CN111389376A - Polypyrrole-modified magnetic kaolin nanocomposite and preparation method and application thereof - Google Patents
Polypyrrole-modified magnetic kaolin nanocomposite and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a polypyrrole modified magnetic kaolin nanocomposite and a preparation method and application thereof, belonging to the technical field of magnetic nanocomposites. The preparation method provided by the invention comprises the following steps: mixing first ferric chloride, sodium acetate, kaolin, polyether polyol and glycol, and carrying out hydrothermal reaction to obtain magnetic kaolin; and mixing the magnetic kaolin, sodium dodecyl benzene sulfonate, water, pyrrole and second ferric chloride, performing polymerization reaction, and washing and drying polymerization reaction products in sequence to obtain the polypyrrole modified magnetic kaolin nanocomposite. The polypyrrole modified magnetic kaolin nanocomposite prepared by the invention has extremely high removal efficiency on heavy metal ions and organic pollutants in water, can simultaneously remove various coexisting heavy metal ions, and can be repeatedly used for many times.
Description
Technical Field
The invention belongs to the technical field of magnetic nano composite materials, and particularly relates to a polypyrrole modified magnetic kaolin nano composite material as well as a preparation method and application thereof.
Background
At present, the problem of heavy metal pollution in industrial wastewater is more and more serious, the source of the heavy metal pollution is wide, and the heavy metal pollution is from industries such as metallurgy, mining, printing and dyeing and the like. The industrial wastewater contains a variety of pollutants, and among them, heavy metals are the most common and one of the most difficult pollutants to treat.
At present, the methods for treating the heavy metal pollution of the water body mainly comprise a biological method, a chemical precipitation method, an adsorption method, a membrane separation method, an ion exchange method and the like. Among them, the adsorption method has the advantages of low cost, difficult secondary pollution, high removal efficiency and the like, and is widely applied to practical engineering. The conventional adsorbing materials such as activated carbon, silica gel, polyacrylamide, magnetic kaolin and the like have low adsorption efficiency on certain heavy metals, and the development space of the materials is limited.
The preparation of Huangming magnetic kaolin and the adsorption performance of the Huangming magnetic kaolin to Cu (2+) and Pb (2+) are [ D ]2016 ], and the magnetic kaolin is prepared by a coprecipitation method and is used for carrying out adsorption experiments on lead ions, so that the adsorption capacity reaches 12.5mg/g, and the adsorption performance is weaker.
The' performance research on the preparation of the Qinluilu nano magnetic mineral material and the removal of heavy metals in water [ D ].2017 ] discloses that magnetic kaolin is synthesized by a solvothermal method, and adsorption experiments are carried out on lead, chromium and copper, wherein the maximum adsorption amounts are 86.1mg/g, 16.5mg/g and 22.1mg/g respectively, and the adsorption effect is general.
Disclosure of Invention
In view of the above, the present invention provides a polypyrrole-modified magnetic kaolin nanocomposite, and a preparation method and an application thereof. The polypyrrole modified magnetic kaolin nanocomposite prepared by the preparation method provided by the invention has extremely high removal efficiency on heavy metal ions in water.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a polypyrrole modified magnetic kaolin nanocomposite, which comprises the following steps:
mixing first ferric chloride, sodium acetate, kaolin, polyether polyol and glycol, and carrying out hydrothermal reaction to obtain magnetic kaolin;
and mixing the magnetic kaolin, sodium dodecyl benzene sulfonate, water, pyrrole and second ferric chloride, performing polymerization reaction, and washing and drying polymerization reaction products in sequence to obtain the polypyrrole modified magnetic kaolin nanocomposite.
Preferably, the temperature of the hydrothermal reaction is 150-250 ℃, and the time of the hydrothermal reaction is 6-10 h.
Preferably, the temperature of the polymerization reaction is room temperature, and the time of the polymerization reaction is 4-8 h.
Preferably, the mass ratio of the first ferric chloride, the sodium acetate, the kaolin and the polyether polyol is 2-10: 2-10: 2-10: 2 to 5.
Preferably, the mass ratio of the magnetic kaolin to the pyrrole to the second iron chloride is 0.15-0.8: 0.017-0.087: 3 to 15.
The invention also provides the polypyrrole modified magnetic kaolin nanocomposite prepared by the preparation method in the technical scheme, wherein the polypyrrole modified magnetic kaolin nanocomposite has a core-shell structure, the core is magnetic kaolin, and the shell is polypyrrole; the particle size of the polypyrrole modified magnetic kaolin nanocomposite is 20-100 nm.
The invention also provides application of the polypyrrole modified magnetic kaolin nanocomposite material in the technical scheme in sewage treatment containing heavy metal ions and/or organic pollutants.
Preferably, the application comprises the steps of:
and adjusting the pH value of the sewage to 2-10, mixing the sewage with the polypyrrole modified magnetic kaolin nano composite material, and performing adsorption treatment.
Preferably, the sewage contains heavy metal ions and organic pollutants, the concentration of the heavy metal ions is 10-100 mg/L, and the concentration of the organic pollutants is 10-100 mg/L.
The invention provides a preparation method of a polypyrrole modified magnetic kaolin nanocomposite, which comprises the following steps: mixing first ferric chloride, sodium acetate, kaolin, polyether polyol and glycol, and carrying out hydrothermal reaction to obtain magnetic kaolin; and mixing the magnetic kaolin, sodium dodecyl benzene sulfonate, water, pyrrole and second ferric chloride, performing polymerization reaction, and washing and drying polymerization reaction products in sequence to obtain the polypyrrole modified magnetic kaolin nanocomposite. The invention prepares the magnetic kaolin (Fe) by hydrothermal reaction3O4@ Kaolin) under the action of sodium dodecyl benzene sulfonate, Fe3O4@ Kaolin is uniformly dispersed in the reaction medium system and FeCl is used3·6H2O is oxidant to polymerize monomer pyrrole in Fe3O4The magnetic composite material of polypyrrole-coated magnetic Kaolin is formed on the surface of Kaolin, a large number of amino groups in a polypyrrole polymer chain are utilized to chelate heavy metal ions, the specific surface area of the prepared polypyrrole-modified magnetic Kaolin nanocomposite is increased, and charges generated on the surface of the composite material can generate strong electrostatic action on heavy metals, so that the obtained polypyrrole-modified magnetic Kaolin nanocomposite has high adsorption capacity and anti-interference capacity, and the adsorption capacity on the heavy metal ions is greatly improved. The raw materials adopted by the invention are all nontoxic or low-toxicity materials, so the application cost is low and the application value is high. The preparation method provided by the invention is simple and easy in process, safe, green and environment-friendly. The example results show that the polypyrrole modified magnetic kaolin nanocomposite prepared by the invention has large adsorption capacity, has extremely high removal efficiency on heavy metal ions and organic pollutants in water, and can remove Hg2+、Cr6+And Cd2+The removal efficiency of (a) is 97.6%, 91.8% and 96%, respectively, and the removal efficiency of p-phenol is 96.5%; has strong anti-interference capability, can simultaneously remove various coexisting heavy metal ions when Hg is used2+、Cr6+And Cd2+In the sewageFor Hg when present in water2+、Cr6+And Cd2+The removal rates of (a) are respectively 90.6%, 84.1% and 70.6%; and can be repeatedly used for a plurality of times, and the adsorption capacity after 8 times of desorption is 79.4 percent of the initial adsorption capacity.
Drawings
FIG. 1 is Fe3O4SEM picture of @ Kaolin nanocomposite;
FIG. 2 is Ppy-Fe prepared in example 13O4SEM picture of @ Kaolin nanocomposite;
FIG. 3 is Ppy-Fe prepared in example 13O4FTIR profile of @ Kaolin nanocomposite;
FIG. 4 is Ppy-Fe prepared in example 13O4The hysteresis curve of @ Kaolin nanocomposite;
FIG. 5 is Ppy-Fe prepared in example 13O4@ Kaolin nanocomposite magnetic effect diagram.
Detailed Description
The invention provides a preparation method of a polypyrrole modified magnetic kaolin nanocomposite, which comprises the following steps:
mixing first ferric chloride, sodium acetate, kaolin, polyether polyol and glycol, and carrying out hydrothermal reaction to obtain magnetic kaolin;
and mixing the magnetic kaolin, sodium dodecyl benzene sulfonate, water, pyrrole and second iron chloride, performing polymerization reaction, and then sequentially washing and drying to obtain the polypyrrole modified magnetic kaolin nanocomposite.
In the invention, the raw materials are all conventional commercial products in the field or are prepared by conventional methods in the field if no special indication is given.
According to the invention, first ferric chloride, sodium acetate, kaolin, polyether polyol and ethylene glycol are mixed and subjected to hydrothermal reaction to obtain the magnetic kaolin.
In the invention, the mass volume ratio of the first ferric chloride, the sodium acetate, the kaolin, the polyether polyol and the ethylene glycol is preferably 2-10 g: 2-5 g: 50-300 m L, and more preferably 6 g: 5 g: 3 g: 4 g: 150m L.
In the present invention, the mixing sequence of the first ferric chloride, the sodium acetate, the kaolin polyethylene glycol, the polyether polyol and the ethylene glycol is preferably that the first ferric chloride, the sodium acetate and the ethylene glycol are firstly mixed and then secondly mixed with the kaolin and the polyether polyol. In the present invention, the first mixing is preferably performed by stirring. In the present invention, the first mixing method is not particularly limited, and the raw materials may be mixed uniformly. In the present invention, the second mixing means is preferably ultrasound; the time of the ultrasonic treatment is preferably 2-4 h. The invention has no special limitation on the frequency of the ultrasonic wave, and the raw materials can be uniformly mixed.
In the invention, the temperature of the hydrothermal reaction is preferably 150-250 ℃, and more preferably 200 ℃; the time of the hydrothermal reaction is preferably 6-10 h, and more preferably 8 h. The invention adopts a hydrothermal method to prepare the magnetic kaolin, and Fe on the surface of the prepared magnetic kaolin3O4The particle size is small and uniform, thus improving the magnetic property of the magnetic kaolin.
After the hydrothermal reaction, the magnetic kaolin is preferably obtained by sequentially washing and drying the obtained hydrothermal reaction product.
The washing operation is not particularly limited in the invention, and a washing mode known to a person skilled in the art can be adopted; the invention removes unreacted raw materials by washing. In the invention, the drying temperature is preferably 50-105 ℃, and more preferably 70 ℃; the drying time is preferably 4-12 h, and more preferably 6. The drying operation is not particularly limited, and the drying operation can be carried out to a constant weight.
After the magnetic kaolin is obtained, the magnetic kaolin, sodium dodecyl benzene sulfonate, water, pyrrole and second iron chloride are mixed, and after polymerization reaction, the mixture is washed and dried in sequence to obtain the polypyrrole modified magnetic kaolin nanocomposite.
In the invention, the mass ratio of the magnetic kaolin, sodium dodecyl benzene sulfonate, water, pyrrole and second ferric chloride is preferably 0.15-0.8: 0.025 to 0.2: 100-500: 0.017-0.087: 3 to 15, and more preferably 0.15: 0.035: 150: 0.5: 3. in the present invention, the mass of the magnetic kaolin is preferably a dry mass.
In the present invention, the magnetic kaolin, sodium dodecylbenzenesulfonate, water, pyrrole and second ferric chloride are preferably mixed in the order of first mixing the magnetic kaolin, sodium dodecylbenzenesulfonate with part of water to obtain a magnetic kaolin dispersion, second mixing the magnetic kaolin dispersion with pyrrole to obtain a first mixture, third mixing a second ferric chloride with the rest of water to obtain a ferric chloride solution, mixing the ferric chloride solution with the first mixture to perform a polymerization reaction to obtain a polymerization reaction product, wherein the volume ratio of the part of water to the rest of water is preferably 10-50: 1-5.
The present invention preferably performs the polymerization reaction while mechanically stirring. In the present invention, the polymerization reaction is preferably started at the time of dropping the ferric chloride solution. In the present invention, the polymerization reactionThe temperature of (b) is preferably room temperature; the time of the polymerization reaction is preferably 4 to 8 hours, and more preferably 6 hours. The invention prepares Fe by hydrothermal reaction3O4@ Kaolin, Fe under the action of sodium dodecylbenzenesulfonate3O4@ Kaolin is uniformly dispersed in the reaction medium system and FeCl is used3·6H2O is oxidant to polymerize monomer pyrrole in Fe3O4The surface of @ Kaolin forms a magnetic composite material of magnetic Kaolin coated with polypyrrole, and a large amount of amino groups in a polypyrrole polymer chain are utilized to chelate heavy metal ions, so that the obtained polypyrrole modified magnetic Kaolin nanocomposite has higher adsorption capacity and anti-interference capability, and the adsorption capability of heavy metal ions is greatly improved.
The washing operation is not particularly limited in the present invention, and the unreacted raw materials are removed by washing in a washing manner known to those skilled in the art. In the invention, the drying temperature is preferably 50-105 ℃, and more preferably 70 ℃; the drying time is preferably 4-12 h, and more preferably 6 h. The drying operation is not particularly limited, and the drying operation can be carried out to a constant weight.
The invention also provides the polypyrrole modified magnetic kaolin nanocomposite prepared by the preparation method in the technical scheme, wherein the polypyrrole modified magnetic kaolin nanocomposite has a core-shell structure, the core is magnetic kaolin, and the shell is polypyrrole; the particle size of the polypyrrole modified magnetic kaolin nanocomposite is 20-100 nm.
The invention also provides the application of the polypyrrole modified magnetic kaolin nanocomposite material in the technical scheme or the polypyrrole modified magnetic kaolin nanocomposite material prepared by the preparation method in the technical scheme in sewage treatment containing heavy metal ions and organic pollutants.
In the present invention, the source of the sewage preferably includes one or more of chemical wastewater, electroplating wastewater, printing wastewater, machining wastewater, mineral processing wastewater, nonferrous metal processing wastewater, and electrolysis, pesticides, medicines, paints, and pigments.
In the present invention, the application preferably comprises the steps of:
and adjusting the pH value of the sewage to 2-10, mixing the sewage with the polypyrrole modified magnetic kaolin nano composite material, and performing adsorption treatment.
In the invention, the pH value of the adjusted sewage is preferably 6-7, the pH value adjusting agent is preferably nitric acid, hydrochloric acid or sodium hydroxide, the concentration of heavy metal ions in the sewage containing the heavy metal ions and organic pollutants is preferably 10-100 mg/L, and the heavy metal ions preferably comprise Hg2+、Pb2+、As5+、Cr6+、Ni2+And Cd2+The concentration of the organic pollutants in the sewage containing the heavy metal ions and the organic pollutants is preferably 10-100 mg/L, the organic pollutants preferably comprise one or more of phenol, orange IV and methyl orange, and the dosage of the polypyrrole modified magnetic kaolin composite material is preferably 0.5-2 mg/L relative to the volume of the sewage.
In the present invention, the mixing is preferably performed by shaking; the temperature of the mixing is preferably room temperature; the mixing time is preferably 6-12 h.
After the adsorption treatment is finished, the polypyrrole modified magnetic kaolin composite material and the treated sewage are preferably separated by adding an external magnetic field.
The invention preferably detects the concentration of the residual heavy metal ions in the treated sewage by an inductively coupled plasma emission spectrometer (ICP-OES), if the concentration of the residual heavy metal ions reaches the national discharge standard, the discharge is carried out, otherwise, the adsorption treatment is carried out again.
The polypyrrole modified magnetic kaolin composite material obtained by separation is preferably recycled, and the recycling mode is preferably desorption. In the present invention, the method of desorption preferably comprises the steps of:
mixing the recycled polypyrrole modified magnetic kaolin composite material with a hydrochloric acid solution, and then washing and drying the mixture in sequence to obtain a regenerated polypyrrole modified magnetic kaolin composite material;
and adjusting the pH value of the sewage to 2-10, mixing the sewage with the regenerated polypyrrole modified magnetic kaolin nano composite material, and performing adsorption treatment.
In the invention, the molar concentration of the hydrochloric acid solution is preferably 1-10 mol/L, the mass-to-volume ratio of the recycled polypyrrole modified magnetic kaolin composite material to the hydrochloric acid is 1 g: 20m L, the mixing mode is preferably normal-temperature water bath oscillation, the mixing time is preferably 40-120 min, the washing operation is not particularly limited by the invention, and a washing mode well known to a person skilled in the art can be adopted.
In the invention, the calculation formula of the adsorption capacity of the polypyrrole modified magnetic kaolin composite material is preferably as shown in formula 1:
Qe＝(C0–Ce) V/m formula 1
QeThe adsorption quantity of the adsorbent is mg/g; c0The unit is the initial concentration of the mercury solution in mg/L, the unit is mg/L of the solution after adsorption, the unit is the volume of the mercury solution in L, and the unit of m is the adding mass of the adsorbent in g.
The polypyrrole-modified magnetic kaolin nanocomposite material, the preparation method and the application thereof provided by the present invention are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Respectively weighing 3g of ferric chloride hexahydrate and 2g of sodium acetate, dissolving the ferric chloride hexahydrate and the sodium acetate in 100m L ethylene glycol, stirring the mixture uniformly to obtain a first mixed solution, adding 2g of kaolin and 2g of polyethylene glycol into the mixed solution, carrying out ultrasonic treatment for 2 hours, moving the mixture into a reaction kettle for reaction for 6 hours at the temperature of 150 ℃, washing the obtained product, and drying the product at the temperature of 60 ℃ to obtain magnetic kaolin powder;
(2) dissolving 0.15g of magnetic kaolin powder and 0.025g of sodium dodecyl benzene sulfonate in 50m L pure water, performing ultrasonic treatment for 30min, mechanically stirring for 30min, and adding 0.25m L pyrrole to obtain a second mixed solution.
(3) Weighing 3g of ferric trichloride hexahydrate, dissolving the ferric trichloride hexahydrate in 10m L pure water, performing ultrasonic treatment until the ferric trichloride hexahydrate is completely dissolved, slowly dropwise adding the ferric trichloride hexahydrate into the second mixed solution at the dropwise adding rate of 1m L/s, continuously performing mechanical stirring reaction for 4 hours, washing, and drying at the temperature of 60 ℃ to obtain a product polypyrrole modified magnetic kaolin composite material, namely Ppy-Fe3O4@Kaolin。
FIG. 1 is Fe3O4SEM picture of @ Kaolin nanocomposite; FIG. 2 is Ppy-Fe prepared in example 13O4SEM image of @ Kaolin nanocomposite. As can be seen from FIGS. 1-2, Ppy-Fe was prepared by adding polypyrrole3O4The surface of the @ Kaolin nano composite material forms a compact polypyrrole shell.
FIG. 3 is Ppy-Fe prepared in example 13O4The FTIR pattern of @ Kaolin nano composite material can be seen in the figure, and is in the range of 1350-1600 cm-1The appearance of a new adsorption peak due to stretching and bending of the amino group from polypyrrole, indicating successful Fe3O4The surface of @ Kaolin is grafted with amino groups.
FIG. 4 is Ppy-Fe prepared in example 13O4Hysteresis curve of @ Kaolin nano composite material, wherein, as can be seen from the figure, Ppy-Fe prepared3O4The @ Kaolin nano composite material has the saturation magnetic strength of 33.2emu/g and has better magnetic separation characteristic.
FIG. 5 is Ppy-Fe prepared in example 13O4The magnetic effect graph of the @ Kaolin nano composite material can show that the Ppy-Fe prepared by the graph3O4The @ Kaolin nano composite material has good magnetism, and the Ppy-Fe prepared by the invention3O4The @ Kaolin nano composite material is mixed in water and placed in a container, and can be easily separated from the water under the action of an external magnetic field, so that Ppy-Fe is realized3O4The @ Kaolin nano composite material is subjected to solid-liquid separation with sewage, so that the purpose of recycling the adsorbent is achieved.
Example 2
(1) Respectively weighing 6g of ferric chloride hexahydrate and 5g of sodium acetate, dissolving the ferric chloride hexahydrate and the sodium acetate in 150m L ethylene glycol, stirring the mixture uniformly to obtain a first mixed solution, adding 3g of kaolin and 3g of polypropylene glycol into the mixed solution, carrying out ultrasonic treatment for 2 hours, moving the mixture into a reaction kettle to react for 6 hours at 200 ℃, washing the obtained product, and drying the product at 50 ℃ to obtain magnetic kaolin powder;
(2) dissolving 0.15g of magnetic kaolin powder and 0.035g of sodium dodecyl benzene sulfonate in 100m L pure water, performing ultrasonic treatment for 30min, mechanically stirring for 30min, and adding 0.5m L pyrrole to obtain a second mixed solution.
(3) Weighing 6g of ferric trichloride hexahydrate, dissolving the ferric trichloride hexahydrate in 25m L pure water, performing ultrasonic treatment until the ferric trichloride hexahydrate is completely dissolved, slowly dropwise adding the ferric trichloride hexahydrate into the second mixed solution at the dropwise adding rate of 1m L/s, continuously performing mechanical stirring reaction for 6 hours, washing, and drying at 50 ℃ to obtain a product polypyrrole modified magnetic kaolin composite material, namely Ppy-Fe3O4@Kaolin。
Example 3
(1) Respectively weighing 9g of ferric chloride hexahydrate and 8g of sodium acetate, dissolving the ferric chloride hexahydrate and the sodium acetate in 200m L ethylene glycol, stirring the mixture uniformly to obtain a first mixed solution, adding 4g of kaolin and 4g of polyethylene glycol into the mixed solution, carrying out ultrasonic treatment for 2 hours, moving the mixture into a reaction kettle to react for 8 hours at the temperature of 250 ℃, washing the obtained product, and drying the product at the temperature of 60 ℃ to obtain magnetic kaolin powder;
(2) dissolving 0.30g of magnetic kaolin powder and 0.050g of sodium dodecyl benzene sulfonate in 150m L pure water, performing ultrasonic treatment for 30min, mechanically stirring for 30min, and slowly adding 1.2m L pyrrole to obtain a second mixed solution.
(3) Weighing 6g of ferric trichloride hexahydrate, dissolving the ferric trichloride hexahydrate in 20m L pure water, performing ultrasonic treatment until the ferric trichloride hexahydrate is completely dissolved, slowly dropwise adding the ferric trichloride hexahydrate into the second mixed solution at the dropwise adding rate of 1m L/s, continuously performing mechanical stirring reaction for 6 hours, washing, and drying at 60 ℃ to obtain a product polypyrrole modified magnetic kaolin composite material, namely Ppy-Fe3O4@Kaolin。
SEM images, FTIR images, and hysteresis curves of the polypyrrole-modified magnetic kaolin composites prepared in examples 2 to 3 are similar to those of example 1, and are not described in detail here.
Application example 1
100m of L heavy metal Hg of 30 mg/L is taken2+The ionic solution is placed in a conical flask with the thickness of 250m L, the pH value is adjusted to 8 by using sodium hydroxide, 10mg of the polypyrrole modified magnetic kaolin nanocomposite prepared in the embodiment 1 is added, the conical flask is placed in an external magnetic field after being vibrated for 6 hours at normal temperature, and the adsorption material is magnetized by using the external magnetic field and then is separated from the solution.
The separated supernatant adopts ICP-OES to treat the residual heavy metal Hg in the solution2+Detecting the ion concentration, the detection result and Hg in the solution before adsorption2+After the initial concentrations of the ions are compared, the polypyrrole modified magnetic kaolin nanocomposite for the heavy metal Hg is obtained by calculation2+Has an adsorption capacity of 292.8mg/g of the heavy metal Hg2+The removal efficiency of (3) was 97.6%.
Application example 2
100m of L heavy metal Cr containing 30 mg/L is taken6+The ionic solution is placed in a conical flask with the thickness of 250m L, the pH value is adjusted to 5 by nitric acid or sodium hydroxide and the like, 10mg of the polypyrrole modified magnetic kaolin nanocomposite prepared in the embodiment 1 is added, the conical flask is placed in an external magnetic field after being vibrated for 6 hours at normal temperature, and the adsorption material is magnetized by the external magnetic field and then is separated from the solution.
The separated supernatant adopts ICP-OES to treat the residual heavy metal Cr in the solution6+Detecting the ion concentration, the detection result and Cr in the solution before adsorption6+Comparing the initial concentration of ions, and calculating to obtain the polypyrrole modified magnetic kaolin nanocomposite as the heavy metal Cr6+Has an adsorption capacity of 275.4mg/g, at which time the heavy metal Cr6+The removal efficiency of (3) was 91.8%.
Application example 3
Taking 100m L heavy metal Cd with the concentration of 35 mg/L2+The ionic solution is placed in a conical flask of 250m L, the pH value is adjusted to 5 by nitric acid, 10mg of the polypyrrole modified magnetic kaolin nanocomposite prepared in the example 1 is added, the conical flask is placed in an external magnetic field after being vibrated for 6 hours at normal temperature, and the adsorption material is magnetized by the external magnetic field and then is separated from the solution.
The separated supernatant adopts ICP-OES to treat the residual heavy metal Cd in the solution2+Detecting the ion concentration, the detection result and Cd in the solution before adsorption2+Comparing the initial concentrations of the ions, and calculating to obtain the polypyrrole modified magnetic kaolin nanocomposite heavy metal Cd2+Has an adsorption capacity of 336mg/g, at which time the heavy metal Cd2+The removal efficiency of (a) was 96%.
Application example 4
Taking 100m of L mass containing Hg2+、Cr6+And Cd2+The solutions with the concentration of 10 mg/L are placed in a conical flask with the concentration of 250m L, the pH value is adjusted to 7 by nitric acid, 5mg of the polypyrrole modified magnetic kaolin nanocomposite prepared in the example 1 is added, the conical flask is placed in an external magnetic field after being vibrated for 6 hours at normal temperature, and the adsorption material is magnetized by the external magnetic field and then is separated from the solution.
The separated supernatant adopts ICP-OES to treat the residual heavy metal Hg in the solution2+、Cr6+And Cd2+Detecting the ion concentration, the detection result and Hg in the solution before adsorption2+、Cr6+And Cd2+After the initial concentrations of the ions are compared, the polypyrrole modified magnetic kaolin nanocomposite for the heavy metal Hg is obtained by calculation2+、Cr6+And Cd2+The adsorption capacities of (A) were 183.2mg/g, 170.2mg/g and 140.2 mg/g. The removal efficiency of the heavy metal at this time is: 90.6%, 84.1% and 70.6%.
Application example 5
(1) Analytical process
100M L, 1M HCl solution was taken in a 250M L conical flask and added to the Hg adsorbed in example 12+And (4) oscillating the recycled material in a normal-temperature water bath in a shaking table for 40min, washing the material with pure water after acid washing and resolving are finished, and drying the material for later use.
(2) Adsorption process after desorption
After the analysis is finished, the adsorption experiment is carried out again, 100m L is taken, and the heavy metal Hg of 40 mg/L is contained2+Placing the ionic solution in a conical flask with the thickness of 250m L, adjusting the pH value to 8 by using sodium hydroxide, and carrying out water bath oscillation at normal temperature for 6h to carry out an adsorption experiment。
The adsorption capacity after 5 times of desorption-adsorption is 92.8 percent of the initial adsorption capacity, the adsorption capacity after 8 times of desorption-adsorption is 79.4 percent of the initial adsorption capacity, and the regeneration utilization rate of the material is high.
Application example 6
Taking 100m L and 25 mg/L phenol solution in a 250m L conical flask, adjusting the pH value to 6 by using hydrochloric acid or sodium hydroxide and the like, then adding 10mg of the polypyrrole modified magnetic kaolin nanocomposite prepared in the example 1, placing the conical flask in an external magnetic field after shaking in water bath at normal temperature for 8 hours, magnetizing the adsorption material by using the external magnetic field, and then separating the adsorption material from the solution, detecting the concentration of residual phenol in the solution by using an ultraviolet spectrophotometer after separation, comparing the detection result with the initial concentration of phenol in the solution before adsorption, and obtaining the adsorption capacity of the polypyrrole modified magnetic kaolin nanocomposite to phenol of 241.3mg/g by calculation, wherein the removal efficiency of phenol is 96.5%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a polypyrrole modified magnetic kaolin nanocomposite comprises the following steps:
mixing first ferric chloride, sodium acetate, kaolin, polyether polyol and glycol, and carrying out hydrothermal reaction to obtain magnetic kaolin;
and mixing the magnetic kaolin, sodium dodecyl benzene sulfonate, water, pyrrole and second ferric chloride, performing polymerization reaction, and washing and drying polymerization reaction products in sequence to obtain the polypyrrole modified magnetic kaolin nanocomposite.
2. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction is 150 to 250 ℃ and the time of the hydrothermal reaction is 6 to 10 hours.
3. The preparation method according to claim 1, wherein the polymerization reaction temperature is room temperature, and the polymerization reaction time is 4-8 h.
4. The preparation method according to claim 1 or 2, wherein the mass ratio of the first ferric chloride, the sodium acetate, the kaolin and the polyether polyol is 2-10: 2-10: 2-10: 2 to 5.
5. The preparation method according to claim 1 or 3, wherein the mass ratio of the magnetic kaolin to the pyrrole to the second iron chloride is 0.15-0.8: 0.017-0.087: 3 to 15.
6. The polypyrrole-modified magnetic kaolin nanocomposite material prepared by the preparation method according to any one of claims 1 to 5, wherein the polypyrrole-modified magnetic kaolin nanocomposite material has a core-shell structure, the core is magnetic kaolin, and the shell is polypyrrole; the particle size of the polypyrrole modified magnetic kaolin nanocomposite is 20-100 nm.
7. The polypyrrole-modified magnetic kaolin nanocomposite material according to claim 6, wherein the polypyrrole-modified magnetic kaolin nanocomposite material is used for treating sewage containing heavy metal ions and/or organic pollutants.
8. The application according to claim 7, characterized in that it comprises the following steps:
and adjusting the pH value of the sewage to 2-10, mixing the sewage with the polypyrrole modified magnetic kaolin nano composite material, and performing adsorption treatment.
9. The use of claim 8, wherein the wastewater contains heavy metal ions and organic pollutants, the concentration of the heavy metal ions is 10-100 mg/L, and the concentration of the organic pollutants is 10-100 mg/L.
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