CN-122010276-A - Ball-milling MoS2Method for removing antibiotics by activating permanganate

Abstract

The invention discloses a method for removing antibiotics by activating permanganate with ball milling MoS 2 , belonging to the field of water treatment technology and environmental functional materials. The method comprises the steps of synthesizing MgAl-layered double metal hydroxide through coprecipitation, performing hydrothermal compounding and ball milling bonding to obtain a ball milling modified composite material and water treatment application thereof. Aiming at the technical problems that the active species of a homogeneous system are easy to deactivate, the activation efficiency of a heterogeneous system is low, and the interface electron transfer barrier is high due to only physical contact between materials in the existing permanganate activation technology, the continuous electron transfer network is constructed by adopting sodium thiosulfate to assist ball milling to induce chemical bonding, so that the surface of MoS 2 is in an electron-rich state, the high-valence manganese intermediate and the free radical dual-path synergistic oxidation antibiotic are utilized, and simultaneously, the sulfur coordination, sulfur vacancy anchoring and hydroxyl complexation multiple mechanisms are utilized to adsorb heavy metals. Under the optimal condition, the method realizes that the SMX removal rate reaches 96.8 percent and the lead ion removal rate reaches 99.2 percent.

Inventors

• HE DONGLIN
• WEI WEI
• LIU BO
• SONG HAILONG
• ZHAO WENJIE
• WANG LIYAN
• LIN PEIJUN
• YUAN YE
• Luan Yujiao

Assignees

• 山东正元环境科技有限公司

Dates

Publication Date

20260512

Application Date

20260414

Claims (7)

1. 1. A method for removing antibiotics by ball milling MoS 2 activated permanganate, comprising the steps of: S1, synthesizing MgAl-layered double hydroxide: Dissolving magnesium salt and aluminum salt in water according to a molar ratio of 2-4:1, dropwise adding the mixture into a solution containing alkali and carbonate in an inert atmosphere, crystallizing for 12-24 hours, and centrifuging, washing and drying to obtain MgAl-layered double hydroxide; S2, hydrothermal compounding: Dispersing MgAl-layered double hydroxide in water, adding a molybdenum source and a sulfur source in a molar ratio of 1:3-5, performing ultrasonic dispersion, transferring into a high-pressure reaction kettle for hydrothermal reaction, and performing centrifugation, washing and drying to obtain a MoS 2 -MgAl-layered double hydroxide heterojunction; s3, ball milling bonding: Mixing MoS 2 -MgAl-layered double hydroxide heterojunction with ferrous sulfide according to the mass ratio of 1:0.2-1, adding sodium thiosulfate, ball milling together, alternately washing deoxidized deionized water and absolute ethyl alcohol, and vacuum drying to obtain a ball milling modified composite material; S4, water treatment application: And (3) adding the ball-milling modified composite material and permanganate into water to be treated containing antibiotics and heavy metals, and reacting under the stirring condition to remove pollutants.
2. 2. The method for removing antibiotics by ball milling MoS 2 to activate permanganate, according to claim 1, wherein the magnesium salt in S1 is MgCl 2 ·6H 2 O or Mg (NO 3 ) 2 ·6H 2 O), the aluminum salt is AlCl 3 ·6H 2 O or Al (NO 3 ) 3 ·9H 2 O, the alkali is NaOH or KOH, the carbonate is Na 2 CO 3 or K 2 CO 3 , the crystallization temperature is 60-80 ℃ and the pH is 9.5-10.5.
3. 3. The method for removing antibiotics by ball milling MoS 2 activated permanganate, which is characterized in that the concentration of MgAl-layered double hydroxide dispersed in water in S2 is 5-20 g/L, the ultrasonic dispersion time is 20-60min, the molybdenum source is sodium molybdate or ammonium molybdate, the sulfur source is thiourea or thioacetamide, and the mass ratio of MgAl-layered double hydroxide to molybdenum source is 5-10:1.
4. 4. The method for removing antibiotics by ball milling MoS 2 activated permanganate, as claimed in claim 1, wherein the mass ratio of sodium thiosulfate to mixed powder is 0.05-0.4:1, and the related technological parameters of ball milling are that zirconium oxide ball milling beads with the diameter of 3-10mm are adopted, the ball material ratio is 10-30:1, and the ball milling is carried out under the protection of argon or nitrogen at the rotating speed of 200-500 rpm.
5. 5. The method for removing antibiotics by ball milling MoS 2 activated permanganate, which is characterized in that the antibiotics in S4 are one or more of sulfamethoxazole and tetracycline, and the heavy metal ions are one or more of lead, copper, cadmium and zinc.
6. 6. The method for removing antibiotics by ball milling MoS 2 activated permanganate, which is characterized in that the permanganate in S4 is potassium permanganate or sodium permanganate, the mass ratio of the ball milling modified composite material to the permanganate is 0.5-2:1, the reaction time is 10-60min, and the reaction pH is 3-9.
7. 7. The method for removing antibiotics by ball milling MoS 2 activated permanganate, as claimed in claim 1, wherein the ball milling modified composite material in S4 realizes continuous transfer of electrons from ferrous sulfide to MoS 2 -MgAl-layered double hydroxide heterojunction through a cross-heterojunction interface continuous bonding network composed of Fe-S-Mo bonds and Fe-O-Al (Mg) hydroxyl bonds.

Description

Method for removing antibiotics by activating permanganate through ball milling MoS 2 Technical Field The invention relates to the field of water treatment technology and environmental functional materials, in particular to a method for removing antibiotics by activating permanganate through ball milling MoS 2. Background The combined pollution of antibiotics and heavy metals is a key challenge for the agricultural reuse of reclaimed water, antibiotics such as sulfamethoxazole, tetracycline and the like and lead ions often coexist in the environment, and the synchronous and efficient removal is difficult to realize by the traditional biological treatment technology. Advanced oxidation technology based on Permanganate (PM) is widely focused in the field of water treatment because of the advantages of strong oxidation capability, simple operation, few byproducts and the like. However, permanganate has limited self-oxidizing ability and low removal efficiency of refractory organic contaminants, and requires the formation of high valence manganese intermediates (Mn (VI)/Mn (V)) and reactive oxygen species by activation techniques to enhance oxidation efficiency. Currently, permanganate activation is predominantly carried out using homogeneous transition metal ions (e.g., co 2+、Fe2+) or heterogeneous catalysts. Although the homogeneous phase activation system has high reaction rate, the homogeneous phase activation system has the problems of easy hydrolysis and deactivation of metal ions, narrow applicable pH range, short service life of active species, secondary pollution risk caused by metal ion residues, and the like. In heterogeneous catalysts, layered molybdenum disulfide (MoS 2) exhibits good permanganate activation potential due to its unique two-dimensional structure, abundant edge active sites, and controllable electronic properties. The existing research carries out modification on MoS 2 by methods such as liquid phase stripping and hydrothermal compounding, but the activation efficiency is still limited by bottlenecks such as low active site density, poor electron transfer efficiency and the like, and a single MoS 2 system mainly depends on a free radical activation path and is easily interfered by matrixes such as natural organic matters, inorganic anions and the like in a water body. To solve the above problems, researchers have attempted to compound MoS 2 with iron-based materials, enhance permanganate activation ability through redox cycling of iron species, while adsorbing heavy metals with sulfur coordination sites of MoS 2. However, the existing composite strategy mostly adopts physical mixing or simple loading, only forms physical contact between MoS 2 and an iron-based material, has high interface electron transfer barrier, is difficult to realize atomic level coordination, is easy to run off iron species and poor in circulation stability, has single material function, and is difficult to simultaneously realize multiple targets of high-efficiency activation of permanganate, deep degradation of antibiotics and rapid adsorption of heavy metals. Therefore, a preparation method of the composite material which can construct a chemical bonding interface between MoS 2 and an iron-based material, realize continuous electron transfer and have multiple functions in cooperation is developed, and the preparation method has important technical value and application prospect. Disclosure of Invention In order to solve the technical problems, the invention provides a method for removing antibiotics by activating permanganate with MoS 2 by ball milling. The technical scheme provided by the embodiment of the invention is as follows: A method for removing antibiotics by ball milling MoS 2 activated permanganate, comprising the following steps: S1, synthesizing MgAl-layered double hydroxide: Dissolving magnesium salt and aluminum salt in water according to a molar ratio of 2-4:1, dropwise adding the mixture into a solution containing alkali and carbonate under the protection of inert atmosphere, controlling the pH value to be 9.5-10.5, crystallizing the mixture for 12-24 hours at 60-80 ℃, centrifuging, washing and drying the mixture to obtain MgAl-layered double hydroxide; The process of co-precipitation synthesis of MgAl-layered double hydroxides can be divided into four successive stages, each of which cooperates by specific chemical and physical mechanisms to finally form a structured layered crystal structure: in the first stage, metal ions are hydrolyzed and initially precipitated, when a mixed solution of magnesium salt and aluminum salt is slowly added into an alkaline solution containing sodium hydroxide and sodium carbonate in a dropwise manner, the pH value of the solution is rapidly increased to 9.5-10.5, and magnesium ions and aluminum ions immediately react with hydroxide ions to respectively generate initial precipitation nuclei of magnesium hydroxide and aluminum hydroxide: Mg2++2OH-→Mg(OH)2↓ Al3+