CN115738995A - Fiber-based composite adsorbent material and preparation method thereof - Google Patents
Fiber-based composite adsorbent material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000003463 adsorbent Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 10
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011159 matrix material Substances 0.000 claims abstract description 36
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- 238000000034 method Methods 0.000 claims description 13
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- KOVPXZDUVJGGFU-UHFFFAOYSA-N 8-methoxy-8-oxooctanoic acid Chemical compound COC(=O)CCCCCCC(O)=O KOVPXZDUVJGGFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 3
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 235000009120 camo Nutrition 0.000 claims description 3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a fiber-based composite adsorbent material, which comprises modified fibers, wherein the modified fibers comprise a fiber matrix and a plurality of gallic acid crosslinked on the fiber matrix. The invention also discloses a fiber base a preparation method of the composite adsorbent material. The introduction of gallic acid in the invention greatly improves the adsorption performance of the fiber material, and increases the ion selectivity of the fiber material, so that the fiber material can be more widely applied to the ion removal work in a water system.
Description
Technical Field
The invention relates to the field of composite fiber adsorbent materials, in particular to a fiber-based composite adsorbent material and a preparation method thereof.
Background
The nuclear power industry in China develops rapidly, uranium resources are in a scarcity day by day, at present, the uranium resources in China depend on import seriously, and in order to effectively relieve the situation, research on adsorbent materials and development of adsorption technology for adsorbing uranium in seawater play an important role. The research on extracting uranium from seawater has great practical significance for strengthening the competitiveness and the energy safety of the nuclear power industry in China. The selection of the adsorbent is an important part of a project for extracting uranium from seawater, and the uranium extraction adsorbent material from inorganic adsorbent, organic chelating resin and ocean developable polymer is developed into fiber material and nano-structure material with high specific surface area in the research process. The fiber material has the characteristics of easy modification and low cost, and has better economic applicability. The fiber material is easy to separate from the water body, is convenient to recycle after an adsorption test is carried out, and is an ideal structural material of the adsorbent. But because the surface of the material has less active adsorption sites, the material has no obvious adsorption capacity on uranyl ions. Practice shows that adsorption sites can be attached to the surface of the fiber through chemical modification to achieve better adsorption performance.
Disclosure of Invention
The invention aims to provide a fiber-based composite adsorbent material.
The invention also provides a preparation method of the fiber-based composite adsorbent material.
The innovation point of the invention is that the adsorption performance of the fiber material is greatly improved by introducing the gallic acid, and the ion selectivity is increased, so that the fiber material can be more widely applied to ion removal work in a water system.
In order to achieve the above-mentioned objects of the invention, the technical scheme of the invention is as follows: a fiber-based composite adsorbent material comprises modified fibers, the modified fiber comprises a fiber matrix and a plurality of gallic acid crosslinked on the fiber matrix.
Further, the mass ratio of the gallic acid to the fibrous matrix is 0.5 to 2.5:10.
further, the fiber substrate is one of hemp fiber, cotton fiber, polyacrylonitrile fiber, modified palm fiber, cellulose fiber, electrospun cellulose fiber, activated carbon fiber, biomass fiber, regenerated bionic fiber, porous carbon fiber, aramid fiber and sepiolite fiber.
The preparation method of the fiber-based composite adsorbent material is characterized by comprising the following steps of:
and (3) hydrolysis reaction: mixing a fiber matrix, sodium hydroxide and deionized water to obtain a mixture, wherein the mass ratio of the fiber matrix to the sodium hydroxide is 1:9 to 11, stirring until the sodium hydroxide is fully dissolved, continuously fully reacting at 70 to 90 ℃ for 30 to 40 minutes after the sodium hydroxide is dissolved, standing for 3~5 minutes to obtain a hydrolyzed fiber solution, and taking out the hydrolyzed fiber and washing with deionized water until the washing liquid is neutral; drying the hydrolyzed fiber to obtain a hydrolyzed fiber material; the reaction time is preferably 30 to 40 minutes because the fiber is embrittled and the mechanical properties of the fiber are reduced due to the excessively long reaction time.
And (3) crosslinking reaction: dissolving the hydrolyzed fiber material and the gallic acid in deionized water, stirring at room temperature, dropwise adding the cross-linking agent while stirring, and mixing the hydrolyzed fiber material and the gallic acid: of crosslinking agents the mass ratio is 10: <xnotran> 0.5~2.5: </xnotran> 5363 and (3) 5363) after the cross-linking agent is added, the temperature is increased to 50 to 55 ℃, the mixture is stirred and reacts for 4 to 4.5 hours to obtain a cross-linked fiber solution, taking out the crosslinked fibers from the fiber-reinforced composite material, and washing the crosslinked fibers with deionized water until the washing liquid is neutral; will crosslink fiber drying to obtain the finished product.
Further, the cross-linking agent is at least one of glutaraldehyde, acetic anhydride, diglycidyl ether, methyl suberate, natural biological cross-linking agent, dicumyl peroxide, benzoyl peroxide and di-tert-butyl peroxide.
Further, the drying temperature for drying the hydrolyzed fiber and the crosslinked fiber is 60 ℃, and the drying time is 12 to 13 hours.
The invention has the beneficial effects that:
1. the introduction of gallic acid in the invention greatly improves the adsorption performance of the fiber material, and increases the ion selectivity of the fiber material, so that the fiber material can be more widely applied to the ion removal work in a water system.
2. The fiber-based composite adsorbent material prepared by the method has the advantages of high adsorption capacity, high cycle stability, high ion selectivity and the like, and also shows good adsorption capacity in a low ion concentration solution.
Drawings
FIG. 1 shows the fibers of comparative example 1 a microscopic topography of the material;
FIG. 2 is a microscopic topography of the fibrous material of example 2;
FIG. 3 is a microscopic topography of the fibrous material of comparative example 2;
FIG. 4 shows pH of the solution before and after modification influence curve of fiber adsorption performance;
FIG. 5 is a Zeta potential diagram for fibers of comparative example 1 and example 2;
FIG. 6 shows the uranium adsorption capacity under competitive ion conditions for example 2;
figure 7 shows the desorption efficiency of example 2 for different desorbents;
figure 8 is a graph of the effect of 5 adsorption-desorption cycles on the adsorption of example 2.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.
Example 1: a fiber-based composite adsorbent material comprises modified fibers, wherein the modified fibers comprise a fiber matrix and a plurality of gallic acids crosslinked on the fiber matrix; the mass ratio of the gallic acid to the fiber matrix is 0.5:10. the fiber matrix is hemp fiber.
Practice of example 2: a fiber-based composite adsorbent material comprises modified fibers, wherein the modified fibers comprise a fiber matrix and a plurality of gallic acids crosslinked on the fiber matrix; the mass ratio of the gallic acid to the fiber matrix is 1:10; the fiber matrix is polyacrylonitrile fiber.
Example 3: a fiber-based composite adsorbent material comprises modified fibers, wherein the modified fibers comprise a fiber matrix and a plurality of gallic acids crosslinked on the fiber matrix; the mass ratio of the gallic acid to the fiber matrix is 2.5:10; the fiber matrix is cotton fiber.
Example 4: referring to example 1, the mass ratio of several gallic acids to the fiber matrix was 1.5:10.
practice of example 5: referring to example 1, the mass ratio of several gallic acids to the fibrous matrix was 2:10.
example 6: referring to example 1, the fibrous substrate is one of modified palm fiber, cellulose fiber, electrospun cellulose fiber, activated carbon fiber, biomass fiber, regenerated bionic fiber, porous carbon fiber, aramid fiber, and sepiolite fiber.
Example 7: a preparation method of a fiber-based composite adsorbent material comprises the following steps:
and (3) hydrolysis reaction: mixing a fiber matrix, sodium hydroxide and deionized water to obtain a mixture, wherein the mass ratio of the fiber matrix to the sodium hydroxide is 1:9, stirring until the sodium hydroxide is fully dissolved, continuing to fully react for 30 minutes at 70 ℃ after the sodium hydroxide is dissolved, standing for 3 minutes to obtain a hydrolyzed fiber solution, and taking out the hydrolyzed fiber and washing with deionized water until a washing liquid is neutral; drying the hydrolyzed fiber to obtain a hydrolyzed fiber material; the drying temperature for the hydrolyzed fiber was 60 ℃ and the drying time was 12 hours.
And (3) crosslinking reaction: dissolving the hydrolyzed fiber material and the gallic acid in deionized water, stirring at room temperature, and dropwise adding a cross-linking agent while stirring, wherein the cross-linking agent is glutaraldehyde. Hydrolyzed fibrous material, gallic acid: the mass ratio of the cross-linking agent is 10:0.5:3, after the cross-linking agent is added, raising the temperature to 50 ℃, stirring and reacting for 4 hours to obtain a cross-linked fiber solution, taking out the cross-linked fiber, and washing with deionized water until the washing liquid is neutral; and drying the crosslinked fibers to obtain a finished product. The drying temperature for drying the crosslinked fibers was 60 ℃ and the drying time was 12 hours.
Example 8: a preparation method of a fiber-based composite adsorbent material, the method comprises the following steps:
and (3) hydrolysis reaction: mixing a fiber matrix, sodium hydroxide and deionized water to obtain a mixture, wherein the mass ratio of the fiber matrix to the sodium hydroxide is 1: stirring until sodium hydroxide is fully dissolved, continuing to fully react at 80 ℃ for 35 minutes after the sodium hydroxide is dissolved, standing for 4 minutes to obtain a hydrolyzed fiber solution, and taking out the hydrolyzed fiber and washing with deionized water until a washing liquid is neutral; drying the hydrolyzed fiber to obtain a hydrolyzed fiber material; the drying temperature for the hydrolyzed fiber was 60 ℃ and the drying time was 12.5 hours.
And (3) crosslinking reaction: dissolving hydrolyzed fiber material and gallic acid in deionized water, stirring at room temperature, and dropwise adding a crosslinking agent while stirring, wherein the crosslinking agent is acetic anhydride. Hydrolyzed fibrous material, gallic acid: the mass ratio of the cross-linking agent is 10:1:4, after the cross-linking agent is added, raising the temperature to 52 ℃, stirring and reacting for 4.2 hours to obtain a cross-linked fiber solution, taking out the cross-linked fiber, and washing with deionized water until the washing liquid is neutral; and drying the crosslinked fibers to obtain a finished product. The drying temperature for drying the crosslinked fibers was 60 ℃ and the drying time was 12.5 hours.
Example 9: a preparation method of a fiber-based composite adsorbent material comprises the following steps:
and (3) hydrolysis reaction: mixing a fiber matrix, sodium hydroxide and deionized water to obtain a mixture, wherein the mass ratio of the fiber matrix to the sodium hydroxide is 1:11, stirring until the sodium hydroxide is fully dissolved, continuing to fully react for 40 minutes at 90 ℃ after the sodium hydroxide is dissolved, standing for 5 minutes to obtain a hydrolyzed fiber solution, and taking out the hydrolyzed fiber and washing with deionized water until a washing liquid is neutral; drying the hydrolyzed fiber to obtain a hydrolyzed fiber material; the drying temperature for the hydrolyzed fiber was 60 ℃ and the drying time was 13 hours.
And (3) crosslinking reaction: dissolving the hydrolyzed fiber material and the gallic acid in deionized water, stirring at room temperature, and dropwise adding the cross-linking agent while stirring, wherein the cross-linking agent is diglycidyl ether. Hydrolyzed fibrous material, gallic acid: the mass ratio of the cross-linking agent is 10:2.5:5, after the cross-linking agent is added, raising the temperature to 55 ℃, stirring and reacting for 4.5 hours to obtain a cross-linked fiber solution, and taking out the cross-linked fiber from the cross-linked fiber solution and washing the cross-linked fiber with deionized water until the washing liquid is neutral; and drying the crosslinked fibers to obtain a finished product. The drying temperature for drying the crosslinked fibers was 60 ℃ and the drying time was 13 hours.
Example 10: referring to example 7, the crosslinking agent is one of methyl suberate, natural biological crosslinking agent, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide or at least two of glutaraldehyde, acetic anhydride, diglycidyl ether, methyl suberate, natural biological crosslinking agent, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide.
Comparative example 1: fibrous matrix in example 2.
Comparative example 2: example 2 adsorption experiments were performed.
As can be seen from fig. 1, 2 and 3, the unmodified fiber matrix surface was very smooth, the surface roughness of the fiber material was slightly increased after modification with gallic acid, and the size was increased by 1 μm. After the adsorption experiment of the uranyl ions is carried out, the overall structure of the fiber is not obviously changed, and the fiber material has certain structural stability.
The measuring method comprises the following steps: as the adsorption experiment method, a static blocking adsorption experiment method, which is also called a dipping method, is used. Respectively adding an adsorbent material with the same mass and a standard uranium solution with known concentration and a certain volume into a clean and sealable container, adjusting the pH value to 7 to obtain a prepared solution, sealing the container by using a sealing plug, placing the container into a constant-temperature shaking table, and performing adsorption reaction until the adsorption reaches balance. And after the adsorption experiment is finished, according to the obtained variables of the uranium concentration before and after adsorption, calculating to obtain the adsorption capacity of the adsorbent material.
And (4) preparing a standard uranium solution. Weighing a certain amount of uranyl nitrate powder, and dispersing the uranyl nitrate powder into a proper amount of deionized water. A small amount of nitric acid solution is dropped into the solution to prevent the solution from precipitation during the preparation process (the concentration of the nitric acid solution can be 1 mg. L-1). And transferring the solution in the beaker into a volumetric flask for constant volume, and shaking up to obtain the standard uranium solution (the concentration can be 1000 mg. L-1).
Table 1 shows the adsorption capacity for uranyl ions for example 1~5 and for comparative example 1 (solution pH 7.0 was prepared and reaction temperature 25 ℃ C.).
As can be seen from table 1, the adsorption capacity of example 1~5 for uranyl ions is greatly increased compared to comparative example 1, for reasons that can be explained as follows: the introduction of gallic acid adds a large number of active adsorption sites to the fibrous material. With the increase of the content of the gallic acid, the adsorption performance of the fiber material is increased to a certain degree, and the ratio of the gallic acid: fiber =1:10 the best adsorption effect is achieved, the reason for which can be explained as follows: a large amount of hydroxyl is introduced for adsorbing ions due to the increase of the gallic acid, but carboxyl groups of the fiber material are limited, and when the upper limit is reached, the effect of increasing the proportion of the gallic acid on improving the adsorption performance of the fiber is small, so that resource waste is caused to a certain degree. The data in table 1 demonstrate that the mass ratio of several gallic acids to the fibrous matrix is 1:10.
as can be seen from FIG. 4, the pH of the prepared solutions was adjusted, and both of example 2 and comparative example 1 were greatly affected by the pH. The adsorption capacity of example 2 was greatly improved compared to comparative example 1. Example 2 the optimum adsorption value was reached at pH 7.0, and the amount of adsorption subsequently decreased as the pH of the prepared solution increased.
As is clear from FIG. 5, the isoelectric point of example 2 was 6.7. When the pH in the prepared solution is low, UO22+ is the predominant form of uranium present. When the pH value of the prepared solution is less than 6.7, the surface of the adsorbent is positively charged and has a repulsive effect with uranium ions, and under the condition of low pH value of the prepared solution, H & lt + & gt in the prepared solution and uranyl ions compete for effective binding sites of the fiber material; when the pH value of the solution is more than 6.7, the concentration of OH-ions in the prepared solution increases along with the increase of the pH value, the surface of the example 2 is negatively charged, uranium ions are gradually present in a negative form, such as UO2 (OH) 3-, UO2 (OH) 3 (OH) 7-and the like, the electrostatic repulsion between the adsorbent material and the uranium ions is increased, and the removal rate of uranium in the prepared solution is reduced. While comparative example 1 has an isoelectric point of 5.35, which is also close to its optimum pH.
Table 2 shows the adsorption data fitting parameters for uranyl ions of example 2 by the quasi-first order kinetic model and the quasi-second order kinetic model.
Table 2 is the kinetic fit parameters for uranyl ions for example 2:
the fitting parameters for example 2 are listed in table 2. Because the correlation coefficient (R2) of the quasi-second order kinetic model is higher than that of the quasi-first order kinetic model, the method is more suitable for describing a material adsorption process. The adsorption kinetics of example 2 are therefore closer to the quasi-second order kinetic model, the adsorption process being dominated by chemisorption.
Table 3 example 2 thermodynamic fitting parameters for uranyl ions:
as can be seen from the data in table 3, R2 of the Langmuir model is significantly higher than that of the Freundlich model, and the result can prove that the process of example 2 for adsorbing uranium is more suitable to be described by the Langmuir isothermal adsorption model. It is thus assumed that the process of adsorbing uranyl ions in example 2 is mainly monolayer adsorption.
And (3) preparing various competitive ion solutions. Weighing a certain amount of UO2 (NO 3) 2 crystal powder and metal nitrate of which the metal ions are K +, na +, ba2+, ca2+, zn2+, co2+, fe2+, mg2+, ni2+ and Sr2+ (the molar weight of the substances is equal). The materials are put into a beaker, a proper amount of deionized water is added, and the materials are thoroughly dispersed by ultrasonic until a uniform solution is formed. The solution in the beaker was transferred to a 1L volumetric flask, and deionized water was added to a constant volume and shaken until uniform. The ion competition solution is obtained.
From fig. 6, it can be seen that the sequence of the removal rates of example 2 for different metal ions from high to low is UO 2+ > > Mg2+ > Ba2+ > Na + > K + > Ca2+ > Co2+ > Fe2+ > Zn2+ > Ni2+ > Sr2+, and the removal rate of each competitive ion is less than 5%. In the presence of interfering cations, the adsorption efficiency of example 2 on uranium still reaches about 80%, which shows that example 2 has good selectivity on uranyl ions.
And (4) preparing desorption liquid. A certain amount of HCL, naCl, naHCO3, naOH and HNO3 (which can be 0.1 mol) are respectively weighed. Putting the materials into a beaker, adding a proper amount of deionized water, and stirring until a uniform solution is obtained. The solution in the beaker is transferred into a volumetric flask with the specification of 1L, and deionized water is added to shake up and fix the volume. So as to obtain desorption solution.
As shown in fig. 7, among the 5 kinds of desorption agents, the uranyl ions in HNO3 comparative example 2 have the best desorption effect, and the desorption rate can reach 92%.
FIG. 8 shows data of the product of example 2 after 5 cycles of adsorption-desorption experiments, and the adsorption capacity of the product of example 2 for uranyl ions is reduced from the initial 366.22 mg. G-1 to 305.96 mg. G-1, which shows that the product of example 2 has good recycling performance and has certain potential when applied to extraction of uranium from an actual aqueous solution.
The described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (6)
1. The fiber-based composite adsorbent material is characterized by comprising modified fibers, wherein the modified fibers comprise a fiber matrix and a plurality of gallic acids crosslinked on the fiber matrix.
2. The fiber-based composite adsorbent material according to claim 1, wherein the mass ratio of the gallic acid to the fiber matrix is 0.5 to 2.5:10.
3. the fiber-based composite adsorbent material of claim 1, wherein the fiber matrix is one of hemp fiber, cotton fiber, polyacrylonitrile fiber, modified palm fiber, cellulose fiber, electrospun cellulose fiber, activated carbon fiber, biomass fiber, regenerated biomimetic fiber, porous carbon fiber, aramid fiber, and sepiolite fiber.
4. A method of making a fiber-based composite sorbent material according to any one of claims 1~3 comprising the steps of:
and (3) hydrolysis reaction: mixing a fiber matrix, sodium hydroxide and deionized water to obtain a mixture, wherein the mass ratio of the fiber matrix to the sodium hydroxide is 1:9 to 11, stirring until the sodium hydroxide is fully dissolved, continuously fully reacting at 70 to 90 ℃ for 30 to 40 minutes after the sodium hydroxide is dissolved, standing for 3~5 minutes to obtain a hydrolyzed fiber solution, and taking out the hydrolyzed fiber and washing with deionized water until the washing liquid is neutral; drying the hydrolyzed fiber to obtain a hydrolyzed fiber material;
and (3) crosslinking reaction: dissolving the hydrolyzed fiber material and the gallic acid in deionized water, stirring at room temperature, dropwise adding the cross-linking agent while stirring, and mixing the hydrolyzed fiber material and the gallic acid: the mass ratio of the cross-linking agent is 10:0.5 to 2.5:3~5, after the cross-linking agent is added, raising the temperature to 50 to 55 ℃, stirring and reacting for 4 to 4.5 hours to obtain a cross-linked fiber solution, taking out the cross-linked fiber, and washing with deionized water until the washing liquid is neutral; and drying the crosslinked fibers to obtain a finished product.
5. The method for preparing the fiber-based composite adsorbent material according to claim 4, wherein the cross-linking agent is at least one of glutaraldehyde, acetic anhydride, diglycidyl ether, methyl suberate, natural biological cross-linking agent, dicumyl peroxide, benzoyl peroxide, and di-tert-butyl peroxide.
6. The method for preparing the fiber-based composite adsorbent material according to claim 4, wherein the drying temperature for drying the hydrolyzed fiber and the crosslinked fiber is 60 ℃ and the drying time is 12 to 13 hours.
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