CN112316927A - Water treatment agent capable of rapidly adsorbing methylene blue and preparation method thereof - Google Patents
Water treatment agent capable of rapidly adsorbing methylene blue and preparation method thereof Download PDFInfo
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- CN112316927A CN112316927A CN202011254043.4A CN202011254043A CN112316927A CN 112316927 A CN112316927 A CN 112316927A CN 202011254043 A CN202011254043 A CN 202011254043A CN 112316927 A CN112316927 A CN 112316927A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
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- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
Dispersing a functional carbon nano tube and magnetic nano particles in ethanol, ultrasonically assembling the magnetic nano particles on the surface of the functional carbon nano tube, centrifuging for many times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in an organic solvent, adding polymerizable glycidyl ether, acrylonitrile and an initiator, filling nitrogen to replace air in a bottle, stirring and reacting for 2-3 hours in an oil bath kettle at 60-70 ℃, removing the solvent after the reaction is finished, and drying the solid in vacuum to obtain the adsorbent. The modified carbon nanotube/polyacrylonitrile composite material is prepared by taking the carbon nanotube, the acrylonitrile and the polymerizable glycidyl ether as raw materials and is used as a methylene blue fast adsorbent, so that the adsorption capacity to methyl blue is large, and the adsorption time is short; in addition, after the methylene blue is adsorbed, the adsorbent can be recovered through an external magnetic field so as to prevent the adsorbent from remaining in the water body to cause secondary pollution.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a water treatment agent capable of rapidly adsorbing methylene blue and a preparation method thereof.
Background
Methylene blue is a phenothiazine salt, is widely applied to aspects such as chemical indicators, dyes, biological coloring agents and the like, has good curative effect on preventing and treating saprolegniasis, ichthyophthiriasis and the like of freshwater fish, and therefore, can also be used in aquaculture. However, the use of methylene blue in a large amount can generate certain toxic and side effects on cultured aquatic organisms, and a certain amount of residues are accumulated in aquatic organisms through the biological enrichment effect, so that new hidden dangers are caused to the life safety of fishes. However, most of the currently used methylene blue adsorbents are wastewater treatment agents used in dye wastewater, and have low adsorption speed and long adsorption time.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the adsorbent capable of quickly adsorbing the residual methylene blue in the water body.
In order to achieve the purpose, the invention provides the following technical scheme:
dispersing functional carbon nano tubes and magnetic nano particles in ethanol, ultrasonically assembling the magnetic nano particles on the surfaces of the functional carbon nano tubes, centrifuging for many times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in an organic solvent, adding polymerizable glycidyl ether, acrylonitrile and an initiator, filling nitrogen to replace the air in a bottle, stirring and reacting for 2-3h in an oil bath kettle at 60-70 ℃, removing the solvent by reduced pressure distillation after the reaction is finished, and drying the solid in vacuum to obtain the adsorbent.
Further, the functional carbon nanotube is a hydroxylated carbon nanotube or an aminated carbon nanotube.
Further, the magnetic nanoparticles are oleic acid modified ferroferric oxide magnetic nanoparticles.
Further, the polymerizable glycidyl ether is selected from one of allyl glycidyl ether, glycidyl methacrylate and 4-hydroxybutyl glycidyl acrylate.
Further, the organic solvent is one of N, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane or dimethyl sulfoxide.
Further, the initiator is azobisisobutyronitrile or benzoyl peroxide.
Further, the mass ratio of the functional carbon nano tubes to the magnetic nano particles is 1: 0.05-0.2, and the concentration of the functional carbon nano tubes is 0.1 g/ml.
Further, the molar ratio of the polymerizable glycidyl ether to the acrylonitrile to the initiator is 1:1:0.01, and the mass ratio of the acrylonitrile to the functional carbon nanotube is 0.5-1.5: 1.
An adsorbent for rapidly adsorbing methylene blue prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that: the method takes the carbon nano tube, the acrylonitrile and the polymerizable glycidyl ether as raw materials to prepare the methylene blue fast adsorbent, and the polyacrylonitrile has the characteristics of excellent chemical stability, good weather resistance, aging resistance, pollution resistance, easy cleaning and the like; the surface of the carbon nano tube is of a porous structure, has a very large specific surface area and has a very strong adsorption effect on methylene blue, and the functional carbon nano tube is selected, the surface of the carbon nano tube is rich in hydroxyl or amino, so that the dispersibility of the carbon nano tube in a polymerization system is effectively improved, and the carbon nano tube can perform a ring-opening reaction with glycidyl ether; the polymerizable glycidyl ether can be polymerized with acrylonitrile free radicals on one hand, and can be grafted with the functional carbon nano tube on the other hand, so that the modified carbon nano tube/polyacrylonitrile composite material is formed, methyl blue can be quickly adsorbed, the adsorption capacity is large, the adsorption time is short, and the death of cultured fishes caused by methylene blue residues is effectively avoided; in addition, the magnetic nanoparticles are added, and the adsorbent can be recovered through an external magnetic field after the methylene blue is adsorbed, so that the adsorbent is prevented from remaining in a water body for a long time to cause secondary pollution.
Description of the drawings:
FIG. 1 is a graph of methylene blue adsorption rate versus time for examples 1-3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
dispersing 1g of functional carbon nano tube and 50mg of magnetic nano particles in 10ml of ethanol, ultrasonically assembling the magnetic nano particles on the surface of the functional carbon nano tube, centrifuging for multiple times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in 10ml of organic solvent, adding 10mmol of polymerizable glycidyl ether, 10mmol of acrylonitrile and 0.1mmol of initiator, filling nitrogen to replace the air in a bottle, stirring and reacting for 2-3h in an oil bath kettle at 60-70 ℃, decompressing and distilling to remove the solvent after the reaction is finished, and vacuum drying the solid to obtain the adsorbent.
Example 2:
dispersing 1g of functional carbon nano tube and 50mg of magnetic nano particles in 10ml of ethanol, performing ultrasonic treatment to assemble the magnetic nano particles on the surface of the functional carbon nano tube, centrifuging for multiple times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in 10ml of organic solvent, adding 15mmol of polymerizable glycidyl ether, 15mmol of acrylonitrile and 0.15mmol of initiator, filling nitrogen to replace the air in a bottle, stirring and reacting for 2-3h in an oil bath kettle at 60-70 ℃, removing the solvent by reduced pressure distillation after the reaction is finished, and performing vacuum drying on the solid to obtain the adsorbent.
Example 3:
dispersing 1g of functional carbon nano tube and 50mg of magnetic nano particles in 10ml of ethanol, ultrasonically assembling the magnetic nano particles on the surface of the functional carbon nano tube, centrifuging for multiple times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in 10ml of organic solvent, adding 20mmol of polymerizable glycidyl ether, 20mmol of acrylonitrile and 0.2mmol of initiator, filling nitrogen to replace the air in a bottle, stirring and reacting for 2-3h in an oil bath kettle at 60-70 ℃, decompressing and distilling to remove the solvent after the reaction is finished, and vacuum drying the solid to obtain the adsorbent.
In examples 1 to 3, the functional carbon nanotubes are hydroxylated carbon nanotubes or aminated carbon nanotubes;
the magnetic nanoparticles are oleic acid modified ferroferric oxide magnetic nanoparticles;
the polymerizable glycidyl ether is selected from one of allyl glycidyl ether, glycidyl methacrylate and 4-hydroxybutyl glycidyl acrylate;
the organic solvent is one of N, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane or dimethyl sulfoxide;
the initiator is azobisisobutyronitrile or benzoyl peroxide.
The adsorbent prepared in example 1-3 was used for water treatment of culture water containing methylene blue, 20mg of the adsorbent was put into 50ml of methylene blue solution with an initial concentration of 100mg/L, the mixture was placed in a constant temperature shaking table at 30 ℃ and shaken for a certain period of time, and the absorbance of the adsorbed solution was measured by an ultraviolet spectrophotometer. As shown in FIG. 1, which is the relationship between the absorption rate of methylene blue and time of examples 1-3, it can be seen that the absorbent prepared by the invention can absorb methylene blue by 80% in a short time, and can absorb methylene blue by more than 95% with the passage of time.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (9)
1. The preparation method of the adsorbent for rapidly adsorbing methylene blue is characterized by comprising the following steps: dispersing a functional carbon nano tube and magnetic nano particles in ethanol, ultrasonically assembling the magnetic nano particles on the surface of the functional carbon nano tube, centrifuging for many times after the ultrasonic treatment is finished, drying and grinding the obtained solid product, then dispersing the solid product in an organic solvent, adding polymerizable glycidyl ether, acrylonitrile and an initiator, filling nitrogen to replace air in a bottle, stirring and reacting for 2-3h in an oil bath kettle at the temperature of 60-70 ℃, distilling under reduced pressure to remove the solvent after the reaction is finished, and drying the solid in vacuum to obtain the adsorbent.
2. The method for preparing the adsorbent capable of rapidly adsorbing methylene blue according to claim 1, wherein the functional carbon nanotube is a hydroxylated carbon nanotube or an aminated carbon nanotube.
3. The preparation method of the adsorbent for rapidly adsorbing methylene blue as claimed in claim 1, wherein the magnetic nanoparticles are oleic acid-modified ferroferric oxide magnetic nanoparticles.
4. The method for preparing the adsorbent capable of rapidly adsorbing methylene blue according to claim 1, wherein the polymerizable glycidyl ether is one selected from allyl glycidyl ether, glycidyl methacrylate and 4-hydroxybutyl glycidyl acrylate.
5. The method for preparing the adsorbent capable of rapidly adsorbing methylene blue according to claim 1, wherein the organic solvent is one of N, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane or dimethylsulfoxide.
6. The method for preparing the absorbent capable of rapidly absorbing methylene blue according to claim 1, wherein the initiator is azobisisobutyronitrile or benzoyl peroxide.
7. The preparation method of the adsorbent for rapidly adsorbing methylene blue as claimed in claim 1, wherein the mass ratio of the functional carbon nanotubes to the magnetic nanoparticles is 1: 0.05-0.2, and the concentration of the functional carbon nanotubes is 0.1 g/ml.
8. The preparation method of the adsorbent for rapidly adsorbing methylene blue as claimed in claim 1, wherein the molar ratio of the polymerizable glycidyl ether, the acrylonitrile and the initiator is 1:1:0.01, and the mass ratio of the acrylonitrile to the functional carbon nanotube is 0.5-1.5: 1.
9. An adsorbent for rapidly adsorbing methylene blue, which is prepared by the preparation method as claimed in claims 1 to 8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11987500B2 (en) | 2022-02-25 | 2024-05-21 | Imam Abdulrahman Bin Faisal University | Nanomaterial, method of preparing the nanomaterial and application thereof |
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| CN111495319A (en) * | 2020-04-24 | 2020-08-07 | 匡秋茂 | Hyperbranched polymer-based magnetic porous carbon adsorption material and preparation method thereof |
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2020
- 2020-11-11 CN CN202011254043.4A patent/CN112316927B/en active Active
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| CN101735416A (en) * | 2009-12-29 | 2010-06-16 | 浙江大学 | Method for preparing water-soluble cross-linked polymer grafted carbon nano tube |
| CN102553532A (en) * | 2012-01-17 | 2012-07-11 | 同济大学 | Method for preparing magnetic carbon nano-tube adsorbent having high adsorption capacity and used for removing dye from aqueous phase |
| US20160243523A1 (en) * | 2013-09-30 | 2016-08-25 | Council Of Scientific & Industrial Research | Magnetic nanoparticles decorated activated carbon nanocomposites for purification of water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11987500B2 (en) | 2022-02-25 | 2024-05-21 | Imam Abdulrahman Bin Faisal University | Nanomaterial, method of preparing the nanomaterial and application thereof |
| US12091321B2 (en) | 2022-02-25 | 2024-09-17 | Imam Abdulrahman Bin Faisal University | Solid nanomaterial adsorbent |
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| CN112316927B (en) | 2023-04-25 |
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