CN113318710A - Preparation method of graphene oxide/chitosan composite material adsorbent - Google Patents
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention relates to the technical field of sewage treatment, and discloses a graphene oxide/chitosan composite material adsorbent, which is prepared by mixing graphene oxide and chitosan, wherein functional groups on the surfaces of the graphene oxide and the chitosan are combined through electrostatic interaction and hydrogen bonds, glutaraldehyde is added, the crosslinking of the graphene oxide and the chitosan is enhanced through the reaction of aldehyde groups and amino groups in the chitosan, the composite material adsorbent is prevented from being difficult to separate from a solution after adsorption is finished, and compared with single graphene oxide or chitosan, the adsorption performance of the graphene oxide/chitosan composite material adsorbent to Cr (VI) is remarkably enhanced, the heavy metal ions Cr (VI) in sewage can be removed, the graphene oxide/chitosan composite material adsorbent has excellent adsorption effect, and meanwhile, the recoverability of the graphene oxide/chitosan composite material adsorbent reduces the cost of the adsorbent.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a preparation method of a graphene oxide/chitosan composite material adsorbent.
Background
At present, the adsorption method is a simple and feasible chromium-containing wastewater treatment method, and the adsorption method for treating chromium-containing wastewater is divided into three types according to the adsorption principle: electrostatic adsorption, van der waals adsorption, and chemical bond adsorption, which are low in cost, simple and convenient to operate, and less in secondary pollution, and some of which can be recovered and recycled, have been favored by researchers and environmental protection workers in recent years, and are considered to be the most potential wastewater treatment methods.
Graphene Oxide (GO) is an ideal novel two-dimensional material, and has the advantages of no toxicity, biodegradability, good mechanical strength and hydrophilicity, large specific surface area, high adsorption rate, safety, environmental friendliness and the like, so that the graphene oxide becomes an ideal adsorbent, the surface activity of the graphene oxide is increased by rich oxygen-containing groups on the surface of the graphene oxide, the graphene oxide is easy to combine with other substances to form a compound, the adsorption capacity is improved, and the graphene oxide and the compound derivative thereof are widely applied to the field of environmental water treatment.
Chitosan (CS) is a basic polysaccharide polymer, is also the only basic natural polysaccharide, also called chitosan, is obtained by deacetylating chitin widely existing in the nature, is a renewable natural high molecular resource with the natural content inferior to that of cellulose, has the advantages of no pollution, easy biodegradation and the like, and contains a large amount of-NH in the molecule2and-OH can provide stable cyclic chelate formed by active adsorption sites and heavy metal ions, so that linear chitosan forms a crosslinked high polymer, thereby having stable coordination effect on the metal ions, and can be used as a high-performance adsorbent for various heavy metal ions.
Chromium (Cr) is silver white and glossy metal, is hard and brittle, has strong corrosion resistance, is positioned in the sixth subgroup of the periodic table of elements, is widely distributed in the environment, is one of essential trace elements of a human body, is mainly distributed in bones, adrenal glands, skins, brains, muscles and the like of the human body, maintains the health of the human body by controlling and regulating the blood sugar balance of the human body, reducing cholesterol, protecting heart vessels and other ways, influences the metabolism of saccharides and lipids and the like when the intake of the chromium element in the human body is insufficient, thereby causing a series of chromium deficiency diseases, wherein the chromium is generally trivalent under the reducing condition, has poor activity, is difficult to transfer and has less toxicity to animals and plants; chromium is generally hexavalent under the oxidation condition, hexavalent chromium is easy to transfer, has high toxicity and strong water solubility, and the existence form of hexavalent chromium in the water environment can also be changed according to the change of the pH condition.
According to the invention, the graphene oxide and the chitosan are compounded, the advantages of the graphene oxide and the chitosan are combined, the advantages of each other are fully utilized, and the capacity of adsorbing Cr (VI) is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a graphene oxide/chitosan composite material adsorbent, which has a strong adsorption effect on heavy metal ions in sewage, such as Cr (VI), and the like.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a graphene oxide/chitosan composite material adsorbent comprises the following steps:
(1) under the condition of stirring, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare a graphene oxide dispersion liquid;
(2) mixing and fully stirring the graphene oxide dispersion solution and the chitosan solution at room temperature, adding glutaraldehyde for crosslinking, then washing with deionized water, and freeze-drying to prepare a graphene oxide/chitosan composite material adsorbent;
(3) examining the adsorption performance of the graphene oxide/chitosan composite adsorbent on Cr (VI), researching the influence of different mass ratios of graphene oxide to chitosan, pH values, contact time, initial concentrations, adsorbent dosages and temperatures on the adsorption performance of the graphene oxide/chitosan composite adsorbent, preparing a Cr (VI) stock solution by potassium dichromate, adding deionized water to dilute to a required concentration, adjusting the initial pH of each sample solution, oscillating, adding the adsorbent into an experimental solution with a known concentration to perform an adsorption experiment on Cr (VI), filtering the adsorption solution by a filter after adsorption equilibrium, taking supernatant, analyzing the concentration of Cr (VI) in an aqueous solution by an ultraviolet spectrophotometer,
the adsorption capacity (qe) of the graphene oxide/chitosan composite adsorbent to cr (vi) is obtained according to eq 1:
wherein C is0Initial concentration of Cr (VI) (mg/L); ceIs the equilibrium concentration (mg/L) of Cr (VI); v (L) is the volume of the adsorption solution; m (g) is the mass of the adsorbent.
Preferably, the concentration of the graphene oxide dispersion liquid in the step (1) is 3 mg/mL.
Preferably, the mass ratio of the graphene oxide to the chitosan in the step (2) is 1: 0.5-30.
Preferably, the chitosan in step (2) is dissolved in 2% acetic acid solution to obtain chitosan solution.
Preferably, the amount of glutaraldehyde used in step (2) is 1 mL.
Preferably, the pH value in the step (3) is adjusted by using 0.1 mol/L nitric acid or sodium hydroxide solution.
Advantageous technical effects
Compared with the prior art, the invention has the following chemical experiment principle and beneficial technical effects:
according to the graphene oxide/chitosan composite material adsorbent, graphite is subjected to intercalation oxidation reaction in three stages of low temperature, medium temperature and high temperature under the action of an oxidant, graphene oxide is obtained through ultrasonic stripping, the graphene oxide and chitosan are mixed, functional groups on the surfaces of the graphene oxide and the chitosan are combined through electrostatic action or hydrogen bonds, glutaraldehyde enhances the crosslinking of the graphene oxide and the chitosan, the problem that the graphene oxide is difficult to separate from a solution after adsorption is completed can be solved, compared with single graphene oxide or chitosan, the graphene oxide/chitosan composite material adsorbent has the advantages that the adsorption performance of the graphene oxide/chitosan composite material adsorbent to Cr (VI) is remarkably enhanced, the heavy metal ions Cr (VI) in sewage are removed, and the graphene oxide/chitosan composite material adsorbent has excellent adsorption effect and sewage treatment effect.
Drawings
Fig. 1 is a graph comparing the adsorption capacities of graphene oxide/chitosan composite adsorbents with different ratios for different concentrations of cr (vi) provided in example 1 of the present application.
Fig. 2 is a graph comparing the effect of different pH values on the adsorption capacity of the graphene oxide/chitosan composite adsorbent provided in example 2 of the present application.
Fig. 3 is a graph comparing the effect of different contact times on the adsorption capacity of graphene oxide/chitosan composite adsorbents provided in example 3 of the present application.
Fig. 4 is a graph comparing the effect of different initial concentrations on the adsorption capacity of graphene oxide/chitosan composite adsorbents provided in example 4 of the present application.
Fig. 5 is a graph comparing the effect of different amounts of adsorbents on the adsorption capacity of graphene oxide/chitosan composite adsorbents provided in example 5 of the present application.
Fig. 6 is a graph comparing the effect of different temperatures on the adsorption capacity of graphene oxide/chitosan composite adsorbent provided in example 6 of the present application.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a graphene oxide/chitosan composite material adsorbent comprises the following steps:
(1) under the stirring condition, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare graphene oxide dispersion liquid with the concentration of 3 mg/mL;
(2) 4.2 g of chitosan is dissolved in 100 ml of 2% acetic acid solution to prepare 42 mg/ml of chitosan solution; ultrasonically dispersing 300 mg of graphene oxide in 100 ml of deionized water to obtain 3mg/ml of graphene oxide dispersion liquid; mixing the graphene oxide dispersion liquid with a chitosan solution, wherein the mass ratio of graphene oxide to chitosan is 1: 0.5-30, fully stirring for more than 2 hours at room temperature, adding 1ml of glutaraldehyde for crosslinking, soaking and washing with deionized water, and freeze-drying to obtain the graphene oxide/chitosan composite adsorbent;
(3) investigating the adsorption performance of the graphene oxide/chitosan composite adsorbent on Cr (VI), researching the influence of different mass ratios of graphene oxide to chitosan, pH value, contact time, initial concentration, adsorbent dosage and temperature on the adsorption performance of the graphene oxide/chitosan composite adsorbent, preparing Cr (VI) stock solution by potassium dichromate, adding deionized water to dilute to required concentration, and using 0.1 mol/L HNO3Or adjusting the initial pH of each sample solution by NaOH solution, oscillating, adding an adsorbent into the test solution with known concentration to perform adsorption experiment on Cr (VI), filtering the adsorption solution by using a filter after adsorption equilibrium, taking supernatant, and analyzing the concentration of Cr (VI) in the aqueous solution by using an ultraviolet spectrophotometer.
Example 1
(1) Under the stirring condition, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare graphene oxide dispersion liquid with the concentration of 3 mg/mL;
(2) 4.2 g of chitosan is dissolved in 100 ml of 2% acetic acid solution to prepare 42 mg/ml of chitosan solution; ultrasonically dispersing 300 mg of graphene oxide in 100 ml of deionized water to obtain 3mg/ml of graphene oxide dispersion liquid; mixing the graphene oxide dispersion liquid with a chitosan solution, wherein the mass ratio of graphene oxide to chitosan is 1: 0.5-30, fully stirring for more than 2 hours at room temperature, adding 1ml of glutaraldehyde for crosslinking, soaking and washing with deionized water, and freeze-drying to obtain the graphene oxide/chitosan composite adsorbent;
(3) investigating the adsorption performance of the graphene oxide/chitosan composite material adsorbent on Cr (VI), researching the influence of different mass ratios of graphene oxide to chitosan on the adsorption performance of the graphene oxide/chitosan composite material adsorbent, preparing Cr (VI) stock solution by using potassium dichromate, adding deionized water to dilute to a required concentration, and using 0.1 mol/L HNO3Or NaOH solution adjusting the initial pH of each sample solution, shaking, at a known concentrationAdding an adsorbent into the experimental solution to perform an adsorption experiment on Cr (VI), filtering the adsorption solution by using a filter to obtain a supernatant after the adsorption is balanced, analyzing the concentration of Cr (VI) in the aqueous solution by using an ultraviolet spectrophotometer, wherein the experimental result shows that the optimal mass ratio of graphene oxide to chitosan is 1: 7.
example 2
(1) Under the stirring condition, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare graphene oxide dispersion liquid with the concentration of 3 mg/mL;
(2) 4.2 g of chitosan is dissolved in 100 ml of 2% acetic acid solution to prepare 42 mg/ml of chitosan solution; ultrasonically dispersing 300 mg of graphene oxide in 100 ml of deionized water to obtain 3mg/ml of graphene oxide dispersion liquid; mixing the graphene oxide dispersion liquid with a chitosan solution, wherein the mass ratio of graphene oxide to chitosan is 1: 7, fully stirring for more than 2 hours at room temperature, adding 1ml of glutaraldehyde for crosslinking, soaking and washing with deionized water, and freeze-drying to obtain the graphene oxide/chitosan composite material adsorbent;
(3) examining the adsorption performance of the graphene oxide/chitosan composite adsorbent on Cr (VI), researching the influence of different pH values on the adsorption performance of the graphene oxide/chitosan composite adsorbent, preparing a Cr (VI) stock solution by using potassium dichromate, adding deionized water to dilute the stock solution to a required concentration, oscillating the stock solution, adding the adsorbent into an experimental solution with a known concentration to perform an adsorption experiment on the Cr (VI), filtering the adsorption solution by using a filter after adsorption balance, taking a supernatant, analyzing the concentration of the Cr (VI) in an aqueous solution by using an ultraviolet spectrophotometer, wherein the experimental result shows that the optimal pH value is 2.
Example 3
(1) Under the stirring condition, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare graphene oxide dispersion liquid with the concentration of 3 mg/mL;
(2) 4.2 g of chitosan is dissolved in 100 ml of 2% acetic acid solution to prepare 42 mg/ml of chitosan solution; ultrasonically dispersing 300 mg of graphene oxide in 100 ml of deionized water to obtain 3mg/ml of graphene oxide dispersion liquid; mixing the graphene oxide dispersion liquid with a chitosan solution, wherein the mass ratio of graphene oxide to chitosan is 1: 7, fully stirring for more than 2 hours at room temperature, adding 1ml of glutaraldehyde for crosslinking, soaking and washing with deionized water, and freeze-drying to obtain the graphene oxide/chitosan composite material adsorbent;
(3) investigating the adsorption performance of the graphene oxide/chitosan composite material adsorbent on Cr (VI), researching the influence of different contact time on the adsorption performance of the graphene oxide/chitosan composite material adsorbent, preparing Cr (VI) stock solution by using potassium dichromate, adding deionized water to dilute to a required concentration, and using 0.1 mol/L HNO3Or adjusting the initial pH of each sample solution by NaOH solution, oscillating, adding an adsorbent into the test solution with known concentration to perform adsorption experiment on Cr (VI), filtering the adsorption solution by using a filter to obtain supernatant after adsorption balance, analyzing the concentration of Cr (VI) in the aqueous solution by using an ultraviolet spectrophotometer, and the experimental result shows that the adsorbent reaches adsorption balance after 60 min.
Example 4
(1) Under the stirring condition, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare graphene oxide dispersion liquid with the concentration of 3 mg/mL;
(2) 4.2 g of chitosan is dissolved in 100 ml of 2% acetic acid solution to prepare 42 mg/ml of chitosan solution; ultrasonically dispersing 300 mg of graphene oxide in 100 ml of deionized water to obtain 3mg/ml of graphene oxide dispersion liquid; mixing the graphene oxide dispersion liquid with a chitosan solution, wherein the mass ratio of graphene oxide to chitosan is 1: 7, fully stirring for more than 2 hours at room temperature, adding 1ml of glutaraldehyde for crosslinking, soaking and washing with deionized water, and freeze-drying to obtain the graphene oxide/chitosan composite material adsorbent;
(3) investigating the adsorption performance of the graphene oxide/chitosan composite material adsorbent on Cr (VI), and researching the adsorption performance of different initial concentrations on the graphene oxide/chitosan composite material adsorbentThe effect of (1) is to prepare stock solution of Cr (VI) by potassium dichromate, add deionized water to dilute to the required concentration, and use 0.1 mol/L HNO3Or adjusting the initial pH of each sample solution by NaOH solution, oscillating, adding an adsorbent into the test solution with known concentration to perform adsorption experiment on Cr (VI), filtering the adsorption solution by using a filter to obtain supernatant after adsorption balance, analyzing the concentration of Cr (VI) in the aqueous solution by using an ultraviolet spectrophotometer, and the experimental result shows that the concentration reaches the adsorption balance at 150 mg/L.
Example 5
(1) Under the stirring condition, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare graphene oxide dispersion liquid with the concentration of 3 mg/mL;
(2) 4.2 g of chitosan is dissolved in 100 ml of 2% acetic acid solution to prepare 42 mg/ml of chitosan solution; ultrasonically dispersing 300 mg of graphene oxide in 100 ml of deionized water to obtain 3mg/ml of graphene oxide dispersion liquid; mixing the graphene oxide dispersion liquid with a chitosan solution, wherein the mass ratio of graphene oxide to chitosan is 1: 7, fully stirring for more than 2 hours at room temperature, adding 1ml of glutaraldehyde for crosslinking, soaking and washing with deionized water, and freeze-drying to obtain the graphene oxide/chitosan composite material adsorbent;
(3) investigating the adsorption performance of the graphene oxide/chitosan composite material adsorbent on Cr (VI), researching the influence of different adsorbent dosages on the adsorption performance of the graphene oxide/chitosan composite material adsorbent, preparing Cr (VI) stock solution by using potassium dichromate, adding deionized water to dilute to a required concentration, and using 0.1 mol/L HNO3Or adjusting the initial pH of each sample solution by NaOH solution, oscillating, adding an adsorbent into the test solution with known concentration to perform adsorption experiment on Cr (VI), filtering the adsorption solution by using a filter to obtain supernatant after adsorption balance, and analyzing the concentration of Cr (VI) in the aqueous solution by using an ultraviolet spectrophotometer, wherein the experiment result shows that the adsorption capacity is maximum when the dosage of the adsorbent is 5 mg.
Example 6
(1) Under the stirring condition, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare graphene oxide dispersion liquid with the concentration of 3 mg/mL;
(2) 4.2 g of chitosan is dissolved in 100 ml of 2% acetic acid solution to prepare 42 mg/ml of chitosan solution; ultrasonically dispersing 300 mg of graphene oxide in 100 ml of deionized water to obtain 3mg/ml of graphene oxide dispersion liquid; mixing the graphene oxide dispersion liquid with a chitosan solution, wherein the mass ratio of graphene oxide to chitosan is 1: 7, fully stirring for more than 2 hours at room temperature, adding 1ml of glutaraldehyde for crosslinking, soaking and washing with deionized water, and freeze-drying to obtain the graphene oxide/chitosan composite material adsorbent;
(3) investigating the adsorption performance of the graphene oxide/chitosan composite material adsorbent on Cr (VI), researching the influence of different temperatures on the adsorption performance of the graphene oxide/chitosan composite material adsorbent, preparing Cr (VI) stock solution by using potassium dichromate, adding deionized water to dilute to a required concentration, and using 0.1 mol/L HNO3Or adjusting the initial pH of each sample solution by NaOH solution, oscillating, adding an adsorbent into the test solution with known concentration to perform adsorption experiment on Cr (VI), filtering the adsorption solution by using a filter to obtain supernatant after adsorption balance, and analyzing the concentration of Cr (VI) in the aqueous solution by using an ultraviolet spectrophotometer, wherein the experiment result shows that the temperature has little influence on the adsorption performance.
Claims (7)
1. The graphene oxide/chitosan composite material adsorbent is characterized in that: the preparation method of the graphene oxide/chitosan composite material adsorbent comprises the following steps:
under the condition of stirring, sequentially adding graphite, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide into a three-necked bottle, washing with deionized water, centrifuging to be neutral, and ultrasonically stripping to prepare a graphene oxide dispersion liquid;
mixing and fully stirring the graphene oxide dispersion solution and the chitosan solution at room temperature, adding glutaraldehyde for crosslinking, then washing with deionized water, and freeze-drying to prepare a graphene oxide/chitosan composite material adsorbent;
examining the adsorption performance of the graphene oxide/chitosan composite adsorbent on Cr (VI), researching the influence of different mass ratios of graphene oxide to chitosan, pH values, contact time, initial concentrations, adsorbent dosages and temperatures on the adsorption performance of the graphene oxide/chitosan composite adsorbent, preparing a Cr (VI) stock solution by potassium dichromate, adding deionized water to dilute to a required concentration, adjusting the initial pH of each sample solution, oscillating, adding the adsorbent into an experimental solution with a known concentration to perform an adsorption experiment on Cr (VI), filtering the adsorption solution by a filter after adsorption equilibrium, taking supernatant, analyzing the concentration of Cr (VI) in an aqueous solution by an ultraviolet spectrophotometer,
the adsorption capacity (qe) of the graphene oxide/chitosan composite adsorbent to cr (vi) is obtained according to eq 1:
wherein C is0Initial concentration of Cr (VI) (mg/L); ceThe equilibrium concentration (mg/L) of Cr (VI), V (L) is the volume of the adsorption solution; m (g) is the mass of the adsorbent.
2. The graphene oxide/chitosan composite adsorbent according to claim 1, wherein: the concentration of the graphene oxide dispersion liquid in the step (1) is 3 mg/mL.
3. The graphene oxide/chitosan composite adsorbent according to claim 1, wherein: the mass ratio of the graphene oxide to the chitosan in the step (2) is 1: 0.5-30.
4. The graphene oxide/chitosan composite adsorbent according to claim 1, wherein: and (3) dissolving the chitosan in the step (2) in a 2% acetic acid solution to obtain a chitosan solution.
5. The graphene oxide/chitosan composite adsorbent according to claim 1, wherein: the dosage of the glutaraldehyde in the step (2) is 1 mL.
6. The graphene oxide/chitosan composite adsorbent according to claim 1, wherein: the pH value in the step (3) is adjusted by using 0.1 mol/L nitric acid or sodium hydroxide solution.
7. The graphene oxide/chitosan composite adsorbent according to claim 1, wherein: according to the adsorption method, after adsorbents with different weights are added and put into pollutant solutions with corresponding concentrations, shaking tables are subjected to constant-temperature oscillation.
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| CN113617342A (en) * | 2021-09-24 | 2021-11-09 | 长春工业大学 | Preparation method of aminated bagasse/graphene composite aerogel and application of aminated bagasse/graphene composite aerogel in wastewater treatment |
| CN113786815A (en) * | 2021-09-26 | 2021-12-14 | 桂林清研皓隆复合材料研究院有限公司 | Adsorbing material for water pollution treatment and preparation method thereof |
| CN114307980A (en) * | 2021-12-27 | 2022-04-12 | 中国人民解放军火箭军工程大学 | Composite material and composition for treating unsymmetrical dimethylhydrazine pollutants, and treatment method and experimental method thereof |
| CN115254039A (en) * | 2022-06-21 | 2022-11-01 | 浙江理工大学 | Chitosan/gelatin/biochar composite heavy metal adsorption non-woven fabric and preparation method thereof |
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