CN112774621B - Hollow microsphere and preparation method and application thereof - Google Patents
Hollow microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of material preparation and sewage treatment, and discloses a preparation method of hollow microspheres, which comprises the following steps: synthesizing silicon dioxide microspheres by using styrene emulsion as a template, synthesizing iron-manganese oxide-silicon dioxide microspheres by using the silicon dioxide microspheres as a template, and finally removing silicon dioxide to obtain the hollow microspheres. The hollow microspheres prepared by the invention have the function of adsorbing thallium which is a highly toxic element in wastewater, the hollow microspheres adsorbing thallium naturally settle under the action of a magnet, and thallium in upper-layer clear liquid is reduced to meet the requirement of environmental protection. The hollow microspheres adsorbing thallium can be recycled, so that hazardous waste is avoided, and thallium resource utilization can be realized. The hollow microspheres can adsorb and settle thallium in wastewater with the pH value of 2-10, are easy to prepare, have good selectivity, are less influenced by other impurities, have strong adsorption capacity, are quick, are small in use amount and low in cost, and can reduce the thallium content of the treated thallium-containing wastewater to below 2 mu g/L so as to reach the thallium pollutant discharge standard of industrial wastewater (DB 44-1989-2017).
Description
Technical Field
The invention relates to the technical field of material synthesis and wastewater treatment, in particular to a hollow microsphere and a preparation method and application thereof.
Background
In the environment, thallium is distributed sparsely and dispersedly, independent ore deposits can be formed in a few areas, trace elements are often accompanied in oxidized ores such as mica, feldspar, alunite and jarosite and sulphide ores such as galena, pyrite and sphalerite, wherein a pyrite area is often accompanied with thallium metal resources, the storage capacity is large, the grade is high, the distribution is wide, and therefore a large amount of thallium-containing wastewater can be released in the steel mining and smelting process. In a water body, thallium mainly exists in a monovalent form, has similar properties with potassium elements, is a dispersive element with strong mobility and high toxicity, has a poisoning effect on organisms far exceeding that of common heavy metals such As As, Cr, Cd and the like, and can cause human poisoning by trace thallium. With the development of modern industry, a large amount of thallium enters the environment from approaches such as mining, metal smelting and the like, and thallium poisoning and thallium pollution events occur sometimes. In recent years, thallium pollution events are respectively outbreaked in the north river, the Hejiang river, the Guizhou Xingren and the like in China. Under the condition of rainstorm and the washing of running water, thallium element is easy to diffuse from bottom mud of a river bed and the surface layer of soil into a water body to form secondary pollution, and meanwhile, the thallium element harms the downstream cultivated land of a river or a water supply system. Therefore, thallium is one of heavy metal pollutants needing important protection, the discharge standard of thallium-containing wastewater is regulated to be 5 mug/L (GB31573-2015) or even 2 mug/L (DB 44/1989-.
At present, thallium-containing wastewater treatment technologies mainly comprise a precipitation method, an adsorption method, ion exchange, solvent extraction and the like, however, the traditional adsorbents such as clay minerals, natural metal oxides and the like are limited in wide application due to the defects of poor selectivity, low adsorption capacity, poor environmental friendliness and the like, and the ion exchange method needs special equipment and has poor material regeneration capacity; the solvent extraction method needs to consume a large amount of organic reagents, wastes a large amount of energy consumption, causes secondary pollution, and is difficult to realize industrial application. Therefore, the development of an environment-friendly and efficient purification and repair material becomes crucial. The ideal thallium adsorbent has the characteristics of stability, high efficiency, high selectivity, low cost, reusability and the like. In recent years, with the development of new technology, the variety of materials is rapidly increased, and great advantages and potentials are shown in the field of environmental toxic element pollution treatment. The novel functional materials researched and developed at home and abroad have great breakthroughs in the aspects of adsorption performance, stability and the like, and show good application prospects. However, no hollow microsphere adsorption technology capable of removing thallium pollution is reported so far, and especially, thallium can be deeply removed to reduce thallium-containing wastewater to an adsorption material below 2 mug/L.
Disclosure of Invention
In view of the problems, the invention aims to provide a hollow microsphere and a preparation method and application thereof. The hollow microspheres can remove 97% of thallium in the wastewater at one time, basically realize harmless treatment of a water body through secondary adsorption, reduce the thallium in the wastewater to be below 2 mug/L, realize resource utilization of thallium, realize regeneration of the desorbed hollow microspheres, and avoid generation of dangerous waste or secondary pollution. The hollow microspheres can be used under a wider pH range, are suitable for quickly removing thallium in wastewater with the pH of 2-10, have no strict requirement on temperature, achieve adsorption balance within 120 minutes of reaction, and provide a new feasible method for treating toxic element thallium in wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of hollow microspheres comprises the following steps:
(1) preparing polystyrene microspheres: adding absolute ethyl alcohol and water into a reaction container, uniformly stirring, adding styrene, polyvinylpyrrolidone and azobisisobutyronitrile, and stirring and reacting for 10-14 hours at the temperature of 60-80 ℃; centrifuging and settling the reaction solution, and pouring out supernatant; adding absolute ethyl alcohol, performing ultrasonic dispersion, centrifuging again, and repeating the steps for 3 times to remove unreacted monomers and dispersion stabilizers; vacuum drying at 50-70 ℃ for 7-9 h to obtain white powdery polystyrene microspheres;
wherein the mass ratio of styrene to polyvinylpyrrolidone to azobisisobutyronitrile is 60:5: 1; adding at least 1ml of absolute ethyl alcohol for each 1g of dissolved styrene; adding 1-2 ml of water for every 10g of styrene;
(2) preparing hollow porous silica microspheres: dissolving polystyrene microspheres in absolute ethyl alcohol to prepare polystyrene microsphere emulsion with the mass percentage of 20-30%; adding 25-30 ml of polystyrene microsphere emulsion, 1.0-2.0 g of cetyltrimethylammonium bromide (CTAB), 35-40 ml of water and 100-150 ml of absolute ethyl alcohol into a reaction container, and uniformly stirring; adding ammonia water to adjust the pH value to 10; adding 15-20 ml of Tetraethoxysilane (TEOS), and stirring at room temperature of 25 ℃ for reaction for 2-4 hours; after suction filtration, placing the product in a muffle furnace to be fired for 5-7 h at 500-600 ℃ to obtain hollow porous silica microspheres;
(3) preparing hollow microspheres:
1) weighing 3.0-5.0 g of hollow porous silica microspheres, dissolving in 120-200 ml of water, and uniformly stirring to obtain emulsion A.
2) 0.6-0.8 g of KMnO4Dissolving in 130-160 ml of water, adjusting the pH value to 10 by using ammonia water, adding into the emulsion A, and uniformly stirring to obtain emulsion B;
3) 3.0 to 5.0g of FeSO4·7H2Dissolving O in 4-60 ml of water, and dropwise adding the O into the emulsion B; stirring and reacting for 0.5-2 h, then carrying out suction filtration, and drying the product in an oven at 90-120 DEG C0.5-2 h to obtain Fe-Mn-SiO2The composite microspheres are prepared by mixing the raw materials,
4) mixing Fe-Mn-SiO2Dissolving silicon dioxide in 2-5 mol/L sodium hydroxide solution of the composite microsphere, filtering, collecting filter residue, washing the filter residue to be neutral by using deionized water, filtering again, washing twice by using 5mL absolute ethyl alcohol, and drying in a vacuum drying oven at 50-80 ℃ to obtain the hollow microsphere of the iron-manganese composite material.
Preferably, the step (1) of preparing the polystyrene microsphere specifically comprises: adding 50-60 ml of absolute ethyl alcohol and 6-10 ml of water into a reaction container, uniformly stirring, adding 50-60 g of styrene, 3-5 g of polyvinylpyrrolidone and 0.5-1.0 g of azobisisobutyronitrile, and stirring and reacting for 10-14 h at the temperature of 60-80 ℃; centrifuging and settling the reaction solution, and pouring out supernatant; adding absolute ethyl alcohol, performing ultrasonic dispersion, centrifuging again, and repeating the steps for 3 times to remove unreacted monomers and dispersion stabilizers; and (3) drying for 7-9 h at 50-70 ℃ in vacuum to obtain white powdery polystyrene microspheres.
Preferably, the step (2) of preparing the hollow porous silica microspheres specifically comprises: adding 25ml of polystyrene microsphere emulsion, 1.5g of Cetyl Trimethyl Ammonium Bromide (CTAB), 38ml of water and 120ml of absolute ethyl alcohol into a reaction container, and uniformly stirring; adding ammonia water to adjust the pH value to 10; adding 18ml of Tetraethoxysilane (TEOS), and stirring at room temperature of 25 ℃ for reaction for 3 hours; and after suction filtration, placing the product in a muffle furnace to be fired for 6h at 550 ℃ to obtain the hollow porous silica microspheres.
Preferably, the step (3) of preparing the hollow microspheres specifically comprises the following steps:
1) 4.0g of hollow porous silica microspheres are weighed and dissolved in 150ml of water, and the mixture is stirred uniformly to form emulsion A.
2) 0.7g of KMnO4Dissolving in 150ml water, adjusting pH to 10 with ammonia water, adding into emulsion A, stirring to obtain emulsion B;
3) 4.0g of FeSO4·7H2Dissolving O in 50ml of water, and dropwise adding the dissolved O into the emulsion B; stirring for reaction for 1.5h, performing suction filtration, and drying the product in an oven at 105 ℃ for 1h to obtain Fe-Mn-SiO2The composite microspheres are prepared by mixing the raw materials,
4) mixing Fe-Mn-SiO2Dissolving silicon dioxide in 3.5mol/L sodium hydroxide solution for 2 hours, filtering, collecting filter residue, washing with deionized water to be neutral, filtering again, washing with 5mL absolute ethyl alcohol twice, and drying in a vacuum drying oven at 70 ℃ to obtain the hollow microsphere of the iron-manganese composite material.
The invention also aims to disclose the hollow microsphere prepared by the method.
The invention also aims to disclose an application of the hollow microspheres in thallium removal from wastewater, which comprises the following steps:
(1) adding the hollow microspheres into the thallium-containing wastewater, fully stirring, and then placing the wastewater on a magnet for standing; in each liter of thallium-containing wastewater, the mass of the added hollow microspheres is 20-100 times of that of thallium-containing wastewater;
(2) and (3) the reaction solution after standing is subjected to coagulation under the attraction of a magnet, and is filtered to obtain upper layer clarified liquid, wherein the thallium content of the upper layer clarified liquid is lower than 2 mug/L, and filter residue is hollow microspheres adsorbing thallium.
Preferably, the application of the hollow microspheres in thallium removal of wastewater comprises the following steps:
(1) adding the hollow microspheres into the thallium-containing wastewater, fully stirring for reaction for 120 minutes, and then placing the wastewater on a magnet for standing; in each liter of thallium-containing wastewater, the mass of the added hollow microspheres is 60 times of that of thallium-containing wastewater;
(2) and (3) the reaction solution after standing is subjected to coagulation under the attraction of a magnet, and is filtered to obtain upper layer clarified liquid, wherein the thallium content of the upper layer clarified liquid is lower than 2 mug/L, and filter residue is hollow microspheres adsorbing thallium.
When examining the adsorption effect of the thallium-containing wastewater with a concentration of 10mg/L adsorbed by the hollow microspheres of 0.6g/L and pH 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, it was found that the adsorption rate increases with the increase in pH, and an equilibrium is reached at pH 6, so that pH 6 is the optimum adsorption acidity. Preferably, the optimum acidity of adsorption of the thallium-containing wastewater added with the hollow microspheres in the step (1) is pH 6.
Preferably, the filter residue in the step (2) can realize thallium resource utilization and hollow microsphere regeneration and reuse, and specifically comprises the following steps: soaking the thallium-adsorbed hollow microspheres in a sodium carbonate solution with the pH value of 9-12 for 1-4h for desorption, filtering to obtain first filter residue and first filtrate, washing the first filter residue with deionized water, filtering, and placing in a vacuum drying oven at 50-80 ℃ for 0.5-4h to obtain regenerated hollow microspheres, wherein the first filtrate contains enriched thallium ions, so that resource utilization can be realized.
More preferably, the filter residue in the step (2) can realize the resource utilization of thallium and the regeneration and reuse of the hollow microspheres, and specifically comprises the following steps: soaking the hollow microspheres adsorbing the thallium in a sodium carbonate solution with the pH value of 10 for 2h for desorption, filtering to obtain first filter residue and first filtrate, washing the first filter residue with deionized water, filtering, and placing in a vacuum drying oven at 60 ℃ for 2h to obtain regenerated hollow microspheres, wherein the first filtrate contains enriched thallium ions, so that resource utilization can be realized.
Preferably, the stirring in the step (1) is sufficient, and the specific stirring reaction time is 60-360 minutes.
The removal effect was examined from the difference in thallium concentration in the wastewater before and after adsorption, and the thallium removal rate (R, 100%) was calculated as follows:
R＝(C0-Ct)×100/C0
in the formula, C0Is the concentration (mg/L) of thallium in the wastewater before adsorption; ct is the concentration (mg/L) of thallium after adsorption.
The principle of the invention is as follows: thallium in the water body needs to be oxidized into Tl (III) under certain pH value, then is adsorbed by the hollow microspheres of the iron-manganese composite material, and then is adsorbed and precipitated by the permanent magnet, and finally the purification of the water body is realized. And the hollow microspheres after adsorption are desorbed and regenerated in a sodium carbonate solution with certain acidity.
Compared with the prior art, the invention has the following beneficial effects:
the hollow microsphere is easy to prepare, has good selectivity, is less influenced by other impurities, has strong adsorption capacity, is quick, has small using amount and low cost, and can reduce thallium to be below 2 mu g/L in the treated thallium-containing wastewater so as to reach the thallium pollutant discharge standard of industrial wastewater (DB 44-1989) -2017.
The hollow microspheres can remove 97% of thallium in the wastewater at one time, basically realize harmless treatment of a water body through secondary adsorption, reduce the thallium in the wastewater to be below 2 mug/L, realize resource utilization of thallium, realize regeneration of the desorbed hollow microspheres, and avoid generation of dangerous waste or secondary pollution.
The hollow microspheres can be used under a wider pH range, are suitable for quickly removing thallium in wastewater with the pH of 2-10, have no strict requirement on temperature, achieve adsorption balance within 120 minutes of reaction, and provide a new feasible method for treating toxic element thallium in wastewater.
Drawings
FIG. 1 is a schematic diagram of the application of the hollow microspheres of the present invention to thallium removal from wastewater;
FIG. 2 is an SEM image of hollow microspheres of the present invention;
FIG. 3 is an SEM image of thallium-adsorbed hollow microspheres;
wherein, the 1-thallium-containing wastewater; 2-hollow microspheres; 3-thallium-containing wastewater added with hollow microspheres; 4-permanent magnets; 5-supernatant clear liquid; 6-coagulated thallium-adsorbing hollow microspheres; 7-soaking the desorbed hollow microspheres in a sodium carbonate solution; 8-regenerated hollow microspheres.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following examples.
Example 1
A preparation method of hollow microspheres comprises the following steps:
(1) preparing polystyrene microspheres: adding 50-60 ml of absolute ethyl alcohol and 6-10 ml of water into a reaction container, uniformly stirring, adding 50-60 g of styrene, 3-5 g of polyvinylpyrrolidone and 0.5-1.0 g of azobisisobutyronitrile, and stirring and reacting for 10-14 h at the temperature of 60-80 ℃; the reaction solution was centrifuged and settled and the supernatant was decanted; adding absolute ethyl alcohol, performing ultrasonic dispersion, centrifuging again, and repeating the steps for 3 times to remove unreacted monomers and dispersion stabilizers; and (3) drying for 7-9 h at 50-70 ℃ in vacuum to obtain white powdery polystyrene microspheres.
(2) Preparing hollow porous silica microspheres: dissolving polystyrene microspheres in absolute ethyl alcohol to prepare polystyrene microsphere emulsion with the mass percentage of 20-30%; adding 25ml of polystyrene microsphere emulsion, 1.5g of cetyltrimethylammonium bromide (CTAB), 38ml of water and 120ml of absolute ethyl alcohol into a reaction container, and uniformly stirring; adding ammonia water (the concentration of ammonia water used in the embodiment of the present invention is not limited as long as the pH can be adjusted to 10, and the same applies below) to adjust the pH to 10; adding 18ml of Tetraethoxysilane (TEOS), and stirring at room temperature of 25 ℃ for reaction for 3 hours; and after suction filtration, placing the product in a muffle furnace to be fired for 6h at 550 ℃ to obtain the hollow porous silica microspheres.
(3) The preparation method of the hollow microspheres comprises the following steps:
1) 4.0g of hollow porous silica microspheres were weighed and dissolved in 150ml of water, and stirred uniformly to form emulsion A.
2) 0.7g of KMnO4Dissolving in 150ml water, adjusting pH to 10 with ammonia water, adding into emulsion A, stirring to obtain emulsion B;
3) 4.0g of FeSO4·7H2Dissolving O in 50ml of water, and dropwise adding the dissolved O into the emulsion B; stirring for reaction for 1.5h, performing suction filtration, and drying the product in an oven at 105 ℃ for 1h to obtain Fe-Mn-SiO2The composite microspheres are prepared by mixing the raw materials,
4) mixing Fe-Mn-SiO2Dissolving silicon dioxide in 3.5mol/L sodium hydroxide solution for 2 hours, filtering, collecting filter residue, washing with deionized water to be neutral, filtering again, washing with 5mL absolute ethyl alcohol twice, and drying in a vacuum drying oven at 70 ℃ to obtain the hollow microsphere of the iron-manganese composite material.
The SEM image of the hollow microsphere of the prepared ferro-manganese composite material is shown in figure 2.
Examples 2 to 5 below are specific examples of applying the hollow microspheres prepared in example 1 to an adsorption removal experiment (thallium content in wastewater is 10mg/L) for thallium-containing wastewater of a certain steel smelting plant in Guangdong Shaoguan, and are used for illustrating the application of the hollow microspheres in thallium removal from wastewater. FIG. 1 is a schematic diagram of the application of the hollow microspheres of the present invention to thallium removal from wastewater; wherein, the 1-thallium-containing wastewater; 2-hollow microspheres; 3-thallium-containing wastewater added with hollow microspheres; 4-permanent magnets; 5-supernatant liquor; 6-coagulated hollow microspheres adsorbing thallium; 7-soaking the desorbed hollow microspheres in a sodium carbonate solution; 8-regenerated hollow microspheres.
Example 2:
adsorption removal experiment on thallium-containing wastewater of a certain steel smelting plant of Guangdong Shaokuan (the wastewater contains 10mg/L of thallium):
respectively taking 50ml of thallium-containing wastewater into 4 beakers (pH is 7.0), respectively adding hollow microspheres according to 0.2g/L, 0.6g/L, 0.8g/L and 1g/L, then pneumatically stirring uniformly to react for 180min, stopping, placing on a permanent magnet to stand, after the thallium-containing wastewater is completely precipitated, taking upper-layer clarified wastewater to detect the concentration of thallium, and calculating the removal rate of thallium, wherein the removal rate of thallium is respectively 80%, 97%, 97% and 97%. And taking the supernatant, and adding hollow microspheres according to 0.6g/L, wherein the final thallium removal rate is close to 100%, and the thallium concentration is reduced to below 2 mug/L.
Example 3:
an adsorption removal experiment of thallium-containing wastewater from a certain steel smeltery in Guangdong Shaokou (the wastewater contains thallium 10 mg/L):
respectively taking 50ml of thallium-containing wastewater into 4 beakers (pH is 7.0), respectively adding hollow microspheres according to 0.6g/L, then pneumatically stirring uniformly, respectively reacting for 60min, 120min, 180min and 240min, stopping, placing on a permanent magnet, standing, after complete precipitation, taking upper layer clarified wastewater to detect the concentration of thallium, and calculating the removal rate of thallium, wherein the removal rate of thallium is 82%, 97%, 97% and 97%, respectively, so that the reaction time reaches equilibrium within 120 min.
Example 4:
adsorption removal experiment on thallium-containing wastewater of a certain steel smelting plant of Guangdong Shaokuan (the wastewater contains 10mg/L of thallium):
respectively taking 50ml of thallium-containing wastewater into 11 beakers, respectively adjusting the acidity to pH 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, respectively adding hollow microspheres according to 0.6g/L, then, pneumatically stirring uniformly, stopping the reaction after 120min, placing the beakers on a permanent magnet for standing, after the thallium is completely precipitated, taking upper-layer clarified wastewater for detecting the concentration of thallium, and calculating the removal rate of thallium, wherein the removal rates of thallium are 65%, 68%, 73%, 82%, 97%, 97%, 97%, 97%, 97%, 97% and 97%, respectively, so that the adsorption effect is increased along with the increase of the pH, and the adsorption effect is optimal when the acidity is more than or equal to 6.
Example 5
Adsorption removal experiment on thallium-containing wastewater of a certain steel smelting plant of Guangdong Shaokuan (the wastewater contains 10mg/L of thallium):
respectively taking 50mL of thallium-containing wastewater into 4 beakers, respectively adjusting the acidity to pH 6, respectively adding 0mL, 0.5mL, 2mL and 5mL of hydrogen peroxide with the mass percent of 30%, respectively adding hollow microspheres according to 0.6g/L, then pneumatically stirring uniformly, stopping reaction after 60min, placing on a permanent magnet for standing, after the thallium is completely precipitated, taking upper layer clarified wastewater to detect the concentration of thallium, calculating the removal rate of thallium, wherein the removal rates of thallium are respectively 80%, 92%, 97% and 97%, and as the addition amount of hydrogen peroxide is increased, the adsorption effect is increased, when 2mL of 30% hydrogen peroxide is added for reaction for 60min, the adsorption achieves the best effect, and the addition of hydrogen peroxide can shorten the adsorption balance time.
The experiments show that the ideal result can be achieved only by adsorbing the thallium hollow microspheres at a certain pH and for a certain adsorption time; the addition of hydrogen peroxide is favorable for removing thallium, probably because thallium in the acid wastewater has valence of +1 and +3, and the hydrogen peroxide completely oxidizes the thallium with valence of +1 into thallium with valence of +3, so that the adsorption of the hollow microspheres is more favorable.
The following table 1 shows the removal of thallium by the first adsorption of the hollow microspheres prepared in example 1 into thallium-containing wastewater,
table 1: removal of thallium from thallium-containing wastewater by first adsorption of hollow microspheres (V50 mL, C)0＝10mg/L)
As can be seen from the data in the table, the ideal effect is achieved through the hollow microsphere adsorption experiment under certain conditions, and the maximum removal rate of thallium in the wastewater is 97%.
In the examples 2-5, the hollow microspheres adsorbing thallium are precipitated on the lower layer of the reaction solution, and after filtration, the filter residue can realize the recycling of thallium and the regeneration and reuse of the hollow microspheres. Soaking the filter residue in a sodium carbonate solution with the pH value of 9, the pH value of 10, the pH value of 11 and the pH value of 12 for 1-4h to investigate the desorption effect, filtering to obtain a first filter residue and a first filtrate, washing the first filter residue with deionized water, filtering, and placing in a vacuum drying oven at the temperature of 50-80 ℃ for 0.5-4h to obtain regenerated hollow microspheres, wherein the first filtrate contains enriched thallium ions, so that resource utilization can be realized.
In the above experiment, it was found that the desorption effect was best when the solution was soaked in sodium carbonate solution at pH 10 for 2 h. The desorbed material is placed in a vacuum drying oven at 50-80 ℃ for 0.5-4h, and drying at 60 ℃ for 2h is found to obtain an ideal hollow microsphere shape (as shown in figure 2).
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the embodiments are only used to help understanding the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, there may be variations in the specific implementation manners and application ranges, and in summary, the content of the present description should not be construed as a limitation to the present invention.
Claims (10)
1. The preparation method of the hollow microspheres is characterized by comprising the following steps of:
(1) preparing polystyrene microspheres: adding absolute ethyl alcohol and water into a reaction container, uniformly stirring, adding styrene, polyvinylpyrrolidone and azobisisobutyronitrile, and stirring and reacting for 10-14 hours at the temperature of 60-80 ℃; centrifuging and settling the reaction solution, and pouring out supernatant; adding absolute ethyl alcohol, performing ultrasonic dispersion, centrifuging again, and repeating the steps for 3 times to remove unreacted monomers and dispersion stabilizers; vacuum drying at 50-70 ℃ for 7-9 h to obtain white powdery polystyrene microspheres;
wherein the mass ratio of styrene to polyvinylpyrrolidone to azobisisobutyronitrile is 60:5: 1; adding at least 1ml of absolute ethyl alcohol for each 1g of dissolved styrene; adding 1-2 ml of water every 10g of styrene;
(2) preparing hollow porous silica microspheres: dissolving polystyrene microspheres in absolute ethyl alcohol to prepare polystyrene microsphere emulsion with the mass percent of 20-30%; adding 25-30 ml of polystyrene microsphere emulsion, 1.0-2.0 g of cetyltrimethylammonium bromide (CTAB), 35-40 ml of water and 100-150 ml of absolute ethyl alcohol into a reaction container, and uniformly stirring; adding ammonia water to adjust the pH value to 10; adding 15-20 ml of Tetraethoxysilane (TEOS), and stirring at room temperature of 25 ℃ for reaction for 2-4 hours; after suction filtration, placing the product in a muffle furnace to be fired for 5-7 h at 500-600 ℃ to obtain hollow porous silica microspheres;
(3) preparing hollow microspheres:
1) weighing 3.0-5.0 g of hollow porous silica microspheres, dissolving the hollow porous silica microspheres in 120-200 ml of water, and uniformly stirring to obtain emulsion A;
2) 0.6-0.8 g of KMnO4Dissolving in 130-160 ml of water, adjusting the pH value to 10 by using ammonia water, adding into the emulsion A, and uniformly stirring to obtain emulsion B;
3) 3.0 to 5.0g of FeSO4·7H2Dissolving O in 4-60 ml of water, and dropwise adding the solution into the emulsion B; stirring and reacting for 0.5-2 h, then carrying out suction filtration, and drying the product in an oven at 90-120 ℃ for 0.5-2 h to obtain Fe-Mn-SiO2The composite micro-spheres are formed by compounding micro-spheres,
4) mixing Fe-Mn-SiO2Dissolving the composite microspheres in 2-5 mol/L sodium hydroxide solution to obtain silicon dioxide, filtering, collecting filter residues, washing the filter residues to be neutral by using deionized water, filtering, washing the filter residues twice by using 5mL of absolute ethyl alcohol, and drying the filter residues in a vacuum drying oven at 50-80 ℃ to obtain the hollow microspheres of the iron-manganese composite material.
2. The method for preparing hollow microspheres according to claim 1, wherein the step (1) of preparing polystyrene microspheres specifically comprises: adding 50-60 ml of absolute ethyl alcohol and 6-10 ml of water into a reaction container, uniformly stirring, adding 60g of styrene, 5g of polyvinylpyrrolidone and 1.0g of azobisisobutyronitrile, and stirring and reacting at 60-80 ℃ for 10-14 hours; the reaction solution was centrifuged and settled and the supernatant was decanted; adding absolute ethyl alcohol, performing ultrasonic dispersion, centrifuging again, and repeating the steps for 3 times to remove unreacted monomers and dispersion stabilizers; and (3) drying for 7-9 h at 50-70 ℃ in vacuum to obtain white powdery polystyrene microspheres.
3. The method for preparing hollow microspheres according to claim 1, wherein the step (2) is to prepare hollow porous silica microspheres, specifically: adding 25ml of polystyrene microsphere emulsion, 1.5g of cetyltrimethylammonium bromide (CTAB), 38ml of water and 120ml of absolute ethyl alcohol into a reaction container, and uniformly stirring; adding ammonia water to adjust the pH value to 10; adding 18ml of Tetraethoxysilane (TEOS), and stirring at room temperature of 25 ℃ for reaction for 3 hours; and after suction filtration, placing the product in a muffle furnace to be fired for 6h at 550 ℃ to obtain the hollow porous silica microspheres.
4. The method for preparing hollow microspheres according to claim 1, wherein the step (3) of preparing hollow microspheres specifically comprises the following steps:
1) weighing 4.0g of hollow porous silica microspheres, dissolving the hollow porous silica microspheres in 150ml of water, and uniformly stirring to obtain emulsion A;
2) 0.7g of KMnO4Dissolving in 150ml of water, adjusting the pH value to 10 by using ammonia water, adding the mixture into the emulsion A, and uniformly stirring to obtain emulsion B;
3) 4.0g of FeSO4·7H2Dissolving O in 50ml of water, and dropwise adding the dissolved O into the emulsion B; stirring for reaction for 1.5h, performing suction filtration, and drying the product in an oven at 105 ℃ for 1h to obtain Fe-Mn-SiO2The composite micro-spheres are formed by compounding micro-spheres,
4) mixing Fe-Mn-SiO2Dissolving silicon dioxide in 3.5mol/L sodium hydroxide solution for 2 hours, filtering, collecting filter residue, washing with deionized water to be neutral, filtering again, washing with 5mL absolute ethyl alcohol twice, and drying in a vacuum drying oven at 70 ℃ to obtain the hollow microsphere of the iron-manganese composite material.
5. Hollow microspheres produced by the process according to any one of claims 1 to 4.
6. The use of hollow microspheres according to claim 5 for thallium removal from wastewater comprising the steps of:
(1) adding the hollow microspheres into the thallium-containing wastewater, fully stirring, and then placing the wastewater on a magnet for standing; in each liter of thallium-containing wastewater, the mass of the added hollow microspheres is 20-100 times of that of thallium-containing wastewater;
(2) and (3) the reaction solution after standing is subjected to coagulation under the attraction of a magnet, and is filtered to obtain upper-layer clear liquid, wherein the thallium content of the upper-layer clear liquid is lower than 2 mu g/L, and filter residues are hollow microspheres adsorbing thallium.
7. The application of the hollow microspheres in thallium removal from wastewater according to claim 6, characterized by comprising the following steps:
(1) adding the hollow microspheres into the thallium-containing wastewater, fully stirring for reaction for 120 minutes, and then placing the wastewater on a magnet for standing; in each liter of thallium-containing wastewater, the mass of the added hollow microspheres is 60 times of that of thallium-containing wastewater;
(2) and (3) the reaction solution after standing is subjected to coagulation under the attraction of a magnet, and is filtered to obtain upper layer clarified liquid, wherein the thallium content of the upper layer clarified liquid is lower than 2 mug/L, and filter residue is hollow microspheres adsorbing thallium.
8. Use of hollow microspheres according to claim 6 for thallium removal from wastewater wherein the optimum acidity of adsorption of thallium containing wastewater from step (1) with the addition of hollow microspheres is pH 6.
9. The application of the hollow microspheres in thallium removal from wastewater according to claim 6, wherein the filter residue in step (2) can realize thallium resource utilization and hollow microsphere regeneration and reuse, and specifically comprises: soaking the hollow microspheres adsorbing the thallium in a sodium carbonate solution with the pH value of 9-12 for 1-4h for desorption, filtering to obtain first filter residue and first filtrate, washing the first filter residue with deionized water, filtering, and placing in a vacuum drying oven at 50-80 ℃ for 0.5-4h to obtain regenerated hollow microspheres, wherein the first filtrate contains enriched thallium ions, so that resource utilization can be realized.
10. The application of the hollow microspheres in thallium removal from wastewater according to claim 9, wherein the filter residue in step (2) can realize thallium resource utilization and hollow microsphere regeneration and reuse, and specifically comprises: soaking the hollow microspheres adsorbing the thallium in a sodium carbonate solution with the pH value of 10 for 2h for desorption, filtering to obtain first filter residue and first filtrate, washing the first filter residue with deionized water, filtering, and placing in a vacuum drying oven at 60 ℃ for 2h to obtain regenerated hollow microspheres, wherein the first filtrate contains enriched thallium ions, so that resource utilization can be realized.
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