CN-121990677-A - Based on AMnO3Method for removing organic complex heavy metal by one-step method of/PMS system and application

Abstract

The invention provides a method for removing organic complex state heavy metals based on an AMnO 3 /PMS system by a one-step method, which comprises the steps of mixing perovskite transition metal oxide AMnO 3 with an A-site element being alkaline earth metal element with a solution containing organic complex state heavy metals, adding an oxidant PMS to oxidize the complex breaking organic complex state heavy metals, releasing free heavy metal ions, and simultaneously carrying out adsorption removal on the released heavy metal ions. The method is based on a heterogeneous advanced oxidation system of PMS, utilizes the gradual leaching of A-site metal elements in perovskite oxide AMnO 3 original materials in advanced oxidation reaction to increase the specific surface area of the materials, strengthen the surface electronegativity of the materials, greatly improves the activation of the materials to PMS and the adsorption of free heavy metals released after the breaking of the collaterals, and remarkably promotes the removal effect and the cyclic accumulation removal capacity of the AMnO 3 /PMS system to organic complex heavy metals. The method is simple, environment-friendly, novel in thought, wide in application range and has industrial application value.

Inventors

• WANG TIAN
• QIAN JIE
• QIAN JIESHU
• JIA YUQIAN
• WU XIAOPENG
• XU TIAN
• LI HAIYU

Assignees

• 无锡学院

Dates

Publication Date

20260508

Application Date

20260213

Claims (10)

1. 1. A method for removing organic complex heavy metals based on an AMnO 3 /PMS system by a one-step method is characterized by comprising the following steps: Mixing perovskite transition metal oxide AMnO 3 with a solution containing organic complex state heavy metal, adding an oxidant PMS to oxidize the complex state heavy metal to release free heavy metal ions, and simultaneously adsorbing and removing the released heavy metal ions, wherein the A-site element in the perovskite transition metal oxide AMnO 3 is alkaline earth metal element with inert reaction.
2. 2. The method of claim 1, wherein the organic complex heavy metal is any one of EDTA-Pb, EDTA-Cu, EDTA-Cd, or EDTA-Zn.
3. 3. The method according to claim 1, wherein the element at the a-position in the perovskite transition metal oxide ambo 3 is selected from alkaline earth metals Ca, mg, sr or Ba.
4. 4. The method according to claim 1, wherein the concentration of the organic complex heavy metal solution is 0.01-0.1 mmol/L, the addition amount of the perovskite transition metal oxide AMnO 3 is 0.1-1 g/L, and the addition amount of the PMS is 0.4-1.6 mmol/L.
5. 5. The method according to claim 1, wherein the perovskite transition metal oxide ambo 3 is mixed with the solution containing the organic complex heavy metal, and further subjected to ultrasonic dispersion, wherein the ultrasonic power is 50-200W, and the ultrasonic time is 2-10 min.
6. 6. The method of claim 1, wherein the perovskite transition metal oxide ambo 3 is mixed with the solution containing the organic complex heavy metal to provide an initial pH of the solution of 4.0 to 9.0.
7. 7. The method according to claim 1, wherein after the oxidant PMS is added, the reaction conditions of the reaction process are that the reaction is carried out for 1-4 hours under continuous magnetic stirring, the magnetic stirring speed is 400-1000 rmp, and the reaction temperature is 20-35 ℃.
8. 8. A method according to claim 3, wherein the perovskite transition metal oxide ambo 3 is prepared by a process comprising the steps of: S1, respectively adding calcium nitrate, magnesium nitrate, strontium nitrate or barium nitrate hydrate, manganese nitrate, ferric nitrate and organic acid into a solvent, and uniformly stirring; s2, heating the obtained solution at 60-100 ℃ for 6-48 hours to obtain a homogeneous colloid; And S3, calcining the colloid at 800-1200 ℃ for 2-6 hours to obtain the perovskite transition metal oxide AMnO 3 .
9. 9. The method of claim 8, wherein the organic acid in the step S1 is citric acid or acetic acid, the addition amount of the organic acid is 1-4 times of metal ion equivalent, the solvent in the step S1 is an alcohol-water mixed solution, the alcohol is ethylene glycol, the mixing ratio of the alcohol to the water is 1:1-1:5, and the temperature rising rate of the calcination in the step S1 is 2-10 ℃ per minute.
10. 10. The application of perovskite transition metal oxide AMnO 3 and PMS advanced oxidation system in removing organic complex state heavy metal is characterized in that perovskite transition metal oxide AMnO 3 is mixed with solution containing organic complex state heavy metal, and then oxidant PMS is added to oxidize and break complex organic complex state heavy metal, release free heavy metal ions, and simultaneously adsorb and remove the released heavy metal ions, so that the organic complex state heavy metal is removed by a one-step method.

Description

Method for removing organic complex heavy metal based on AMnO 3/PMS system by one-step method and application Technical Field The invention belongs to the technical field of heavy metal treatment, and particularly relates to a method for removing organic complex heavy metals based on an AMnO 3/PMS system by a one-step method and application thereof. Background The waste water discharged from industries such as mining, electroplating and the like contains a large amount of organic complex heavy metals such as EDTA-Pb, EDTA-Ni and the like of ethylenediamine tetraacetic acid lead. The organic complex heavy metal has high toxicity, strong mobility, easy enrichment and stable existence in a wider pH range, and the pollution seriously endangers human health. How to efficiently remove the organic complex heavy metals in the wastewater is urgent. Because of the strong complexation between heavy metals and organic matters and larger steric hindrance, the organic complex heavy metals cannot be effectively removed by conventional precipitation methods, adsorption methods and the like. Therefore, it is generally necessary to perform oxidation and decomplexation, and then remove free heavy metal ions released after decomplexation from water by using the above method. In the prior art, a plurality of composite materials with peroxide activating capability and heavy metal adsorption capability are constructed, and the materials are utilized to activate peroxide such as H 2O2 to oxidize the organic complex state heavy metal and realize the adsorption removal of released free state heavy metal ions. To increase the adsorption of free heavy metal ions, researchers have mostly used adsorbents with high specific surface areas (specific surface area, SSA) to construct composite materials such as α -Fe 2O3 @ activated biochar, hydrated iron oxide @ cation exchange resins, nano manganese oxide modified biochar (BC-MnO x), and the like. However, most of reported composite materials still face the problems of complex synthesis method, low pollutant treatment capacity, easy inactivation and the like, and the reactive sites and adsorption sites in the materials are difficult to balance, so that the removal of the heavy metals in the organic complex state is limited. In order to improve the removal efficiency of the organic complex heavy metal, the prior art builds a porous structure through a template method to increase SSA, however, the template method has complicated steps and residual templates influence the performance of the material, and doping electron-rich elements can enhance electronegativity of the material, but as heavy metal ions are adsorbed and accumulated on the surface of the material, the electronegativity strength of the surface of the material is reduced, so that the continuous adsorption of the heavy metal is not facilitated. Therefore, a simple and effective method for increasing the SSA of the material and enhancing and maintaining the electronegativity of the surface thereof is required. Disclosure of Invention The invention aims to solve the technical problems and provides a method for removing organic complex heavy metals based on an AMnO 3/PMS system by a one-step method. The method can improve the removal efficiency of the organic complex heavy metal, is simple, has high pollutant treatment capacity, can be recycled and is not easy to inactivate. A second object of the invention is to provide an application of the method. In order to achieve the above purpose, the invention adopts the following technical scheme: The invention provides a method for removing organic complex heavy metals based on an AMnO 3/PMS system, which comprises the following steps: Firstly mixing perovskite transition metal oxide AMnO 3 with a solution containing organic complex state heavy metal, adding oxidant Peroxomonosulfate (PMS) to oxidize and break the complex state heavy metal, releasing free heavy metal ions, and simultaneously adsorbing and removing the released heavy metal ions, wherein the A-site element in the perovskite transition metal oxide AMnO 3 is alkaline earth metal element with inert reaction. Further, the organic complex heavy metal is any one of EDTA-Pb, EDTA-Cu, EDTA-Cd or EDTA-Zn. Further, the element at the A-position in the perovskite transition metal oxide AMnO 3 is selected from alkaline earth metals Ca, mg, sr or Ba. Further, the concentration of the organic complex heavy metal solution is 0.01-0.1 mmol/L, the addition amount of the perovskite transition metal oxide AMnO 3 is 0.1-1 g/L, and the addition amount of the PMS is 0.4-1.6 mmol/L. Further, the perovskite transition metal oxide AMnO 3 is mixed with the solution containing the organic complex heavy metal, and the solution is further dispersed by ultrasonic, wherein the ultrasonic power is 50-200W, and the ultrasonic time is 2-10 min. Further, the initial pH of the solution after the perovskite transition metal oxide AMnO 3 is mixed with the soluti