CN105601915A - Magnetic graphene and polyaniline nano-composite and preparation method thereof - Google Patents

Abstract

The invention discloses a magnetic graphene polyaniline nanocomposite material, a preparation method and an application thereof, and belongs to the technical field of composite materials. Described magnetic graphene polyaniline nano-composite material takes the alcohol that contains 1～5 carbon atoms as solvent, and graphene/polyaniline composite material, FeCl ₃ and sodium acetate are dissolved in described solvent and sonicated, then in The reaction is carried out in a high-pressure reactor to obtain a magnetic graphene-polyaniline nanocomposite material. The composite material prepared by the method of the invention overcomes the shortcomings of easy stacking of graphene sheets and easy agglomeration of simple polyaniline. Using this kind of adsorbent to adsorb phenolic estrogen in water shows better adsorption performance than magnetic graphene materials and magnetic polyaniline materials. Graphene modified by magnetic materials and polyaniline not only improves the adsorption efficiency of phenolic estrogens, but also makes the separation quite easy due to the magnetic properties of the material itself. Therefore, the present invention has the advantages of high adsorption efficiency and simple operation.

Description

A kind of magnetic graphene polyaniline nanocomposite material and preparation method thereof

technical field

The invention belongs to the technical field of composite materials, and relates to a graphene-modified composite adsorption material, in particular to a magnetic graphene-polyaniline nanocomposite material, a preparation method thereof, and an application of the material in phenolic environmental estrogen enrichment.

Background technique

Nonylphenol, octylphenol and bisphenol A are all phenolic environmental estrogens, and their potential risks to the environment and human health have attracted widespread attention. As endocrine disrupting substances, nonylphenol and octylphenol will accumulate in the body and enter the human body through the food chain, which will have a serious impact on the growth and reproductive ability of human cancer cells, so they have been listed as priority hazardous substances by the European Union. EU Directive 2003/53/EC stipulates that the content of nonylphenol in textiles and other commodities shall not exceed 0.1%. The "Oeko-Tex Standard 1000" formulated and promulgated by the International Environmental Textile Association clearly stipulates that the use of nonylphenol in the textile production process is prohibited. Bisphenol A is also an endocrine disruptor, which can affect the reproductive development of mammals and aquatic animals to varying degrees. On October 18, 2008, Health Canada officially announced bisphenol A as a hazardous substance and banned the import and sale of polycarbonate baby bottles containing bisphenol A. The "Restriction of the Use of Certain Hazardous Substances in Consumer Products" (PoHS Directive) issued by the Norwegian Pollution Control Agency also restricts the use of bisphenol A in consumer products.

At present, the main analysis and detection methods used to detect phenolic environmental estrogens include spectrophotometry, fluorescence measurement, gas chromatography, gas-mass spectrometry, liquid chromatography, and liquid-mass spectrometry. Among them, the color-mass spectrometry technology has low detection limit, high sensitivity and good selectivity, but the instrument is expensive and the detection cost is high. In addition, because the content of phenolic estrogens in environmental samples is very low and the background interference is large, even the expensive chromatography-mass spectrometry technology is powerless for the detection of some samples, and other existing analysis methods cannot meet the environmental requirements. For the detection of trace amounts of phenolic estrogen, it is necessary to develop a sample pretreatment method with high selectivity and enrichment rate, and the key is to develop an adsorption material with high adsorption performance.

Contents of the invention

The electron-rich π-π conjugation in graphene provides the possibility for the induced adsorption of organic matter. However, the graphene sheet structure is easy to agglomerate, and its high specific surface area advantage cannot be effectively reflected in actual use, and the surface functional group of graphene is single. Aiming at the characteristics of phenolic environmental estrogens, the inventors have paid creative labor to select in The surface of the graphene is modified with an amino polymer to improve the adsorption of the material to the phenolic environmental estrogen through the hydrogen bond and inductive force between the protonated amino group on the surface of the material and the hydroxyl group in the phenolic environmental estrogen. Therefore the present invention has following three invention purposes:

The first purpose of the present invention is to provide a magnetic graphene-polyaniline nanocomposite material for the above technical problems.

Another object of the present invention is to provide a method for preparing a magnetic graphene-polyaniline nanocomposite for the above-mentioned technical problems.

Another purpose of the present invention is to provide a method for enriching phenolic environmental estrogens by using magnetic graphene polyaniline nanocomposite materials for the above-mentioned technical problems

The purpose of the present invention can be achieved through the following technical solutions:

A kind of magnetic graphene polyaniline nanocomposite material, this material is prepared by following method:

Using an alcohol containing 1 to 5 carbon atoms as a solvent, the graphene/polyaniline composite material, FeCl and sodium acetate with a mass ratio of ₁ to 5:1 to 10:1 to 10 are dissolved in the solvent and Ultrasonic treatment, followed by reaction in a high-pressure reactor, can obtain the magnetic graphene-polyaniline nanocomposite material.

A preparation method of a magnetic graphene polyaniline nanocomposite material, the method uses an alcohol containing 1 to 5 carbon atoms as a solvent, and the graphene/polyaniline with a mass ratio of 1 to 5:1 to 10:1 to 10 The composite material, FeCl ₃ and sodium acetate are dissolved in the solvent and ultrasonically treated, and then reacted in a high-pressure reactor to obtain the magnetic graphene-polyaniline nanocomposite material.

As a preference: in the magnetic graphene polyaniline nanocomposite material and its preparation method, the graphene/polyaniline composite material: FeCl ₃ : the mass ratio of sodium acetate is 1～3:1～5:5～10; the power of ultrasonic treatment 300~500W, the time is 0.5~1.5h; the reaction temperature in the autoclave is 150~250℃, the reaction time is 4~48h, preferably the reaction temperature in the autoclave is 180~200℃, the reaction time For 4 ~ 10h. The alcohol containing 1 to 5 carbon atoms is selected from at least one of methanol, ethanol, ethylene glycol and diethylene glycol, preferably the alcohol containing 1 to 5 carbon atoms is a mixture of ethylene glycol and diethylene glycol .

The graphene/polyaniline composite material described in the technical solution of the present invention is prepared by the following method: graphite oxide and solvent are mixed and ultrasonically treated to obtain a graphene oxide solution; aniline is added to the graphene oxide solution. The hydrochloric acid solution is stirred evenly to obtain a mixed solution; the hydrochloric acid solution containing (NH4) ₂ S ₂ O ₈ is added to the mixed solution for reaction, and a graphene/polyaniline composite material is obtained after the reaction.

As preferably: in the preparation method of graphene/polyaniline composite material, described solvent is selected from at least one in water, ethanol, ethylene glycol and diethylene glycol; Graphite oxide: aniline: (NH ₄ ) ₂ S ₂ The mass ratio of O ₈ is 1-5:1-5:4-10. The mass ratio of aniline and hydrochloric acid in the hydrochloric acid solution containing aniline is 1.5-3:1, and the mass ratio of (NH ₄ ) ₂ S ₂ O ₈ and hydrochloric acid in the hydrochloric acid solution containing (NH4) ₂ S ₂ O ₈ is 15～35:1. The power of ultrasonic treatment is 300-500W, and the time is 0.5-1.5h.

A method for enriching estrogen in a phenolic environment using the magnetic graphene polyaniline nanocomposite prepared above, the method uses the magnetic graphene polyaniline nanocomposite as an adsorption material, and adds the adsorption material to the environment containing phenols estrogen solution and mixed evenly to ensure sufficient adsorption; after the adsorption is sufficient, a magnet is used to separate the adsorption material from the solution; After the completion, the eluted solution is collected to obtain the enriched phenolic environmental estrogen; preferably, the eluent is selected from at least one of methanol, ethanol and acetic acid.

The GO/PANI described in the technical solution of the present invention is a graphene polyaniline composite material, the described MGO/PANI is a magnetic graphene polyaniline nanocomposite material, and the described M/PANI is a magnetic polyaniline composite material, and the described M/GO is a magnetic graphene material.

Beneficial effects of the present invention:

The magnetic graphene polyaniline nano composite material prepared by the invention has stable chemical performance, large specific surface area and strong adsorption performance. Using aniline and magnetic materials to modify graphene overcomes the shortcomings of easy stacking of graphene sheets and easy agglomeration of pure polyaniline. Using this kind of adsorbent to adsorb phenolic estrogen in water shows better adsorption performance than magnetic graphene materials and magnetic polyaniline materials. Graphene modified by magnetic materials and polyaniline not only improves the adsorption efficiency of phenolic estrogens, but also makes the separation quite easy due to the magnetic properties of the material itself. Therefore, the present invention has the advantages of high adsorption efficiency and simple operation.

Description of drawings

Fig. 1 (a) is the transmission electron microscope figure of graphene oxide used in embodiment 1, and Fig. 1 (b) is the transmission electron microscope figure of the graphene/polyaniline composite material that embodiment 1 prepares, and Fig. 1 (c) is embodiment 1 Transmission electron microscope image of the prepared MGO/PANI-1 material.

Fig. 2 is the adsorption efficiency curve of several phenolic estrogens by the magnetic graphene-polyaniline nanocomposite prepared in Example 1 under different pH conditions.

Fig. 3 is the hysteresis curve of the magnetic graphene polyaniline nanocomposite material prepared in Example 1.

FIG. 4 is a comparison diagram of the effects before and after magnetic separation of the magnetic graphene-polyaniline nanocomposite prepared in Example 1.

detailed description

The present invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this:

Example 1

0.14 g of graphite oxide was weighed and placed in a three-necked flask filled with 60 mL of deionized water, and ultrasonically treated with an ultrasonic power of 300 W for 1 h to obtain a graphene oxide solution. Add 0.28 g of aniline and 20 mL of 0.2 mol/L hydrochloric acid solution to the graphene oxide solution, and stir it electrically for 30 min. Afterwards, 20 mL of 0.05 mol/L hydrochloric acid solution containing 0.68 g (NH ₄ ) ₂ S ₂ O ₈ was added dropwise under an ice-water bath, and the color of the reaction solution changed to dark green within 5 minutes. After electric stirring for 6 hours, stop the reaction, wash with water and ethanol several times, and vacuum dry at 60°C to obtain a dark green product, which is the graphene/polyaniline composite material.

Using a mixture of ethylene glycol and diethylene glycol with a volume ratio of 1:1 as a solvent, 0.1g of graphene/polyaniline composite material, 0.4g of FeCl ₃ and 0.7g of sodium acetate were dissolved in the solvent, and the ultrasonic power was 300W. Treat for 1 hour, then transfer to a stainless steel autoclave lined with polytetrafluoroethylene, heat the autoclave to 190°C, maintain the reaction for 6 hours, and cool to room temperature. Collect the product by magnetic separation, wash the product several times with ethanol and water, and obtain the MGO/PANI-1 material in a vacuum oven at 60°C. Its saturation magnetization is 48.14emu/g, as shown in Figure 3.

In addition, it can be seen from Figure 1(a) that graphene oxide (GO) is a very thin sheet structure with a smooth surface and many wrinkles; it can be seen from Figure 1(b) that graphene poly The aniline composite (GO/PANI) also has a sheet structure, polyaniline evenly covers the graphene surface without destroying the sheet structure, but it can be seen from the shadow of the wrinkle that the thickness of the sheet increases; from Figure 1(c ), it can be seen that the magnetic graphene-polyaniline composite (MGO/PANI-1) is still a lamellar structure, and Fe ₃ O ₄ magnetic particles are scattered on the surface, and the particle diameter is between 100-200nm.

Example 2

0.14 g of graphite oxide was weighed and placed in a three-necked flask filled with 60 mL of deionized water, and ultrasonically treated with an ultrasonic power of 450 W for 1 h to obtain a graphene oxide solution. Add 0.42 g of aniline and 20 mL of 0.2 mol/L hydrochloric acid solution, and stir for 30 min with an electric motor. Then, 20 mL of 0.05 mol/L hydrochloric acid solution containing 1.24 g (NH ₄ ) ₂ S ₂ O ₈ was added dropwise under an ice-water bath, and the reaction solution changed color to dark green within 5 minutes. After electric stirring for 6 hours, stop the reaction, wash with water and ethanol several times, and vacuum dry at 60°C to obtain a dark green product, which is the graphene/polyaniline composite material.

Using a mixture of ethylene glycol and diethylene glycol with a volume ratio of 1:1 as a solvent, 0.2g of graphene/polyaniline composite material, 0.4g of FeCl ₃ and 0.9g of sodium acetate were dissolved in the solvent, and the ultrasonic power was 450W. Treat for 1 hour, then transfer to a stainless steel autoclave lined with polytetrafluoroethylene, heat the autoclave to 190°C, maintain the reaction for 6 hours, and cool to room temperature. The product was collected, washed with ethanol and water for several times, and the MGO/PANI-2 material was obtained in a vacuum oven at 60°C.

Comparative example 1

0.42g of aniline and 20mL of 0.2mol/L hydrochloric acid solution were mixed and then stirred electrically for 30min. Add 20 mL of 0.05 mol/L hydrochloric acid solution containing 1.24 g (NH ₄ ) ₂ S ₂ O ₈ dropwise under an ice-water bath, stop the reaction after 6 hours of electric stirring, wash with water and ethanol for several times, and dry in vacuo at 60°C to obtain PANI material.

Using a mixture of ethylene glycol and diethylene glycol with a volume ratio of 1:1 as a solvent, 0.2g of PANI material, 0.4g of FeCl ₃ and 0.9g of sodium acetate were dissolved in the solvent, treated with ultrasonic power of 450W for 1h, and then transferred to In a stainless steel autoclave lined with polytetrafluoroethylene, heat the autoclave to 190°C, maintain the reaction for 6h, and cool to room temperature. The product is collected, washed with ethanol and water several times, and the M/PANI material can be obtained in a vacuum drying oven at 60°C.

Comparative example 2

Using a mixture of ethylene glycol and diethylene glycol with a volume ratio of 1:1 as a solvent, dissolve 0.2g of graphene, 0.4g of FeCl ₃ and 0.9g of sodium acetate in the solvent, ultrasonically treat with ultrasonic power 450W for 1h, and then transfer Put it into a stainless steel autoclave lined with polytetrafluoroethylene, heat the autoclave to 190°C, maintain the reaction for 6h, and cool to room temperature. The product was collected, washed with ethanol and water several times, and the M/GO material was obtained in a vacuum oven at 60°C.

performance testing

The materials prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were respectively applied to the determination of nonylphenol, octylphenol and bisphenol A adsorption properties, specifically as follows:

4 mg of the MGO/PANI-1 material prepared in Example 1, the MGO/PANI-2 material prepared in Example 2, the M/PANI prepared in Comparative Example 1 and the M/GO material prepared in Comparative Example 2 were placed in In a 15mL glass test tube, add 0.5mL of a mixed standard solution of nonylphenol, octylphenol and bisphenol A with a concentration of 1mg/mL, and dilute to 5mL with water to obtain a concentration C of _100mg /L. liquid, plug the stopper. Vortex at 2200 rpm/min on a vortex instrument at room temperature for a period of time to ensure sufficient adsorption. Use a magnet to separate the material that has adsorbed the analyte from the water sample, and use HPLC to measure the mass concentration of the supernatant after adsorption, according to the formula Calculate the adsorption capacity. The adsorption capacity (mg/g) of each material was obtained. C ₀ and C are the mass concentration of the solution before and after adsorption, mg/L; m is the mass of the adsorbent, in g; Q is the adsorption capacity of the adsorbent, mg/g.

Table 1 Concentration of nonylphenol, octylphenol and bisphenol A supernatant after adsorption

Table 2 The adsorption capacity of nonylphenol, octylphenol and bisphenol A

Material Nonylphenol Octylphenol Bisphenol A MGO/PANI-1 70.5mg/g 79.8mg/g 60.38mg/g MGO/PANI-2 73.4mg/g 82.1mg/g 64.26mg/g M/PANI 22.8mg/g 23.4mg/g 18.2mg/g M/GO 40.5mg/g 42.7mg/g 38.3mg/g

From the contents of Table 1 and Table 2, we can find out that in the adsorption of the material phenolic estrogen prepared by the method of the present invention, the adsorption capacity of each substance is more than that of the magnetic polyaniline nanomaterial composited with graphene oxide. An increase of about 50mg/g was achieved. Compared with the adsorption capacity of the magnetic graphene nanomaterials not modified with polyaniline, there is also an increase of close to 20-30mg/g. The adsorption properties of the products prepared by changing the ratio of different raw materials are slightly different, and the adsorption capacity is significantly improved.

2. The material prepared in embodiment 1 and embodiment 2 is applied to the determination of nonylphenol, octylphenol and bisphenol A scavenging rate

Weigh 4mg of MGO/PANI-1, MGO/PANI-2, M/PANI and M/GO materials respectively into 15mL glass test tubes, add nonylphenol, octylphenol and bisphenol A at a concentration of 0.1mg/mL 0.5mL of the mixed standard solution, dilute to 5mL with water to obtain the test solution with a concentration of 10mg/L, and put on the stopper. Vortex at 2200 rpm/min on a vortex instrument at room temperature for a period of time to ensure sufficient adsorption. Use a magnet to separate the material that has adsorbed the analyte from the water sample, measure the mass concentration of the supernatant after adsorption by HPLC, and calculate the clearance rate (%) according to the formula clearance rate=(c ₀ -c)/c ₀ . c ₀ and c are the mass concentration of the solution before and after adsorption, mg/L, respectively.

Table 3 Mass concentration of nonylphenol, octylphenol and bisphenol A supernatant after adsorption

The scavenging rate of nonylphenol, octylphenol and bisphenol A after table 4 adsorption

From the contents of Table 3 and Table 4, we can find out that the material prepared by the method of the present invention is used in the adsorption of a certain concentration of phenolic estrogen, and the removal rate of the material for each substance is higher than that of the magnetic material not compounded with graphene oxide. Polyaniline nanomaterials have been improved by more than 50%. There is also a 30% improvement in the removal rate compared to the magnetic graphene nanomaterials not modified with polyaniline. The products prepared by changing the proportion of different raw materials have slightly different clearance rates of phenolic estrogens, but the clearance rates are all significantly improved.

3. Stability of enrichment environment

The MGO/PANI-1 material prepared in Example 1 is used to adsorb nonylphenol, octylphenol and bisphenol A with a concentration of 10mg/L under different pH conditions, and the adsorption efficiency is shown in Figure 2. From In Figure 2, we can see that the change of pH has almost no effect on the adsorption effect, which shows that the adsorption and removal of phenolic environmental estrogen in environmental water samples by this material is almost not affected by the fluctuation of acidity and alkalinity of water quality, which reflects the application of Good acid and alkali resistance stability in actual environmental water samples.

4. Separation effect

Disperse 4mg of the MGO/PANI-1 material prepared in implementation 1 into 5mL of bisphenol A adsorption solution with a concentration of 10mg/L, the MGO/PANI/PAab-1 material can be completely separated in ≤1min, and the separation effect is shown in the figure 4. However, the existing centrifugation needs to be centrifuged at 5000rpm for 15 minutes to achieve similar separation effect, and the solution after centrifugation cannot have a slight vibration when taking the supernatant, otherwise the precipitated particles are easy to redisperse, increasing Therefore, the application of magnetic materials greatly improves the separation efficiency and simplifies the separation operation from the perspective of the separation process.

5. Enrichment effect

Weigh 4 mg of the MGO/PANI-1 and M/PANI materials prepared in Example 1 and Comparative Example 1 respectively and place them in a solution containing 10 mL of nonylphenol, octylphenol and bisphenol A with a concentration of 1 mg/L , placed on a vortex instrument at room temperature and vortexed at a speed of 2000rpm for 40min. Remove the supernatant by magnetic separation, keep the magnetic material, add 1mL methanol solution to each tube, place it on a vortex instrument at room temperature and vortex at a speed of 2000rpm for 30min, collect the eluate after magnetic separation, and measure the concentration of the eluate by HPLC , according to the formula γ=C/C ₀ to calculate the enrichment factor γ. C ₀ and C are the mass concentration of the solution before adsorption and the mass concentration of the eluent, mg/L, respectively.

Table 5 MGO/PANI-1 material used in eluent concentration and enrichment factor in phenolic estrogen solution

C (mg/L) Enrichment factorγ Nonylphenol 9.42 9.4 Octylphenol 9.28 9.3 Bisphenol A 9.03 9.0

Table 6M/PANI material used in phenolic estrogen solution eluent concentration and enrichment factor

C (mg/L) Enrichment factorγ Nonylphenol 3.13 3.1 Octylphenol 3.28 3.3 Bisphenol A 2.83 2.8

It can be seen from Table 5 and Table 6 that the polyaniline material enrichment rate of composite graphene has been greatly improved, which is attributed to the increase of its surface area and the enhancement of dispersion. In this experiment, a higher enrichment factor can also be obtained by increasing the volume of the adsorption solution.

Claims (10)

1. a magnetic graphite alkene polyaniline nano-composite material, is characterized in that: this material is to prepare by the following methodObtain:

Taking the alcohol that contains 1～5 carbon atom as solvent, the graphene/polyaniline that mass ratio is followed successively by 1～5:1～10:1～10 is multipleCondensation material, FeCl₃Be dissolved in described solvent and ultrasonic processing with sodium acetate, in autoclave, react afterwards,Can obtain magnetic graphite alkene polyaniline nano-composite material.

2. magnetic graphite alkene polyaniline nano-composite material according to claim 1, is characterized in that: Graphene/poly-Aniline composite: FeCl₃: the mass ratio of sodium acetate is 1～3:1～5:5～10.

3. magnetic graphite alkene polyaniline nano-composite material according to claim 1, is characterized in that: ultrasonic processingPower be 300～500W, the time is 0.5～1.5h.

4. magnetic graphite alkene polyaniline nano-composite material according to claim 1, is characterized in that: reaction under high pressureThe temperature of reacting in still is 150～250 DEG C, and the time of reaction is 4～48h; The temperature of preferably reacting in autoclave is180～200 DEG C, the time of reaction is 4～10h.

5. magnetic graphite alkene polyaniline nano-composite material according to claim 1, is characterized in that: Graphene/poly-Aniline composite is to prepare by the following method: by ultrasonic processing after graphite oxide and solvent, obtain being oxidized stoneChina ink alkene solution; In described graphene oxide solution, add containing the hydrochloric acid solution of aniline and stir, obtaining mixed liquor;Will be containing (NH4)₂S₂O₈Hydrochloric acid solution join in described mixed liquor and react, after reaction finishes, obtain Graphene/polyphenylAmine composite.

6. magnetic graphite alkene polyaniline nano-composite material according to claim 5, is characterized in that: described is moltenAgent is selected from least one in water, ethanol, ethylene glycol and diethylene glycol; Graphite oxide: aniline: (NH₄)₂S₂O₈QualityThan being 1～5:1～5:4～10.

7. a preparation method for magnetic graphite alkene polyaniline nano-composite material claimed in claim 1, is characterized in that:Taking the alcohol that contains 1～5 carbon atom as solvent, mass ratio is followed successively by the graphene/polyaniline composite wood of 1～5:1～10:1～10Material, FeCl₃Be dissolved in described solvent and ultrasonic processing with sodium acetate, in autoclave, react afterwards, get final productTo magnetic graphite alkene polyaniline nano-composite material.

8. the preparation method of magnetic graphite alkene polyaniline nano-composite material according to claim 7, is characterized in that:Grapheme/polyaniline composite material: FeCl₃: the mass ratio of sodium acetate is 1～3:1～5:5～10; The power of ultrasonic processing is300～500W, the time is 0.5～1.5h; The temperature of reacting in autoclave is 150～250 DEG C, and the time of reaction is 4～48h;The temperature of preferably reacting in autoclave is 180～200 DEG C, and the time of reaction is 4～10h.

9. the preparation method of magnetic graphite alkene polyaniline nano-composite material according to claim 7, is characterized in that:Grapheme/polyaniline composite material is to prepare by the following method: by ultrasonic processing after graphite oxide and solvent,To graphene oxide solution; In described graphene oxide solution, add containing the hydrochloric acid solution of aniline and stir, obtainingMixed liquor; Will be containing (NH₄)₂S₂O₈Hydrochloric acid solution join in described mixed liquor and react, reaction finish rear washing,The dry grapheme/polyaniline composite material that obtains; Preferably described solvent is selected from water, ethanol, ethylene glycol and diethylene glycolAt least one; Preferential oxidation Graphene: aniline: (NH₄)₂S₂O₈Mass ratio be 1～5:1～5:4～10.

10. utilize material described in claim 1 method to the enrichment of phenols environmental estrogens, it is characterized in that: shouldMethod is taking magnetic graphite alkene polyaniline nano-composite material as sorbing material, and sorbing material is joined and contains that phenols environment is female to swashIn the solution of element and mix, to ensure absorption fully; After absorption fully, adopt magnet that sorbing material and solution are dividedFrom; After separating, adopt eluting solvent to carry out wash-out to the sorbing material that has adsorbed phenols environmental estrogens, wash-out finishes rear collectionSolution after wash-out, obtains the phenols environmental estrogens after enrichment; Preferably described eluant, eluent is selected from methyl alcohol, ethanol and secondAny one in acid.