CN112709068B - Composite material for petrochemical wastewater treatment and preparation method thereof - Google Patents
Composite material for petrochemical wastewater treatment and preparation method thereof Download PDFInfo
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- CN112709068B CN112709068B CN202011592210.6A CN202011592210A CN112709068B CN 112709068 B CN112709068 B CN 112709068B CN 202011592210 A CN202011592210 A CN 202011592210A CN 112709068 B CN112709068 B CN 112709068B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/236—Esters of carboxylic acids; Esters of carbonic acid containing halogen atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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Abstract
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 good treatment effect.
Description
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 oil, 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 rubber) with basic chemical materials.
The petrochemical industry is an important industry in China, the production capacity is large, the production process is complex, so that more waste water is generated 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 the water body, the petrochemical wastewater immediately diffuses on the water surface to form an oil film, so that the water body is prevented from reoxygenating from the atmosphere, the dissolved oxygen in the water is reduced, and the petrochemical wastewater is adhered to the surface of an aquatic organism 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 water bottom are decomposed anaerobically to generate poisons such as hydrogen sulfide and the like, heavy oil products can be adhered to silt, activities such as inhabitation and reproduction of aquatic organisms can be influenced, growth of the aquatic organisms is seriously influenced, and finally the ecological environment and 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.
The 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 to destabilize oil, emulsified oil and the like in sewage, adsorb the destabilized oil, emulsified oil and the like on a flocculating constituent, and finally realize flocculation and sedimentation. 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) in the impregnation liquid obtained in the step (3) for impregnation treatment, and carrying out surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical engineering 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 the magnet is 10000-20000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.
Preferably, in the step (2), the spinning solution is prepared by the following steps: firstly, 100 parts of acrylonitrile, 0.8-1.2 parts of itaconic acid and 8-10 parts of methyl methacrylate are added into a polymerization kettle, then 2-3 parts of azodiisobutyronitrile and 450-500 parts of dimethyl sulfoxide are added, polymerization reaction is carried out for 4-6 hours at the temperature of 45-55 ℃, then 10-15 parts of modified magnetic fly ash is added, and heat preservation polymerization reaction is carried out for 5-7 hours continuously, thus obtaining 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 for spinning comprises the following steps: and 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 for coagulating bath to obtain the fiber.
More preferably, the spinning solution is metered by a metering pump and extruded through 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.
More 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 to 3.5:0.3 to 0.4: 0.6-0.8: 1.8 to 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 steps: evaporating under reduced pressure to obtain oily matter, adding the oily matter into tetrahydrofuran in 5-7 times weight, stirring to dissolve, and filtering to remove 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: adding 1 part of fiber into 5-7 parts of impregnation liquid, standing and impregnating for 3-4 hours, 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.
Further preferably, the fiber is placed on a sample platform at the bottom of the chemical vapor deposition chamber, a heating wire is arranged at a position 30-40 mm above the sample platform, the temperature of the sample platform 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.
Further preferably, the vapor of t-butyl hydroperoxide and perfluorophenyl methacrylate are supplied at a flow rate of 1mL/min and 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 aftertreatment to prepare an impregnation liquid; finally, the fiber is placed in impregnation liquid for impregnation treatment, and surface treatment is realized through surface polymerization of perfluorophenyl methacrylate, so that the composite material is obtained. The composite material has good hydrophobicity, is suitable for petrochemical wastewater treatment, and has 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-phenylamino methyl triethoxysilane, octamethylcyclotetrasiloxane, 2-pyridylaldehyde and the like are used as raw materials to prepare a steeping fluid, fibers are placed in the steeping fluid for steeping 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, in addition, hydrogen bonds exist among introduced cyano groups, fluorine groups, amino groups and the like, a net structure is formed, the pores are abundant, and better adsorption is realized.
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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to 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) in the impregnation liquid obtained in the step (3) for impregnation treatment, and carrying out surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical engineering wastewater treatment.
The specific method of the step (1) comprises the following steps: 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, centrifuging and taking 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 is removed and the bubbles are removed, and the method comprises the following specific steps: and treating for 30 minutes under the condition of 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 25mm.
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 drying.
In the step (4), the surface treatment method is as follows: the impregnated 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 2Pa.
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, carrying out polymerization reaction by taking acrylonitrile, itaconic acid and methyl methacrylate as raw materials, adding modified magnetic fly ash in the reaction process to obtain spinning solution, and spinning to obtain fibers;
(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) in the impregnation liquid obtained in the step (3) for impregnation treatment, and carrying out surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical engineering wastewater treatment.
The specific method of the step (1) comprises the following steps: 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: firstly 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 carrying out heat preservation 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 22mm.
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 7 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substance 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 5Pa.
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 engineering 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, carrying out polymerization reaction by taking acrylonitrile, itaconic acid and methyl methacrylate as raw materials, adding modified magnetic fly ash in the reaction process to obtain spinning solution, and spinning to obtain fibers;
(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) in the impregnation liquid obtained in the step (3) for impregnation treatment, and carrying out surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical engineering 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 carrying out primary selection on the fly ash by adopting a magnet, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the primarily selected fly ash until cleaning liquid 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 the primary election is 15000 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, 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: and 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 for 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 24mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 7%; the temperature of the coagulation bath was 32 ℃.
In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous solution of potassium hydroxide to glacial acetic acid to 2-pyridinecarboxaldehyde 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 4Pa.
The vapor of t-butyl hydroperoxide and perfluorophenyl methacrylate was fed at 1mL/min and 0.15mL/min in this order.
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: and treating for 30 minutes under the condition of 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 flow, and the thickness of an air layer is 25mm.
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 substance 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 drying.
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 2Pa.
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 adopting a water bath volatilization method, wherein the tert-butyl hydroperoxide is volatilized at a water bath temperature of 25 ℃, and the perfluoro-phenyl methacrylate is volatilized at a water bath temperature of 100 ℃.
The surface treatment time was 2 hours.
Comparative example 2
A preparation method of a composite material for petrochemical engineering 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 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 carrying out primary selection on the fly ash by adopting a magnet, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the primarily selected fly ash until cleaning liquid 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 is removed and the bubbles are removed, and the method comprises the following specific steps: and treating for 30 minutes under the condition of 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 25mm.
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 2Pa.
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, carrying out polymerization reaction by taking acrylonitrile, itaconic acid and methyl methacrylate as raw materials, adding modified magnetic fly ash in the reaction process to obtain spinning solution, and spinning to obtain fibers;
(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 is removed and the bubbles are removed, and the method comprises the following specific steps: and treating for 30 minutes under the condition of 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 flow, and the thickness of an air layer is 25mm.
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 substance 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 to 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 model of the injection needle is SNS 052/026, the volume of the injection liquid drop (water) is 1 muL, and the liquid contour fitting calculation adopts an 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 hydrophobic Property examination results
| 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 examples 1-3 or the comparative examples 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 the magnet except for the composite material in the comparative example 1 (the composite material is filtered and taken out in the comparative example 1), and the composite material 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 (Shanghai fly detection FD-680), 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 ratio 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 is clear from tables 1 and 2, the composite materials obtained in examples 1 to 3 are excellent in hydrophobicity and effect of treating 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 petrochemical wastewater is obviously deteriorated, the addition of the fly ash is beneficial to the improvement of the adsorption effect, the hydrophobicity of comparative examples 2 and 3 is deteriorated, and the treatment effect on the petrochemical wastewater is further 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 specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.
Claims (9)
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, carrying out polymerization reaction by taking acrylonitrile, itaconic acid and methyl methacrylate as raw materials, adding modified magnetic fly ash in the reaction process to obtain spinning solution, and spinning to obtain fibers;
(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 ethanol, 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, centrifuging and taking precipitate to obtain 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 to 3.5:0.3 to 0.4: 0.6-0.8: 1.8 to 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: adding 1 part of fiber into 5-7 parts of impregnation liquid, standing and impregnating for 3-4 hours, 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 of any one of claims 1 to 8.
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| US4973409A (en) * | 1988-09-21 | 1990-11-27 | Ciba-Geigy Corporation | Treatment of aqueous systems |
| EP0608845A2 (en) * | 1993-01-26 | 1994-08-03 | National Starch and Chemical Investment Holding Corporation | Multifunctional maleate polymers |
| CN103693710A (en) * | 2014-01-10 | 2014-04-02 | 中国科学院新疆理化技术研究所 | Preparation and oil-water separation method of humic acid modified fly ash magnetic material |
| CN105461846A (en) * | 2014-09-05 | 2016-04-06 | 南京大学 | Magnetic acrylic-acid polyamine resin capable of removing heavy metal ions and preparation method thereof |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973409A (en) * | 1988-09-21 | 1990-11-27 | Ciba-Geigy Corporation | Treatment of aqueous systems |
| EP0608845A2 (en) * | 1993-01-26 | 1994-08-03 | National Starch and Chemical Investment Holding Corporation | Multifunctional maleate polymers |
| CN103693710A (en) * | 2014-01-10 | 2014-04-02 | 中国科学院新疆理化技术研究所 | Preparation and oil-water separation method of humic acid modified fly ash magnetic material |
| CN105461846A (en) * | 2014-09-05 | 2016-04-06 | 南京大学 | Magnetic acrylic-acid polyamine resin capable of removing heavy metal ions and preparation method thereof |
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