Search

CN-122010277-A - Manganese-containing ore smelting wastewater treatment method based on iron-mineral-based material catalytic oxidation self-precipitation technology

CN122010277ACN 122010277 ACN122010277 ACN 122010277ACN-122010277-A

Abstract

The invention discloses a treatment method of manganese-containing ore smelting wastewater based on an iron-mineral-based material catalytic oxidation self-precipitation technology, which comprises the steps of pre-regulating the pH value of the manganese-containing ore smelting wastewater, and removing uncomplexed divalent manganese ions and coexisting pollutants; adding an iron mineral-based catalyst and introducing ozone to form strong oxidative free radicals, carrying out ore phase reconstruction on the iron mineral-based catalyst to generate homogeneous dissolution, converting iron atoms into high-valence iron, carrying out synergistic catalysis and oxidation on complex-state and non-complex-state divalent manganese ions by ozone, the strong oxidative free radicals and the high-valence iron to generate self-precipitation, bridging the high-valence iron to form a net, carrying out iron self-flocculation, carrying out flocculation-coprecipitation reaction on ferromanganese ions to obtain flocculation-coprecipitate, and separating by a inclined tube sedimentation tank. According to the invention, by introducing the iron mineral-based catalyst, the efficient conversion of ozone, the oxidation and deep removal of complex and non-complex manganese ions are realized, the cost is reduced, and the treatment of waste by waste is realized.

Inventors

  • XIANG HUAHAO
  • HU SHUANG
  • QI YOUXIANG
  • WANG ZHIQIANG
  • LEI JIANMING
  • QI CHUANLEI
  • ZHOU HUI
  • LUO ZIHAN
  • LU HAO
  • TAN KAIWEN

Assignees

  • 芷兰生态环境建设有限公司

Dates

Publication Date
20260512
Application Date
20260415

Claims (10)

  1. 1. The manganese-containing ore smelting wastewater treatment method based on the iron-mineral-based material catalytic oxidation self-precipitation technology is characterized by comprising the following steps of: Pre-regulating the pH value of the manganese ore-containing metallurgical wastewater to 6-9, and removing uncomplexed divalent manganese ions and coexisting pollutants under the weak alkaline condition; Adding an iron mineral-based catalyst into the pre-adjusted manganese ore-containing metallurgical wastewater, and introducing ozone, wherein the ozone forms strong oxidative free radicals under the action of the iron mineral-based catalyst, and meanwhile, the iron mineral-based catalyst is subjected to ore phase reconstruction to generate homogeneous dissolution, and iron atoms are converted and released into high-valence iron; The high-valence iron is bridged to form a net, self-flocculation of iron occurs, and ferromanganese ions undergo flocculation-coprecipitation reaction to obtain flocculation-coprecipitation; and separating the flocculation-coprecipitate by a inclined tube sedimentation tank.
  2. 2. The method for treating manganese-containing ore smelting wastewater based on the iron-based material catalytic oxidation autoprecipitation technology according to claim 1, wherein the manganese-containing ore smelting wastewater has water quality conditions of Mn 2+ concentration of 50-2000 mg/L, pH of 2.0-7.0, water temperature of 10-35 ℃ and coexisting pollutants including Al 3+ 、Fe 2+ , SS and COD.
  3. 3. The method for treating manganese-containing mining and metallurgy wastewater based on the iron-mineral-based material catalytic oxidation autodeposition technology according to claim 1, wherein the preconditioning of the pH to 6-9 is performed under the weak alkaline condition by generating Mn (OH) 2 flocs with OH - , and simultaneously performing coprecipitation removal reaction with Fe 2+ 、Al 3+ and Ca 2+ coexisting metal ions in the wastewater, so that the rear-end oxidation load is reduced.
  4. 4. The method for treating manganese-containing ore smelting wastewater based on the iron-based material catalytic oxidation autoprecipitation technology according to claim 1, wherein the iron-based catalyst is a low-grade porous iron-based catalyst, the low-grade porous iron-based catalyst is obtained by crushing and ball milling the low-grade porous iron-based catalyst to 50-200 meshes, roasting the low-grade porous iron-based catalyst at 300-500 ℃ for 1-2 hours, the specific surface area of the low-grade porous iron-based catalyst is 10-50 m 2 /g, the total iron content is more than or equal to 40%, and the active Fe 2+ accounts for 10% -30%.
  5. 5. The method for treating manganese-containing mining and metallurgy wastewater based on the iron-based material catalytic oxidation autodeposition technology according to claim 1, wherein the formation of strong oxidative free radicals by ozone under the action of an iron-based catalyst is that ozone undergoes chain decomposition under the action of an Fe 2+ /Fe 3+ active site of the iron-based catalyst, and is directionally converted into hydroxyl free radicals, superoxide free radicals and singlet oxygen.
  6. 6. The method for treating manganese-containing ore smelting wastewater based on the iron-based material catalytic oxidation autoprecipitation technology according to claim 1, wherein the homogeneous dissolution of the iron-based catalyst ore phase reconstruction means heterogeneous dissolution of the original crystal phase of the catalyst under the continuous action of ozone/free radicals, and Fe on the surface of the catalyst dissolves out in an ionic state or a colloid state in the reconstruction process and is dissociated into amorphous Fe (OH) 3 and gamma-FeOOH.
  7. 7. The method for treating manganese-containing mining and metallurgy wastewater based on the catalytic oxidation autoprecipitation technology of iron-based materials according to claim 1, wherein the high-valence iron which is converted and released into high-valence iron by iron atoms is referred to as Fe 3+ , the high-valence iron comprises free Fe 3+ 、Fe(OH) 3 colloid and amorphous iron oxide, the amorphous iron oxide comprises gamma-FeOOH and FeOOH.nH2 2 O, and Fe 2+ in the iron-based catalyst is preferentially released and oxidized into Fe 3+ under the action of ozone/free radicals.
  8. 8. The method for treating manganese-containing mining and metallurgy wastewater based on the technology of catalytic oxidation and autoprecipitation of iron-based materials according to claim 1, wherein the manganese ion morphology transformation means that Mn 2+ is oxidized into MnO 2 and permanganate (MnO 4 - ) under the synergistic effect of ozone/free radicals, and the MnO 2 exists in the form of amorphous nano particles with a particle size of 10-50nm and is primarily self-precipitated.
  9. 9. The method for treating manganese-containing ore smelting wastewater based on the iron-based material catalytic oxidation autoprecipitation technology according to claim 1, wherein the high-valence iron bridging net is formed by hydroxyl bridging, wherein MnO 2 particles, heavy metal ions and residual suspended matters generated by net capturing oxidation of the Fe-O-Fe form three-dimensional net-shaped polymeric flocs, and iron self-flocculation and ferromanganese ion flocculation-coprecipitation reactions occur.
  10. 10. The method for treating manganese-containing ore smelting wastewater based on the iron-based material catalytic oxidation and autoprecipitation technology according to any one of claims 1 to 9, wherein the manganese-containing ore smelting wastewater treatment method based on the iron-based material catalytic oxidation and autoprecipitation technology is reacted in an integrated baffled reactor.

Description

Manganese-containing ore smelting wastewater treatment method based on iron-mineral-based material catalytic oxidation self-precipitation technology Technical Field The invention relates to the field of industrial wastewater treatment methods, in particular to a manganese-containing ore smelting wastewater treatment method based on an iron-mineral-based material catalytic oxidation self-precipitation technology. Background The wastewater discharged by mining and metallurgy industries (such as manganese mining, hydrometallurgy, electrolytic manganese production, battery material processing and the like) often contains high-concentration Mn 2+, and the concentration range of the high-concentration Mn 2+ can reach 50-2000 mg/L, which is far beyond the limit value of 0.1 mg/L in the discharge standard of copper, nickel and cobalt industrial pollutants (GB 25467-2010) and the discharge requirement of the comprehensive wastewater discharge standard (GB 8978-1996). Conventional manganese ion removal methods include chemical precipitation, adsorption, biological, and advanced oxidation methods (AOPs), but they all have major drawbacks such as: (1) The chemical precipitation method is to add excessive oxidant (such as potassium permanganate and chlorine) or alkali (such as NaOH) to oxidize Mn 2+ into MnO 2 for precipitation, and has high cost (more than 60% of treatment cost) and easy introduction of heavy metal impurities; (2) Adsorption method, which relies on adsorbents such as active carbon and molecular sieve, and has insufficient adsorption capacity (50 mg/g) for high-concentration Mn 2+ (500 mg/L), and high regeneration frequency leads to increased operation cost; (3) Biological method is limited by sensitivity of microorganism to pH (6.5-8.5) and temperature (20-30deg.C), and has poor tolerance to coexisting Fe 2+ and COD, etc., and is difficult to reach standard; (4) The advanced oxidation method (AOPs) is characterized by high oxidation efficiency, but the addition of H 2O2, ultraviolet light source, etc. has obvious energy consumption and cost, and when Mn 2+ is oxidized by ozone alone, the reduction potential of Mn 2+ is higher (E 0 =1.23V), the direct oxidation efficiency is less than 30%, and the strengthening by a catalyst is needed. Most of the existing ozone catalytic oxidation catalysts are noble metals (Pt and Pd) or artificially synthesized materials, and have the problems of complex preparation, high cost, easy deactivation and the like. The low-grade iron minerals (such as magnetite, hematite, goethite and limonite) are rich in reserves and low in cost, the Fe 2+/Fe3+ active site contained in the low-grade iron minerals can catalyze ozone to decompose into strong oxidizing species such as hydroxyl radicals (OH) and the like, and the low-grade iron minerals can participate in an oxidation-flocculation process, but the existing research on multi-focus organic matter degradation lacks systematic resolution on a synergistic mechanism of 'catalytic oxidation-ore phase reconstruction-self precipitation' of deep removal of manganese ions, and the association of technological parameters and recycling recovery is not clarified. Therefore, development of a mining and metallurgy wastewater manganese ion removal method combining ozone oxidation and self-precipitation by using an iron ore material as a catalyst is urgently needed. Disclosure of Invention In view of the defects of the existing mining and metallurgy wastewater manganese ion removal method, the invention provides a manganese-containing mining and metallurgy wastewater treatment method based on an iron mineral-based material catalytic oxidation self-precipitation technology, and by introducing an iron mineral-based catalyst, the efficient conversion of ozone, the oxidation and deep removal of complex-state and non-complex-state manganese ions are realized, the cost is reduced, and the treatment of waste with waste is realized. In order to achieve the above object, the embodiment of the present invention adopts the following method scheme: A manganese-containing ore smelting wastewater treatment method based on an iron-based material catalytic oxidation self-precipitation technology, wherein the manganese-containing ore smelting wastewater comprises manganese ions, and the steps of the manganese-containing ore smelting wastewater treatment method based on the iron-based material catalytic oxidation self-precipitation technology comprise the following steps: Pre-regulating the pH value of the manganese ore-containing metallurgical wastewater to 6-9, and removing uncomplexed divalent manganese ions and coexisting pollutants under the weak alkaline condition; Adding an iron mineral-based catalyst into the pre-adjusted manganese ore-containing metallurgical wastewater, and introducing ozone, wherein the ozone forms strong oxidative free radicals under the action of the iron mineral-based catalyst, and meanwhile, the iron mineral-based catalyst is su