CN112110502B - Removing agent for micro-plastics in water body - Google Patents
Removing agent for micro-plastics in water body Download PDFInfo
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- CN112110502B CN112110502B CN202011028122.3A CN202011028122A CN112110502B CN 112110502 B CN112110502 B CN 112110502B CN 202011028122 A CN202011028122 A CN 202011028122A CN 112110502 B CN112110502 B CN 112110502B
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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
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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
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Abstract
The invention discloses a remover for micro-plastics in water, which comprises a carbon nano tube component and an iron oxide component, wherein the preparation method of the carbon nano tube component comprises the following steps: (1) Firstly, treating the carbon nano tube by hydrogen peroxide, then adding sodium sulfanilate, vitamin C and hydrochloric acid solution, and further treating to obtain a solid phase A; (2) The solid phase A is firstly placed below 0.2 standard atmospheric pressure, and is placed in an ozone environment with 1.6-2 standard atmospheric pressures to obtain the carbon nano tube component; the preparation method of the ferric oxide component comprises the following steps: and (2) treating the iron oxide powder in an ethanol solution of ferric chloride and mesitylene, and then dropwise adding aqueous solutions of sodium hydroxide and sodium lignosulfonate to obtain the iron oxide component. The invention can effectively remove micro plastic in the water body, improve the water quality and reduce the pollution of the water body; and the preparation process is simple, the cost is low, the preparation method is suitable for large-scale production, and the preparation method has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of environmental management, in particular to a remover for micro-plastics in a water body.
Background
The plastic entering the environment can be degraded into plastic with the grain diameter less than 5mm under the actions of physical erosion, biological degradation or photocatalytic oxidation and the like, and the plastic is called as micro plastic. Micro-plastics are widely present in human living environments, and micro-plastics of different compositions and contents have been found in food, soil, water and atmospheric environments at present. Due to the characteristics of small particle size, large specific surface area, strong hydrophobicity and the like, the micro plastic is easy to adsorb various pollutants in the environment, such as Polycyclic Aromatic Hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), heavy metals and the like. The adsorbed pollutants can enter the organism along with the micro-plastics, and have toxic effect on the organism.
At present, the removal technology of the micro plastic mainly comprises physical, chemical, biological and other methods, the removal rate of different methods is different, and the type and the preparation process of the used remover have great influence.
Disclosure of Invention
The invention provides a remover for micro-plastics in water, which comprises a carbon nano tube component and an iron oxide component, wherein the preparation method of the carbon nano tube component comprises the following steps:
(1) Dispersing carbon nano tubes in an aqueous solution of sodium pyrophosphate, adding hydrogen peroxide into the solution, keeping the temperature to 50 +/-5 ℃, keeping the temperature, cooling the solution to room temperature by air after the heat preservation is finished, sequentially adding sodium sulfanilate, vitamin C and hydrochloric acid solution into the solution, stirring for 4-5 hours after the addition is finished, then carrying out solid-liquid separation, and drying a solid phase in an environment at 50-60 ℃ until the weight is constant to obtain a solid phase A;
(2) Placing the solid phase A in a closed container, sealing the container, pumping the air pressure in the container to be below 0.2 standard atmospheric pressure, maintaining the pressure for 10-20 min, then filling ozone into the container until the air pressure in the container is 1.6-2 standard atmospheric pressures, maintaining the pressure for 40-70 min, balancing the air pressure inside and outside the container after the pressure maintenance is finished, and taking out the solid phase to obtain the carbon nano tube component;
the preparation method of the iron oxide component comprises the following steps:
preparing ethanol solution of ferric chloride and mesitylene and water solution of sodium hydroxide and sodium lignosulfonate, washing ferric oxide powder with acetone for 2-3 times, drying, soaking the dried powder in the ethanol solution of ferric chloride and mesitylene, stirring the solution, and dropwise adding the water solution of sodium hydroxide and sodium lignosulfonate into the solution under the stirring state until no precipitate is generated; and (4) carrying out solid-liquid separation, washing the solid phase with deionized water for 2-3 times, and drying to obtain the iron oxide component.
Further, in the aqueous solution of sodium pyrophosphate, the mass percentage of the solute is 3% to 6%, and the solid-liquid mass ratio of the carbon nanotubes dispersed in the aqueous solution of sodium pyrophosphate is solid/liquid = 1; the mass fraction of hydrogen peroxide in hydrogen peroxide is 10%, and the mass of hydrogen peroxide added is 1/8 of that of the aqueous solution of sodium pyrophosphate.
Further, the mass fraction of hydrogen chloride in the hydrochloric acid solution is 5%, and the balance is water; the mass ratio of the added sodium sulfanilate, the added vitamin C and the added hydrochloric acid solution to the aqueous solution of sodium pyrophosphate is sodium sulfanilate: vitamin C: hydrochloric acid solution: sodium pyrophosphate aqueous solution =1 to 5.
Further, the mass fraction of ferric chloride in the ethanol solution of ferric chloride and mesitylene is 1-2%, the mass fraction of mesitylene is 0.8-1.5%, and the balance is ethanol; the mass fraction of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium lignosulphonate is 5-7%, the mass fraction of sodium lignosulphonate is 1-2%, and the balance is water; the solid-liquid mass ratio of the powder soaked in the ethanol solution of ferric chloride and mesitylene is solid/liquid = 1.
Further, in the remover, the mixing mass ratio of the carbon nanotube component to the iron oxide component is (1) - (10).
The invention has the beneficial effects that: the invention can effectively remove micro plastic in the water body, improve the water quality and reduce the pollution of the water body; and the preparation process is simple, the cost is low, the preparation method is suitable for large-scale production, and the preparation method has a wide application prospect.
Drawings
FIG. 1 is a graph showing the effect of the removing agent prepared in each example and comparative example on the removal of micro-plastics in sewage.
Detailed Description
The invention is further described with reference to the following embodiments and drawings.
Example 1
A remover for micro-plastics in a water body comprises a carbon nano tube component and an iron oxide component, wherein the mixing mass ratio of the carbon nano tube component to the iron oxide component is that the iron oxide component = 1. Mixing and bonding the carbon nanotube component and the iron oxide component with a PVDF binder, the content of the PVDF binder in the remover being 5% by weight. The mixture is coated on a 316 stainless steel wire net, dried at 80 ℃, soaked in deionized water for 10 hours after being dried, taken out and dried again at 80 ℃ to constant weight, and the remover is obtained.
The preparation method of the carbon nano tube component comprises the following steps:
(1) Preparing a sodium pyrophosphate aqueous solution with a solute content of 3% by mass, and dispersing multi-walled carbon nanotubes in the sodium pyrophosphate aqueous solution, wherein the solid-liquid mass ratio of the carbon nanotubes dispersed in the sodium pyrophosphate aqueous solution is solid/liquid = 1; hydrogen peroxide with the mass fraction of 10 percent is added into the solution, and the mass of the added hydrogen peroxide is 1/8 of that of the aqueous solution of sodium pyrophosphate. Keeping the solution at the constant temperature of 50 +/-5 ℃ for 10min, air-cooling the solution to the normal temperature after the heat preservation is finished, sequentially adding sodium sulfanilate, vitamin C and hydrochloric acid solution (the mass fraction of hydrogen chloride is 5%, and the balance is water) into the solution, wherein the mass ratio of the added mass of the sodium sulfanilate, the vitamin C and the hydrochloric acid solution to the mass of the aqueous solution of sodium pyrophosphate is sodium sulfanilate: vitamin C: hydrochloric acid solution: aqueous solution of sodium pyrophosphate = 1. Stirring for 4h after feeding, then performing solid-liquid separation, and drying a solid phase to constant weight at the temperature of 55 +/-5 ℃ to obtain a solid phase A;
(2) And (3) placing the solid phase A in a closed container, sealing the container, pumping the air pressure in the container to 0.2 standard atmospheric pressure, maintaining the pressure for 20min, then filling ozone into the container until the air pressure in the container reaches 1.6 standard atmospheric pressures, maintaining the pressure for 60min, balancing the air pressure inside and outside the container after the pressure maintenance is finished, and taking out the solid phase to obtain the carbon nano tube component.
The preparation method of the ferric oxide component comprises the following steps:
preparing ethanol solutions of ferric chloride and mesitylene and aqueous solutions of sodium hydroxide and sodium lignosulfonate, wherein the mass fraction of ferric chloride in the ethanol solutions of ferric chloride and mesitylene is 1%, the mass fraction of mesitylene is 0.8%, and the balance is ethanol; the mass fraction of the sodium hydroxide in the aqueous solution of the sodium hydroxide and the sodium lignosulfonate is 5%, the mass fraction of the sodium lignosulfonate is 1%, and the balance is water. And (2) performing ball milling treatment on the iron oxide powder, then screening the iron oxide powder by using a 10-mesh screen, collecting screened powder, washing the powder for 3 times by using acetone, drying the powder at 60 +/-5 ℃, and soaking the dried powder in an ethanol solution of ferric chloride and mesitylene, wherein the soaking solid/liquid ratio is = 1. Stirring the solution, and dropwise adding the aqueous solution of sodium hydroxide and sodium lignosulphonate into the solution under the stirring state until no precipitate is generated; and (3) carrying out solid-liquid separation, washing the solid phase with deionized water for 3 times, and drying at 60 +/-5 ℃ to obtain the iron oxide component.
Example 2
A remover for micro-plastics in a water body comprises a carbon nano tube component and an iron oxide component, wherein the mixing mass ratio of the carbon nano tube component to the iron oxide component is that the iron oxide component = 1. Mixing and bonding the carbon nanotube component and the iron oxide component with a PVDF binder, wherein the content of the PVDF binder in the remover is 5% by weight. The mixture is coated on a 316 stainless steel wire net, dried at 80 ℃, soaked in deionized water for 10 hours after being dried, taken out and dried again at 80 ℃ to constant weight, and the remover is obtained.
The preparation method of the carbon nano tube component comprises the following steps:
(1) Preparing a sodium pyrophosphate aqueous solution with a solute content of 4% by mass, and dispersing multi-walled carbon nanotubes in the sodium pyrophosphate aqueous solution, wherein the solid-liquid mass ratio of the carbon nanotubes dispersed in the sodium pyrophosphate aqueous solution is solid/liquid = 1; adding hydrogen peroxide with the mass fraction of 10% into the solution, wherein the mass of the added hydrogen peroxide is 1/8 of that of the aqueous solution of sodium pyrophosphate. Keeping the solution at the constant temperature of 50 +/-5 ℃ for 10min, air-cooling the solution to the normal temperature after the heat preservation is finished, sequentially adding sodium sulfanilate, vitamin C and hydrochloric acid solution (the mass fraction of hydrogen chloride is 5%, and the balance is water) into the solution, wherein the mass ratio of the added mass of the sodium sulfanilate, the vitamin C and the hydrochloric acid solution to the mass of the aqueous solution of sodium pyrophosphate is sodium sulfanilate: vitamin C: hydrochloric acid solution: aqueous solution of sodium pyrophosphate = 2. Stirring for 4h after feeding, then performing solid-liquid separation, and drying a solid phase to constant weight in an environment of 55 +/-5 ℃ to obtain a solid phase A;
(2) And (3) placing the solid phase A in a closed container, sealing the container, pumping the air pressure in the container to 0.2 standard atmospheric pressure, maintaining the pressure for 20min, then filling ozone into the container until the air pressure in the container reaches 1.6 standard atmospheric pressures, maintaining the pressure for 60min, balancing the air pressure inside and outside the container after the pressure maintenance is finished, and taking out the solid phase to obtain the carbon nano tube component.
The preparation method of the ferric oxide component comprises the following steps:
preparing an ethanol solution of ferric chloride and mesitylene and an aqueous solution of sodium hydroxide and sodium lignosulfonate, wherein the mass fraction of ferric chloride in the ethanol solution of ferric chloride and mesitylene is 1%, the mass fraction of mesitylene is 1.0%, and the balance is ethanol; the mass fraction of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium lignosulfonate is 6%, the mass fraction of sodium lignosulfonate is 1%, and the balance is water. And (2) performing ball milling treatment on the iron oxide powder, then screening the iron oxide powder by using a 10-mesh screen, collecting screened powder, washing the powder for 3 times by using acetone, drying the powder at 60 +/-5 ℃, and soaking the dried powder in an ethanol solution of ferric chloride and mesitylene, wherein the soaking solid/liquid ratio is = 1. Stirring the solution, and dropwise adding the aqueous solution of sodium hydroxide and sodium lignosulphonate into the solution under the stirring state until no precipitate is generated; and (3) carrying out solid-liquid separation, washing the solid phase with deionized water for 3 times, and drying at the temperature of 60 +/-5 ℃ to obtain the iron oxide component.
Example 3
A remover for micro-plastics in a water body comprises a carbon nano tube component and an iron oxide component, wherein the mixing mass ratio of the carbon nano tube component to the iron oxide component is that the iron oxide component = 1. Mixing and bonding the carbon nanotube component and the iron oxide component with a PVDF binder, the content of the PVDF binder in the remover being 5% by weight. The mixture is coated on a 316 stainless steel wire net, dried at 80 ℃, soaked in deionized water for 10 hours after being dried, taken out and dried again at 80 ℃ to constant weight, and the remover is obtained.
The preparation method of the carbon nano tube component comprises the following steps:
(1) Preparing a sodium pyrophosphate aqueous solution with a solute content of 5% by mass, and dispersing multi-walled carbon nanotubes in the sodium pyrophosphate aqueous solution, wherein the solid-liquid mass ratio of the carbon nanotubes dispersed in the sodium pyrophosphate aqueous solution is solid/liquid = 1; hydrogen peroxide with the mass fraction of 10 percent is added into the solution, and the mass of the added hydrogen peroxide is 1/8 of that of the aqueous solution of sodium pyrophosphate. Keeping the temperature of the solution constant to 50 +/-5 ℃ for 10min, air-cooling the solution to normal temperature after heat preservation is finished, sequentially adding sodium sulfanilate, vitamin C and hydrochloric acid solution (the mass fraction of hydrogen chloride is 5%, and the balance is water) into the solution, wherein the mass ratio of the added mass of the sodium sulfanilate, the vitamin C and the hydrochloric acid solution to the mass of the aqueous solution of sodium pyrophosphate is sodium sulfanilate: vitamin C: hydrochloric acid solution: aqueous solution of sodium pyrophosphate = 3. Stirring for 4h after feeding, then performing solid-liquid separation, and drying a solid phase to constant weight in an environment of 55 +/-5 ℃ to obtain a solid phase A;
(2) And (3) placing the solid phase A in a closed container, sealing the container, pumping the air pressure in the container to 0.2 standard atmospheric pressure, maintaining the pressure for 20min, then filling ozone into the container until the air pressure in the container reaches 1.6 standard atmospheric pressures, maintaining the pressure for 60min, balancing the air pressure inside and outside the container after the pressure maintenance is finished, and taking out the solid phase to obtain the carbon nano tube component.
The preparation method of the iron oxide component comprises the following steps:
preparing ethanol solutions of ferric chloride and mesitylene and aqueous solutions of sodium hydroxide and sodium lignosulfonate, wherein the mass fraction of ferric chloride in the ethanol solutions of ferric chloride and mesitylene is 2%, the mass fraction of mesitylene is 1.2%, and the balance is ethanol; in the aqueous solution of sodium hydroxide and sodium lignosulfonate, the mass fraction of the sodium hydroxide is 6%, the mass fraction of the sodium lignosulfonate is 2%, and the balance is water. And (2) performing ball milling treatment on the iron oxide powder, then screening the iron oxide powder by using a 10-mesh screen, collecting screened powder, washing the powder for 3 times by using acetone, drying the powder at 60 +/-5 ℃, and soaking the dried powder in an ethanol solution of ferric chloride and mesitylene, wherein the soaking solid/liquid ratio is = 1. Stirring the solution, and dropwise adding the aqueous solution of sodium hydroxide and sodium lignosulphonate into the solution under a stirring state until no precipitate is generated; and (3) carrying out solid-liquid separation, washing the solid phase with deionized water for 3 times, and drying at 60 +/-5 ℃ to obtain the iron oxide component.
Example 4
A remover for micro-plastics in a water body comprises a carbon nano tube component and an iron oxide component, wherein the mixing mass ratio of the carbon nano tube component to the iron oxide component is that the iron oxide component = 1. Mixing and bonding the carbon nanotube component and the iron oxide component with a PVDF binder, the content of the PVDF binder in the remover being 5% by weight. The mixture is coated on a 316 stainless steel wire net, dried at 80 ℃, soaked in deionized water for 10 hours after being dried, taken out and dried again at 80 ℃ to constant weight, and the remover is obtained.
The preparation method of the carbon nano tube component comprises the following steps:
(1) Preparing a sodium pyrophosphate aqueous solution with solute content of 5% by mass, and dispersing multi-walled carbon nanotubes in the sodium pyrophosphate aqueous solution, wherein the solid-liquid mass ratio of the carbon nanotubes dispersed in the sodium pyrophosphate aqueous solution is (solid/liquid = 1); adding hydrogen peroxide with the mass fraction of 10% into the solution, wherein the mass of the added hydrogen peroxide is 1/8 of that of the aqueous solution of sodium pyrophosphate. Keeping the solution at the constant temperature of 50 +/-5 ℃ for 10min, air-cooling the solution to the normal temperature after the heat preservation is finished, sequentially adding sodium sulfanilate, vitamin C and hydrochloric acid solution (the mass fraction of hydrogen chloride is 5%, and the balance is water) into the solution, wherein the mass ratio of the added mass of the sodium sulfanilate, the vitamin C and the hydrochloric acid solution to the mass of the aqueous solution of sodium pyrophosphate is sodium sulfanilate: vitamin C: hydrochloric acid solution: aqueous solution of sodium pyrophosphate = 4. Stirring for 4h after feeding, then performing solid-liquid separation, and drying a solid phase to constant weight at the temperature of 55 +/-5 ℃ to obtain a solid phase A;
(2) And (3) placing the solid phase A in a closed container, sealing the container, pumping the air pressure in the container to 0.2 standard atmospheric pressure, maintaining the pressure for 20min, then filling ozone into the container until the air pressure in the container reaches 1.6 standard atmospheric pressures, maintaining the pressure for 60min, balancing the air pressure inside and outside the container after the pressure maintenance is finished, and taking out the solid phase to obtain the carbon nano tube component.
The preparation method of the ferric oxide component comprises the following steps:
preparing an ethanol solution of ferric chloride and mesitylene, and an aqueous solution of sodium hydroxide and sodium lignosulfonate, wherein the mass fraction of ferric chloride in the ethanol solution of ferric chloride and mesitylene is 2%, the mass fraction of mesitylene is 1.4%, and the balance is ethanol; in the aqueous solution of sodium hydroxide and sodium lignosulfonate, the mass fraction of the sodium hydroxide is 6%, the mass fraction of the sodium lignosulfonate is 2%, and the balance is water. And (2) performing ball milling treatment on the iron oxide powder, then screening the powder by using a 10-mesh screen, collecting the screened powder, washing the powder by using acetone for 3 times, drying the powder at 60 +/-5 ℃, and soaking the dried powder in an ethanol solution of ferric chloride and mesitylene to obtain a solid/liquid = 1. Stirring the solution, and dropwise adding the aqueous solution of sodium hydroxide and sodium lignosulphonate into the solution under the stirring state until no precipitate is generated; and (3) carrying out solid-liquid separation, washing the solid phase with deionized water for 3 times, and drying at the temperature of 60 +/-5 ℃ to obtain the iron oxide component.
Example 5
A remover for micro-plastics in a water body comprises a carbon nano tube component and an iron oxide component, wherein the mixing mass ratio of the carbon nano tube component to the iron oxide component is that the iron oxide component = 1. Mixing and bonding the carbon nanotube component and the iron oxide component with a PVDF binder, the content of the PVDF binder in the remover being 5% by weight. The mixture is coated on a 316 stainless steel wire mesh, dried at 80 ℃, soaked in deionized water for 10 hours after being dried, taken out and dried again at 80 ℃ to constant weight, and the remover is obtained.
The preparation method of the carbon nano tube component comprises the following steps:
(1) Preparing an aqueous solution of sodium pyrophosphate with 6 mass percent of solute, and dispersing multi-walled carbon nanotubes in the aqueous solution of sodium pyrophosphate, wherein the solid-liquid mass ratio of the carbon nanotubes dispersed in the aqueous solution of sodium pyrophosphate is solid/liquid = 1; adding hydrogen peroxide with the mass fraction of 10% into the solution, wherein the mass of the added hydrogen peroxide is 1/8 of that of the aqueous solution of sodium pyrophosphate. Keeping the temperature of the solution constant to 50 +/-5 ℃ for 10min, air-cooling the solution to normal temperature after heat preservation is finished, sequentially adding sodium sulfanilate, vitamin C and hydrochloric acid solution (the mass fraction of hydrogen chloride is 5%, and the balance is water) into the solution, wherein the mass ratio of the added mass of the sodium sulfanilate, the vitamin C and the hydrochloric acid solution to the mass of the aqueous solution of sodium pyrophosphate is sodium sulfanilate: vitamin C: hydrochloric acid solution: aqueous solution of sodium pyrophosphate = 5. Stirring for 4h after feeding, then performing solid-liquid separation, and drying a solid phase to constant weight in an environment of 55 +/-5 ℃ to obtain a solid phase A;
(2) And (3) placing the solid phase A in a closed container, sealing the container, pumping the air pressure in the container to 0.2 standard atmospheric pressure, maintaining the pressure for 20min, then filling ozone into the container until the air pressure in the container reaches 1.6 standard atmospheric pressures, maintaining the pressure for 60min, balancing the air pressure inside and outside the container after the pressure maintenance is finished, and taking out the solid phase to obtain the carbon nano tube component.
The preparation method of the ferric oxide component comprises the following steps:
preparing an ethanol solution of ferric chloride and mesitylene, and an aqueous solution of sodium hydroxide and sodium lignosulfonate, wherein the mass fraction of ferric chloride in the ethanol solution of ferric chloride and mesitylene is 2%, the mass fraction of mesitylene is 1.5%, and the balance is ethanol; the mass fraction of the sodium hydroxide in the aqueous solution of the sodium hydroxide and the sodium lignosulfonate is 7%, the mass fraction of the sodium lignosulfonate is 2%, and the balance is water. And (2) performing ball milling treatment on the iron oxide powder, then screening the powder by using a 10-mesh screen, collecting the screened powder, washing the powder by using acetone for 3 times, drying the powder at 60 +/-5 ℃, and soaking the dried powder in an ethanol solution of ferric chloride and mesitylene to obtain a solid/liquid = 1. Stirring the solution, and dropwise adding the aqueous solution of sodium hydroxide and sodium lignosulphonate into the solution under the stirring state until no precipitate is generated; and (3) carrying out solid-liquid separation, washing the solid phase with deionized water for 3 times, and drying at the temperature of 60 +/-5 ℃ to obtain the iron oxide component.
Comparative example 1
The comparative example prepares the remover for the micro-plastics in the water body, and only comprises an iron oxide component. Mixed coating with PVDF binder, water and iron oxide components, the content of PVDF binder in the remover being 5% by weight. The mixture is coated on a 316 stainless steel wire mesh, dried at 80 ℃, soaked in deionized water for 10 hours after being dried, taken out and dried again at 80 ℃ to constant weight, and the remover of the comparative example is obtained.
The preparation method of the iron oxide component comprises the following steps:
preparing an ethanol solution of ferric chloride and mesitylene and an aqueous solution of sodium hydroxide and sodium lignosulfonate, wherein the mass fraction of ferric chloride in the ethanol solution of ferric chloride and mesitylene is 1%, the mass fraction of mesitylene is 1.0%, and the balance is ethanol; in the aqueous solution of sodium hydroxide and sodium lignosulfonate, the mass fraction of the sodium hydroxide is 6%, the mass fraction of the sodium lignosulfonate is 1%, and the balance is water. And (2) performing ball milling treatment on the iron oxide powder, then screening the iron oxide powder by using a 10-mesh screen, collecting screened powder, washing the powder for 3 times by using acetone, drying the powder at 60 +/-5 ℃, and soaking the dried powder in an ethanol solution of ferric chloride and mesitylene, wherein the soaking solid/liquid ratio is = 1. Stirring the solution, and dropwise adding the aqueous solution of sodium hydroxide and sodium lignosulphonate into the solution under a stirring state until no precipitate is generated; and (3) carrying out solid-liquid separation, washing the solid phase with deionized water for 3 times, and drying at 60 +/-5 ℃ to obtain the iron oxide component.
Comparative example 2
The comparative example prepares a remover for micro-plastics in a water body, and the remover comprises components of multi-walled carbon nanotubes and ferric oxide, wherein the mixing mass ratio of the components of the multi-walled carbon nanotubes to the components of the ferric oxide is that the components of the multi-walled carbon nanotubes to the components of the ferric oxide = 1.
The multi-walled carbon nanotubes described in this comparative example were commercially available samples that were not processed, i.e., the same batch as example 2 but were not processed by the processing method described in example 2. The PVDF binder was used to mix and bond the multi-walled carbon nanotubes and the iron oxide component, and the content of the PVDF binder in the remover was 5% by weight. The mixture is coated on a 316 stainless steel wire mesh, dried at 80 ℃, soaked in deionized water for 10 hours after being dried, taken out and dried again at 80 ℃ to constant weight, and the remover is obtained.
The preparation method of the ferric oxide component comprises the following steps:
preparing ethanol solutions of ferric chloride and mesitylene and aqueous solutions of sodium hydroxide and sodium lignosulfonate, wherein the mass fraction of ferric chloride in the ethanol solutions of ferric chloride and mesitylene is 1%, the mass fraction of mesitylene is 1.0%, and the balance is ethanol; in the aqueous solution of sodium hydroxide and sodium lignosulfonate, the mass fraction of the sodium hydroxide is 6%, the mass fraction of the sodium lignosulfonate is 1%, and the balance is water. And (2) performing ball milling treatment on the iron oxide powder, then screening the powder by using a 10-mesh screen, collecting the screened powder, washing the powder by using acetone for 3 times, drying the powder at 60 +/-5 ℃, and soaking the dried powder in an ethanol solution of ferric chloride and mesitylene to obtain a solid/liquid = 1. Stirring the solution, and dropwise adding the aqueous solution of sodium hydroxide and sodium lignosulphonate into the solution under the stirring state until no precipitate is generated; and (3) carrying out solid-liquid separation, washing the solid phase with deionized water for 3 times, and drying at 60 +/-5 ℃ to obtain the iron oxide component.
Comparative example 3
A remover for micro-plastics in a water body comprises a carbon nanotube component and iron oxide, wherein the mixing mass ratio of the carbon nanotube component to the iron oxide is that the iron oxide = 1. Mixing and bonding the carbon nanotube component and the iron oxide component with a PVDF binder, wherein the content of the PVDF binder in the remover is 5% by weight. The mixture is coated on a 316 stainless steel wire mesh, dried at 80 ℃, soaked in deionized water for 10 hours after being dried, taken out and dried again at 80 ℃ to constant weight, and the remover is obtained.
The preparation method of the carbon nano tube component comprises the following steps:
(1) Preparing a sodium pyrophosphate aqueous solution with a solute content of 4% by mass, and dispersing multi-walled carbon nanotubes in the sodium pyrophosphate aqueous solution, wherein the solid-liquid mass ratio of the carbon nanotubes dispersed in the sodium pyrophosphate aqueous solution is solid/liquid = 1; adding hydrogen peroxide with the mass fraction of 10% into the solution, wherein the mass of the added hydrogen peroxide is 1/8 of that of the aqueous solution of sodium pyrophosphate. Keeping the temperature of the solution constant to 50 +/-5 ℃ for 10min, air-cooling the solution to normal temperature after heat preservation is finished, sequentially adding sodium sulfanilate, vitamin C and hydrochloric acid solution (the mass fraction of hydrogen chloride is 5%, and the balance is water) into the solution, wherein the mass ratio of the added mass of the sodium sulfanilate, the vitamin C and the hydrochloric acid solution to the mass of the aqueous solution of sodium pyrophosphate is sodium sulfanilate: vitamin C: hydrochloric acid solution: aqueous solution of sodium pyrophosphate = 2. Stirring for 4h after feeding, then performing solid-liquid separation, and drying a solid phase to constant weight in an environment of 55 +/-5 ℃ to obtain a solid phase A;
(2) And (3) placing the solid phase A in a closed container, sealing the container, pumping the air pressure in the container to 0.2 standard atmospheric pressure, maintaining the pressure for 20min, then filling ozone into the container until the air pressure in the container reaches 1.6 standard atmospheric pressures, maintaining the pressure for 60min, balancing the air pressure inside and outside the container after the pressure maintenance is finished, and taking out the solid phase to obtain the carbon nano tube component.
The preparation method of the iron oxide comprises the following steps:
and (3) ball-milling the iron oxide powder, then sieving the powder by a 10-mesh sieve, collecting the sieved powder, washing the powder by acetone for 3 times, drying the powder at 60 +/-5 ℃, and drying the powder to obtain the iron oxide of the comparative example.
Example 6
Preparing a micro-plastic sewage sample, wherein the preparation method of the sewage sample comprises the following steps: mixing polyethylene plastic and nylon powder according to the mass ratio of 1. The removers prepared in examples 1 to 5 and comparative examples 1 to 3 were respectively placed in the sewage samples in a ratio of 10g of the remover to 500mL of the sewage samples, the sewage samples were magnetically stirred at a speed of 80r/min for 30min, then the removers were taken out, the sewage samples were taken to detect the content of the micro-plastics, and the micro-plastic removal rate was calculated, with the results shown in FIG. 1.
As can be seen from figure 1, the micro-plastic remover prepared by the invention can effectively remove micro-plastics in water, improve water quality and reduce pollution of the water. It can be seen from comparative example 2 and comparative example 1 that the effect of removing the micro plastic by using the iron oxide prepared by the method of the present invention alone as a remover is apparently inferior to the effect of the carbon nanotube component and the iron oxide component acting together. Comparing example 2 with comparative example 2 and comparative example 3, it can be seen that the carbon nanotubes or iron oxide which are not treated by the method of the present invention have poor effect of removing the micro-plastics, and thus the actual requirements are difficult to meet.
The technical solutions provided by the present invention are described in detail above, and for those skilled in the art, the ideas according to the embodiments of the present invention may be changed in the specific implementation manners and the application ranges, and in summary, the content of the present description should not be construed as limiting the present invention.
Claims (1)
1. The remover for the micro-plastics in the water body is characterized by comprising a carbon nano tube component and an iron oxide component, wherein the mixing mass ratio of the carbon nano tube component to the iron oxide component is that the carbon nano tube component is as follows, the iron oxide component =1 to 20; the preparation method of the carbon nano tube component comprises the following steps:
(1) Dispersing carbon nanotubes in an aqueous solution of sodium pyrophosphate, adding hydrogen peroxide into the solution, keeping the temperature to 50 +/-5 ℃, and keeping the temperature, wherein the mass percentage of a solute in the aqueous solution of sodium pyrophosphate is 3-6%, and the solid-liquid mass ratio of the carbon nanotubes dispersed in the aqueous solution of sodium pyrophosphate is solid/liquid = 1; the mass fraction of hydrogen peroxide in the hydrogen peroxide is 10%, and the mass of the added hydrogen peroxide is 1/8 of that of the aqueous solution of sodium pyrophosphate; after the heat preservation is finished, cooling the solution to room temperature by air, and then sequentially adding sodium sulfanilate, vitamin C and hydrochloric acid solution into the solution, wherein the mass fraction of hydrogen chloride in the hydrochloric acid solution is 5 percent, and the balance is water; the mass ratio of the added sodium sulfanilate, the added vitamin C and the added hydrochloric acid solution to the aqueous solution of sodium pyrophosphate is that the sodium sulfanilate is: vitamin C: hydrochloric acid solution: sodium pyrophosphate aqueous solution =1 to 5; stirring for 4-5 h after feeding, then carrying out solid-liquid separation, and drying a solid phase at 50-60 ℃ to constant weight to obtain a solid phase A;
(2) Placing the solid phase A in a closed container, sealing the container, pumping the air pressure in the container to be below 0.2 standard atmospheric pressure, maintaining the pressure for 10-20 min, then filling ozone into the container until the air pressure in the container is 1.6-2 standard atmospheric pressures, maintaining the pressure for 40-70 min, balancing the air pressure inside and outside the container after the pressure maintenance is finished, and taking out the solid phase to obtain the carbon nano tube component;
the preparation method of the iron oxide component comprises the following steps:
preparing ethanol solutions of ferric chloride and mesitylene and aqueous solutions of sodium hydroxide and sodium lignosulfonate, wherein the mass fraction of ferric chloride in the ethanol solutions of ferric chloride and mesitylene is 1-2%, the mass fraction of mesitylene is 0.8-1.5%, and the balance is ethanol; the mass fraction of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium lignosulfonate is 5-7%, the mass fraction of sodium lignosulfonate is 1-2%, and the balance is water; washing iron oxide powder with acetone for 2-3 times, drying, soaking the dried powder in the ethanol solution of ferric chloride and mesitylene, wherein the solid-liquid mass ratio of the powder soaked in the ethanol solution of ferric chloride and mesitylene is solid/liquid = 1; stirring the solution, and dropwise adding the aqueous solution of sodium hydroxide and sodium lignosulphonate into the solution under the stirring state until no precipitate is generated; and (4) carrying out solid-liquid separation, washing the solid phase with deionized water for 2-3 times, and drying to obtain the iron oxide component.
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