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CN-116732332-B - Method for selectively recovering copper, lead and arsenic from acid mine wastewater

CN116732332BCN 116732332 BCN116732332 BCN 116732332BCN-116732332-B

Abstract

A process for selectively recovering copper, lead and arsenic from acidic mine wastewater, comprising the steps of 1) preparing iron-manganese oxide having strong stability under acidic conditions, 2) converting acidic mine wastewater containing copper, cadmium, lead, arsenic and zinc into wastewater enriched with copper-cadmium-zinc and iron-manganese oxide enriched with lead-arsenic, 3) converting iron-manganese oxide enriched with lead-arsenic into lead-containing solution and iron-manganese oxide enriched with arsenic, 4) converting iron-manganese oxide enriched with arsenic into arsenic-containing solution and arsenic-loaded iron-manganese oxide, 5) converting wastewater enriched with copper-cadmium-zinc into wastewater enriched with cadmium-zinc and iron-manganese oxide enriched with copper, 6) desorbing copper from iron-manganese oxide enriched with copper to obtain copper-containing solution. The method can be used for respectively enriching and recovering copper, lead and arsenic in the acid mine wastewater, realizes the recycling of heavy metal resources while treating the heavy metal polluted wastewater, and has very wide application prospect.

Inventors

  • YIN HUA
  • CAI YUHAO
  • LOU KEJIA
  • LU GUINING
  • DANG ZHI

Assignees

  • 华南理工大学

Dates

Publication Date
20260505
Application Date
20230710

Claims (10)

  1. 1. A method for selectively recovering copper, lead and arsenic from acid mine wastewater, comprising the steps of: 1) Dispersing soluble permanganate in water, adding a strong acid solution for acidification, adding a ferrous salt solution for oxidation-reduction reaction, adding an alkali solution for regulating the pH value of a system to 7-8, and stirring to obtain a stabilized iron-manganese oxide; 2) Adding the stabilized iron-manganese oxide into acid mine wastewater containing copper, cadmium, lead, arsenic and zinc for adsorption reaction, and then carrying out solid-liquid separation to obtain wastewater enriched with copper-cadmium-zinc and iron-manganese oxide enriched with lead-arsenic respectively; 3) Adding the iron-manganese oxide enriched with lead-arsenic into an acid solution for desorption reaction, and then carrying out solid-liquid separation to respectively obtain a lead-containing solution and the iron-manganese oxide enriched with arsenic; 4) Adding the iron-manganese oxide enriched with arsenic into an alkali solution for desorption reaction, and then carrying out solid-liquid separation to obtain an arsenic-containing solution and arsenic-loaded iron-manganese oxide respectively; 5) Adding the iron-manganese oxide loaded by arsenic into wastewater enriched with copper-cadmium-zinc for adsorption reaction, then carrying out solid-liquid separation, Respectively obtaining waste water enriched with cadmium-zinc and iron-manganese oxide enriched with copper; 6) Adding the iron-manganese oxide enriched with copper into an acid solution to perform desorption reaction, and then performing solid-liquid separation to obtain a copper-containing solution.
  2. 2. The method according to claim 1, wherein the soluble permanganate is at least one of sodium permanganate, potassium permanganate and calcium permanganate in step 1), the strong acid solution is at least one of concentrated sulfuric acid and concentrated nitric acid in step 1), the pH of the acidified solution in step 1) is less than 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, and the alkaline solution in step 1) is at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water.
  3. 3. The method according to claim 1 or 2, wherein the molar ratio of ferrous salt in the soluble permanganate and ferrous salt solution in the step 1) is 1:0.5-5.
  4. 4. The method according to claim 1 or 2, wherein the redox reaction in step 1) is carried out at 20-60 ℃ for 20-40 min, and the stirring in step 1) is carried out at normal temperature for 1-5h.
  5. 5. The method according to claim 1, wherein the pH of the acid mine wastewater containing copper, cadmium, lead, arsenic and zinc is 2-3 in the step 2), and the addition amount of the stabilized iron manganese oxide in the acid mine wastewater containing copper, cadmium, lead, arsenic and zinc is 0.01-1 g/L in the step 2).
  6. 6. The method according to claim 1 or 5, wherein the adsorption reaction time in step 2) is 1h to 12h.
  7. 7. The method according to any one of claims 1,2 and 5, wherein the acid solution in the step 3) is a nitric acid solution with the concentration of 0.01 mol/L-1 mol/L, the adding amount of the iron manganese oxide enriched with lead-arsenic in the step 3) in the acid solution is 0.01 g/L-1 g/L, and the desorption reaction time in the step 3) is 1 h-12 h.
  8. 8. The method according to any one of claims 1, 2 and 5, wherein the alkaline solution in the step 4) is sodium hydroxide solution with the concentration of 0.01-0.05 mol/L, the adding amount of the iron-manganese oxide enriched with arsenic in the step 4) in the alkaline solution is 0.01-1 g/L, and the desorption reaction time in the step 4) is 1-12 h.
  9. 9. The method according to any one of claims 1,2 and 5, wherein the arsenic-loaded iron-manganese oxide in step 5) is added into the wastewater enriched with copper-cadmium-zinc in an amount of 0.01g/L to 1g/L, and the adsorption reaction in step 5) is carried out for 1h to 12h.
  10. 10. The method according to any one of claims 1,2 and 5, wherein the acid solution in the step 6) is a nitric acid solution with the concentration of 0.01mol/L to 1mol/L, the adding amount of the iron manganese oxide enriched with copper in the acid solution in the step 6) is 0.01g/L to 1g/L, and the desorption reaction time in the step 6) is 1h to 12h.

Description

Method for selectively recovering copper, lead and arsenic from acid mine wastewater Technical Field The invention relates to the technical field of treatment of heavy metal polluted wastewater, in particular to a method for selectively recovering copper, lead and arsenic from acid mine wastewater. Background In the mining process, a large amount of heavy metal pollution wastewater containing toxic and harmful heavy metal ions such as copper, cadmium, lead, arsenic, zinc and the like can be generated, and the treatment and disposal of the wastewater are very important. At present, the common method for treating the heavy metal polluted wastewater is an adsorption method, and the method can well remove heavy metal ions in the heavy metal polluted wastewater, and is simple to operate and low in treatment cost. It is worth noting that the heavy metal ions in the heavy metal polluted wastewater are also resources with great application value, and the common adsorption method can only selectively separate one or a certain class of heavy metal ions in the heavy metal polluted wastewater, and can not simultaneously and selectively recover a plurality of heavy metal ions (anions and cations) in the heavy metal polluted wastewater, so that the recovery and utilization effects of the heavy metal resources are very limited, and serious resource waste is caused. Therefore, the development of a method capable of selectively recovering copper, lead and arsenic in heavy metal polluted wastewater has great significance. Disclosure of Invention The invention aims to provide a method for selectively recovering copper, lead and arsenic from acid mine wastewater. The technical scheme adopted by the invention is as follows: a method for selectively recovering copper, lead and arsenic from acid mine wastewater, comprising the steps of: 1) Dispersing soluble permanganate in water, adding a strong acid solution for acidification, adding a ferrous salt solution for oxidation-reduction reaction, adding an alkali solution for regulating the pH value of a system to 7-8, and stirring to obtain a stabilized iron-manganese oxide; 2) Adding the stabilized iron-manganese oxide into acid mine wastewater containing copper, cadmium, lead, arsenic and zinc for adsorption reaction, and then carrying out solid-liquid separation to obtain wastewater enriched with copper-cadmium-zinc and iron-manganese oxide enriched with lead-arsenic respectively; 3) Adding the iron-manganese oxide enriched with lead-arsenic into an acid solution for desorption reaction, and then carrying out solid-liquid separation to respectively obtain a lead-containing solution and the iron-manganese oxide enriched with arsenic; 4) Adding the iron-manganese oxide enriched with arsenic into an alkali solution for desorption reaction, and then carrying out solid-liquid separation to obtain an arsenic-containing solution and arsenic-loaded iron-manganese oxide respectively; 5) Adding arsenic-loaded iron-manganese oxide into wastewater enriched with copper-cadmium-zinc for adsorption reaction, and then carrying out solid-liquid separation to obtain wastewater enriched with cadmium-zinc and iron-manganese oxide enriched with copper respectively; 6) Adding the iron-manganese oxide enriched with copper into an acid solution to perform desorption reaction, and then performing solid-liquid separation to obtain a copper-containing solution. Preferably, the soluble permanganate in the step 1) is at least one of sodium permanganate, potassium permanganate and calcium permanganate. Preferably, the strong acid solution in the step 1) is at least one of concentrated sulfuric acid and concentrated nitric acid. Preferably, the pH of the solution after acidification in step 1) is <1.5. Preferably, the ferrous salt in the ferrous salt solution in the step 1) is at least one of ferrous sulfate, ferrous chloride and ferrous nitrate. Preferably, the molar ratio of the ferrous salt in the soluble permanganate and ferrous salt solution in the step 1) is 1:0.5-5. Preferably, the redox reaction in the step 1) is carried out at 20-60 ℃ for 20-40 min. Preferably, the alkali solution in the step 1) is at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water. Preferably, the stirring in the step 1) is performed at normal temperature, and the stirring time is 1-5 h. Preferably, the pH value of the acid mine wastewater containing copper, cadmium, lead, arsenic and zinc in the step 2) is 2-3. Preferably, the addition amount of the stabilized iron-manganese oxide in the step 2) in the acid mine wastewater containing copper, cadmium, lead, arsenic and zinc is 0.01 g/L-1 g/L. Preferably, the adsorption reaction time in the step 2) is 1-12 h. Preferably, the acid solution in the step 3) is a nitric acid solution with the concentration of 0.01 mol/L-1 mol/L. Preferably, the adding amount of the lead-arsenic enriched ferro-manganese oxide in the step 3) in the acid solution is 0.01