CN113457645B - High-adsorptivity water treatment diaphragm coated with nitrogen-doped porous carbon and preparation process thereof - Google Patents

High-adsorptivity water treatment diaphragm coated with nitrogen-doped porous carbon and preparation process thereof Download PDF

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CN113457645B
CN113457645B CN202110735145.6A CN202110735145A CN113457645B CN 113457645 B CN113457645 B CN 113457645B CN 202110735145 A CN202110735145 A CN 202110735145A CN 113457645 B CN113457645 B CN 113457645B
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porous carbon
nitrogen
doped porous
stirring
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CN113457645A (en
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刘科
张立斌
沈亚定
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Jiangsu Housheng New Energy Technology Co Ltd
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Jiangsu Housheng New Energy Technology Co Ltd
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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Abstract

The invention discloses a high-adsorptivity water treatment diaphragm coated with nitrogen-doped porous carbon and a preparation process thereof, comprising the following steps: (1) preparing nitrogen-doped porous carbon: mixing coal pitch, 2-methylimidazole, magnesium oxide and potassium hydroxide, pyrolyzing in a nitrogen atmosphere, and pickling to obtain nitrogen-doped porous carbon; (2) preparing a coating slurry: pure water is taken, and the nitrogen-doped porous carbon, the thickening agent and the adhesive are added for mixing to obtain coating slurry; (3) preparation of a separator: and coating the coating slurry on the surface of the polyolefin film to prepare the diaphragm. According to the invention, the polyolefin film and the nitrogen-doped porous carbon are used as the diaphragm materials, and the polyolefin film is used as the matrix, so that the cost is low, the processing technology is mature, and the porous carbon can be used in the fields of water filtration, permeation and the like; the nitrogen-doped porous carbon has larger specific surface, controllable pore diameter and larger pore volume, and can enhance the water treatment capacity of the base membrane; the nitrogen-doped porous carbon is coated on the surface of the base film, so that the prepared diaphragm has excellent adsorption performance in the field of water treatment.

Description

High-adsorptivity water treatment diaphragm coated with nitrogen-doped porous carbon and preparation process thereof
Technical Field
The invention relates to the technical field of water treatment, in particular to a high-adsorptivity water treatment membrane coated with nitrogen-doped porous carbon and a preparation process thereof.
Background
In daily production and living of human beings, a large amount of wastewater is generated, and natural water is polluted without being treated, so that the water quality is damaged, and the health of human beings and organisms is endangered. Dye wastewater belongs to one of organic wastewater which is difficult to degrade, and has darker color; the organic aromatic compound is usually a polymer and contains more benzene rings, and H on the benzene rings is replaced by nitro amino halogen and the like to generate dyes, so that most of aromatic compounds have high toxicity and pose a great threat to the health of people; and heavy metals such as lead and chromium in the dye wastewater are continuously enriched and transferred. The more organisms at the top of the food chain are, the greater the damage to them, and the more nuisance events are likely to occur. The existing sewage treatment methods comprise a coagulation sedimentation method, a biological method, a sound wave radiation method and the like, but the coagulation sedimentation method has the defects of high difficulty in treating dye sewage, difficulty in adapting to dye pollutants with complex components and high toxicity by microorganisms, high cost of the sound wave radiation method, high requirements on personnel quality sites, radiation to human bodies in production and application, health damage and many strict protective measures. Therefore, we propose a high adsorptivity water treatment membrane coated with nitrogen-doped porous carbon and a process for preparing the same.
Disclosure of Invention
The invention aims to provide a high-adsorptivity water treatment membrane coated with nitrogen-doped porous carbon and a preparation process thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation process of a high-adsorptivity water treatment membrane coated with nitrogen-doped porous carbon comprises the following steps:
(1) Preparing nitrogen-doped porous carbon: mixing coal tar pitch, 2-methylimidazole, magnesium oxide and potassium hydroxide, pyrolyzing and pickling to obtain nitrogen-doped porous carbon;
(2) Preparing a coating slurry: mixing pure water with nitrogen-doped porous carbon, a thickening agent and an adhesive to obtain coating slurry;
(3) Preparing a diaphragm: and (3) coating the coating slurry on the surface of the polyolefin film, and drying to obtain a coating, thereby preparing the diaphragm.
In the technical scheme, a polyolefin film is used as a base film, coating slurry is coated on the base film, and a diaphragm is obtained after drying; wherein the polyolefin film has lower cost, mature processing technology, thickness of 5-30 mu m, porosity of 35-60%, aperture of 30-100 nm, and can be used in the fields of water filtration and permeation, etc.; the porous carbon is one of carbon materials, has larger specific surface, controllable pore diameter and larger pore volume, and is a good choice for enhancing the water treatment capacity of the base membrane.
Further, the step (1) comprises the following processes:
grinding coal tar pitch, 2-methylimidazole, magnesium oxide and potassium hydroxide in sequence, and uniformly mixing;
placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing the mixture to 700-1000 ℃;
cooling, crushing, adding distilled water, adding hydrochloric acid for pickling, removing template magnesium oxide, and stirring until the reaction is finished;
filtering, and drying at 100-120 deg.c for 24-48 hr to obtain the porous nitrogen doped carbon.
According to the technical scheme, coal tar pitch is used as a carbon source, magnesium oxide is used as a template, potassium hydroxide is used as an activator, and 2-methylimidazole is used as a nitrogen source, so that the nitrogen-doped porous carbon is prepared through the steps, wherein nitrogen elements can be combined on the surface of the porous carbon in a covalent bond form, and the surface modification of the obtained porous carbon is performed, so that the adsorption effect on acidic substances can be enhanced; the nitrogen element contains five valence electrons, and after nitrogen is doped on the surface of the carbon skeleton of the porous carbon, the surface charge density is increased, so that covalent bonds are formed between carbon atoms and nitrogen atoms, and the internal structure of the porous carbon is changed; even nitrogen can partially replace carbon element, regulate pore canal, enhance hydrophilicity, increase active site of the membrane during adsorption, and improve water treatment effect of the membrane.
Further, the step (2) comprises the following processes:
taking pure water, sequentially adding nitrogen-doped porous carbon, and stirring for 30-60 min at a rotating speed of 500-700 rpm; adding a thickening agent, and stirring for 30-60 min at a rotating speed of 500-700 rpm; adding the adhesive, and stirring for 30-60 min at 400-550 rpm to obtain the coating slurry.
In the technical scheme, the nitrogen-doped porous carbon is dispersed in pure water, and a thickening agent and an adhesive are added to prepare black coating slurry; the coating slurry is coated on the polyolefin film in a screen roller coating, rotary spraying, dip coating, electrostatic spinning and the like, and then the coating slurry is dried to obtain a water treatment diaphragm with high adsorptivity, and different plate-type filtering adsorbers, permeable membranes and the like can be manufactured according to downstream application.
Further, the coating speed in the step (3) is 30-150 m/min, the drying temperature is 50-80 ℃, and the coating thickness is 2-30 mu m.
Further, the nitrogen-doped porous carbon is prepared from the following components in parts by mass: 7-11 parts of coal tar pitch, 7-11 parts of 2-methylimidazole, 55-75 parts of magnesium oxide and 30-55 parts of potassium hydroxide.
Further, the coating slurry is prepared from the following components in parts by mass: 55-65 parts of pure water, 15-30 parts of nitrogen-doped porous carbon, 5-15 parts of thickener and 5-20 parts of adhesive.
Further, the thickener is sodium carboxymethyl cellulose, and the adhesive is an acrylic adhesive.
The thickener may be sodium carboxymethyl cellulose but is not limited to sodium carboxymethyl cellulose.
Further, the step (2) comprises the following processes:
a. preparing modified porous carbon:
adding nitrogen-doped porous carbon into sodium carbonate, sequentially adding sodium silicate solution and calcium chloride solution, mixing, regulating the pH of the system to 9-11 by using urea, fully reacting, filtering, drying, placing at 60-90 ℃ in a nitrogen atmosphere, stirring, reacting for 60-90 min, adding a coupling agent, and mixing to obtain modified porous carbon;
b. preparing gallic acid modified organic matters:
dissolving gallic acid in acetone, adding allyl chloride, stirring and mixing, adding potassium carbonate, potassium iodide and sodium sulfite, carrying out reflux reaction for 10-12 h at 60-70 ℃ in nitrogen atmosphere, cooling, distilling under reduced pressure, dissolving solid products in deionized water, adding hydrochloric acid and mixing, extracting with ethyl acetate at the system pH of 3-4, washing with deionized water, and decompressing to obtain a product A;
taking phytic acid, adding glycidyl methacrylate, and stirring for reaction; adding the product A, namely potassium persulfate, stirring and reacting at the temperature of 70-80 ℃, and cleaning to obtain a product B;
dissolving tris (hydroxymethyl) aminomethane in deionized water, and adding hydrochloric acid to adjust the pH to 8-9; sequentially adding the product B and ethylenediamine, stirring, and fully reacting to obtain a modified organic matter;
c. preparing slurry:
taking pure water, sequentially adding modified porous carbon, and stirring for 30-60 min at a rotating speed of 500-700 rpm; adding the modified organic matters, and stirring for 30-60 min at the rotating speed of 400-600 rpm; adding sodium carboxymethylcellulose, and stirring for 30-60 min at 500-700 rpm; adding the adhesive, and stirring for 30-60 min at 400-550 rpm to obtain the coating slurry.
Further, the mol ratio of gallic acid, allyl chloride, potassium carbonate, potassium iodide, sodium sulfite, phytic acid, glycidyl methacrylate and ethylenediamine is 1 (1-2): 4-5): 0.15-0.30): 0.5 (1.0-1.2): 1-2): 1.0-1.5, and the coating slurry is prepared from the following components in parts by mass: 55-65 parts of pure water, 15-30 parts of modified porous carbon, 5-15 parts of sodium carboxymethyl cellulose and 5-20 parts of acrylic acid adhesive.
Through the preparation process, calcite and aragonite phase calcium carbonate are formed on the surface of carburized porous carbon and in pore channels, so that the interaction with sodium carboxymethylcellulose can be enhanced when coating slurry is formed, water molecules are displaced, and the water permeability of the prepared water treatment diaphragm is improved; blending with a coupling agent to improve the dispersibility of the prepared modified porous carbon in slurry;
hydroxyl in gallic acid reacts with potassium carbonate to generate a potassium phenolate group, then reacts with allyl chloride to generate ether bond, and the allyl chloride is grafted on benzene ring of the gallic acid to obtain the gallic acid with double bond; epoxy groups in glycidyl methacrylate react with phosphoric acid carboxyl groups in phytic acid, and the obtained product reacts with double bonds in the product A to obtain a product B; then the hydroxyl on the benzene ring is oxidized to form aldehyde group, and reacts with diamine to obtain quinoamine, so as to prepare modified organic matter;
after being mixed with the modified porous carbon, sodium carboxymethyl cellulose and the acrylic acid adhesive, the hydroxyl in the modified organic matter is coupled with calcium ions in the modified porous carbon, so that the adsorption of acidic dirt on calcium carbonate can be prevented, the enrichment of a thickener and the adhesive in the pores of the nitrogen-doped porous carbon is avoided, and the service performance of the modified porous carbon is ensured; the water resistance and chemical corrosion resistance of the prepared coating are improved, and the influence on the water treatment capacity caused by the change of the prepared water treatment diaphragm along with the pH of sewage can be effectively avoided; the mechanical property of the coating can be improved, the surface polarity of the prepared water treatment diaphragm can be enhanced, the wettability can be improved, and the water permeability can be improved.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the high-adsorptivity water treatment membrane coated with the nitrogen-doped porous carbon and the preparation process thereof, the polyolefin film and the nitrogen-doped porous carbon are used as membrane materials, and the polyolefin film is used as a matrix, so that the cost is low, the processing process is mature, and the high-adsorptivity water treatment membrane can be used in the fields of water filtration, permeation and the like; the nitrogen-doped porous carbon has larger specific surface, controllable pore diameter and larger pore volume, and can enhance the water treatment capacity of the base membrane; the nitrogen-doped porous carbon is coated on the surface of the base film, so that the prepared diaphragm has excellent adsorption performance in the field of water treatment.
2. According to the high-adsorptivity water treatment membrane coated with the nitrogen-doped porous carbon and the preparation process thereof, the nitrogen-doped porous carbon is prepared from coal pitch, magnesium oxide, potassium hydroxide and 2-methylimidazole, wherein nitrogen elements can be combined on the surface of the porous carbon in a covalent bond form, and the surface of the obtained porous carbon is modified, so that the adsorption effect on acidic substances can be enhanced, and the acidic sewage treatment capability is enhanced; the nitrogen element contains five valence electrons, and after nitrogen is doped on the surface of the carbon skeleton of the porous carbon, the surface charge density is increased, so that covalent bonds are formed between carbon atoms and nitrogen atoms, and the internal structure of the porous carbon is changed; even nitrogen can partially replace carbon element, regulate pore canal, enhance hydrophilicity, increase active site of the membrane during adsorption, and improve water treatment effect of the membrane.
3. According to the high-adsorptivity water treatment membrane coated with the nitrogen-doped porous carbon and the preparation process thereof, the nitrogen-doped porous carbon is coated on the surface of the base membrane, and the prepared water treatment membrane realizes multiple water treatment effects: the first filtration, utilize polyolefin membrane to filter and selectively permeate the filth in the dye waste water, the upper strata produces the concentrate, the lower floor permeate, and can recycle; the second exchange adsorption, the nitrogen element in the nitrogen-doped porous carbon partially replaces the carbon element in the carbon skeleton, the pore canal is regulated, the hydrophilicity of the porous carbon is enhanced, the active site in the adsorption process is increased, ions in the wastewater to be treated are accumulated on the surface active potential of the adsorbent, and the adsorption performance of the prepared diaphragm is improved; and thirdly, physical adsorption, wherein the nitrogen-doped porous carbon in the coating has high specific surface pore volume, and the adsorption performance of the prepared diaphragm is improved by utilizing intermolecular acting force to adsorb pollutants.
4. According to the high-adsorptivity water treatment membrane coated with the nitrogen-doped porous carbon and the preparation process thereof, the nitrogen-doped porous carbon is subjected to surface modification, and modified organic matters are added into the coating, so that the surface wettability of the prepared coating can be improved, and the hydrophilicity of the membrane is enhanced; the interaction of the modified porous carbon and the modified organic improves the mechanical property of the coating; gallic acid and phytic acid structures are introduced, so that the produced water treatment diaphragm is effectively prevented from changing along with the pH of sewage, and the stability of the water treatment capacity of the diaphragm is ensured; the quinone amine group is added, and the water resistance and chemical corrosion resistance of the prepared coating are improved.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is an electron microscopic view of the nitrogen-doped porous carbon of example 2 of the present invention;
FIG. 2 is an electron microscopic image of the nitrogen-doped porous carbon of example 2 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The polyolefin films described below are polyethylene porous films.
Example 1
(1) Preparing nitrogen-doped porous carbon:
sequentially taking 9 parts of coal tar pitch, 9 parts of 2-methylimidazole, 66 parts of magnesium oxide and 44 parts of potassium hydroxide, grinding, and uniformly mixing; placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing to 800 ℃; cooling, pulverizing, adding distilled water, adding hydrochloric acid for pickling, and stirring until the reaction is completed; suction filtering, and drying for 30 hours at the temperature of 110 ℃ to obtain the nitrogen-doped porous carbon;
(2) Preparing a coating slurry:
taking 60 parts of pure water, sequentially adding 18 parts of nitrogen-doped porous carbon, and stirring at 600rpm for 45min; adding 8 parts of thickener, and stirring at 600rpm for 45min; adding 14 parts of adhesive, and stirring at 500rpm for 30min to obtain coating slurry; wherein the thickener is sodium carboxymethyl cellulose, and the adhesive is acrylic acid adhesive;
(3) Preparing a diaphragm:
and (3) coating the coating slurry on the surface of the polyolefin film by adopting rotary spraying, wherein the coating speed is 50m/min, drying to obtain a coating, and the drying temperature is 75 ℃, and the thickness of the coating is 5 mu m, so that the diaphragm is prepared.
Example 2
(1) Preparing nitrogen-doped porous carbon:
sequentially taking 9 parts of coal tar pitch, 9 parts of 2-methylimidazole, 66 parts of magnesium oxide and 44 parts of potassium hydroxide, grinding, and uniformly mixing; placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing to 850 ℃; cooling, pulverizing, adding distilled water, adding hydrochloric acid for pickling, and stirring until the reaction is completed; suction filtering, and drying for 30 hours at the temperature of 110 ℃ to obtain the nitrogen-doped porous carbon;
(2) Preparing a coating slurry:
taking 60 parts of pure water, sequentially adding 18 parts of nitrogen-doped porous carbon, and stirring at 600rpm for 45min; adding 8 parts of thickener, and stirring at 600rpm for 45min; adding 14 parts of adhesive, and stirring at 500rpm for 30min to obtain coating slurry; wherein the thickener is sodium carboxymethyl cellulose, and the adhesive is acrylic acid adhesive;
(3) Preparing a diaphragm:
and (3) coating the coating slurry on the surface of the polyolefin film by adopting rotary spraying, wherein the coating speed is 50m/min, drying to obtain a coating, and the drying temperature is 75 ℃, and the thickness of the coating is 5 mu m, so that the diaphragm is prepared.
Example 3
(1) Preparing nitrogen-doped porous carbon:
sequentially taking 9 parts of coal tar pitch, 9 parts of 2-methylimidazole, 66 parts of magnesium oxide and 44 parts of potassium hydroxide, grinding, and uniformly mixing; placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing to 900 ℃; cooling, pulverizing, adding distilled water, adding hydrochloric acid for pickling, and stirring until the reaction is completed; suction filtering, and drying for 30 hours at the temperature of 110 ℃ to obtain the nitrogen-doped porous carbon;
(2) Preparing a coating slurry:
taking 60 parts of pure water, sequentially adding 18 parts of nitrogen-doped porous carbon, and stirring at 600rpm for 45min; adding 8 parts of thickener, and stirring at 600rpm for 45min; adding 14 parts of adhesive, and stirring at 500rpm for 30min to obtain coating slurry; wherein the thickener is sodium carboxymethyl cellulose, and the adhesive is acrylic acid adhesive;
(3) Preparing a diaphragm:
and (3) coating the coating slurry on the surface of the polyolefin film by adopting rotary spraying, wherein the coating speed is 50m/min, drying to obtain a coating, and the drying temperature is 75 ℃, and the thickness of the coating is 5 mu m, so that the diaphragm is prepared.
Example 4
(1) Preparing nitrogen-doped porous carbon:
sequentially taking 9 parts of coal tar pitch, 9 parts of 2-methylimidazole, 66 parts of magnesium oxide and 44 parts of potassium hydroxide, grinding, and uniformly mixing; placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing to 850 ℃; cooling, pulverizing, adding distilled water, adding hydrochloric acid for pickling, and stirring until the reaction is completed; suction filtering, and drying for 30 hours at the temperature of 110 ℃ to obtain the nitrogen-doped porous carbon;
(2) Preparing a coating slurry:
a. preparing modified porous carbon:
adding nitrogen-doped porous carbon into sodium carbonate, sequentially adding sodium silicate solution and calcium chloride solution, mixing, regulating the pH of the system to 9 by using urea, fully reacting, filtering, drying, placing at 60 ℃, stirring in a nitrogen atmosphere, reacting for 60min, adding a coupling agent, and mixing to obtain modified porous carbon;
b. preparing gallic acid modified organic matters:
dissolving gallic acid in acetone, adding allyl chloride, stirring and mixing, adding potassium carbonate, potassium iodide and sodium sulfite, carrying out reflux reaction at 60 ℃ for 10 hours in a nitrogen atmosphere, cooling, distilling under reduced pressure, dissolving a solid product in deionized water, adding hydrochloric acid and mixing, extracting with ethyl acetate at the system pH of 4, washing with deionized water, and decompressing to obtain a product A;
taking phytic acid, adding glycidyl methacrylate, and stirring for reaction; adding the product A, namely potassium persulfate, stirring and reacting at the temperature of 70 ℃, and cleaning to obtain a product B;
dissolving tris (hydroxymethyl) aminomethane in deionized water, and adding hydrochloric acid to adjust the pH to 8; sequentially adding the product B and ethylenediamine, stirring, and fully reacting to obtain a modified organic matter;
wherein the molar ratio of gallic acid, allyl chloride, potassium carbonate, potassium iodide, sodium sulfite, phytic acid, glycidyl methacrylate and ethylenediamine is 1:1:4:0.15:0.5:1:1:1;
c. preparing slurry:
taking pure water, sequentially adding modified porous carbon, and stirring at 500rpm for 30min; adding the modified organic matters, and stirring for 30min at a rotation speed of 400 rpm; adding sodium carboxymethylcellulose, and stirring at 500rpm for 30min; adding an acrylic acid type adhesive, and stirring at 400rpm for 30min to obtain coating slurry; wherein the mass fraction of each material is as follows: 60 parts of pure water, 18 parts of modified porous carbon, 8 parts of sodium carboxymethylcellulose and 14 parts of acrylic acid type adhesive;
(3) Preparing a diaphragm:
and (3) coating the coating slurry on the surface of the polyolefin film by adopting rotary spraying, wherein the coating speed is 50m/min, drying to obtain a coating, and the drying temperature is 75 ℃, and the thickness of the coating is 5 mu m, so that the diaphragm is prepared.
Example 5
(1) Preparing nitrogen-doped porous carbon:
sequentially taking 9 parts of coal tar pitch, 9 parts of 2-methylimidazole, 66 parts of magnesium oxide and 44 parts of potassium hydroxide, grinding, and uniformly mixing; placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing to 850 ℃; cooling, pulverizing, adding distilled water, adding hydrochloric acid for pickling, and stirring until the reaction is completed; suction filtering, and drying for 30 hours at the temperature of 110 ℃ to obtain the nitrogen-doped porous carbon;
(2) Preparing a coating slurry:
a. preparing modified porous carbon:
adding nitrogen-doped porous carbon into sodium carbonate, sequentially adding sodium silicate solution and calcium chloride solution, mixing, regulating the pH of the system to 10 by using urea, fully reacting, filtering, drying, placing at 75 ℃, stirring in nitrogen atmosphere, reacting for 75min, adding a coupling agent, and mixing to obtain modified porous carbon;
b. preparing gallic acid modified organic matters:
dissolving gallic acid in acetone, adding allyl chloride, stirring and mixing, adding potassium carbonate, potassium iodide and sodium sulfite, carrying out reflux reaction for 11h at 65 ℃ in nitrogen atmosphere, cooling, distilling under reduced pressure, dissolving a solid product in deionized water, adding hydrochloric acid and mixing, wherein the pH of the system is 3.5, extracting by using ethyl acetate, washing by using deionized water, and decompressing to obtain a product A;
taking phytic acid, adding glycidyl methacrylate, and stirring for reaction; adding the product A, namely potassium persulfate, stirring and reacting at the temperature of 75 ℃, and cleaning to obtain a product B;
dissolving tris (hydroxymethyl) aminomethane in deionized water, and adding hydrochloric acid to adjust the pH to 8-9; sequentially adding the product B and ethylenediamine, stirring, and fully reacting to obtain a modified organic matter;
wherein the molar ratio of gallic acid, allyl chloride, potassium carbonate, potassium iodide, sodium sulfite, phytic acid, glycidyl methacrylate and ethylenediamine is 1:1.5:4.5:0.22:0.5:1.1:1.5:1.2;
c. preparing slurry:
taking pure water, sequentially adding modified porous carbon, and stirring at 600rpm for 45min; adding the modified organic matters, and stirring for 45min at a rotating speed of 500 rpm; adding sodium carboxymethylcellulose, and stirring at 600rpm for 45min; adding an acrylic acid type adhesive, and stirring at 480rpm for 45min to obtain coating slurry; wherein the mass fraction of each material is as follows: 60 parts of pure water, 18 parts of modified porous carbon, 8 parts of sodium carboxymethylcellulose and 14 parts of acrylic acid type adhesive;
(3) Preparing a diaphragm:
and (3) coating the coating slurry on the surface of the polyolefin film by adopting rotary spraying, wherein the coating speed is 50m/min, drying to obtain a coating, and the drying temperature is 75 ℃, and the thickness of the coating is 5 mu m, so that the diaphragm is prepared.
Example 6
(1) Preparing nitrogen-doped porous carbon:
sequentially taking 9 parts of coal tar pitch, 9 parts of 2-methylimidazole, 66 parts of magnesium oxide and 44 parts of potassium hydroxide, grinding, and uniformly mixing; placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing to 850 ℃; cooling, pulverizing, adding distilled water, adding hydrochloric acid for pickling, and stirring until the reaction is completed; suction filtering, and drying for 30 hours at the temperature of 110 ℃ to obtain the nitrogen-doped porous carbon;
(2) Preparing a coating slurry:
a. preparing modified porous carbon:
taking nitrogen-doped porous carbon, placing the nitrogen-doped porous carbon into sodium carbonate, sequentially adding a sodium silicate solution and a calcium chloride solution for mixing, regulating the pH of the system to 11 by using urea, fully reacting, filtering, drying, placing the mixture at the temperature of 90 ℃, stirring the mixture in a nitrogen atmosphere, reacting for 90min, and adding a coupling agent for mixing to obtain modified porous carbon;
b. preparing gallic acid modified organic matters:
dissolving gallic acid in acetone, adding allyl chloride, stirring and mixing, adding potassium carbonate, potassium iodide and sodium sulfite, carrying out reflux reaction for 12 hours at 70 ℃ in a nitrogen atmosphere, cooling, distilling under reduced pressure, dissolving a solid product in deionized water, adding hydrochloric acid and mixing, extracting with ethyl acetate at the system pH of 4, washing with deionized water, and decompressing to obtain a product A;
taking phytic acid, adding glycidyl methacrylate, and stirring for reaction; adding the product A, potassium persulfate, stirring at 80 ℃ for reaction, and cleaning to obtain a product B;
dissolving tris (hydroxymethyl) aminomethane in deionized water, and adding hydrochloric acid to adjust the pH to 9; sequentially adding the product B and ethylenediamine, stirring, and fully reacting to obtain a modified organic matter;
wherein the molar ratio of gallic acid, allyl chloride, potassium carbonate, potassium iodide, sodium sulfite, phytic acid, glycidyl methacrylate and ethylenediamine is 1:2:5:0.30:0.5:1.2:2:1.5;
c. preparing slurry:
taking pure water, sequentially adding modified porous carbon, and stirring at 700rpm for 60min; adding the modified organic matters, and stirring for 60min at 600 rpm; adding sodium carboxymethylcellulose, and stirring at 700rpm for 60min; adding an acrylic acid type adhesive, and stirring at 550rpm for 60min to obtain coating slurry; wherein the mass fraction of each material is as follows: 60 parts of pure water, 18 parts of modified porous carbon, 8 parts of sodium carboxymethylcellulose and 14 parts of acrylic acid type adhesive;
(3) Preparing a diaphragm:
and (3) coating the coating slurry on the surface of the polyolefin film by adopting rotary spraying, wherein the coating speed is 50m/min, drying to obtain a coating, and the drying temperature is 75 ℃, and the thickness of the coating is 5 mu m, so that the diaphragm is prepared.
Comparative example 1
(1) Preparing nitrogen-doped porous carbon:
sequentially taking 9 parts of coal tar pitch, 9 parts of 2-methylimidazole, 66 parts of magnesium oxide and 44 parts of potassium hydroxide, grinding, and uniformly mixing; placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing to 850 ℃; cooling, pulverizing, adding distilled water, adding hydrochloric acid for pickling, and stirring until the reaction is completed; suction filtering, and drying for 30 hours at the temperature of 110 ℃ to obtain the nitrogen-doped porous carbon;
(2) Preparing a coating slurry:
a. preparing gallic acid modified organic matters:
dissolving gallic acid in acetone, adding allyl chloride, stirring and mixing, adding potassium carbonate, potassium iodide and sodium sulfite, carrying out reflux reaction for 11h at 65 ℃ in nitrogen atmosphere, cooling, distilling under reduced pressure, dissolving a solid product in deionized water, adding hydrochloric acid and mixing, wherein the pH of the system is 3.5, extracting by using ethyl acetate, washing by using deionized water, and decompressing to obtain a product A;
taking phytic acid, adding glycidyl methacrylate, and stirring for reaction; adding the product A, namely potassium persulfate, stirring and reacting at the temperature of 75 ℃, and cleaning to obtain a product B;
dissolving tris (hydroxymethyl) aminomethane in deionized water, and adding hydrochloric acid to adjust the pH to 8-9; sequentially adding the product B and ethylenediamine, stirring, and fully reacting to obtain a modified organic matter;
wherein the molar ratio of gallic acid, allyl chloride, potassium carbonate, potassium iodide, sodium sulfite, phytic acid, glycidyl methacrylate and ethylenediamine is 1:1.5:4.5:0.22:0.5:1.1:1.5:1.2;
b. preparing slurry:
taking pure water, sequentially adding nitrogen-doped porous carbon, and stirring at 600rpm for 45min; adding the modified organic matters, and stirring for 45min at a rotating speed of 500 rpm; adding sodium carboxymethylcellulose, and stirring at 600rpm for 45min; adding an acrylic acid type adhesive, and stirring at 480rpm for 45min to obtain coating slurry; wherein the mass fraction of each material is as follows: 60 parts of pure water, 18 parts of modified porous carbon, 8 parts of sodium carboxymethylcellulose and 14 parts of acrylic acid type adhesive;
(3) Preparing a diaphragm:
and (3) coating the coating slurry on the surface of the polyolefin film by adopting rotary spraying, wherein the coating speed is 50m/min, drying to obtain a coating, and the drying temperature is 75 ℃, and the thickness of the coating is 5 mu m, so that the diaphragm is prepared.
Comparative example 2
(1) Preparing a coating slurry:
taking 60 parts of pure water, sequentially adding 18 parts of porous carbon, and stirring at 600rpm for 45min; adding 8 parts of sodium carboxymethylcellulose, and stirring at 600rpm for 45min; adding 14 parts of acrylic adhesive, and stirring at 500rpm for 30min to obtain coating slurry;
(2) Preparing a diaphragm:
and (3) coating the coating slurry on the surface of the polyolefin film by adopting rotary spraying, wherein the coating speed is 50m/min, drying to obtain a coating, and the drying temperature is 75 ℃, and the thickness of the coating is 5 mu m, so that the diaphragm is prepared.
Experiment
Taking the nitrogen-doped porous carbon and the water treatment membrane obtained in examples 1-6 and comparative examples 1-2, preparing samples, respectively detecting the performances of the samples and recording the detection results:
taking a sample, operating a membrane testing device in a dead-end filtering mode, taking pure water as a testing solution, stabilizing the testing water temperature at 25 ℃, prepressing for 30min at an inlet pressure of 0.15MPa, regulating the pressure to 0.10MPa, stabilizing for 10min, recording and calculating the water yield of the sample per square meter hour, and recording as the pure water flux;
taking a diaphragm sample, adopting a cross-flow filtration mode to operate a membrane testing device, taking methyl orange and methylene blue dye solutions with pH of 4 and 9 and concentration of 100mg/L as testing solutions, testing water temperature at 25 ℃, transmembrane pressure difference at 0.10MPa, membrane surface flow rate at 0.3m/s, operating for 10min after the system is stable, collecting filtrate and feed liquid, and calculating retention rate R= (1-C) p /C f )×100％，C p And C f Respectively representing the concentration of the filtered liquid and the concentration of the feed liquid;
Figure GDA0004150909650000111
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Figure GDA0004150909650000121
from the data in the above table, the following conclusions can be clearly drawn:
the water treatment separator obtained in examples 1 to 6 was compared with the water treatment separator obtained in comparative examples 1 to 2, and the detection results revealed that:
1. the water treatment membranes obtained in examples 1-6 were substantially higher in rejection rate for different dyes for examples 1-6 than for comparative example 2, where the porous carbon was conventional non-nitrogen-doped porous carbon, as compared to the water treatment membrane obtained in comparative example 2, which fully demonstrates that the membranes made in this application can improve the rejection capacity for contaminants;
2. the water treatment membranes obtained in examples 4-6 had an improved rejection rate compared to the water treatment membrane obtained in example 2, and the change in rejection rate for different pH of the dye was relatively small;
the water treatment membrane obtained in comparative example 1 was not modified with nitrogen-doped porous carbon in comparative example 1, and the rejection rate of the dye was changed at different pH, as compared with the water treatment membrane obtained in example 5; the modification of the nitrogen-doped porous carbon can stabilize the water treatment capability of the prepared diaphragm under different pH conditions.
3. Fig. 1-2 are electron microscope pictures of the nitrogen-doped porous carbon in example 2, and it can be seen from the pictures that the nitrogen-doped porous carbon has a rich pore structure, contains micropores and small mesopores, and shows that the nitrogen-doped porous carbon is a graded porous carbon. It can be seen from SEM that the prepared nitrogen-doped porous carbon is in the shape of an open-celled spherical shell. Wherein the magnesium oxide template functions as: in the carbonization process of coal pitch, spherical magnesium oxide templates are firstly softened and melted to be wrapped to form spherical porous carbon materials, and then the magnesium oxide templates wrapped inside are removed through acid washing to form porous spherical shell-shaped nitrogen-doped porous carbon.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. The preparation process of the high-adsorptivity water treatment membrane coated with the nitrogen-doped porous carbon is characterized by comprising the following steps of:
(1) Preparing nitrogen-doped porous carbon:
mixing coal tar pitch, 2-methylimidazole, magnesium oxide and potassium hydroxide, pyrolyzing and pickling to obtain nitrogen-doped porous carbon;
(2) Preparing a coating slurry;
(3) Preparing a diaphragm:
coating the surface of a polyolefin film with the coating slurry, and drying to obtain a coating, thereby preparing a diaphragm;
the step (1) comprises the following processes:
grinding coal tar pitch, 2-methylimidazole, magnesium oxide and potassium hydroxide in sequence, and uniformly mixing;
placing the mixture in a vacuum tube furnace, charging nitrogen, and pyrolyzing the mixture to 700-1000 ℃;
cooling, pulverizing, adding distilled water, adding hydrochloric acid for pickling, and stirring until the reaction is completed;
suction filtering, and drying at 100-120 ℃ for 24-48 h to obtain the nitrogen-doped porous carbon;
the step (2) comprises the following processes:
a. preparing modified porous carbon:
adding nitrogen-doped porous carbon into sodium carbonate, sequentially adding sodium silicate solution and calcium chloride solution, mixing, regulating the pH of the system to 9-11 by using urea, fully reacting, filtering, drying, placing at 60-90 ℃ in a nitrogen atmosphere, stirring, reacting for 60-90 min, adding a coupling agent, and mixing to obtain modified porous carbon;
b. preparing gallic acid modified organic matters:
dissolving gallic acid in acetone, adding allyl chloride, stirring and mixing, adding potassium carbonate, potassium iodide and sodium sulfite, carrying out reflux reaction for 10-12 h at 60-70 ℃ in nitrogen atmosphere, cooling, distilling under reduced pressure, dissolving solid products in deionized water, adding hydrochloric acid and mixing, extracting with ethyl acetate at the system pH of 3-4, washing with deionized water, and decompressing to obtain a product A;
taking phytic acid, adding glycidyl methacrylate, and stirring for reaction; adding the product A, namely potassium persulfate, stirring and reacting at the temperature of 70-80 ℃, and cleaning to obtain a product B;
dissolving tris (hydroxymethyl) aminomethane in deionized water, and adding hydrochloric acid to adjust the pH to 8-9; sequentially adding the product B and ethylenediamine, stirring, and fully reacting to obtain a modified organic matter;
c. preparing slurry:
taking pure water, sequentially adding modified porous carbon, and stirring for 30-60 min at a rotating speed of 500-700 rpm; adding the modified organic matters, and stirring for 30-60 min at the rotating speed of 400-600 rpm; adding sodium carboxymethyl cellulose as thickener, stirring at 500-700 rpm for 30-60 min; adding an adhesive, and stirring for 30-60 min at a rotating speed of 400-550 rpm to obtain coating slurry;
the nitrogen-doped porous carbon is prepared from the following components in parts by mass: 7-11 parts of coal tar pitch, 7-11 parts of 2-methylimidazole, 55-75 parts of magnesium oxide and 30-55 parts of potassium hydroxide;
the molar ratio of gallic acid, allyl chloride, potassium carbonate, potassium iodide, sodium sulfite, phytic acid, glycidyl methacrylate and ethylenediamine is 1 (1-2): 4-5): 0.15-0.30): 0.5 (1.0-1.2): 1-2): 1.0-1.5.
2. The process for preparing a high adsorptivity water treatment membrane coated with nitrogen-doped porous carbon as claimed in claim 1, wherein the process comprises the following steps: the coating speed in the step (3) is 30-150 m/min, the drying temperature is 50-80 ℃, and the coating thickness is 2-30 mu m.
3. The process for preparing a high adsorptivity water treatment membrane coated with nitrogen-doped porous carbon as claimed in claim 1, wherein the process comprises the following steps: the adhesive is an acrylic adhesive.
4. A nitrogen-doped porous carbon-coated high-adsorptivity water treatment membrane made by the process of preparing a nitrogen-doped porous carbon-coated high-adsorptivity water treatment membrane according to any one of claims 1-3.
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