper-cadmium-zinc enriched wastewater for adsorption reaction, followed by solid-liquid separation to obtain cadmium-zinc enriched wastewater and copper-enriched iron-manganese oxides, respectively.

[0012] 6) Add copper-enriched iron-manganese oxides to an acid solution for desorption reaction, followed by solid-liquid separation to obtain a copper-containing solution.

[0013] Preferably, the soluble permanganate in step 1) is at least one of sodium permanganate, potassium permanganate, and calcium permanganate.

[0014] Preferably, the strong acid solution in step 1) is at least one of concentrated sulfuric acid and concentrated nitric acid.

[0015] Preferably, the pH of the solution after acidification in step 1) is <1.5.

[0016] Preferably, the ferrous salt in the ferrous salt solution in step 1) is at least one of ferrous sulfate, ferrous chloride, and ferrous nitrate.

[0017] Preferably, the molar ratio of ferrous salt in the soluble permanganate and ferrous salt solution in step 1) is 1:0.5 to 5.

[0018] Preferably, the redox reaction in step 1) is carried out at 20℃ to 60℃ for 20 min to 40 min.

[0019] Preferably, the alkaline solution in step 1) is at least one of sodium hydroxide solution, potassium hydroxide solution, and ammonia water.

[0020] Preferably, the stirring in step 1) is carried out at room temperature for 1 to 5 hours.

[0021] Preferably, the pH of the acidic mine wastewater containing copper, cadmium, lead, arsenic and zinc in step 2) is 2 to 3.

[0022] Preferably, the dosage of the stabilized iron-manganese oxide in step 2) in acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc is 0.01 g / L to 1 g / L.

[0023] Preferably, the adsorption reaction time in step 2) is 1h to 12h.

[0024] Preferably, the acid solution in step 3) is a nitric acid solution with a concentration of 0.01 mol / L to 1 mol / L.

[0025] Preferably, the amount of lead-arsenic enriched iron-manganese oxide added to the acid solution in step 3) is 0.01 g / L to 1 g / L.

[0026] Preferably, the desorption reaction in step 3) takes 1 to 12 hours.

[0027] Preferably, the alkaline solution in step 4) is a sodium hydroxide solution with a concentration of 0.01 mol / L to 0.05 mol / L.

[0028] Preferably, the amount of arsenic-enriched iron-manganese oxide added to the alkaline solution in step 4) is 0.01 g / L to 1 g / L.

[0029] Preferably, the desorption reaction in step 4) takes 1 to 12 hours.

[0030] Preferably, the dosage of the arsenic-loaded iron-manganese oxide in step 5) in the copper-cadmium-zinc enriched wastewater is 0.01 g / L to 1 g / L.

[0031] Preferably, the adsorption reaction time in step 5) is 1h to 12h.

[0032] Preferably, the acid solution in step 6) is a nitric acid solution with a concentration of 0.01 mol / L to 1 mol / L.

[0033] Preferably, the amount of copper-enriched iron-manganese oxide added to the acid solution in step 6) is 0.01 g / L to 1 g / L.

[0034] Preferably, the desorption reaction in step 6) takes 1 to 12 hours.

[0035] The beneficial effects of this invention are as follows: This invention utilizes the strong selectivity of stabilized iron-manganese oxide for arsenic and lead under acidic conditions to achieve selective adsorption of arsenic and lead ions, and utilizes different desorption solutions to achieve separate recovery of arsenic and lead ions. Moreover, while recovering arsenic, it also achieves in-situ utilization of arsenic ions, transforming some arsenic ions in the water into adsorption sites on the surface of iron-manganese oxide, endowing iron-manganese oxide with the ability to selectively separate copper ions under acidic conditions (the original iron-manganese oxide does not possess this ability). Ultimately, it achieves the effect of highly efficient and selective separation of copper, lead, and arsenic from acidic mining wastewater containing multiple heavy metal ions. It realizes the efficient recovery and utilization of heavy metal resources while treating heavy metal polluted wastewater, and has a very broad application prospect.

[0036] Specifically:

[0037] 1) This invention improves the stability of iron minerals in iron-manganese oxides under complex hydraulic and acidic conditions by regulating the morphology of iron minerals, thereby enabling efficient removal of heavy metals under acidic conditions.

[0038] 2) This invention utilizes the selectivity of stabilized iron and manganese oxides and their ability to simultaneously adsorb arsenic and lead ions to achieve selective enrichment and recovery of lead and arsenic ions in acidic mine wastewater. Furthermore, it utilizes the opposite charge properties of arsenic and lead ions to sequentially desorb them using different eluents, thereby achieving the purpose of separating lead and arsenic ions.

[0039] 3) This invention utilizes the characteristic that stabilized iron-manganese oxides adsorb arsenic ions. When recovering arsenic ions using alkaline solutions, a lower concentration of alkaline solution is selected so that some stable arsenate ions remain on the surface of the iron-manganese oxides. After treatment with a weak alkali, the stable arsenate ions can serve as sites for selectively adsorbing copper ions in acidic heavy metal wastewater. This endows the iron-manganese oxides with the ability to selectively adsorb copper ions in acidic heavy metal wastewater. Not only are copper ions selectively separated, but arsenic ions in acidic mining wastewater are also reduced and utilized. Resource reuse is directly achieved during the wastewater treatment process.

[0040] 4) This invention develops a method for efficiently recovering arsenic, lead, and copper from acidic mine wastewater containing multiple metals / metalloids by utilizing the selective adsorption characteristics of stabilized iron and manganese oxides, the adsorption and oxidation function of arsenic ions, and the precise use and control of different desorbents. Attached Figure Description

[0041] Figure 1 This is a process flow diagram of the method for selectively recovering copper, lead, and arsenic from acidic mine wastewater according to the present invention.

[0042] Figure 2 The images show the XRD patterns of the iron-manganese oxides in Example 1 and the comparative example.

[0043] Figure 3 The graph shows the sedimentation performance test results of iron and manganese oxides in Example 1 and the comparative example.

[0044] Figure 4 The graph shows the results of the copper ion adsorption capacity test for samples 1 to 4. Detailed Implementation

[0045] The present invention will be further explained and described below with reference to specific embodiments.

[0046] Example 1:

[0047] A method for selectively recovering copper, lead, and arsenic from acidic mine wastewater (process flow diagram shown) Figure 1 (As shown), it includes the following steps:

[0048] 1) Dissolve 0.79 g of potassium permanganate in 25 mL of deionized water, then add 0.05 mL of 90% concentrated sulfuric acid for acidification (the pH of the solution after acidification is <1.5). Then, add ferrous sulfate solution (prepared by 4.17 g of ferrous sulfate heptahydrate and 25 mL of deionized water) dropwise at 60 °C. After the addition is complete, stir at room temperature for 30 min. Then, add 3 mol / L sodium hydroxide solution to adjust the pH of the system to 7. Stir at room temperature for 3 h, filter, and place the filtered solid in an oven to dry at 60 °C for 24 h to obtain stabilized iron-manganese oxide.

[0049] 2) Stabilized iron-manganese oxide was added to acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc (simulated heavy metal polluted wastewater, the concentration of copper, cadmium, lead, arsenic and zinc is 1 ppm, and the pH value of the wastewater is 2.5). The dosage of stabilized iron-manganese oxide in acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc was 0.6 g / L. After 8 h of adsorption reaction, the mixture was filtered to obtain wastewater enriched with copper-cadmium-zinc and iron-manganese oxide enriched with lead-arsenic (selectivity for lead and arsenic >99%).

[0050] 3) The lead-arsenic-enriched iron-manganese oxide was added to a 0.1 mol / L nitric acid solution for a 12-hour desorption reaction. The dosage of the lead-arsenic-enriched iron-manganese oxide in the nitric acid solution was 1 g / L. After filtration, lead-containing solution (lead purity was 99.3%, lead recovery rate was 85.72%) and arsenic-enriched iron-manganese oxide were obtained respectively.

[0051] 4) The arsenic-enriched iron-manganese oxide was added to a 0.03 mol / L sodium hydroxide solution for a 12-hour desorption reaction. The amount of arsenic-enriched iron-manganese oxide added to the sodium hydroxide solution was 0.6 g / L. After filtration, arsenic-containing solution (arsenic purity was 99.2%, and arsenic recovery rate was 65.47%) and arsenic-loaded iron-manganese oxide were obtained respectively.

[0052] 5) Arsenic-loaded iron-manganese oxide was added to the copper-cadmium-zinc enriched wastewater for 12 hours for adsorption reaction. The dosage of arsenic-loaded iron-manganese oxide in the copper-cadmium-zinc enriched wastewater was 0.6 g / L. After filtration, cadmium-zinc enriched wastewater and copper-enriched iron-manganese oxide (selectivity for copper >98.8%) were obtained respectively.

[0053] 6) The copper-enriched iron-manganese oxide was added to a 0.05 mol / L nitric acid solution for a 12-hour desorption reaction, followed by filtration. The amount of copper-enriched iron-manganese oxide added to the nitric acid solution was 0.6 g / L, resulting in a copper-containing solution (copper purity was 98.2%, and copper recovery rate was 58.72%).

[0054] Comparative example:

[0055] An iron-manganese oxide, the preparation method of which includes the following steps:

[0056] Dissolve 0.79 g of potassium permanganate in 25 mL of deionized water by stirring. Then, add ferrous sulfate solution (prepared by 4.17 g of ferrous sulfate heptahydrate and 25 mL of deionized water) dropwise at 60 °C. After the addition is complete, stir at room temperature for 30 min. Then, add sodium hydroxide solution with a concentration of 3 mol / L to adjust the pH of the system to 7. Stir at room temperature for 3 h, filter, and place the filtered solid in an oven to dry at 60 °C for 24 h to obtain iron-manganese oxide.

[0057] Performance testing:

[0058] 1) X-ray diffraction (XRD) patterns of iron-manganese oxides in Example 1 and the comparative example are shown below. Figure 2 As shown.

[0059] Depend on Figure 2 It can be seen that the iron-manganese oxide in Example 1 showed the characteristic peak of goethite at the position of 21.6°, indicating that the morphology of the iron mineral changed from ferrohydrate to goethite, which has better reaction stability, while the iron-manganese oxide in the comparative example has ferrohydrate as the main structure.

[0060] 2) The iron-manganese oxides from Example 1 and the comparative example were added to acidic wastewater with a pH of 2.5 and stirred for 4 hours. The sedimentation performance of the obtained iron-manganese oxides was tested as follows: Figure 3 As shown in the table below, the results of the iron leaching test are as follows:

[0061] Table 1 Results of iron leaching test

[0062] Test Project Iron leaching amount (mg / g) Comparative Example 9.13 Example 1 4.33

[0063] Depend on Figure 3 As shown in Table 1, the amount of iron leached from the stabilized iron-manganese oxide in Example 1 is significantly lower than that in the comparative example. Furthermore, the stabilized iron-manganese oxide in Example 1 basically completes sedimentation within 10 minutes of reaction, while the iron-manganese oxide in the comparative example remains suspended on the liquid surface 1 hour after the reaction ends. This indicates that the stabilized iron-manganese oxide in Example 1 is more suitable for reaction under acidic conditions and has better reaction stability and sedimentation performance.

[0064] 3) The stabilized iron-manganese oxide from Example 1 (referred to as Sample 1) was added to 100 mL of a 10 mol / L trivalent arsenic solution at a dosage of 0.1 g / L. The reaction was carried out for 4 h, followed by washing and drying to obtain arsenic-loaded iron-manganese oxide (referred to as Sample 2). Sample 2 was then added to 100 mL of a 0.03 mol / L sodium hydroxide solution and a 0.3 mol / L sodium hydroxide solution at a dosage of 0.1 g / L, respectively, and the reactions were carried out for 4 h (arsenic recovery) to obtain Sample 3 and Sample 4. Samples 1-4 were then added to 100 mL of a 10 mg / L copper solution (pH = 5) at a dosage of 0.1 g / L, respectively. The copper ion adsorption capacity of each sample was tested, and the test results are as follows: Figure 4 As shown.

[0065] Depend on Figure 4 It can be known that:

[0066] a) The adsorption capacity of stabilized iron-manganese oxide for copper ions after reaction with trivalent arsenic increased from 13.61 mg / g to 18.32 mg / g;

[0067] b) From the results of samples 3 and 4, it can be found that sample 3 combines the alkalization effect of alkaline solution and the effect of arsenic, and the adsorption capacity is increased to 32.68 mg / g, while sample 4, due to the use of excessive sodium hydroxide, has a lower adsorption capacity of 25.66 mg / g compared with sample 3.

[0068] In summary, arsenic can serve as an adsorption site for iron-manganese oxides, promoting the removal of copper ions. Furthermore, the alkalization effect of alkaline solutions can further enhance the adsorption performance of copper ions while recovering arsenic. However, excessive desorbent (sodium hydroxide) can cause arsenic to dissolve from the surface of iron-manganese oxides, thereby weakening the adsorption capacity of arsenic-loaded iron-manganese oxides for copper ions. The above experiments confirm that arsenic can be utilized in situ by iron-manganese oxides during the treatment of acidic wastewater to promote the separation of copper ions. Precise control of the amount of alkaline solution is also crucial (excessive alkali will weaken the adsorption capacity of arsenic-loaded iron-manganese oxides).

[0069] 4) 0.05 g of the iron-manganese oxide from Example 1 was added to 100 mL of arsenic solution with a concentration of 1 ppm (pH 2.5) and reacted for 4 h. After filtration, the filtered solid was washed with 0.03 mol / L sodium hydroxide solution to obtain arsenic-loaded iron-manganese oxide. The iron-manganese oxide and the arsenic-loaded iron-manganese oxide were then added to a copper-zinc-cadmium mixed solution (copper, zinc, and cadmium concentrations were all 1 ppm, and the solution pH was 2.5) at a dosage of 0.2 g / L for 12 h of adsorption reaction. After filtration, the filtered solid was washed and desorbed with 50 mL of 0.05 mol / L HNO3 solution. The concentrations of copper, zinc, and cadmium in the solution after the adsorption reaction were tested. The test results of the copper ion separation effect of the obtained iron-manganese oxide and the arsenic-loaded iron-manganese oxide are shown in Tables 2 and 3.

[0070] Table 2. Test results of copper ion separation effect of iron-manganese oxides

[0071]

[0072] Table 3. Test results of copper ion separation effect of arsenic-supported iron-manganese oxides

[0073]

[0074] As shown in Tables 2 and 3, iron-manganese oxides have no ability to separate Cu ions under strongly acidic conditions, while arsenic-supported iron-manganese oxides have a selectivity of up to 95.2% for Cu ions under strongly acidic conditions, with a purity of 94.7% and a recovery rate of 58.9%. This indicates that arsenic-supported iron-manganese oxides can effectively separate and purify copper ions in the Cu-Zn-Cd ternary system.

[0075] Example 2:

[0076] A method for selectively recovering copper, lead, and arsenic from acidic mine wastewater (process flow diagram shown) Figure 1 (As shown), it includes the following steps:

[0077] 1) Dissolve 0.79 g of potassium permanganate in 25 mL of deionized water, then add 0.075 mL of 80% concentrated sulfuric acid for acidification (the pH of the solution after acidification is <1.5). Then, add ferrous sulfate solution (prepared by 4.17 g of ferrous sulfate heptahydrate and 25 mL of deionized water) dropwise at 60 °C. After the addition is complete, stir at room temperature for 30 min. Then, add 3 mol / L sodium hydroxide solution to adjust the pH of the system to 7. Stir at room temperature for 3 h, filter, and place the filtered solid in an oven to dry at 60 °C for 24 h to obtain stabilized iron-manganese oxide.

[0078] 2) Stabilized iron-manganese oxide was added to acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc (simulated heavy metal polluted wastewater, the concentration of copper, cadmium, lead, arsenic and zinc was 1.2 ppm, and the pH value of the wastewater was 2.7). The dosage of stabilized iron-manganese oxide in acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc was 0.7 g / L. After 8 h of adsorption reaction, the mixture was filtered to obtain wastewater enriched with copper-cadmium-zinc and iron-manganese oxide enriched with lead-arsenic, respectively.

[0079] 3) The lead-arsenic-enriched iron-manganese oxide was added to a 0.08 mol / L nitric acid solution for a 6-hour desorption reaction. The dosage of the lead-arsenic-enriched iron-manganese oxide in the nitric acid solution was 0.7 g / L. After filtration, lead-containing solution (lead purity was 99.7%, lead recovery rate was 83.73%) and arsenic-enriched iron-manganese oxide were obtained respectively.

[0080] 4) The arsenic-enriched iron-manganese oxide was added to a 0.05 mol / L sodium hydroxide solution for a 12-hour desorption reaction. The amount of arsenic-enriched iron-manganese oxide added to the sodium hydroxide solution was 0.7 g / L. After filtration, arsenic-containing solution (arsenic purity was 99.4%, arsenic recovery rate was 77.8%) and arsenic-loaded iron-manganese oxide were obtained respectively.

[0081] 5) Arsenic-loaded iron-manganese oxide was added to the copper-cadmium-zinc enriched wastewater for 12 hours for adsorption reaction. The dosage of arsenic-loaded iron-manganese oxide in the copper-cadmium-zinc enriched wastewater was 0.6 g / L. After filtration, cadmium-zinc enriched wastewater and copper-enriched iron-manganese oxide (selectivity for copper >96.5%) were obtained respectively.

[0082] 6) The copper-enriched iron-manganese oxide was added to a 0.04 mol / L nitric acid solution for a 12-hour desorption reaction, followed by filtration. The amount of copper-enriched iron-manganese oxide added to the nitric acid solution was 0.7 g / L, resulting in a copper-containing solution (copper purity was 96.62%, and copper recovery rate was 50.12%).

[0083] Example 3:

[0084] A method for selectively recovering copper, lead, and arsenic from acidic mine wastewater (process flow diagram shown) Figure 1 (As shown), it includes the following steps:

[0085] 1) Stabilized iron-manganese oxide (same as in Example 1) was added to acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc (acidic mining wastewater generated by a mining enterprise in the Dabaoshan mining area, with concentrations of copper, cadmium, lead, arsenic and zinc of 1.032 ppm, 0.953 ppm, 1.523 ppm, 0.718 ppm and 14.142 ppm, respectively, and the pH value of the wastewater was 2.63). The dosage of stabilized iron-manganese oxide in the acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc was 0.4 g / L. After 6 h of adsorption reaction, the mixture was filtered to obtain wastewater enriched with copper-cadmium-zinc and iron-manganese oxide enriched with lead-arsenic, respectively.

[0086] 2) The lead-arsenic-enriched iron-manganese oxide was added to a 0.1 mol / L nitric acid solution for a 12-hour desorption reaction. The dosage of the lead-arsenic-enriched iron-manganese oxide in the nitric acid solution was 0.4 g / L. After filtration, lead-containing solution (lead purity 99.7%, recovery rate 89.47%) and arsenic-enriched iron-manganese oxide were obtained respectively.

[0087] 3) The arsenic-enriched iron-manganese oxide was added to a 0.05 mol / L sodium hydroxide solution for a 12-hour desorption reaction. The amount of arsenic-enriched iron-manganese oxide added to the sodium hydroxide solution was 0.4 g / L. After filtration, arsenic-containing solution (arsenic purity was 99.4%, recovery rate was 80.43%) and arsenic-loaded iron-manganese oxide were obtained respectively.

[0088] 4) Arsenic-loaded iron-manganese oxide was added to the copper-cadmium-zinc enriched wastewater for 12 hours for adsorption reaction. The dosage of arsenic-loaded iron-manganese oxide in the copper-cadmium-zinc enriched wastewater was 0.4 g / L. After filtration, cadmium-zinc enriched wastewater and copper-enriched iron-manganese oxide (selectivity for copper >95.47%) were obtained respectively.

[0089] 5) The copper-enriched iron-manganese oxide was added to a 0.05 mol / L nitric acid solution for a 12-hour desorption reaction, followed by filtration. The amount of copper-enriched iron-manganese oxide added to the nitric acid solution was 0.4 g / L, resulting in a copper-containing solution (copper purity was 98.74%, recovery rate was 51.92%).

[0090] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for selectively recovering copper, lead, and arsenic from acidic mine wastewater, characterized in that, Includes the following steps: 1) Disperse soluble permanganate in water, then add strong acid solution for acidification, then add ferrous salt solution for redox reaction, then add alkaline solution to adjust the pH of the system to 7-8 and stir to obtain stabilized iron-manganese oxide. 2) Stabilized iron-manganese oxides were added to acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc for adsorption reaction, followed by solid-liquid separation to obtain wastewater enriched with copper-cadmium-zinc and iron-manganese oxides enriched with lead-arsenic, respectively. 3) The lead- and arsenic-enriched iron-manganese oxides were added to an acid solution for desorption reaction, followed by solid-liquid separation to obtain a lead-containing solution and arsenic-enriched iron-manganese oxides, respectively. 4) The arsenic-enriched iron-manganese oxides were added to an alkaline solution for desorption reaction, followed by solid-liquid separation to obtain an arsenic-containing solution and arsenic-loaded iron-manganese oxides, respectively. 5) Arsenic-loaded iron-manganese oxides were added to copper-cadmium-zinc enriched wastewater for adsorption reaction, followed by solid-liquid separation. Wastewater enriched with cadmium and zinc and iron-manganese oxides enriched with copper were obtained, respectively. 6) Add copper-enriched iron-manganese oxides to an acid solution for desorption reaction, followed by solid-liquid separation to obtain a copper-containing solution.

2. The method according to claim 1, characterized in that: The soluble permanganate in step 1) is at least one of sodium permanganate, potassium permanganate, and calcium permanganate; the strong acid solution in step 1) is at least one of concentrated sulfuric acid and concentrated nitric acid; the pH of the solution after acidification in step 1) is <1.5; the ferrous salt in the ferrous salt solution in step 1) is at least one of ferrous sulfate, ferrous chloride, and ferrous nitrate; the alkaline solution in step 1) is at least one of sodium hydroxide solution, potassium hydroxide solution, and ammonia water.

3. The method according to claim 1 or 2, characterized in that: In step 1), the molar ratio of ferrous salt in the soluble permanganate and ferrous salt solution is 1:0.5 to 5.

4. The method according to claim 1 or 2, characterized in that: The redox reaction in step 1) is carried out at 20℃~60℃ for 20min~40min; the stirring in step 1) is carried out at room temperature for 1h~5h.

5. The method according to claim 1, characterized in that: Step 2) The pH of the acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc is 2 to 3; Step 2) The dosage of the stabilized iron-manganese oxide in the acidic mining wastewater containing copper, cadmium, lead, arsenic and zinc is 0.01 g / L to 1 g / L.

6. The method according to claim 1 or 5, characterized in that: The adsorption reaction in step 2) takes 1 to 12 hours.

7. The method according to any one of claims 1, 2, and 5, characterized in that: Step 3) The acid solution is a nitric acid solution with a concentration of 0.01 mol / L to 1 mol / L; Step 3) The amount of iron-manganese oxide enriched for lead-arsenic added to the acid solution is 0.01 g / L to 1 g / L; Step 3) The desorption reaction time is 1 h to 12 h.

8. The method according to any one of claims 1, 2 and 5, characterized in that: Step 4) The alkaline solution is a sodium hydroxide solution with a concentration of 0.01 mol / L to 0.05 mol / L; Step 4) The amount of arsenic-enriched iron-manganese oxide added to the alkaline solution is 0.01 g / L to 1 g / L; Step 4) The desorption reaction time is 1 h to 12 h.

9. The method according to any one of claims 1, 2 and 5, characterized in that: In step 5), the dosage of arsenic-loaded iron-manganese oxide in the copper-cadmium-zinc enriched wastewater is 0.01 g / L to 1 g / L; the adsorption reaction time in step 5) is 1 h to 12 h.

10. The method according to any one of claims 1, 2, and 5, characterized in that: Step 6) The acid solution is a nitric acid solution with a concentration of 0.01 mol / L to 1 mol / L; Step 6) The amount of copper-enriched iron-manganese oxide added to the acid solution is 0.01 g / L to 1 g / L; Step 6) The desorption reaction time is 1 h to 12 h.

Images