CN111501339A - Composite material for wastewater treatment and preparation method thereof - Google Patents

Composite material for wastewater treatment and preparation method thereof Download PDF

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CN111501339A
CN111501339A CN202010447173.3A CN202010447173A CN111501339A CN 111501339 A CN111501339 A CN 111501339A CN 202010447173 A CN202010447173 A CN 202010447173A CN 111501339 A CN111501339 A CN 111501339A
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parts
treatment
ethylenediamine
spinning
solution
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王和森
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Nanjing Bizhou Biotechnology Co ltd
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Nanjing Bizhou Biotechnology Co ltd
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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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • 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
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
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    • 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
    • D06M13/322—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 nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
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    • 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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  • Environmental & Geological Engineering (AREA)
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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention provides a composite material for wastewater treatment and a preparation method thereof, wherein reed stem powder is treated by 3-mercaptopropyl trimethoxy silane and ethylenediamine to prepare modified powder; then acrylonitrile, itaconic acid and methyl methacrylate are taken as raw materials to carry out polymerization reaction, modified powder is added after the polymerization reaction is finished, the spinning solution is obtained by microwave treatment, and the composite fiber is prepared by spinning; and finally, modifying the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite fiber. The composite material is suitable for adsorbing and removing various heavy metal ions in wastewater, and has excellent adsorption performance.

Description

Composite material for wastewater treatment and preparation method thereof
Technical Field
The invention relates to the technical field, in particular to a composite material for wastewater treatment and a preparation method thereof.
Background
Along with the rapid development of modern industry, the discharge amount of industrial wastewater is also increased sharply, the accumulation of heavy metals in water is aggravated, and the heavy metal pollution is serious. Particularly, industrial production such as mining, electroplating, chemical industry, printing and dyeing, paper making and the like can generate wastewater containing a large amount of heavy metals, the wastewater is discharged into various natural water bodies, heavy metal ions circulate through underground water and migrate through soil, so that the pollution of drinking water and food of human beings is caused, and the living environment and life safety of the human beings are seriously harmed. When heavy metals are adsorbed by organisms, the heavy metals exist in the form of single ions and can be combined with proteins, amino acids, fatty acids, carboxylic acids, phosphoric acids and the like in organisms to form organic acid salts, inorganic acid salts and chelate compounds, and the heavy metals generate toxic action on the organisms along with the combination with the organisms. Currently, the control and treatment of heavy metal water pollution has become an environmental problem which needs to be solved properly in environmental protection of all countries.
Heavy metal wastewater is usually high in acidity, complex in heavy metal ion species, and high in treatment difficulty due to the existence of multiple valence states and forms. Heavy metals in the heavy metal wastewater cannot be decomposed and destroyed, and only the existing positions of the heavy metals can be transferred and the physical and chemical forms of the heavy metals can be converted. The traditional treatment methods of heavy metal industrial wastewater mainly comprise a chemical precipitation method, a redox method, a membrane technology, an ion exchange method, a concentration method, an extraction method, a biological method and the like, and the treatment methods respectively have advantages to a certain extent, but have defects to different extents.
The adsorption method has the advantages of wide source of adsorption materials, large adsorption capacity, high adsorption speed, high removal efficiency, simple and convenient operation, repeated regeneration and recycling and the like, so that the adsorption method is generally concerned by people. Therefore, the development and research of high-performance adsorbents which are easier to prepare, low in price, high in efficiency, non-toxic and recyclable are one of the leading and most remarkable researches in the field at present.
Patent CN106215883B discloses a heavy metal wastewater adsorbing material and a preparation method thereof, wherein activated clay, lignocellulose and the like are used as raw materials, and compared with the simple use of activated clay or lignocellulose or the simple mixing of the activated clay and the lignocellulose, the composite material has good affinity and adsorption selectivity for heavy metal ions in wastewater, but only for zinc ions, which is a heavy metal ion, the application range is narrow, and the adsorption effect is not ideal.
Disclosure of Invention
The invention aims to provide a composite material for wastewater treatment and a preparation method thereof, which are suitable for adsorption removal of various heavy metal ions and have excellent adsorption performance.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of a composite material for wastewater treatment comprises the following specific steps in parts by weight:
(1) firstly, processing reed stem powder by using 3-mercaptopropyl trimethoxy silane and ethylenediamine to obtain modified powder;
(2) then adding 100 parts of acrylonitrile, 1.5-2 parts of itaconic acid and 8-12 parts of methyl methacrylate into a polymerization kettle, then adding 2-3 parts of initiator and 450-500 parts of solvent, carrying out polymerization reaction, adding 10-15 parts of modified powder, carrying out microwave treatment to obtain spinning stock solution, and spinning to prepare composite fibers;
(3) and finally, carrying out modification treatment on the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite material for treating the wastewater.
Preferably, in the step (1), the reed stem powder is obtained by crushing and grinding dry reed stems to 200-300 meshes.
Preferably, in the step (1), the mass ratio of the reed stem powder, the 3-mercaptopropyltrimethoxysilane and the ethylenediamine is 1: 5-8: 2 to 3.
Preferably, the specific method of step (1) is: adding ethylenediamine into 3-mercaptopropyl-trimethoxysilane, uniformly stirring, adding reed stem powder, stirring for 3-5 hours at 90-100 ℃, centrifuging, washing with deionized water, and drying to obtain the modified powder.
Preferably, in step (2), the solvent is dimethyl sulfoxide, and the initiator is azobisisobutyronitrile.
Preferably, in the step (2), the process conditions of the polymerization reaction are as follows: reacting for 15-18 hours at 50-60 ℃.
Preferably, in step (2), the monomer-removing and bubble-removing treatment is carried out after the polymerization reaction is finished, and the specific method is as follows: treating for 20-30 minutes under the condition of 3-4 kPa.
Preferably, in the step (2), the microwave irradiation is carried out at 300-500W by adopting an intermittent heating method, the heating is suspended for 30-40 s every 30s, and the circulation is carried out until the accumulated heating time is 3-5 minutes.
Preferably, in the step (2), the specific method for spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, entering a coagulating liquid through an air layer to perform coagulating bath, and performing post-treatment to obtain the composite 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.
More preferably, the solidification solution is a dimethyl sulfoxide aqueous solution with the mass concentration of 6-9%, and the temperature of the solidification bath is 35-45 ℃.
Further preferably, the post-treatment method comprises the following specific steps: pre-stretching the coagulated fiber obtained after coagulation bath for 1.1-1.3 times in a water bath at 75-85 ℃, washing with water at 70-80 ℃, treating in aminosiloxane emulsion to obtain oiled fiber, performing drying densification treatment at 140-150 ℃, performing thermal relaxation treatment through a hot air box, performing high-temperature high-pressure high-power drafting treatment through steam, and performing heat setting.
Further preferably, the time of the drying densification treatment is 40-50 s, the temperature of the thermal relaxation treatment is 90-95 ℃, the time is 10-20 s, the saturated steam pressure of the steam high-temperature high-pressure high-power drafting treatment is 0.1-0.2 MPa, the drafting multiplying factor is 3-5 times, the temperature of the heat setting is 320-330 ℃, and the time is 2-3 minutes.
Preferably, in the step (3), the preparation method of the premix comprises the following steps: mixing 1 part of p-methylthiophenol, 1-1.2 parts of 35-37 mass% formaldehyde solution and 10-12 parts of water, stirring at 60-70 ℃ for 80-100 minutes, and cooling to room temperature (25 ℃) to obtain a first mixed solution; then mixing 2-3 parts of thiourea, 3-5 parts of 35-37 mass% formaldehyde solution and 10-12 parts of water, stirring for 2-3 hours at 30-40 ℃, and cooling to room temperature (25 ℃) to obtain a second mixed solution; and stirring and uniformly mixing the first mixed solution, the second mixed solution and 3-4 parts of ethylenediamine to obtain the premixed solution.
Preferably, the specific method of step (3) is as follows by weight parts: adding 1 part of composite fiber into 5-8 parts of premix, performing microwave treatment, and then treating for 6-8 hours at 400-500 ℃ in a nitrogen atmosphere to obtain the composite fiber.
Further preferably, the microwave irradiation is carried out at 300-500W by adopting an intermittent heating method, the heating is suspended for 30-40 s every 30s, and the circulation is carried out until the accumulated heating time is 5-8 minutes.
The composite material for wastewater treatment is obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method comprises the steps of processing reed stem powder by using 3-mercaptopropyl trimethoxysilane and ethylenediamine to prepare modified powder; then acrylonitrile, itaconic acid and methyl methacrylate are taken as raw materials to carry out polymerization reaction, modified powder is added after the polymerization reaction is finished, the spinning solution is obtained by microwave treatment, and the composite fiber is prepared by spinning; and finally, modifying the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite material for treating the wastewater. The composite material is suitable for adsorbing and removing various heavy metal ions in wastewater, and has excellent adsorption performance.
(2) The reed stem powder has a pore structure, contains cellulose, starch, protein and other components, is rich in hydroxyl, amino and the like, and introduces sulfydryl and more amino by modification treatment of 3-mercaptopropyl trimethoxy silane and ethylenediamine. Acrylonitrile, itaconic acid and methyl methacrylate are polymerized in a ternary way, the generated polymer contains cyano, hydroxyl and the like, the polymer is mixed with modified powder and then subjected to microwave treatment, the entanglement of organic groups is promoted, hydrogen bonds are formed on the hydroxyl, amino, cyano and the like, and along with the formation of the hydrogen bonds, a network structure is formed inside, more pore structures are formed, so that the adsorption effect of the product is obviously enhanced.
(3) The composite fiber is modified by using the premixed liquid containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water, so that more sulfydryl, amino and the like are introduced to the surface of the composite fiber, thereby forming a chelate structure for heavy metal ions in the wastewater and realizing the removal of the heavy metal ions in the wastewater. On the other hand, the surface modification treatment of the composite fiber also makes the surface branched, increases the specific surface area, and enhances the adsorption effect. Sulfydryl, amino and the like on the surface of the composite fiber can also form hydrogen bond action with internal amino, hydroxyl, cyano and the like, so that more pores are formed, the adsorption action is further enhanced, and the heavy metal ions in the wastewater can be quickly adsorbed and removed.
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 wastewater treatment comprises the following specific steps:
(1) firstly, processing reed stem powder by using 3-mercaptopropyl trimethoxy silane and ethylenediamine to obtain modified powder;
(2) then adding 100kg of acrylonitrile, 1.5kg of itaconic acid and 12kg of methyl methacrylate into a polymerization kettle, then adding 2kg of initiator and 500kg of solvent, carrying out polymerization reaction, adding 10kg of modified powder, carrying out microwave treatment to obtain spinning stock solution, and spinning to prepare composite fibers;
(3) and finally, carrying out modification treatment on the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite material for treating the wastewater.
In the step (1), the reed stem powder is obtained by crushing and grinding dry reed stems to 300 meshes.
In the step (1), the mass ratio of the reed stem powder, the 3-mercaptopropyl trimethoxy silane and the ethylenediamine is 1: 5: 3.
the specific method of the step (1) is as follows: adding ethylenediamine into 3-mercaptopropyl-trimethoxysilane, uniformly stirring, adding reed stem powder, stirring for 5 hours at 90 ℃, centrifuging, washing with deionized water, and drying to obtain the modified powder.
In the step (2), the solvent is dimethyl sulfoxide, and the initiator is azobisisobutyronitrile.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 18 hours.
In the step (2), 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 3 kPa.
In the step (2), 300W microwave irradiation is carried out by adopting an intermittent heating method, heating is suspended for 40s every 30s, and the process is circulated until the accumulated heating time is 3 minutes.
In the step (2), the specific method for spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, entering a coagulating liquid through an air layer to perform coagulating bath, and performing post-treatment to obtain the composite fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.08mm to form a trickle, and the thickness of an air layer is 22 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 9%, and the temperature of the solidification bath is 35 ℃.
The specific method of post-treatment is as follows: pre-stretching the coagulated fiber obtained after coagulation bath by 1.1 times in a water bath at 85 ℃, washing with water at 80 ℃, treating in aminosiloxane emulsion to obtain oiled fiber, drying and densifying at 140 ℃, performing thermal relaxation treatment through a hot air box, performing high-temperature high-pressure high-power drafting treatment through steam, and performing heat setting.
The time of drying densification treatment is 50s, the temperature of thermal relaxation treatment is 90 ℃, the time is 20s, the saturated water vapor pressure of steam high-temperature high-pressure high-power drafting treatment is 0.1MPa, the drafting multiplying factor is 5 times, the temperature of heat setting is 320 ℃, and the time is 3 minutes.
In the step (3), the preparation method of the premix liquid is as follows: mixing 1kg of p-methylthiophenol, 1kg of formaldehyde solution with the mass concentration of 37% and 10kg of water, stirring for 80 minutes at 70 ℃, and cooling to room temperature (25 ℃) to obtain a first mixed solution; then mixing 3kg of thiourea, 3kg of formaldehyde solution with the mass concentration of 37% and 10kg of water, stirring for 2 hours at 40 ℃, and cooling to room temperature (25 ℃) to obtain a second mixed solution; and uniformly stirring the first mixed solution, the second mixed solution and 4kg of ethylenediamine to obtain the premixed solution.
The specific method of the step (3) is as follows: adding 1kg of composite fiber into 5kg of premix, performing microwave treatment, and then treating for 6 hours at 500 ℃ in a nitrogen atmosphere to obtain the composite fiber. And (3) performing 500W microwave irradiation by adopting a batch heating method, pausing heating for 30s every 30s, and circulating until the cumulative heating time is 8 minutes.
Example 2
A preparation method of a composite material for wastewater treatment comprises the following specific steps:
(1) firstly, processing reed stem powder by using 3-mercaptopropyl trimethoxy silane and ethylenediamine to obtain modified powder;
(2) then adding 100kg of acrylonitrile, 2kg of itaconic acid and 8kg of methyl methacrylate into a polymerization kettle, then adding 3kg of initiator and 450kg of solvent, carrying out polymerization reaction, adding 15kg of modified powder, carrying out microwave treatment to obtain spinning stock solution, and spinning to prepare composite fibers;
(3) and finally, carrying out modification treatment on the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite material for treating the wastewater.
In the step (1), the reed stem powder is obtained by crushing and grinding dry reed stems to 200 meshes.
In the step (1), the mass ratio of the reed stem powder, the 3-mercaptopropyl trimethoxy silane and the ethylenediamine is 1: 8: 2.
the specific method of the step (1) is as follows: adding ethylenediamine into 3-mercaptopropyl-trimethoxysilane, uniformly stirring, adding reed stem powder, stirring for 3 hours at 100 ℃, centrifuging, washing with deionized water, and drying to obtain the modified powder.
In the step (2), the solvent is dimethyl sulfoxide, and the initiator is azobisisobutyronitrile.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 60 ℃ for 15 hours.
In the step (2), 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 20 minutes under the condition of 4 kPa.
In the step (2), 500W microwave irradiation is carried out by adopting an intermittent heating method, heating is suspended for 30s every 30s, and the process is circulated until the cumulative heating time is 5 minutes.
In the step (2), the specific method for spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, entering a coagulating liquid through an air layer to perform coagulating bath, and performing post-treatment to obtain the composite fiber.
The spinning solution is metered by a metering pump and extruded by a spinneret with the aperture of 0.05mm to form a trickle, and the thickness of an air layer is 25 mm.
The solidification liquid is dimethyl sulfoxide water solution with the mass concentration of 6%, and the temperature of the solidification bath is 45 ℃.
The specific method of post-treatment is as follows: pre-stretching the coagulated fiber obtained after coagulation bath by 1.3 times in a water bath at 75 ℃, washing with water at 70 ℃, treating in aminosiloxane emulsion to obtain oiled fiber, drying and densifying at 150 ℃, performing thermal relaxation treatment through a hot air box, performing high-temperature high-pressure high-power drafting treatment through steam, and performing heat setting.
The time of drying densification treatment is 40s, the temperature of thermal relaxation treatment is 95 ℃, the time is 10s, the saturated water vapor pressure of steam high-temperature high-pressure high-power drafting treatment is 0.2MPa, the drafting multiplying factor is 3 times, the temperature of heat setting is 330 ℃, and the time is 2 minutes.
In the step (3), the preparation method of the premix liquid is as follows: mixing 1kg of p-methylthiophenol, 1.2kg of 35% formaldehyde solution with the mass concentration and 12kg of water, stirring for 100 minutes at the temperature of 60 ℃, and cooling to room temperature (25 ℃) to obtain a first mixed solution; then mixing 2kg of thiourea, 5kg of 35% formaldehyde solution with mass concentration and 12kg of water, stirring for 3 hours at 30 ℃, and cooling to room temperature (25 ℃) to obtain a second mixed solution; and uniformly stirring the first mixed solution, the second mixed solution and 3kg of ethylenediamine to obtain the premixed solution.
The specific method of the step (3) is as follows: adding 1kg of composite fiber into 8kg of premixed solution, performing microwave treatment, and then treating for 8 hours at 400 ℃ in a nitrogen atmosphere to obtain the composite fiber. And (3) performing 300W microwave irradiation by adopting a batch heating method, pausing heating for 40s every 30s, and circulating until the cumulative heating time is 5 minutes.
Example 3
A preparation method of a composite material for wastewater treatment comprises the following specific steps:
(1) firstly, processing reed stem powder by using 3-mercaptopropyl trimethoxy silane and ethylenediamine to obtain modified powder;
(2) then adding 100kg of acrylonitrile, 1.8kg of itaconic acid and 10kg of methyl methacrylate into a polymerization kettle, then adding 2.5kg of initiator and 480kg of solvent, carrying out polymerization reaction, adding 12kg of modified powder, carrying out microwave treatment to obtain spinning stock solution, and spinning to prepare composite fibers;
(3) and finally, carrying out modification treatment on the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite material for treating the wastewater.
In the step (1), the reed stem powder is obtained by crushing and grinding dry reed stems to 200 meshes.
In the step (1), the mass ratio of the reed stem powder, the 3-mercaptopropyl trimethoxy silane and the ethylenediamine is 1: 6: 2.5.
the specific method of the step (1) is as follows: adding ethylenediamine into 3-mercaptopropyl-trimethoxysilane, uniformly stirring, adding reed stem powder, stirring for 4 hours at 95 ℃, centrifuging, washing with deionized water, and drying to obtain the modified powder.
In the step (2), the solvent is dimethyl sulfoxide, and the initiator is azobisisobutyronitrile.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 55 ℃ for 17 hours.
In the step (2), 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 25 minutes under the condition of 3 kPa.
In the step (2), the microwave irradiation of 450W is carried out by adopting an intermittent heating method, the heating is suspended for 35s every 30s, and the process is circulated until the cumulative heating time is 4 minutes.
In the step (2), the specific method for spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, entering a coagulating liquid through an air layer to perform coagulating bath, and performing post-treatment to obtain the composite fiber.
The spinning solution is metered by a metering pump and extruded by a spinneret with the aperture of 0.06mm to form a trickle, and the thickness of an air layer is 24 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 8%, and the temperature of the solidification bath is 40 ℃.
The specific method of post-treatment is as follows: pre-stretching the coagulated fiber obtained after coagulation bath by 1.2 times in a water bath at 80 ℃, washing with water at 75 ℃, treating in aminosiloxane emulsion to obtain oiled fiber, drying and densifying at 145 ℃, performing thermal relaxation treatment through a hot air box, performing high-temperature high-pressure high-power drafting treatment through steam, and performing heat setting.
The time of drying densification treatment is 45s, the temperature of thermal relaxation treatment is 92 ℃ and the time is 15s, the saturated water vapor pressure of steam high-temperature high-pressure high-power drafting treatment is 0.15MPa, the drafting multiplying factor is 4 times, the temperature of heat setting is 325 ℃ and the time is 2 minutes.
In the step (3), the preparation method of the premix liquid is as follows: mixing 1kg of p-methylthiophenol, 1.1kg of formaldehyde solution with the mass concentration of 36% and 11kg of water, stirring for 90 minutes at 65 ℃, and cooling to room temperature (25 ℃) to obtain a first mixed solution; then mixing 2.5kg of thiourea, 4kg of formaldehyde solution with the mass concentration of 36% and 11kg of water, stirring for 2.5 hours at 35 ℃, and cooling to room temperature (25 ℃) to obtain a second mixed solution; and uniformly stirring the first mixed solution, the second mixed solution and 3.5kg of ethylenediamine to obtain the premixed solution.
The specific method of the step (3) is as follows: adding 1kg of composite fiber into 7kg of premix, performing microwave treatment, and then treating for 7 hours at 450 ℃ in a nitrogen atmosphere to obtain the composite fiber. And (3) performing 450W microwave irradiation by adopting a batch heating method, pausing heating for 35s every 30s, and circulating until the cumulative heating time is 7 minutes.
Comparative example 1
A preparation method of a composite material for wastewater treatment comprises the following specific steps:
(1) firstly, processing reed stem powder by using ethylenediamine to obtain modified powder;
(2) then adding 100kg of acrylonitrile, 1.5kg of itaconic acid and 12kg of methyl methacrylate into a polymerization kettle, then adding 2kg of initiator and 500kg of solvent, carrying out polymerization reaction, adding 10kg of modified powder, carrying out microwave treatment to obtain spinning stock solution, and spinning to prepare composite fibers;
(3) and finally, carrying out modification treatment on the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite material for treating the wastewater.
In the step (1), the reed stem powder is obtained by crushing and grinding dry reed stems to 300 meshes.
In the step (1), the mass ratio of the reed stem powder to the ethylenediamine is 1: 8.
the specific method of the step (1) is as follows: adding reed stem powder into ethylenediamine, stirring for 5 hours at 90 ℃, centrifuging, washing with deionized water, and drying to obtain the modified powder.
In the step (2), the solvent is dimethyl sulfoxide, and the initiator is azobisisobutyronitrile.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 18 hours.
In the step (2), 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 3 kPa.
In the step (2), 300W microwave irradiation is carried out by adopting an intermittent heating method, heating is suspended for 40s every 30s, and the process is circulated until the accumulated heating time is 3 minutes.
In the step (2), the specific method for spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, entering a coagulating liquid through an air layer to perform coagulating bath, and performing post-treatment to obtain the composite fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.08mm to form a trickle, and the thickness of an air layer is 22 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 9%, and the temperature of the solidification bath is 35 ℃.
The specific method of post-treatment is as follows: pre-stretching the coagulated fiber obtained after coagulation bath by 1.1 times in a water bath at 85 ℃, washing with water at 80 ℃, treating in aminosiloxane emulsion to obtain oiled fiber, drying and densifying at 140 ℃, performing thermal relaxation treatment through a hot air box, performing high-temperature high-pressure high-power drafting treatment through steam, and performing heat setting.
The time of drying densification treatment is 50s, the temperature of thermal relaxation treatment is 90 ℃, the time is 20s, the saturated water vapor pressure of steam high-temperature high-pressure high-power drafting treatment is 0.1MPa, the drafting multiplying factor is 5 times, the temperature of heat setting is 320 ℃, and the time is 3 minutes.
In the step (3), the preparation method of the premix liquid is as follows: mixing 1kg of p-methylthiophenol, 1kg of formaldehyde solution with the mass concentration of 37% and 10kg of water, stirring for 80 minutes at 70 ℃, and cooling to room temperature (25 ℃) to obtain a first mixed solution; then mixing 3kg of thiourea, 3kg of formaldehyde solution with the mass concentration of 37% and 10kg of water, stirring for 2 hours at 40 ℃, and cooling to room temperature (25 ℃) to obtain a second mixed solution; and uniformly stirring the first mixed solution, the second mixed solution and 4kg of ethylenediamine to obtain the premixed solution.
The specific method of the step (3) is as follows: adding 1kg of composite fiber into 5kg of premix, performing microwave treatment, and then treating for 6 hours at 500 ℃ in a nitrogen atmosphere to obtain the composite fiber. And (3) performing 500W microwave irradiation by adopting a batch heating method, pausing heating for 30s every 30s, and circulating until the cumulative heating time is 8 minutes.
Comparative example 2
A preparation method of a composite material for wastewater treatment comprises the following specific steps:
(1) firstly, 100kg of acrylonitrile, 1.5kg of itaconic acid and 12kg of methyl methacrylate are added into a polymerization kettle, then 2kg of initiator and 500kg of solvent are added, polymerization reaction and microwave treatment are carried out to obtain spinning stock solution, and the spinning is carried out to prepare composite fiber;
(2) and finally, carrying out modification treatment on the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite material for treating the wastewater.
In the step (1), the solvent is dimethyl sulfoxide, and the initiator is azobisisobutyronitrile.
In the step (1), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 18 hours.
In the step (1), 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 3 kPa.
In the step (1), 300W microwave irradiation is carried out by adopting an intermittent heating method, heating is suspended for 40s every 30s, and the process is circulated until the accumulated heating time is 3 minutes.
In the step (1), the specific method for spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, entering a coagulating liquid through an air layer to perform coagulating bath, and performing post-treatment to obtain the composite fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.08mm to form a trickle, and the thickness of an air layer is 22 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 9%, and the temperature of the solidification bath is 35 ℃.
The specific method of post-treatment is as follows: pre-stretching the coagulated fiber obtained after coagulation bath by 1.1 times in a water bath at 85 ℃, washing with water at 80 ℃, treating in aminosiloxane emulsion to obtain oiled fiber, drying and densifying at 140 ℃, performing thermal relaxation treatment through a hot air box, performing high-temperature high-pressure high-power drafting treatment through steam, and performing heat setting.
The time of drying densification treatment is 50s, the temperature of thermal relaxation treatment is 90 ℃, the time is 20s, the saturated water vapor pressure of steam high-temperature high-pressure high-power drafting treatment is 0.1MPa, the drafting multiplying factor is 5 times, the temperature of heat setting is 320 ℃, and the time is 3 minutes.
In the step (2), the preparation method of the premix liquid comprises the following steps: mixing 1kg of p-methylthiophenol, 1kg of formaldehyde solution with the mass concentration of 37% and 10kg of water, stirring for 80 minutes at 70 ℃, and cooling to room temperature (25 ℃) to obtain a first mixed solution; then mixing 3kg of thiourea, 3kg of formaldehyde solution with the mass concentration of 37% and 10kg of water, stirring for 2 hours at 40 ℃, and cooling to room temperature (25 ℃) to obtain a second mixed solution; and uniformly stirring the first mixed solution, the second mixed solution and 4kg of ethylenediamine to obtain the premixed solution.
The specific method of the step (2) is as follows: adding 1kg of composite fiber into 5kg of premix, performing microwave treatment, and then treating for 6 hours at 500 ℃ in a nitrogen atmosphere to obtain the composite fiber. And (3) performing 500W microwave irradiation by adopting a batch heating method, pausing heating for 30s every 30s, and circulating until the cumulative heating time is 8 minutes.
Comparative example 3
A preparation method of a composite material for wastewater treatment comprises the following specific steps:
(1) firstly, processing reed stem powder by using 3-mercaptopropyl trimethoxy silane and ethylenediamine to obtain modified powder;
(2) then adding 100kg of acrylonitrile, 1.5kg of itaconic acid and 12kg of methyl methacrylate into a polymerization kettle, then adding 2kg of initiator and 500kg of solvent, carrying out polymerization reaction, adding 10kg of modified powder, carrying out microwave treatment to obtain spinning stock solution, and spinning to prepare composite fibers;
(3) and finally, carrying out modification treatment on the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde and water to obtain the composite material for treating the wastewater.
In the step (1), the reed stem powder is obtained by crushing and grinding dry reed stems to 300 meshes.
In the step (1), the mass ratio of the reed stem powder, the 3-mercaptopropyl trimethoxy silane and the ethylenediamine is 1: 5: 3.
the specific method of the step (1) is as follows: adding ethylenediamine into 3-mercaptopropyl-trimethoxysilane, uniformly stirring, adding reed stem powder, stirring for 5 hours at 90 ℃, centrifuging, washing with deionized water, and drying to obtain the modified powder.
In the step (2), the solvent is dimethyl sulfoxide, and the initiator is azobisisobutyronitrile.
In the step (2), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 18 hours.
In the step (2), 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 3 kPa.
In the step (2), 300W microwave irradiation is carried out by adopting an intermittent heating method, heating is suspended for 40s every 30s, and the process is circulated until the accumulated heating time is 3 minutes.
In the step (2), the specific method for spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, entering a coagulating liquid through an air layer to perform coagulating bath, and performing post-treatment to obtain the composite fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.08mm to form a trickle, and the thickness of an air layer is 22 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 9%, and the temperature of the solidification bath is 35 ℃.
The specific method of post-treatment is as follows: pre-stretching the coagulated fiber obtained after coagulation bath by 1.1 times in a water bath at 85 ℃, washing with water at 80 ℃, treating in aminosiloxane emulsion to obtain oiled fiber, drying and densifying at 140 ℃, performing thermal relaxation treatment through a hot air box, performing high-temperature high-pressure high-power drafting treatment through steam, and performing heat setting.
The time of drying densification treatment is 50s, the temperature of thermal relaxation treatment is 90 ℃, the time is 20s, the saturated water vapor pressure of steam high-temperature high-pressure high-power drafting treatment is 0.1MPa, the drafting multiplying factor is 5 times, the temperature of heat setting is 320 ℃, and the time is 3 minutes.
In the step (3), the preparation method of the premix liquid is as follows: mixing 1kg of p-methylthiophenol, 1kg of formaldehyde solution with the mass concentration of 37% and 10kg of water, stirring for 80 minutes at 70 ℃, and cooling to room temperature (25 ℃) to obtain a first mixed solution; then mixing 3kg of thiourea, 3kg of formaldehyde solution with the mass concentration of 37% and 10kg of water, stirring for 2 hours at 40 ℃, and cooling to room temperature (25 ℃) to obtain a second mixed solution; and uniformly stirring the first mixed solution and the second mixed solution to obtain the premixed solution.
The specific method of the step (3) is as follows: adding 1kg of composite fiber into 5kg of premix, performing microwave treatment, and then treating for 6 hours at 500 ℃ in a nitrogen atmosphere to obtain the composite fiber. And (3) performing 500W microwave irradiation by adopting a batch heating method, pausing heating for 30s every 30s, and circulating until the cumulative heating time is 8 minutes.
Test examples
Preparing a metal ion aqueous solution containing zinc (200 mg/L), lead (220 mg/L), nickel (108 mg/L) and hexavalent chromium (150 mg/L), simulating heavy metal wastewater, then respectively treating the heavy metal wastewater by using the composite materials obtained in examples 1-3 or comparative examples 1-3 (the addition amount is 2 per mill of the weight of the heavy metal wastewater, standing and adsorbing the heavy metal wastewater for 30 minutes), filtering the heavy metal wastewater after treatment to obtain filtrate, analyzing and detecting the concentrations of metal ions in the filtrate and the heavy metal wastewater before treatment by using a flame atomic absorption spectrophotometry, and further calculating the adsorption amount of the composite material, namely the mass of the metal ions adsorbed by the composite material in unit mass, wherein the result is shown in table 1.
TABLE 1 comparison of adsorption Properties
Zn2+Adsorption Capacity (mg/g) Pb2+Adsorption Capacity (mg/g) Ni2+Adsorption Capacity (mg/g) Cr3+Adsorption Capacity (mg/g)
Example 1 405 299 189 220
Example 2 406 300 190 221
Example 3 408 302 192 222
Comparative example 1 301 153 91 101
Comparative example 2 197 95 54 66
Comparative example 3 300 142 95 110
As is clear from Table 1, the composite materials of examples 1 to 3 have excellent adsorption ability to each heavy metal ion in heavy metal wastewater. Comparative example 1 3-mercaptopropyltrimethoxysilane was omitted in step (1), comparative example 2 modified powder was omitted in step (2), and comparative example 3 ethylenediamine was omitted in step (3), and the resulting composite had significantly reduced porosity, reduced mercapto groups or amino groups, and significantly deteriorated adsorption effect on heavy metal ions.
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.

Claims (10)

1. The preparation method of the composite material for wastewater treatment is characterized by comprising the following specific steps in parts by weight:
(1) firstly, processing reed stem powder by using 3-mercaptopropyl trimethoxy silane and ethylenediamine to obtain modified powder;
(2) then adding 100 parts of acrylonitrile, 1.5-2 parts of itaconic acid and 8-12 parts of methyl methacrylate into a polymerization kettle, then adding 2-3 parts of initiator and 450-500 parts of solvent, carrying out polymerization reaction, adding 10-15 parts of modified powder, carrying out microwave treatment to obtain spinning stock solution, and spinning to prepare composite fibers;
(3) and finally, carrying out modification treatment on the composite fiber by using a premixed solution containing methyl thiophenol, thiourea, formaldehyde, ethylenediamine and water to obtain the composite material for treating the wastewater.
2. The preparation method according to claim 1, wherein in the step (1), the reed stem powder is obtained by crushing and grinding dry reed stems to 200-300 meshes.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the reed stem powder, the 3-mercaptopropyltrimethoxysilane and the ethylenediamine is 1: 5-8: 2 to 3.
4. The method for preparing the compound according to claim 1, wherein the specific method of the step (1) is as follows: adding ethylenediamine into 3-mercaptopropyl-trimethoxysilane, uniformly stirring, adding reed stem powder, stirring for 3-5 hours at 90-100 ℃, centrifuging, washing with deionized water, and drying to obtain the modified powder.
5. The method according to claim 1, wherein in the step (2), the polymerization reaction is carried out under the following process conditions: reacting for 15-18 hours at 50-60 ℃.
6. The method according to claim 1, wherein in the step (2), the microwave irradiation is carried out at 300-500W by a batch heating method, the heating is suspended for 30-40 s every 30s, and the process is repeated until the cumulative heating time is 3-5 minutes.
7. The preparation method according to claim 1, wherein in the step (2), the specific method for spinning is as follows: extruding the spinning solution through a spinning nozzle to form a trickle, entering a coagulating liquid through an air layer to perform coagulating bath, and performing post-treatment to obtain the composite fiber.
8. The method according to claim 1, wherein in the step (3), the premix is prepared by the following steps in parts by weight: mixing 1 part of p-methylthiophenol, 1-1.2 parts of 35-37 mass% formaldehyde solution and 10-12 parts of water, stirring at 60-70 ℃ for 80-100 minutes, and cooling to room temperature to obtain a first mixed solution. Then mixing 2-3 parts of thiourea, 3-5 parts of 35-37 mass% formaldehyde solution and 10-12 parts of water, stirring for 2-3 hours at 30-40 ℃, and cooling to room temperature to obtain a second mixed solution; and stirring and uniformly mixing the first mixed solution, the second mixed solution and 3-4 parts of ethylenediamine to obtain the premixed solution.
9. The preparation method according to claim 1, wherein the specific method of step (3) is as follows, in parts by weight: adding 1 part of composite fiber into 5-8 parts of premix, performing microwave treatment, and then treating for 6-8 hours at 400-500 ℃ in a nitrogen atmosphere to obtain the composite fiber.
10. A composite material for wastewater treatment obtained by the production method according to any one of claims 1 to 9.
CN202010447173.3A 2020-05-25 2020-05-25 Composite material for wastewater treatment and preparation method thereof Pending CN111501339A (en)

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