CN113198435A - Magnetic amino carbon nanotube for adsorbing organic anionic dye in water and preparation method thereof - Google Patents

Magnetic amino carbon nanotube for adsorbing organic anionic dye in water and preparation method thereof Download PDF

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CN113198435A
CN113198435A CN202110389909.0A CN202110389909A CN113198435A CN 113198435 A CN113198435 A CN 113198435A CN 202110389909 A CN202110389909 A CN 202110389909A CN 113198435 A CN113198435 A CN 113198435A
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water
magnetic
amino
carbon nanotube
preparation
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丁光辉
师亚威
宋国彬
李安祺
王浩男
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Dalian Maritime University
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Dalian Maritime University
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    • 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
    • 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
    • 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
    • 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
    • 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
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • 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
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/38—Organic compounds containing nitrogen

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
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Abstract

The invention provides a magnetic amino carbon nanotube for adsorbing organic anionic dye in water and a preparation method thereof, belonging to the technical field of treatment of organic dye in water. Adding the oxidized carbon nanotube, an iron source, alkaline organic salt and a water-soluble macromolecular amino polymer into a solvent, and carrying out solvothermal reaction, washing and drying to obtain the magnetic amino carbon nanotube. The carbon nano tube prepared by the invention has a large amount of amino groups on the surface, has positive charges in water, can adsorb organic anionic dye with negative charges in water through the action of electrostatic attraction, synchronously realizes the magnetization and amino functional modification of the carbon nano tube by adopting a one-pot method, has simple preparation process and stable product property, and shows excellent adsorption performance on the organic anionic dye in water.

Description

Magnetic amino carbon nanotube for adsorbing organic anionic dye in water and preparation method thereof
Technical Field
The invention relates to the technical field of treatment of organic dyes in water, in particular to a magnetic amino carbon nanotube for adsorption of organic anionic dyes in water and a preparation method thereof.
Background
The development of the printing and dyeing industry is promoted by the large-scale use of the dye, but the dye entering the water environment after the discharge of wastewater has a stable molecular structure and is difficult to degrade, so that the human health is seriously threatened. The organic anionic dye is a dye which is dissociated in water to form colored anions, comprises an acid dye, a direct dye and the like, can be used for dyeing nylon, wool, paper, leather and the like, and is a widely applied organic dye. For treating printing and dyeing wastewater, various techniques such as adsorption, coagulation/flocculation, advanced oxidation, membrane separation, biological methods, etc. have been used. The adsorption method has the advantages of mild operation conditions, low cost, high efficiency and no generation of new toxic substances, and is a common printing and dyeing wastewater treatment method.
The carbon nano tube is used as a novel nano carbon material and is applied to the adsorption removal of various typical pollutants in water. However, the small size thereof causes difficulty in the separation process after adsorption, and generally, the carbon nanotubes need to be separated by filtration, centrifugation, or the like, which is a complicated process. Magnetic carbon nanotubes are a class of composite materials obtained by magnetizing carbon nanotubes, which can be conveniently and efficiently separated from water by magnetic separation after use. Due to its high adsorption performance and magnetic separation characteristics, magnetic carbon nanotubes have been used for adsorption removal of cationic dyes in water. However, before carbon nanotubes are magnetized to construct magnetic carbon nanotubes, it is generally necessary to subject them to an oxidation treatment. The oxidation treatment introduces hydrophilic functional groups such as hydroxyl, carboxyl and the like on the surface of the carbon nano tube, promotes the infiltration of metal salt solution to the carbon nano tube, and is beneficial to the implementation of the magnetizing process. However, hydroxyl groups and carboxyl groups are functional groups having electronegativity, and there is an electrostatic repulsive force between organic anionic dyes also having negative charges in water. Therefore, although the existing magnetic carbon nanotube can adsorb a part of organic anionic dye through an electron donor-acceptor interaction with a benzene ring structure of the organic anionic dye, the existence of electrostatic repulsive force makes it difficult for the existing magnetic carbon nanotube to exhibit a good effect in the adsorption of the organic anionic dye.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a magnetic amino carbon nanotube, and the obtained magnetic amino carbon nanotube has a large number of electropositive amino functional groups and shows excellent adsorption performance on organic anionic dyes in water.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a magnetic amino carbon nanotube, which comprises the following steps:
(1) adding the carbon oxide nanotube, an iron source, alkaline organic salt and a water-soluble high-molecular amino polymer into a solvent, wherein the carbon oxide nanotube: an iron source: basic organic salt: water-soluble high-molecular amino polymer: the mass-volume ratio of the solvent is (100-300) mg: (400-1000) mg: (1000-5000) mg: (5-10) mL: (20-100) mL;
(2) heating the mixed solution in the step (1) to 150 ℃ and 220 ℃, wherein the reaction time is 4-12 h;
(3) and (3) washing and drying the product obtained in the step (2) to obtain the magnetic amino carbon nanotube.
Preferably, the water-soluble macromolecular amino polymer is one or a mixture of branched polyethyleneimine, linear polyethyleneimine and polypropyleneimine.
Preferably, the iron source is one or a mixture of ferric nitrate, ferric chloride and ferric sulfate.
Preferably, the alkaline organic salt is one or a mixture of sodium ethoxide, potassium ethoxide, sodium acetate and potassium acetate.
Preferably, the solvent is one or a mixture of ethanol, glycol and glycerol.
Preferably, the washing is carried out by using one or a mixture of water, ethanol and acetone, and the drying is vacuum drying or freeze drying.
The invention also provides a magnetic amino carbon nano tube prepared by the method.
Preferably, the content of ferroferric oxide in the magnetic carbon nano tube is 20% -80%, and the content of amino groups is 0.5% -10 wt% calculated by nitrogen.
The invention further provides an application of the magnetic amino carbon nano tube in the adsorption of organic anionic dye in water.
Preferably, the magnetic amino carbon nanotube is added to water containing an organic anionic dye for adsorption.
Preferably, the adsorption temperature is 20-40 ℃.
Preferably, the adsorption pressure is atmospheric pressure.
Preferably, the adsorption time is 0.5 to 72 h.
Preferably, the concentration of the organic anionic dye in the water containing the organic anionic dye is 0.01-500 mg/L.
Preferably, the adding amount of the magnetic carbon nano tube is 0.01-10 g/L.
The invention has the beneficial effects that:
(1) the magnetic carbon nanotube in the prior art has functional groups with electronegativity, such as hydroxyl, carboxyl and the like, and electrostatic repulsion exists between the functional groups and organic anionic dye in water, so that the organic anionic dye is difficult to be effectively adsorbed.
(2) The invention synchronously realizes the magnetization and amino functional modification of the carbon nano tube by adopting a one-pot method, and has simple preparation process and stable product property.
Drawings
FIG. 1 is an infrared spectrum of a magnetic amino carbon nanotube according to example 1 of the present invention;
fig. 2 is a magnetization curve diagram of the magnetic carbon nanotube according to embodiment 1 of the present invention.
Detailed Description
The invention provides a magnetic amino carbon nano tube, a preparation method thereof and application thereof in organic anionic dye adsorption in water. The invention will be further illustrated with reference to the following specific examples. It should be understood that the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention.
The manner of the oxidation treatment according to the present invention is not particularly limited, and may be any oxidation manner known to those skilled in the art, including but not limited to oxidation in an oxidizing atmosphere and oxidation in an oxidizing solution.
The source of the water containing the organic anionic dye is not particularly limited in the present invention, and domestic or industrial waste water well known to those skilled in the art may be used.
Each raw material used in the following examples is a commercially available product.
Example 1
A preparation method of a magnetic amino carbon nanotube comprises the following steps:
(1) carrying out nitric acid oxidation treatment on the carbon nano tube to obtain an oxidized carbon nano tube;
(2) adding the carbon oxide nanotube obtained in the step (1), ferric sulfate, sodium ethoxide and branched polyethyleneimine into glycerol, wherein the carbon oxide nanotube: iron sulfate: sodium ethoxide: branched polyethyleneimine: the mass-volume ratio of the glycerol is 200 mg: 600 mg: 2500 mg: 8mL of: 50mL, and carrying out solvothermal reaction for 6h at 190 ℃;
(3) and (3) washing the product obtained in the step (2) with water and ethanol to obtain the magnetic amino carbon nanotube.
The amino group content (in terms of nitrogen) of the magnetic amino carbon nanotube obtained by the above method was 3.4 wt.%, and the saturation magnetization was 30.6 emu/g.
FIG. 1 is an infrared spectrum of the magnetic amino carbon nanotube prepared in example 1, which shows that amino groups are successfully introduced; fig. 2 is a magnetization curve diagram of the magnetic amino carbon nanotube prepared in example 1, which shows that the carbon nanotube successfully realizes magnetization.
0.3g of the magnetic carbon nanotube obtained in example 1 was weighed and added to 1L of water containing 100mg/L of methyl orange, and the adsorption was carried out at 25 ℃ for 4 hours under normal pressure, and after treatment, the methyl orange adsorption efficiency of the magnetic amino carbon nanotube was 96%.
Comparative example 1
Reference example 1 for the preparation of a magnetic carbon nanotube, comprising the following steps:
(1) carrying out nitric acid oxidation treatment on the carbon nano tube to obtain an oxidized carbon nano tube;
(2) adding the carbon oxide nano tube obtained in the step (1), ferric sulfate and sodium ethoxide into glycerol, wherein the carbon oxide nano tube: iron sulfate: sodium ethoxide: the mass-volume ratio of the glycerol is 200 mg: 600 mg: 2500 mg: 50mL, and carrying out solvothermal reaction for 6h at 190 ℃;
(3) and (3) washing the product obtained in the step (2) with water and ethanol to obtain the magnetic carbon nanotube.
The magnetic carbon nanotube obtained by the above method does not contain an amino group and has a saturation magnetization of 31.2 emu/g.
0.3g of the magnetic carbon nanotube obtained in comparative example 1 was weighed and added to 1L of water containing 100mg/L of methyl orange, and the adsorption was carried out at 25 ℃ for 4 hours under normal pressure, and the methyl orange adsorption efficiency of the magnetic carbon nanotube was 33% after the treatment.

Claims (10)

1. A preparation method of a magnetic amino carbon nanotube is characterized by comprising the following steps:
(1) adding the carbon oxide nanotube, an iron source, alkaline organic salt and a water-soluble high-molecular amino polymer into a solvent, wherein the carbon oxide nanotube: an iron source: basic organic salt: water-soluble high-molecular amino polymer: the mass-volume ratio of the solvent is (100-300) mg: (400-1000) mg: (1000-5000) mg: (5-10) mL: (20-100) mL;
(2) heating the mixed solution in the step (1) to 150 ℃ and 220 ℃, wherein the reaction time is 4-12 h;
(3) and (3) washing and drying the product obtained in the step (2) to obtain the magnetic amino carbon nanotube.
2. The preparation method according to claim 1, wherein the water-soluble high molecular amino polymer is one or a mixture of branched polyethyleneimine, linear polyethyleneimine and polypropyleneimine.
3. The preparation method of claim 1, wherein the iron source is one or a mixture of ferric nitrate, ferric chloride and ferric sulfate.
4. The preparation method according to claim 1, wherein the alkaline organic salt is one or a mixture of sodium ethoxide, potassium ethoxide, sodium acetate and potassium acetate.
5. The preparation method according to claim 1, wherein the solvent is one or more of ethanol, ethylene glycol and glycerol.
6. The preparation method according to claim 1, wherein the washing is performed by using one or more of water, ethanol and acetone, and the drying is vacuum drying or freeze drying.
7. A magnetic amino carbon nanotube prepared by the method of any one of claims 1 to 6.
8. The magnetic amino carbon nanotube of claim 7, wherein the magnetic carbon nanotube has a ferroferric oxide content of 20% to 80% and an amino group content of 0.5% to 10 wt.% calculated on nitrogen.
9. Use of the magnetic amino carbon nanotubes of any one of claims 7 to 8 for the adsorption of organic anionic dyes in water.
10. The application according to claim 9, wherein the application method is as follows: and (2) adding the magnetic amino carbon nano tube into water containing organic anionic dye for adsorption, wherein the adsorption temperature is 20-40 ℃, the adsorption pressure is normal pressure, the adsorption time is 0.5-72h, the concentration of the organic anionic dye in the water containing the organic anionic dye is 0.01-500mg/L, and the adding amount of the magnetic carbon nano tube is 0.01-10 g/L.
CN202110389909.0A 2021-04-12 2021-04-12 Magnetic amino carbon nanotube for adsorbing organic anionic dye in water and preparation method thereof Pending CN113198435A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101320607A (en) * 2008-03-25 2008-12-10 东华大学 Preparation method of ferroferric oxide/multi-wall carbon nano-tube magnetic nanometer composite material
CN105129898A (en) * 2015-08-26 2015-12-09 宁波大学 Renewable amino functionalized magnetic carbon nano composite material, and preparation method therefor and application thereof
CN108786734A (en) * 2018-06-26 2018-11-13 信阳学院 Magnetic oxygenated graphene/polyethyleneimine amine absorber and the preparation method and application thereof
CN109550480A (en) * 2018-11-23 2019-04-02 浙江海洋大学 A kind of preparation method of amination magnetic carbon nano-tube

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101320607A (en) * 2008-03-25 2008-12-10 东华大学 Preparation method of ferroferric oxide/multi-wall carbon nano-tube magnetic nanometer composite material
CN105129898A (en) * 2015-08-26 2015-12-09 宁波大学 Renewable amino functionalized magnetic carbon nano composite material, and preparation method therefor and application thereof
CN108786734A (en) * 2018-06-26 2018-11-13 信阳学院 Magnetic oxygenated graphene/polyethyleneimine amine absorber and the preparation method and application thereof
CN109550480A (en) * 2018-11-23 2019-04-02 浙江海洋大学 A kind of preparation method of amination magnetic carbon nano-tube

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
岳文丽: "PEI功能化磁性碳纳米管的制备及吸附去除水溶液中甲基橙和Cr(Ⅵ)的研究" *

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