阅读说明：本技术 一种石油化工废水处理用复合材料及其制备方法 (Composite material for petrochemical wastewater treatment and preparation method thereof ) 是由 孙琴华 于 2020-12-29 设计创作，主要内容包括：本发明公开了一种石油化工废水处理用复合材料及其制备方法,先将磁性飞灰利用N-苯氨基甲基三乙氧基硅烷进行改性处理,得到改性磁性飞灰；然后以丙烯腈、衣康酸、甲基丙烯酸甲酯为原料进行聚合反应,并在反应过程中加入改性磁性飞灰,得到纺丝液,纺丝得到纤维；再将N-苯氨基甲基三乙氧基硅烷、八甲基环四硅氧烷与氢氧化钾水溶液进行第一次反应,接着加入冰醋酸进行第二次反应,然后加入2-吡啶甲醛进行第三次反应,后处理制成浸渍液；最后将纤维置于浸渍液中进行浸渍处理,并通过全氟苯基甲基丙烯酸酯表面聚合实现表面处理即得。该复合材料具有较好的疏水性,适用于石油化工废水处理,具有良好的处理效果。(The invention discloses a composite material for petrochemical wastewater treatment and a preparation method thereof, wherein magnetic fly ash is modified by N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash; then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning; then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution; and finally, placing the fiber in an impregnation liquid for impregnation treatment, and carrying out surface treatment by surface polymerization of the perfluorophenyl methacrylate. The composite material has good hydrophobicity, is suitable for petrochemical wastewater treatment, and has a good treatment effect.)

1. A preparation method of a composite material for petrochemical wastewater treatment is characterized by comprising the following specific steps:

(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;

(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;

(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;

(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.

2. The preparation method according to claim 1, wherein the specific method of step (1) comprises the following steps in parts by weight: adding 1 part of N-phenylaminomethyltriethoxysilane into 3-4 parts of absolute ethyl alcohol, uniformly oscillating by ultrasonic waves, adding 0.5-0.7 part of magnetic fly ash, heating to reflux, stirring for 2-3 hours under heat preservation, and centrifuging to obtain precipitate, thus obtaining the modified magnetic fly ash.

3. The method according to claim 1, wherein the spinning dope is prepared in the step (2) by the following method in parts by weight: adding 100 parts of acrylonitrile, 0.8-1.2 parts of itaconic acid and 8-10 parts of methyl methacrylate into a polymerization kettle, adding 2-3 parts of azobisisobutyronitrile and 450-500 parts of dimethyl sulfoxide, carrying out polymerization reaction for 4-6 hours at 45-55 ℃, adding 10-15 parts of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 5-7 hours to obtain the spinning solution.

4. The preparation method according to claim 1, wherein in the step (2), the specific method of spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.

5. The method according to claim 1, wherein in the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide to glacial acetic acid to 2-pyridinecarboxaldehyde is 1: 3-3.5: 0.3-0.4: 0.6-0.8: 1.8-2.2; the mass concentration of the potassium hydroxide aqueous solution is 30-40%.

6. The preparation method according to claim 1, wherein in the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 4-6 hours at 80-85 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 20-30 minutes at 50-60 ℃; the process conditions of the third reaction are as follows: stirring and reacting for 20-22 hours at 70-80 ℃.

7. The preparation method according to claim 1, wherein in the step (4), the process conditions of the dipping treatment are as follows in parts by weight: and adding 1 part of fiber into 5-7 parts of impregnation liquid, standing and impregnating for 3-4 hours, and taking out and naturally drying.

8. The production method according to claim 1, wherein in the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.

9. A composite material for petrochemical wastewater treatment obtained by the preparation method according to claims 1 to 8.

Technical Field

The invention relates to the technical field of preparation of wastewater treatment materials, in particular to a composite material for petrochemical wastewater treatment and a preparation method thereof.

Background

Petrochemical industry refers specifically to the processing industry for producing petroleum products and petrochemical products from petroleum and natural gas. The first step in the production of petrochemical products is the cracking of raw oil and gas (such as propane, gasoline, diesel, etc.) to produce basic chemical materials, typically ethylene, propylene, butadiene, benzene, toluene, xylene. The second step is to produce various organic chemical materials (about 200 kinds) and synthetic materials (plastics, synthetic fibers, synthetic rubbers) from basic chemical materials.

The petrochemical industry is an important industry in China, the production capacity is large, and the production process is relatively complex, so that more waste water is produced in the production process, and the change range of the waste water yield is wide due to different production processes. The waste water discharged in the refining processes of cracking, refining, fractionating and synthesizing petroleum contains various toxic organic pollutants, such as benzopyrene, benzanthracene and other polycyclic aromatic hydrocarbon substances, which have carcinogenic, teratogenic or mutagenic effects, and also contains pollutants such as benzene, phenol, sulfur compounds, gasoline, crude oil and the like. The petrochemical wastewater has large discharge amount and high concentration of suspended matters, contains a large amount of soluble salts, various chemical additives, petroleum and the like, has great influence on soil structure without treatment and discharge, and is harmful to plant growth, wherein heavy metal ions, organic polymers which are not easy to degrade and the like enter a food chain through animals and plants and also can be harmful to human health and life safety.

Once entering water, petrochemical wastewater can immediately diffuse on the water surface to form an oil film, so that the water is prevented from reoxygenating from the atmosphere, dissolved oxygen in the water is reduced, and the petrochemical wastewater is adhered to the surface of aquatic organisms and a respiratory system to cause death; after being ingested, the fish can cause poisoning, influence growth, have peculiar smell and cannot eat; pollutants deposited at the bottom of water are decomposed anaerobically to generate poisons such as hydrogen sulfide and the like, heavy oil products can be adhered to silt, inhabitation, reproduction and other activities of aquatic organisms can be influenced, the growth of the aquatic organisms is seriously influenced, and finally the ecological environment and the human health are influenced.

The existing flocculating agent for treating petrochemical wastewater has unsatisfactory treatment effect and is difficult to realize high-efficiency oil removal, so that the development of a novel high-efficiency flocculating agent suitable for petrochemical wastewater is very necessary.

Patent application CN111268776A discloses a flocculant for petrochemical wastewater treatment and a preparation method thereof, wherein the flocculant is prepared from cationic starch flocculant, zeolite mineral, polymeric ferric sulfate, polymeric aluminum chloride, chitosan derivative, bentonite, alum, water and other raw materials, and the working principle of the flocculant is that oil, emulsified oil and the like in sewage are destabilized and adsorbed on a flocculating constituent, and finally flocculation and sedimentation are realized. However, the petrochemical wastewater has high oil content, and the flocculant has poor hydrophobicity, so that the contact area of the flocculant and the wastewater is limited, and the flocculation effect is seriously influenced.

Disclosure of Invention

The invention aims to provide a composite material for petrochemical wastewater treatment and a preparation method thereof, which have good hydrophobicity and good treatment effect on petrochemical wastewater.

In order to achieve the purpose, the invention is realized by the following scheme:

a preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:

(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;

(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;

(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;

(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.

Preferably, the specific method of the step (1) comprises the following steps in parts by weight: adding 1 part of N-phenylaminomethyltriethoxysilane into 3-4 parts of absolute ethyl alcohol, uniformly oscillating by ultrasonic waves, adding 0.5-0.7 part of magnetic fly ash, heating to reflux, stirring for 2-3 hours under heat preservation, and centrifuging to obtain precipitate, thus obtaining the modified magnetic fly ash.

Preferably, in step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of magnet is 10000 ~ 20000 Oe during initial election, the magnet is permanent magnet or electro-magnet.

Preferably, in the step (2), the preparation method of the spinning solution comprises the following steps: adding 100 parts of acrylonitrile, 0.8-1.2 parts of itaconic acid and 8-10 parts of methyl methacrylate into a polymerization kettle, adding 2-3 parts of azobisisobutyronitrile and 450-500 parts of dimethyl sulfoxide, carrying out polymerization reaction for 4-6 hours at 45-55 ℃, adding 10-15 parts of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 5-7 hours to obtain the spinning solution.

Further preferably, the monomer removal and bubble removal treatment is carried out after the polymerization reaction is finished, and the specific method comprises the following steps: treating for 20-30 minutes under the condition of 4-5 kPa.

Preferably, in the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.

Preferably, the spinning solution is metered by a metering pump and extruded by a spinneret with the aperture of 0.05-0.08 mm to form a trickle, and the thickness of the air layer is 22-25 mm.

Preferably, the solidification solution is a dimethyl sulfoxide aqueous solution with the mass concentration of 6-8%; the temperature of the coagulating bath is 30-35 ℃.

Preferably, in the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane, potassium hydroxide aqueous solution, glacial acetic acid and 2-pyridinecarbaldehyde is 1: 3-3.5: 0.3-0.4: 0.6-0.8: 1.8-2.2; the mass concentration of the potassium hydroxide aqueous solution is 30-40%.

Preferably, in the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 4-6 hours at 80-85 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 20-30 minutes at 50-60 ℃; the process conditions of the third reaction are as follows: stirring and reacting for 20-22 hours at 70-80 ℃.

Preferably, in the step (3), the post-treatment method comprises the following specific steps: and (3) evaporating under reduced pressure to obtain an oily substance, adding the oily substance into tetrahydrofuran with the weight 5-7 times that of the oily substance, stirring and dissolving, and filtering insoluble substances to obtain the impregnation liquid.

Preferably, in the step (4), the process conditions of the dipping treatment are as follows in parts by weight: and adding 1 part of fiber into 5-7 parts of impregnation liquid, standing and impregnating for 3-4 hours, and taking out and naturally drying.

Preferably, in the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.

Preferably, the fiber is placed on a sample table at the bottom of the chemical vapor deposition chamber, a heating wire is arranged at a position 30-40 mm above the sample table, the temperature of the sample table is controlled to be 5-9 ℃, the temperature of the heating wire is 230-240 ℃, and the pressure in the chemical vapor deposition chamber is 2-5 Pa.

More preferably, the vapor of t-butyl hydroperoxide and perfluorophenyl methacrylate has an inlet flow rate of 1mL/min and an inlet flow rate of 0.1 to 0.2mL/min in this order.

Further preferably, the vapor is obtained by a water bath evaporation method, wherein the tert-butyl hydroperoxide is evaporated at 25 ℃ in the water bath, and the perfluorophenyl methacrylate is evaporated at 100 ℃ in the water bath.

More preferably, the surface treatment time is 2 to 3 hours.

The composite material for treating petrochemical wastewater is prepared by the preparation method.

Compared with the prior art, the invention has the beneficial effects that:

(1) firstly, carrying out modification treatment on magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash; then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning; then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution; finally, the fiber is placed in impregnating solution for impregnation treatment, and surface treatment is realized through surface polymerization of the perfluorophenyl methacrylate, so that the composite material is obtained. The composite material has good hydrophobicity, is suitable for petrochemical wastewater treatment, and has a good treatment effect.

(2) The main material of the invention is fiber polymerized by acrylonitrile, itaconic acid and methyl methacrylate, the macromolecular polymer itself has a certain adsorption effect, and the cyano group therein has coordination effect on heavy metals and the like and further enhances the adsorption effect. The modified magnetic fly ash is added in the polymerization process, thereby being beneficial to the cyclic utilization of industrial waste, simultaneously endowing magnetism, facilitating magnetic separation and greatly simplifying the wastewater treatment process.

(3) According to the invention, N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane, 2-pyridylaldehyde and the like are used as raw materials to prepare an impregnation liquid, fibers are placed in the impregnation liquid for impregnation treatment, so that abundant hydrophobic groups are introduced to the surfaces of the fibers, and finally surface treatment is realized through surface polymerization of perfluorophenyl methacrylate, so that the hydrophobic groups are more abundant, therefore, the obtained composite material has better hydrophobicity, and in addition, hydrogen bonds exist among introduced cyano groups, fluorine groups, amino groups and the like, so that a net structure is formed, the pores are abundant, and the adsorption effect is better.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:

(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;

(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;

(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;

(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.

The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 3kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.7kg of magnetic fly ash, heating to reflux, stirring for 2 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.

In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of the magnet is 20000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.

In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 0.8kg of itaconic acid and 10kg of methyl methacrylate into a polymerization kettle, then adding 2kg of azodiisobutyronitrile and 500kg of dimethyl sulfoxide, carrying out polymerization reaction for 6 hours at 45 ℃, then adding 10kg of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 7 hours to obtain the spinning solution.

After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment time was 30 minutes under 4 kPa.

In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.

The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.05mm to form a thin stream, and the thickness of an air layer is 25 mm.

The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 6%; the coagulation bath temperature was 35 ℃.

In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3.5: 0.3: 0.8: 1.8; the mass concentration of the potassium hydroxide aqueous solution is 40%.

In the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 6 hours at 80 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 30 minutes at 50 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 70 ℃ for 22 hours.

In the step (3), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 5 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.

In the step (4), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 7kg of impregnation liquid, standing and impregnating for 3 hours, taking out and naturally airing.

In the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.

The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged 40mm above the sample table, the temperature of the sample table is controlled to be 5 ℃, the temperature of the heating wire is 240 ℃, and the pressure in the chemical vapor deposition chamber is 2 Pa.

The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.2mL/min in sequence.

The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.

The surface treatment time was 2 hours.

Example 2

A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:

(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;

(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;

(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;

(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.

The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 4kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.5kg of magnetic fly ash, heating to reflux, stirring for 3 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.

In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of magnet when initially choosing is 10000 Oe, the magnet is permanent magnet or electro-magnet.

In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 1.2kg of itaconic acid and 8kg of methyl methacrylate into a polymerization kettle, then adding 3kg of azodiisobutyronitrile and 450kg of dimethyl sulfoxide, carrying out polymerization reaction for 4 hours at 55 ℃, then adding 15kg of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 5 hours to obtain the spinning solution.

The method comprises the following steps of (1) removing monomers and removing bubbles after the polymerization reaction is finished: and treating for 20 minutes under the condition of 5 kPa.

In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.

The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.08mm to form a thin stream, and the thickness of an air layer is 22 mm.

The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 8%; the coagulation bath temperature was 30 ℃.

In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3: 0.4: 0.6: 2.2; the mass concentration of the potassium hydroxide aqueous solution was 30%.

In the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 4 hours at 85 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 20 minutes at 60 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 80 ℃ for 20 hours.

In the step (3), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 7 times weight of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.

In the step (4), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 5kg of impregnation liquid, standing and impregnating for 4 hours, taking out and naturally airing.

In the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.

The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged at a position 30mm above the sample table, the temperature of the sample table is controlled to be 9 ℃, the temperature of the heating wire is 230 ℃, and the pressure in the chemical vapor deposition chamber is 5 Pa.

The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.1mL/min in sequence.

The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.

The surface treatment time was 3 hours.

Example 3

A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:

(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;

(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;

(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;

(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.

The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 3.5kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.6kg of magnetic fly ash, heating to reflux, stirring for 2.5 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.

In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of the magnet is 15000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.

In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 1kg of itaconic acid and 9kg of methyl methacrylate into a polymerization kettle, then adding 2.5kg of azobisisobutyronitrile and 480kg of dimethyl sulfoxide, carrying out polymerization reaction for 5 hours at 50 ℃, then adding 12kg of modified magnetic fly ash, and continuing to carry out polymerization reaction for 6 hours under heat preservation to obtain the spinning solution.

After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment was carried out under 4kPa for 25 minutes.

In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.

The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.06mm to form a thin stream, and the thickness of an air layer is 24 mm.

The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 7%; the coagulation bath temperature was 32 ℃.

In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3.2: 0.35: 0.7: 2; the mass concentration of the potassium hydroxide aqueous solution was 35%.

In the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 5 hours at 82 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 25 minutes at 55 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 75 ℃ for 21 hours.

In the step (3), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 6 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.

In the step (4), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 6kg of impregnation liquid, standing and impregnating for 3.5 hours, taking out and naturally airing.

In the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.

The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged 35mm above the sample table, the temperature of the sample table is controlled to be 8 ℃, the temperature of the heating wire is 235 ℃, and the pressure in the chemical vapor deposition chamber is 4 Pa.

The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.15mL/min in sequence.

The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.

The surface treatment time was 2.5 hours.

Comparative example 1

A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:

(1) firstly, carrying out polymerization reaction by taking acrylonitrile, itaconic acid and methyl methacrylate as raw materials to obtain spinning solution, and spinning to obtain fibers;

(2) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;

(3) and (3) finally, placing the fiber obtained in the step (1) into the impregnation liquid obtained in the step (2) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.

In the step (1), the preparation method of the spinning solution comprises the following steps: firstly, 100kg of acrylonitrile, 0.8kg of itaconic acid and 10kg of methyl methacrylate are added into a polymerization kettle, then 2kg of azodiisobutyronitrile and 500kg of dimethyl sulfoxide are added, and polymerization reaction is carried out for 13 hours at 45 ℃ to obtain the spinning solution.

After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment time was 30 minutes under 4 kPa.

In the step (1), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.

The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.05mm to form a thin stream, and the thickness of an air layer is 25 mm.

The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 6%; the coagulation bath temperature was 35 ℃.

In the step (2), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3.5: 0.3: 0.8: 1.8; the mass concentration of the potassium hydroxide aqueous solution is 40%.

In the step (2), the process conditions of the first reaction are as follows: stirring and reacting for 6 hours at 80 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 30 minutes at 50 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 70 ℃ for 22 hours.

In the step (2), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 5 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.

In the step (3), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 7kg of impregnation liquid, standing and impregnating for 3 hours, taking out and naturally airing.

In the step (3), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.

The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged 40mm above the sample table, the temperature of the sample table is controlled to be 5 ℃, the temperature of the heating wire is 240 ℃, and the pressure in the chemical vapor deposition chamber is 2 Pa.

The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.2mL/min in sequence.

The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.

The surface treatment time was 2 hours.

Comparative example 2

A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:

(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;

(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;

(3) and (3) finally, carrying out surface treatment on the fiber obtained in the step (2) through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for treating petrochemical wastewater.

The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 3kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.7kg of magnetic fly ash, heating to reflux, stirring for 2 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.

In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of the magnet is 20000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.

In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 0.8kg of itaconic acid and 10kg of methyl methacrylate into a polymerization kettle, then adding 2kg of azodiisobutyronitrile and 500kg of dimethyl sulfoxide, carrying out polymerization reaction for 6 hours at 45 ℃, then adding 10kg of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 7 hours to obtain the spinning solution.

After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment time was 30 minutes under 4 kPa.

In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.

The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.05mm to form a thin stream, and the thickness of an air layer is 25 mm.

The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 6%; the coagulation bath temperature was 35 ℃.

In the step (3), the surface treatment method is as follows: the fiber is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.

The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged 40mm above the sample table, the temperature of the sample table is controlled to be 5 ℃, the temperature of the heating wire is 240 ℃, and the pressure in the chemical vapor deposition chamber is 2 Pa.

The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.2mL/min in sequence.

The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.

The surface treatment time was 2 hours.

Comparative example 3

A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:

(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;

(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;

(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;

(4) and (3) finally, putting the fibers obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment to obtain the composite material for petrochemical wastewater treatment.

The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 3kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.7kg of magnetic fly ash, heating to reflux, stirring for 2 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.

In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of the magnet is 20000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.

In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 0.8kg of itaconic acid and 10kg of methyl methacrylate into a polymerization kettle, then adding 2kg of azodiisobutyronitrile and 500kg of dimethyl sulfoxide, carrying out polymerization reaction for 6 hours at 45 ℃, then adding 10kg of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 7 hours to obtain the spinning solution.

After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment time was 30 minutes under 4 kPa.

In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.

The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.05mm to form a thin stream, and the thickness of an air layer is 25 mm.

The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 6%; the coagulation bath temperature was 35 ℃.

In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3.5: 0.3: 0.8: 1.8; the mass concentration of the potassium hydroxide aqueous solution is 40%.

In the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 6 hours at 80 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 30 minutes at 50 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 70 ℃ for 22 hours.

In the step (3), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 5 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.

In the step (4), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 7kg of impregnation liquid, standing and impregnating for 3 hours, taking out and naturally airing.

Test examples

The hydrophobic properties of the composite materials obtained in examples 1-3 and comparative examples 2 and 3 were examined, and the results are shown in Table 1.

The method for measuring the contact angle by adopting the OCA15Pro type video optical contact angle measuring instrument comprises the following steps: the injection needle model was SNS 052/026, the volume of the injection droplet (water) was 1 μ L, and the liquid profile fitting calculation used the ellipsometry. And (4) performing measurement after tabletting, selecting three different positions on the sample for measurement, and recording the intermediate value as the final experimental result.

TABLE 1 results of hydrophobic Property examination

	Contact angle (°)
		Example 1	162.3
Example 2	163.1
		Example 3	164.5
Comparative example 2	128.2
		Comparative example 3	134.6

The composite material obtained in the embodiment 1-3 or the comparative example 1-3 is used for treating petrochemical wastewater generated by a certain petrochemical enterprise, and the specific treatment method comprises the following steps: 0.1g of the composite material is added into 1L of petrochemical wastewater, the mixture is kept stand and adsorbed for 2 hours at 25 ℃, the treating agent is sucked out by an external magnet except for comparative example 1 (the comparative example 1 is filtered and taken out), and the treating agent is recycled. The wastewater treatment effect was examined and the results are shown in Table 2.

Wherein, the content of heavy metal ions is detected by a heavy metal rapid detector (FD-680 in Shanghai flight detection), COD is detected by a portable COD detector of a TE-3001 Tianer instrument, and the content of mineral oil is determined by an ultraviolet spectrophotometry.

TABLE 2 examination of COD and heavy Metal ion removal Effect

	COD removal Rate (%)	Removal rate of heavy metal ion (%)	Mineral oil removal (%)
				Example 1	99.2	99.1	99.6
Example 2	99.5	99.3	99.7
				Example 3	99.9	99.6	99.9
Comparative example 1	88.5	89.7	93.3
				Comparative example 2	83.7	84.1	80.1
Comparative example 3	85.1	85.8	82.3

As can be seen from tables 1 and 2, the composite materials obtained in examples 1 to 3 have good hydrophobicity and good treatment effect on petrochemical wastewater.

Step (1) is omitted in comparative example 1, the impregnation treatment step of the impregnation liquid is omitted in comparative example 2, the surface polymerization of the perfluorophenyl methacrylate is omitted in comparative example 3, the treatment effect of the obtained composite material on the petrochemical wastewater is obviously deteriorated, the addition of the fly ash is helpful for improving the adsorption effect, and the hydrophobicity of the comparative examples 2 and 3 is deteriorated, so that the treatment effect on the petrochemical wastewater is influenced.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.