Preparation method and application of a slag-based hollow microsphere nano-reactor

Abstract

The application discloses a preparation method of a slag-based hollow microsphere nanoreactor, and specifically comprises the following steps: drying solid waste rich in iron and silicon, ball milling, screening, and then placing the solid waste in 0.5-3 mol / L acid liquor, and leaching at 20-120 DEG C, to obtain iron-containing filtrate and solid through solid-liquid separation; after washing the solid to neutral, the solid is added into 0.5-3 mol / L alkali liquor, and then treated at 50-150 DEG C, to adjust the pH of the reactants to 7-11, and then aged, to obtain SiO2 microspheres through solid-liquid separation, washing and drying; the SiO2 microspheres are dispersed in an aqueous ammonia solution, then Cu 2+ containing solution, NH4Cl and the iron-containing filtrate are added and uniformly stirred, the mixture is aged at 100-200 DEG C, and then the slag-based hollow microsphere nanoreactor is obtained through solid-liquid separation, washing and drying; the catalyst can be used for removing aureomycin hydrochloride and methylene blue in wastewater in a Fenton system, and has good practical value and application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of preparation of functional materials and sewage treatment, and particularly relates to a preparation method and application of a slag-based hollow microsphere nano-reactor. BACKGROUND

[0002] Organic dyes and antibiotics are hotspots of current pollution types, which mainly come from the wastewater discharge of dyeing and printing plants, pharmaceutical plants and aquaculture. Advanced oxidation processes (AOPs) can efficiently oxidize pollutants into simple and harmless small molecules and are widely used for deep purification of water. Transition metals Fe, Mn, Co, Cu (zero-valent metal, oxide, sulfide, silicate, etc.) are usually used to activate persulfate (PMS), and Fe-based materials are particularly favored due to their non-toxicity, abundant reserves and high catalytic efficiency. However, single iron-based catalysts have insufficient active sites and Fe(II) regeneration is difficult, and how to promote the reduction of Fe(III) to Fe(II) to ensure the continuous reaction is still a key issue. In recent years, researchers have introduced different second active species with different oxidation-reduction potentials and intrinsic properties to make up for the lack of single metal active sites, which can greatly improve the catalytic performance.

[0003] Copper slag (CS) is a solid by-product generated during copper smelting, converting and refining. It is estimated that 40 million tons of copper slag is generated worldwide each year. In the past few decades, many studies have focused on the preparation of building materials such as phosphoric acid iron cement, roadbed material and acid-base cement from solid waste such as copper slag. However, 80% of CS is still discarded by on-site stacking and landfill, which threatens the ecological environment and wastes resources. Therefore, it is necessary to use copper slag to prepare high-value-added products. In fact, the main components of copper slag are fayalite and magnetite, which have the potential to make high-value-added catalysts.

[0004] Hollow microspheres (HMs) have adjustable structure and nanometer-defined cavities, pollutants can be quickly enriched in the cavities, and the inner and outer surfaces are rich in active sites, which can be defined as a micro-nano reactor with good mass transfer and durability, and are widely used in adsorption, catalysis, energy storage and transfer. The hollow structure (HMs) constructed by metal silicates usually uses SiO2 as a sacrificial template and introduces metal species to obtain a mesoporous structure with high metal density. Usually, expensive TEOS is used as an organic silicon source, and only a few studies are based on inorganic Na2SiO3, so it is more challenging to use Si in solid waste to prepare HMs. The unique structure of HMs provides special channels for catalysts, thus exhibiting excellent adsorption and catalytic performance. SUMMARY

[0005] The application provides a preparation method of a slag-based hollow microsphere nanoreactor. 2- Under the induced modification of Cu, SiO3 2- is generated in situ to grow a slag containing a large amount of nanotube structures and having good Fe Ⅲ / Fe Ⅱ circulation, which has good activation capacity for PMS / H2O2 and is applied to the efficient degradation of aureomycin hydrochloride and methylene blue in a Fenton-like system. Ⅲ The application solves the problems of slow reduction of Fe Ⅱ and difficult regeneration of Fe Ⅱ .

[0006] The slag-based hollow microsphere nanoreactor is prepared by drying, ball milling and sieving of solid waste rich in iron and silicon, then immersing the solid waste in 0.5-3 mol / L acid solution at 20-120 DEG C for 2-5 h, separating the solid from the liquid to obtain an iron-containing filtrate and a solid, adding the solid to 0.5-3 mol / L alkali solution at 50-150 DEG C for 0.5-5 h, adjusting the pH of the reaction mixture to 7-11, aging for 2-15 h, separating the solid from the liquid, washing and drying the solid to obtain SiO2 microspheres, dispersing the SiO2 microspheres in 1-10% ammonia water solution, then adding Cu 2+ solution, NH4Cl and the iron-containing filtrate, stirring and uniformly mixing, aging the mixture at 100-200 DEG C for 4-48 h, separating the solid from the liquid, washing and drying the solid to obtain the slag-based hollow microsphere nanoreactor.

[0007] The solid waste rich in iron and silicon is selected from smelting copper slag and smelting tin slag, the acid in the acid solution is sulfuric acid, nitric acid or hydrochloric acid, and the alkali solution is sodium hydroxide solution; when the concentration of the acid solution is 0.5-1.5 mol / L, the SiO2 microspheres prepared contain Fe3O4 and have magnetism; when the concentration of the acid solution is 1.5-3 mol / L, the SiO2 microspheres prepared have weak magnetism or no magnetism.

[0008] The smelting copper slag is a solid byproduct generated in the process of copper smelting, conversion and refining, and the main components include FeO 30%-60%, SiO2 10%-39%, CaO 1%-15% and Al2O3 2%-7%.

[0009] The Cu 2+The solutions were selected from copper sulfate solution, copper nitrate solution, and copper chloride solution, with a molar ratio of Cu to Fe of 0.1-2:1 and a molar ratio of NH4Cl to Cu of 0.5-4:1.

[0010] The slag-based hollow microsphere nanoreactor prepared by the above method has a specific surface area of ​​300-550 m². 2 / g, specific surface area of ​​300-550 m² 2 / g, average pore size 3.14-5.74nm, pore volume 0.55-0.75cm³ 3 / g.

[0011] This invention uses a slag-based hollow microsphere nanoreactor as a Fenton catalyst for the removal of chlortetracycline hydrochloride and methylene blue from wastewater.

[0012] Advantages and technical effects of the method of the present invention:

[0013] 1. The method of this invention uses copper smelting slag as raw material, and separates Fe and Si by acid leaching. The resulting filter residue is treated with alkaline solution and the pH is adjusted with acid to obtain SiO2 microspheres; the microspheres generate SiO3 in an alkaline environment. 2- With the aid of Cu-induced modification, SiO3 2- It reacts with Cu and Fe to form silicates and grows in situ to form silicates, thus forming a cavity-shaped urchin-like catalyst. In this process, no external organic / inorganic template agent, silicon source, or iron source is required, and valuable elements in copper smelting slag can be utilized efficiently. This urchin-like structure has numerous nanotubes containing numerous active sites, which accelerates the activation of the activator and is easy to recover, thus improving the Fenton catalytic efficiency.

[0014] 2. The slag-based hollow microsphere nanoreactor of the present invention, by introducing a second active metal Cu, compensates for the lack of active sites of a single metal. I It will accelerate Fe Ⅲ To Fe Ⅱ Reduction, thus solving the problem of single iron-based catalysts Fe Ⅱ The problem of difficult reduction can be addressed by continuously exciting monopersulfate and generating free radicals, thereby increasing catalyst utilization efficiency and enhancing catalytic activity.

[0015] 3. The slag-based hollow microsphere nanoreactor of this invention is used as a Fenton catalyst for the removal of chlortetracycline hydrochloride and methylene blue. The degradation rate of chlortetracycline hydrochloride is 100% in 10 minutes and the removal rate of methylene blue is 100% in 5 minutes, which shows that the removal rate is very high and has good application prospects.

[0016] 4. The preparation method of this invention is the impregnation-hydrothermal method, which is simple to operate, has mild reaction conditions, low cost, and can be industrialized. Attached Figure Description

[0017] Figure 1 This is the result of Example 1, which describes the removal of methylene blue and chlortetracycline hydrochloride from wastewater using a slag-based hollow microsphere nanoreactor.

[0018] Figure 2 The XRD pattern of the slag-based hollow microsphere nanoreactor catalyst prepared in Example 2;

[0019] Figure 3 The images show the SEM, TEM, and EDS spectra of the slag-based hollow microsphere nanoreactor catalyst prepared in Example 2; where images ab are SEM images; image cd is a TEM image; image e is a high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image of the material; image f is the elemental mapping of Cu; image g is the elemental mapping of Fe; and image h is the elemental mapping of Si.

[0020] Figure 4 The N2 isotherm adsorption-desorption curve of the slag-based hollow microsphere nanoreactor catalyst prepared in Example 2;

[0021] Figure 5 The pore size distribution diagram is shown for the slag-based hollow microsphere nanoreactor catalyst prepared in Example 2.

[0022] Figure 6 The images show the removal effects of the slag-based hollow microsphere nanoreactor catalyst, CSS, and CSAR prepared in Example 2 on chlortetracycline hydrochloride (Figure a) and methylene blue (Figure b).

[0023] Figure 7 The image shows the removal effect of the slag-based hollow microsphere nanoreactor catalyst prepared in Example 3 on methylene blue and chlortetracycline hydrochloride.

[0024] Figure 8 The image shows the removal effect of the slag-based hollow microsphere nanoreactor catalyst prepared in Example 4 on methylene blue and chlortetracycline hydrochloride. Detailed Implementation

[0025] The present invention will be further described in detail through the following embodiments, but it should be noted that the scope of the present invention is not limited in any way by the following embodiments;

[0026] Example 1: Preparation of slag-based hollow microsphere nanoreactor

[0027] The smelting copper slag is dried at 80°C, ball-milled, and passed through a 325 mesh sieve. 2 g of the slag is weighed into a three-necked flask, 50 mL of 2.0 mol / L nitric acid solution is added, and stirring is continued at 60°C for 3 h. The filtrate containing iron and the filtrate containing silicon are obtained by filtration, and the filtrate is washed with water until neutral. The filtrate is added to 30 mL of 2.0 mol / L NaOH solution, and stirring is continued at 60°C for 2 h. After the heating is stopped, the pH is adjusted to 10.5 with a nitric acid solution, and stirring is continued at room temperature for 5 h for aging. The solid is washed with water and anhydrous ethanol alternately until neutral, and is dried at 80°C to obtain SiO2 microspheres. 0.12 g of CuSO4·5H2O is dissolved in 20 mL of H2O to obtain solution A, and 0.10 g of NH4Cl is added. 0.2 g of magnetic SiO2 microspheres is weighed into 30 mL of H2O, and is dispersed uniformly by ultrasonic treatment for 10 min to obtain suspension B. 2 mL of NH3·H2O (30 wt%) solution is added, and ultrasonic treatment is continued for 2 min. Solution A containing Cu is added dropwise under stirring, and 6.0 mL of the filtrate containing iron (the concentration of Fe in the filtrate is 4.36 g / L) is added dropwise. After stirring is continued for 20 min, the obtained mixed suspension is transferred into a Teflon-lined autoclave, and is aged at 120°C for 18 h. The residue is washed with water and anhydrous ethanol alternately, and is dried at 80°C to obtain slag-based hollow microsphere nanoreactors. 2+ The slag-based hollow microsphere nanoreactors prepared in this example are applied to a Fenton system to remove chlortetracycline hydrochloride (CTC) in wastewater. As shown in Table 1, the initial concentration of CTC is 50 mg / L, the amount of catalyst is 0.3 g / L, and the amount of PMS is 0.65 mmol / L. The degradation rate of CTC is 98.07% after 20 min.

[0028] The slag-based hollow microsphere nanoreactors prepared in this example are applied to a Fenton system to remove methylene blue (MB) in wastewater. As shown in Table 2, the initial concentration of MB is 50 mg / L, the amount of catalyst is 0.3 g / L, and the amount of PMS is 0.65 mmol / L. The degradation rate of MB is 100% after 5 min. Figure 1

[0029] The slag-based hollow microsphere nanoreactors prepared in this example are applied to a Fenton system to remove methylene blue (MB) in wastewater. As shown in Table 2, the initial concentration of MB is 50 mg / L, the amount of catalyst is 0.3 g / L, and the amount of PMS is 0.65 mmol / L. The degradation rate of MB is 100% after 5 min. Figure 1

[0030] Example 2: Preparation of slag-based hollow microsphere nanoreactors

[0031] ​​The smelting copper slag is dried at 80°C, ball milled, and sieved through a 180 mesh sieve. 2g of the sieved slag is placed in a three-necked flask, 50mL of 1.0mol / L sulfuric acid solution is added, and stirring is continued at 20°C for 3h. The filtrate containing iron and the magnetic filter residue containing silicon are obtained by filtration. The filter residue is washed with water until neutral. The filter residue is added to 30mL of 1.0mol / L NaOH solution, and stirring is continued at 60°C for 2h. The heating is stopped, and the pH is adjusted to 9.5 with sulfuric acid solution. The stirring is continued at room temperature for 4h for aging. The solid is washed with water and anhydrous ethanol alternately until neutral, and dried at 80°C to obtain magnetic SiO2 microspheres. 0.24g of CuSO4*5H2O is dissolved in 20mL of H2O to obtain solution A. 0.15g of NH4Cl is added to solution A. 0.3g of SiO2 microspheres is weighed into 30mL of H2O, and ultrasonic dispersion is continued for 10min to obtain suspension B. 2mL of NH3*H2O (30wt%) solution is added, and ultrasonic dispersion is continued for 2min. Solution A containing Cu is added dropwise under stirring. After the addition is completed, 15.0mL of filtrate containing iron (the concentration of Fe in the filtrate is 2.29g / L) is added dropwise. After stirring for 20min, the obtained mixed suspension is transferred into a polytetrafluoroethylene-lined autoclave, and aged at 160°C for 10h. The filter residue is washed with water and anhydrous ethanol alternately, and dried at 80°C to obtain slag-based hollow microsphere nanoreactor. 2+ The concentration of Fe in the filtrate is 2.29g / L. 2+ The concentration of Fe in the filtrate is 2.29g / L.

[0032] The crystalline phase of the smelting copper slag (CSS), the filter residue after acid immersion (CSAR), and the slag-based hollow microsphere nanoreactor (Cu / Fe PS) of the present example is shown in FIG. 1. The smelting copper slag CSS is mainly composed of Fe3O4 and Fe2SiO4. After leaching with sulfuric acid, the Fe2SiO4 is decomposed, and a clear hump appears at 10° to 30°. The filter residue CSAR is mainly composed of Fe3O4 and amorphous SiO2. After immersion-hydrothermal treatment, the diffraction peaks of coestite appear in the composite material, indicating that the slag-based hollow microsphere nanoreactor is mainly composed of coestite. Figure 2 The apparent morphology, SEM, TEM, and EDS spectrum of the slag-based hollow microsphere nanoreactor prepared in the present example are shown in FIG. 2. As can be seen from the figure, the slag-based hollow microsphere nanoreactor maintains the spherical shape of the original SiO2 microspheres, has a hollow cavity, and has a similar appearance to a sea urchin. The shell layer is composed of nanotubes with an outer diameter of 5-7nm, and the surface of the shell layer is distributed with nanoparticles. According to the XRD results, the shell layer is mainly composed of coestite, and the nanoparticles on the inner and outer surfaces are Fe3O4. The EDS spectrum shows that Cu, Fe, and Si are uniformly distributed.

[0033] Figure 3 The apparent morphology, SEM, TEM, and EDS spectrum of the slag-based hollow microsphere nanoreactor prepared in the present example are shown in FIG. 2. As can be seen from the figure, the slag-based hollow microsphere nanoreactor maintains the spherical shape of the original SiO2 microspheres, has a hollow cavity, and has a similar appearance to a sea urchin. The shell layer is composed of nanotubes with an outer diameter of 5-7nm, and the surface of the shell layer is distributed with nanoparticles. According to the XRD results, the shell layer is mainly composed of coestite, and the nanoparticles on the inner and outer surfaces are Fe3O4. The EDS spectrum shows that Cu, Fe, and Si are uniformly distributed.

[0034] ​The specific surface area (S Figure 4 ) and pore size distribution (D Figure 5 ) of the CSAR and slag-based hollow microspheres nanoreactor (Cu / Fe PS) were analyzed by N2 adsorption-desorption curve; the Brunauer-Emmett-Teller specific surface area (S BET ) of the CSAR was 72.78 m 2 ×g -1 , the pore volume was 0.16 cm 3 ×g -1 , the most probable pore size and the average pore size were 3.93 nm and 9.81 nm respectively, and it could be seen that the pore size distribution of the material was wide and the pore structure was not uniform. The S BET of the slag-based hollow microspheres nanoreactor was 486.5 m 2 ×g -1 (6.68 times of the CSAR), the pore volume was 0.64 cm 3 ×g -1 , the most probable pore size and the average pore size were 3.14 nm and 5.74 nm respectively, the specific surface area of the material was greatly improved compared with the raw material, the pore size distribution was very concentrated, and it indicated that the pore structure of the slag-based hollow microspheres nanoreactor was relatively uniform, and the average pore size measured by BET was consistent with the nanotube diameter measured by TEM. The larger specific surface area was beneficial to adsorption, and more active sites were exposed to play better catalytic performance;

[0035] The slag-based hollow microspheres nanoreactor prepared in Example 2 was applied to Fenton system to remove chlortetracycline hydrochloride in wastewater, and was compared with the raw material CSS and CSAR, the initial concentration of chlortetracycline hydrochloride was 50 mg / L, the catalyst dosage was 0.7 g / L, the potassium monopersulfate (PMS) dosage was 0.16 mmol / L, after 10 min of reaction, the CTC degradation rate of CSS and CSAR corresponding to 10 min was only 19.71% and 31.42% respectively, and the CTC degradation rate of the slag-based hollow microspheres nanoreactor prepared in this example was 100% (a); Figure 6

[0036] The slag-based hollow microspheres nanoreactor prepared in Example 2 was applied to Fenton system to remove methylene blue in wastewater, and was compared with the raw material CSS and CSAR, the initial concentration of methylene blue was 50 mg / L, the catalyst dosage was 0.5 g / L, the potassium monopersulfate (PMS) dosage was 0.16 mmol / L, the MB degradation rate of CSS and CSAR corresponding to 10 min was only 20.50% and 40.88% respectively, and the MB degradation rate of the slag-based hollow microspheres nanoreactor prepared in this example corresponding to 5 min was 100% (b). Figure 6 ​​

[0037] Example 3: Preparation of slag-based hollow microsphere nanoreactor

[0038] After smelting copper slag was dried at 60℃, ball-milling, and sieved through a 325 mesh sieve, 2g was weighed into a three-necked flask, 50mL of 1.5mol / L hydrochloric acid solution was added, and stirring was continued at 20℃ for 5h. The filtrate containing iron and the magnetic filter residue containing silicon were obtained by filtration, and the filter residue was washed with water until it was neutral. The filter residue was added to 30mL of 1.5mol / L NaOH solution, and stirring was continued at 80℃ for 2h. After stopping heating, the pH was adjusted to 9 using a sulfuric acid solution, and stirring was continued at room temperature for 5h for aging. After centrifugation, the solid was washed with water and ethanol alternately until it was neutral, and was dried at 80℃ to obtain magnetic SiO2 microspheres. 0.12g of CuSO4·5H2O was dissolved in 20mL of H2O to obtain solution A, and 0.1g of NH4Cl was added. 0.3g of magnetic SiO2 microspheres was weighed into 30mL of H2O, and was ultrasonically dispersed for 10min to obtain suspension B. 4mL of NH3·H2O (30wt%) solution was added, and ultrasonic dispersion was continued for 2min. Solution A containing Cu2+ was added dropwise under stirring, and after the addition was completed, 10.0mL of filtrate containing Fe (the concentration of Fe in the filtrate was 4.76g / L) was added dropwise. After stirring was continued for 20min, the obtained mixed suspension was transferred into a polytetrafluoroethylene-lined hydrothermal kettle, and was aged at 150℃ for 12h. After filtration, the filter residue was washed with water and ethanol alternately, and was dried at 100℃ to obtain slag-based hollow microsphere nanoreactor. 2+

[0039] The slag-based hollow microsphere nanoreactor prepared in this example was applied to a Fenton system to remove chlortetracycline hydrochloride in wastewater. Figure 7 The initial concentration of chlortetracycline hydrochloride was 100mg / L, the catalyst dosage was 0.7g / L, and the dosage of potassium peroxymonosulfate (PMS) was 0.64mmol / L. After 10min of reaction, the degradation rate of CTC was 96.05%.

[0040] The slag-based hollow microsphere nanoreactor prepared in this example was applied to a Fenton system to remove methylene blue in wastewater. Figure 7 The initial concentration of methylene blue was 75mg / L, the catalyst dosage was 0.5g / L, and the dosage of potassium peroxymonosulfate (PMS) was 0.32mmol / L. After 5min of reaction, the degradation rate of MB was 100%.

[0041] Example 4: Preparation of slag-based Fe-Cu bimetallic hollow microsphere nanoreactor

[0042] ​The smelting copper slag is dried at 100℃, ball-milled, and sieved through a 180-mesh sieve. 2 g of the sieved slag is placed in a three-necked flask, 50 mL of 1.5 mol / L sulfuric acid solution is added, and stirring is performed at 80℃ for 2 h. The filtrate containing iron and the magnetic filter residue containing silicon are obtained by filtration. The filter residue is washed with water until neutral. The filter residue is added to 30 mL of 2 mol / L NaOH solution, and stirring is performed at 80℃ for 2 h. After the heating is stopped, the pH is adjusted to 10 with hydrochloric acid solution. Stirring is continued at room temperature for 4 h for aging. The solid is washed with water until neutral, and dried at 80℃ to obtain magnetic SiO2 microspheres. 0.32 g of CuSO4·5H2O is dissolved in 20 mL of H2O to obtain solution A. 0.15 g of NH4Cl is added to the solution A. 0.2 g of the magnetic SiO2 microspheres is weighed into 30 mL of H2O, and ultrasonic dispersion is performed for 10 min to obtain suspension B. 3 mL of NH3·H2O (30 wt%) solution is added, and ultrasonic dispersion is performed for 2 min. The solution A containing Cu is added dropwise under stirring. After the dropwise addition is completed, 8.0 mL of the filtrate containing iron (the concentration of Fe in the filtrate is 5.11 g / L) is added dropwise. After stirring for 20 min, the obtained mixed suspension is transferred into a polytetrafluoroethylene-lined hydrothermal kettle, and aging is performed at 140℃ for 24 h. The filter residue is washed with water and ethanol alternately, and dried at 80℃ to obtain slag-based hollow microsphere nano-reactors. 2+ The slag-based hollow microsphere nano-reactors prepared in this example are applied to a Fenton system to remove chlortetracycline hydrochloride in wastewater.

[0043] The slag-based hollow microsphere nano-reactors prepared in this example are applied to a Fenton system to remove chlortetracycline hydrochloride in wastewater. Figure 8 The initial concentration of chlortetracycline hydrochloride is 150 mg / L, the catalyst dosage is 0.9 g / L, and the dosage of potassium peroxymonosulfate (PMS) is 0.64 mmol / L. After 20 min of reaction, the degradation rate of CTC is 95.62%.

[0044] The slag-based hollow microsphere nano-reactors prepared in this example are applied to a Fenton system to remove methylene blue in wastewater. Figure 8 The initial concentration of methylene blue is 100 mg / L, the catalyst dosage is 0.7 g / L, and the dosage of potassium peroxymonosulfate (PMS) is 0.32 mmol / L. After 20 min of reaction, the degradation rate of MB is 100%.

Claims

1. A method for preparing a slag-based hollow microsphere nanoreactor, characterized in that, Iron- and silicon-rich solid waste is dried, ball-milled and sieved, then placed in a 0.5-3 mol / L acid solution and extracted at 20-120℃ for 2-5 h. Solid-liquid separation yields an iron-containing filtrate and a solid. The solid is washed until neutral and then added to a 0.5-3 mol / L alkaline solution. Treatment is carried out at 50-150℃ for 0.5-5 h, adjusting the pH of the reactants to 7-11. After aging for 2-15 h, solid-liquid separation is performed, and the solid is washed and dried to obtain SiO2 microspheres. The SiO2 microspheres are dispersed in a 1-10% (v / v) ammonia solution, and then Cu-containing... 2+ The solution, NH4Cl, and iron-containing filtrate were stirred and mixed. The resulting mixed suspension was transferred into a hydrothermal reactor lined with polytetrafluoroethylene and aged at 100-200℃ for 4-48 hours. After solid-liquid separation, the solid was washed and dried to obtain a slag-based hollow microsphere nanoreactor. The iron-silicon-rich solid waste is copper smelting slag.

2. The method for preparing the slag-based hollow microsphere nanoreactor according to claim 1, characterized in that: The acid in the acid solution is sulfuric acid, nitric acid, or hydrochloric acid, and the alkaline solution is sodium hydroxide solution.

3. The method for preparing the slag-based hollow microsphere nanoreactor according to claim 1, characterized in that: Cu 2+ The solution is selected from copper sulfate solution, copper nitrate solution, and copper chloride solution, with a Cu to Fe molar ratio of 0.1-2:1, and NH4Cl and Cu 2+ The molar ratio is 0.5-4:

1.

4. The slag-based hollow microsphere nanoreactor prepared by the method according to any one of claims 1-3, characterized in that: Specific surface area is 300-550 m² 2 / g, average pore size 3.14-5.74nm, pore volume 0.55-0.75cm³ 3 / g.

5. The application of the slag-based hollow microsphere nanoreactor according to claim 4 in the removal of chlortetracycline hydrochloride from wastewater.

6. The application of the slag-based hollow microsphere nanoreactor according to claim 4 in the removal of methylene blue from wastewater.

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