CN112110502A - Removing agent for micro-plastics in water body - Google Patents
Removing agent for micro-plastics in water body Download PDFInfo
- Publication number
- CN112110502A CN112110502A CN202011028122.3A CN202011028122A CN112110502A CN 112110502 A CN112110502 A CN 112110502A CN 202011028122 A CN202011028122 A CN 202011028122A CN 112110502 A CN112110502 A CN 112110502A
- Authority
- CN
- China
- Prior art keywords
- sodium
- solution
- iron oxide
- aqueous solution
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229920003023 plastic Polymers 0.000 title claims abstract description 33
- 239000004033 plastic Substances 0.000 title claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 title claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 126
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 111
- 239000000243 solution Substances 0.000 claims abstract description 106
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000007864 aqueous solution Substances 0.000 claims abstract description 76
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 55
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 55
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 50
- 239000007790 solid phase Substances 0.000 claims abstract description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 39
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 39
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 39
- 229920005552 sodium lignosulfonate Polymers 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229930003268 Vitamin C Natural products 0.000 claims abstract description 25
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 claims abstract description 25
- 235000019154 vitamin C Nutrition 0.000 claims abstract description 25
- 239000011718 vitamin C Substances 0.000 claims abstract description 25
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 9
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 48
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 48
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 48
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 238000012423 maintenance Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000426 Microplastic Polymers 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002033 PVDF binder Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002048 multi walled nanotube Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229910000619 316 stainless steel Inorganic materials 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 239000010865 sewage Substances 0.000 description 8
- 238000012216 screening Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- -1 comprises physical Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
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) placing the solid phase A below 0.2 standard atmospheric pressure, and placing the solid phase A in an ozone environment with 1.6-2 standard atmospheric pressures to obtain the carbon nano tube component; the preparation method of the iron 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 kind and 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 constant to 50 +/-5 ℃, keeping the temperature, cooling the solution to room temperature 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 to constant weight in an environment of 50-60 ℃ 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, washing ferric oxide powder with acetone for 2-3 times, drying, soaking the dried powder in the ethanol solutions of ferric chloride and mesitylene, stirring the solution, and dropwise adding the aqueous solutions of sodium hydroxide and sodium lignosulfonate 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 2-3 times, and drying to obtain the iron oxide component.
Further, in the sodium pyrophosphate aqueous solution, the mass percentage of the solute is 3% -6%, and the solid-liquid mass ratio of the carbon nanotubes dispersed in the sodium pyrophosphate aqueous solution is solid/liquid =1: 10; the mass fraction of hydrogen peroxide in hydrogen peroxide is 10%, and the mass of added hydrogen peroxide is 1/8% of the mass 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: the aqueous solution of sodium pyrophosphate = 1-5: 0.6-1.5: 3-5: 100.
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 lignosulfonate is 5-7%, the mass fraction of sodium lignosulfonate 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 1: 10.
Further, in the remover, the mixing mass ratio of the carbon nanotube component to the iron oxide component is 1: 10-20.
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 in conjunction with the accompanying 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 =1: 10. And mixing and bonding the carbon nanotube component and the iron oxide component by adopting a PVDF binder, wherein the content of the PVDF binder in the remover is 5 wt%. 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 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: 10; hydrogen peroxide with the mass fraction of 10 percent is added into the solution, and the added mass of the hydrogen peroxide is 1/8 of the mass 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 =1:0.6:3: 100. 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 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%, the mass fraction of mesitylene is 0.8%, and the balance is ethanol; the mass fraction of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium lignosulfonate is 5%, 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 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, wherein the soaking solid/liquid ratio is =1: 10. 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 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 =1: 14. And mixing and bonding the carbon nanotube component and the iron oxide component by adopting a PVDF binder, wherein the content of the PVDF binder in the remover is 5 wt%. 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 a solute content of 4% by mass, 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: 10; hydrogen peroxide with the mass fraction of 10 percent is added into the solution, and the added mass of the hydrogen peroxide is 1/8 of the mass 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 =2:0.8:4: 100. 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 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%, 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 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, wherein the soaking solid/liquid ratio is =1: 10. 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 =1: 16. And mixing and bonding the carbon nanotube component and the iron oxide component by adopting a PVDF binder, wherein the content of the PVDF binder in the remover is 5 wt%. 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 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: 10; hydrogen peroxide with the mass fraction of 10 percent is added into the solution, and the added mass of the hydrogen peroxide is 1/8 of the mass 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 =3:1:4: 100. 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 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; 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 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, wherein the soaking solid/liquid ratio is =1: 10. 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 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 =1: 18. And mixing and bonding the carbon nanotube component and the iron oxide component by adopting a PVDF binder, wherein the content of the PVDF binder in the remover is 5 wt%. 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 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: 10; hydrogen peroxide with the mass fraction of 10 percent is added into the solution, and the added mass of the hydrogen peroxide is 1/8 of the mass 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 =4:1.3:4: 100. 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 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 1.4%, 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 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, wherein the soaking solid/liquid ratio is =1: 10. 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 =1: 20. And mixing and bonding the carbon nanotube component and the iron oxide component by adopting a PVDF binder, wherein the content of the PVDF binder in the remover is 5 wt%. 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: 10; hydrogen peroxide with the mass fraction of 10 percent is added into the solution, and the added mass of the hydrogen peroxide is 1/8 of the mass 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 =5:1.5:5: 100. 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 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 1.5%, and the balance is ethanol; the mass fraction of sodium hydroxide in the aqueous solution of sodium hydroxide and sodium lignosulfonate is 7%, the mass fraction of 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, wherein the soaking solid/liquid ratio is =1: 10. 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. PVDF binder, water and iron oxide components are mixed and coated, and the content of the PVDF binder in the remover is 5 wt%. 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 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; 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 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, wherein the soaking solid/liquid ratio is =1: 10. 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 2
The remover for the micro-plastics in the water body is prepared by the comparative example, and 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 multi-walled carbon nanotubes to the components of the ferric oxide =1: 14.
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. PVDF binder is adopted to mix and bond the multi-wall carbon nano-tube and the ferric oxide component, and the content of the PVDF binder in the remover is 5 wt%. 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 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%, 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 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, wherein the soaking solid/liquid ratio is =1: 10. 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 3
A remover for micro-plastics in a water body comprises a carbon nano tube component and iron oxide, wherein the carbon nano tube component and the iron oxide are mixed according to the mass ratio of the carbon nano tube component to the iron oxide =1: 14. And mixing and bonding the carbon nanotube component and the iron oxide component by adopting a PVDF binder, wherein the content of the PVDF binder in the remover is 5 wt%. 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 a solute content of 4% by mass, 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: 10; hydrogen peroxide with the mass fraction of 10 percent is added into the solution, and the added mass of the hydrogen peroxide is 1/8 of the mass 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 =2:0.8:4: 100. 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 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 1:1, sieving the mixture with a 500-mesh sieve, adding the sieved powder into deionized water according to the solid-liquid mass ratio of 50mg/1000g, and stirring and mixing to form a sewage sample. The removing agents prepared in examples 1-5 and comparative examples 1-3 were respectively placed into the sewage samples according to the ratio of 10g removing agent/500 mL sewage sample, the sewage samples were magnetically stirred at the speed of 80r/min for 30min, then the removing agents were taken out, the sewage samples were taken to detect the content of the micro-plastics, and the micro-plastic removal rate was calculated, and the results are 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 iron oxide prepared by the method of the present invention alone as a remover has a significantly less effect on removing the micro plastic than 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 (5)
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 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 constant to 50 +/-5 ℃, keeping the temperature, cooling the solution to room temperature 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 to constant weight in an environment of 50-60 ℃ 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, washing ferric oxide powder with acetone for 2-3 times, drying, soaking the dried powder in the ethanol solutions of ferric chloride and mesitylene, stirring the solution, and dropwise adding the aqueous solutions of sodium hydroxide and sodium lignosulfonate 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 2-3 times, and drying to obtain the iron oxide component.
2. The removing agent for the micro-plastics in the water body according to claim 1, wherein the solute content in the aqueous solution of the sodium pyrophosphate is 3-6% by mass, and the solid-liquid mass ratio of the carbon nanotubes dispersed in the aqueous solution of the sodium pyrophosphate is solid/liquid =1: 10; the mass fraction of hydrogen peroxide in hydrogen peroxide is 10%, and the mass of added hydrogen peroxide is 1/8% of the mass of the aqueous solution of sodium pyrophosphate.
3. The removing agent for the micro-plastics in the water body according to claim 1, wherein the mass fraction of the 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: the aqueous solution of sodium pyrophosphate = 1-5: 0.6-1.5: 3-5: 100.
4. The removing agent for the micro-plastics in the water body according to claim 1, wherein 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 lignosulfonate is 5-7%, the mass fraction of sodium lignosulfonate 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 1: 10.
5. The remover for removing the micro-plastics in the water body according to claim 1, wherein the removing agent is characterized in that the mixing mass ratio of the carbon nanotube component to the iron oxide component is =1: 10-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011028122.3A CN112110502B (en) | 2020-09-26 | 2020-09-26 | Removing agent for micro-plastics in water body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011028122.3A CN112110502B (en) | 2020-09-26 | 2020-09-26 | Removing agent for micro-plastics in water body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112110502A true CN112110502A (en) | 2020-12-22 |
| CN112110502B CN112110502B (en) | 2022-11-29 |
Family
ID=73797046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011028122.3A Active CN112110502B (en) | 2020-09-26 | 2020-09-26 | Removing agent for micro-plastics in water body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112110502B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163163A (en) * | 2021-12-22 | 2022-03-11 | 株洲宏信科技发展有限公司 | Concrete chromium reducing agent |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500318A (en) * | 2011-09-28 | 2012-06-20 | 武汉工程大学 | Surface modification method of carbon nanotube, carbon nanotube and application thereof |
| CN103601252A (en) * | 2013-10-28 | 2014-02-26 | 江苏大学 | Technology for solid phase preparation of nanometer iron oxide through template method |
| CN104891469A (en) * | 2015-05-05 | 2015-09-09 | 上海大学 | Method and device for carboxylation modification of carbon nano-material by ozone and use thereof |
| CN110237821A (en) * | 2019-06-21 | 2019-09-17 | 中国科学院烟台海岸带研究所 | A kind of ferromagnetism nanometer particle preparation and its application in the extraction of micro- plastics and removal |
| WO2019215218A1 (en) * | 2018-05-11 | 2019-11-14 | Abcr Gmbh | Method for removing impurities, especially microplastics particles, from water and/or a body of water and/or for purifying and/or processing water and/or a body of water, a kit, and also uses |
| CN111514868A (en) * | 2020-04-09 | 2020-08-11 | 华东师范大学 | Magnetic nano carbon, preparation method thereof and application thereof in removing micro plastic in water |
| CN111569829A (en) * | 2020-04-15 | 2020-08-25 | 浙江省海洋水产研究所 | Method for removing micro-plastic in water based on graphene material |
| WO2020169591A1 (en) * | 2019-02-18 | 2020-08-27 | Kemira Oyj | Method of evaluating and optionally selecting a suitable chemistry for removal of microplastics in a liquid matrix |
-
2020
- 2020-09-26 CN CN202011028122.3A patent/CN112110502B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500318A (en) * | 2011-09-28 | 2012-06-20 | 武汉工程大学 | Surface modification method of carbon nanotube, carbon nanotube and application thereof |
| CN103601252A (en) * | 2013-10-28 | 2014-02-26 | 江苏大学 | Technology for solid phase preparation of nanometer iron oxide through template method |
| CN104891469A (en) * | 2015-05-05 | 2015-09-09 | 上海大学 | Method and device for carboxylation modification of carbon nano-material by ozone and use thereof |
| WO2019215218A1 (en) * | 2018-05-11 | 2019-11-14 | Abcr Gmbh | Method for removing impurities, especially microplastics particles, from water and/or a body of water and/or for purifying and/or processing water and/or a body of water, a kit, and also uses |
| WO2020169591A1 (en) * | 2019-02-18 | 2020-08-27 | Kemira Oyj | Method of evaluating and optionally selecting a suitable chemistry for removal of microplastics in a liquid matrix |
| CN110237821A (en) * | 2019-06-21 | 2019-09-17 | 中国科学院烟台海岸带研究所 | A kind of ferromagnetism nanometer particle preparation and its application in the extraction of micro- plastics and removal |
| CN111514868A (en) * | 2020-04-09 | 2020-08-11 | 华东师范大学 | Magnetic nano carbon, preparation method thereof and application thereof in removing micro plastic in water |
| CN111569829A (en) * | 2020-04-15 | 2020-08-25 | 浙江省海洋水产研究所 | Method for removing micro-plastic in water based on graphene material |
Non-Patent Citations (2)
| Title |
|---|
| 张思梦等: ""环境中的微塑料及其对人体健康的影响"", 《中国塑料》 * |
| 曹清等: ""碳纳米管纯化的研究进展"", 《电子元件与材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114163163A (en) * | 2021-12-22 | 2022-03-11 | 株洲宏信科技发展有限公司 | Concrete chromium reducing agent |
| CN114163163B (en) * | 2021-12-22 | 2022-11-29 | 湖南润攸科技发展有限公司 | Concrete chromium reducing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112110502B (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Ball milled biochar effectively removes sulfamethoxazole and sulfapyridine antibiotics from water and wastewater | |
| Dong et al. | Stabilization of nanoscale zero-valent iron (nZVI) with modified biochar for Cr (VI) removal from aqueous solution | |
| CN106000311B (en) | Load the charcoal and its preparation method and application of iron/zinc nanoparticle | |
| CN102992566B (en) | A kind of method of lignin-sludge | |
| CN106492761A (en) | A kind of preparation method of magnetic hydrogel microsphere | |
| Nethaji et al. | Graphene oxide coated with porous iron oxide ribbons for 2, 4-Dichlorophenoxyacetic acid (2, 4-D) removal | |
| CN106881059A (en) | A kind of preparation method of iron/carbon composite | |
| CN110052248A (en) | A kind of humic acid modified charcoal of ferrimanganic and the preparation method and application thereof | |
| CN105622960B (en) | A kind of carboxymethyl chitosan/oxidized graphene composite aquogel and its preparation and application | |
| CN104437415B (en) | A kind of chitosan-modified graphite oxide magnetic nanometer adsorbent and preparation thereof and application | |
| CN105536660B (en) | A kind of preparation method of nano-silver loaded oil-tea camellia husks pyrolysis carbosphere | |
| CN103317144B (en) | The preparation method of the modifying iron based nanoscale bimetallic particles of a kind of coating material | |
| CN112110502B (en) | Removing agent for micro-plastics in water body | |
| CN107555521A (en) | A kind of heavy metal-polluted water process multiporous biological matter microballoon and preparation method thereof | |
| CN109499546A (en) | A kind of Fe3O4@bacteria cellulose/graphene oxide composite aerogel and the preparation method and application thereof | |
| CN114316993A (en) | Soil pollution repairing agent and repairing method thereof | |
| Jiang et al. | Preparation of antimicrobial activated carbon fiber by loading with silver nanoparticles | |
| CN109465010A (en) | A kind of preparation and application of magnetism di-iron trioxide-graphitic carbon nano composite material | |
| CN106179215A (en) | The preparation method of water plant charcoal carbon nano tube compound material and application | |
| CN103563984A (en) | Method for preparing graphene oxide/ silver antibacterial composite material through intermediate pneumatic plasma jet | |
| CN114288990A (en) | Preparation method of hydroxylated magnetic graphene oxide adsorbent | |
| CN106861646B (en) | The preparation method of the adsorbent material of selective absorption silver ion | |
| CN107868261A (en) | A kind of carboxymethyl chitosan/oxidized graphene composite aquogel and its preparation and application | |
| CN115532225B (en) | Method for preparing zero-valent iron-loaded biochar by using waste soil as iron source and application of zero-valent iron-loaded biochar | |
| CN114405475B (en) | Adsorption material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |