CN116459802B - High-strength three-dimensional continuous oversized hole uranium adsorption hydrogel and preparation method thereof - Google Patents
High-strength three-dimensional continuous oversized hole uranium adsorption hydrogel and preparation method thereof Download PDFInfo
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- CN116459802B CN116459802B CN202310189421.2A CN202310189421A CN116459802B CN 116459802 B CN116459802 B CN 116459802B CN 202310189421 A CN202310189421 A CN 202310189421A CN 116459802 B CN116459802 B CN 116459802B
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 49
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 13
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
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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 relates to a high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel and a preparation method thereof, and belongs to the technical field of adsorption materials. The hydrogel comprises a first polymer network formed by low-temperature crystallization polymerization crosslinking of polyvinyl alcohol and water-soluble bio-based macromolecules, a second polymer network formed by random copolymerization crosslinking of polyamidoxime and hydrophilic vinyl monomers on the basis of the first network, and a third polymer network formed by self-assembled polyaniline on the surface of the second network, wherein nano silicon dioxide is uniformly distributed in a gel phase of the hydrogel. The hydrogels have the characteristics of high throughput, low resistance, and high strength of the medium. The hydrogel can rapidly realize selective adsorption of uranyl ions in water.
Description
Technical Field
The invention relates to a high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel and a preparation method thereof, and belongs to the technical field of adsorption materials.
Background
With the exhaustion of the traditional petrochemical energy, the nuclear energy is most likely to be one of the main energy sources as new energy sources in the future. Currently, in terms of the nuclear power ratio, the nuclear power accounts for 13% of the total world power production, and the data is still in an ascending trend. Uranium can be used as one of the most important nuclear energy production elements in nuclear power and most industrial production as an important nuclear raw material, so that the provision of enough uranium raw material is a key factor for guaranteeing nuclear energy production, and plays an important role and practical significance for national and even international economic and social development. The invention aims at mainly developing adsorption media with large flux and low flow resistance and certain scale and size in the field of uranium extraction in water bodies, realizing enrichment and separation of uranium in water bodies, and promoting development and engineering application of uranium extraction adsorption materials. The adsorption method in the methods for extracting uranium can effectively enrich low-concentration uranium and recover uranium, and the adsorption separation process is easy to realize, so that the method for extracting uranium by the methods is effective.
The core of uranium extraction by adsorption is the design and application of efficient adsorption media. The uranium ion adsorption material applied to the water body at present mainly comprises a particle-form medium, a fiber adsorption medium, a membrane adsorption medium and a three-dimensional porous series adsorption medium. All studies have been aimed at developing adsorbent media with high adsorption capacity and low flow resistance on a scale. One of the effective strategies for increasing the adsorption capacity of a medium is to modify the surface of the medium with molecules to obtain specific functional groups, such as amidoxime groups, phosphonic acid groups, etc. The most effective method for obtaining amidoxime groups is to subject a medium containing nitrile groups to amidoxime modification, such as polyacrylonitrile fiber material, acrylonitrile surface film material, etc. The N in the amido and the O atom in the oxime group of the amidoxime group molecular modified uranyl ion adsorption medium can form coordination with the uranyl ion together so as to effectively adsorb and separate the uranyl ion in the water body. Another strategy for improving the uranium adsorption capacity is to regulate and control the macrostructure of the adsorption medium matrix, and increase the specific surface area of the adsorption material and the contact probability of the functional group and uranyl ions so as to improve the adsorption capacity. Therefore, developing the adsorption medium with three-dimensional continuous pores as a matrix has important use value, the adsorption medium with three-dimensional form is mostly shown in a space three-dimensional form, the molecular structure is in a three-dimensional cross-linking form, and a large number of pore structures are distributed in the adsorption medium so that the medium has higher specific surface area, and engineering application is easy to realize in adsorption operation. The structure and the size of the pores of the adsorption medium have important influence on the adsorption process, the microporous adsorption medium with the pore diameter smaller than 2nm has huge specific surface area, water phase diffuses on the inner surface of the medium, and uranyl ions are insufficiently contacted with functional groups. If the pore structure of the ultra-large pore adsorption medium with the pore diameter larger than 1 mu m is in a continuous open pore form, the adsorbed water body can pass through rapidly, and the high-efficiency treatment capacity is realized. Since the extraction objects of uranyl ions are mostly aqueous solutions, in recent years, many researches have proposed that hydrophilic adsorption media (such as hydrogel adsorption media) can effectively promote the diffusion of water phase on the surface of the media, thereby being more beneficial to improving the adsorption capacity and the adsorption rate. Uranyl ion adsorption media developed from adsorption media prepared from a variety of hydrophilic monomers such as acrylic acid monomers, acrylamide monomers, vinylsulfonic acid and the like have been demonstrated to be effective in improving the adsorption properties of materials.
If the hydrogel adsorption medium is prepared into the oversized hole uranyl ion adsorption medium with a continuous pore structure, the diffusion and adsorption of uranium-containing water bodies can be effectively realized, but the mechanical strength of the single-network hydrogel matrix becomes a weakness of the medium. The hydrogel adsorption medium is in a porous structure with a super-large pore structure, and the mechanical strength of the medium is weaker along with the increase of the pore volume fraction.
Disclosure of Invention
In view of the above, the invention aims to provide a high-strength three-dimensional continuous super macroporous uranium adsorption hydrogel and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
The high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel comprises a first polymer network formed by low-temperature crystallization polymerization crosslinking of polyvinyl alcohol (PVA) and water-soluble bio-based macromolecules, a second polymer network formed by random copolymerization crosslinking of Polyamidoxime (PAO) and hydrophilic vinyl monomers on the basis of the first network, and a third polymer network formed by self-assembled Polyaniline (PANI) on the surface of the second network, wherein nano silicon dioxide is uniformly distributed in a gel phase of the hydrogel; the hydrogel has a three-dimensional continuous open super macroporous structure, the pore size is 10-200 mu m, the tensile strength is 1-5 MPa, the compressive strength is 5-20 MPa, and the conductivity is 1S/m-5S/m.
The invention discloses a preparation method of a high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, which comprises the following steps:
(1) Preparation of high molecular weight PAO
Dissolving sodium acrylate (AANa) and Acrylonitrile (AN) in H 2 O, charging nitrogen, driving oxygen, adding H 2O2 and ascorbic acid (Vc) at-5-0 ℃, uniformly stirring, cooling to-30-10 ℃ for reaction for 10-20H, and melting after the reaction is finished to obtain a high-viscosity linear random copolymer P (AANa-co-AN) aqueous solution; adding hydroxylamine hydrochloride and sodium carbonate into the P (AANa-co-AN) aqueous solution, reacting for 3-12 h at 60-80 ℃, dialyzing in pure water after the reaction is finished, and concentrating to obtain a linear polymer Polyamidoxime (PAO) aqueous solution with the mass fraction of 10-20%. Since Acrylonitrile (AN) is slightly soluble in water, radical polymerization of acrylonitrile is usually carried out using AN organic solvent such as N, N' -dimethylformamide or dimethylsulfoxide as a solvent. In order to obtain the PAO linear polymer with high molecular weight, the method adopted by the invention is a low-temperature crystallization polymerization method, and the method realizes the aqueous solution copolymerization of the Acrylonitrile (AN) monomer and other aqueous solution vinyl monomers by taking water as a solvent.
Preferably, in the reaction system in the step (1), the mass fraction of AANa is 1-10%, the mass fraction of AN is 2-10%, and the total mass fraction of AANa and AN is 7% -15%; 0.08 to 0.4 percent of H 2O2 and 0.05 to 0.3 percent of Vc; the mass fraction of hydroxylamine hydrochloride is 3-20%, and the mass fraction of sodium carbonate is 2-20%.
(2) Preparation of the first Polymer network
Mixing a polyvinyl alcohol (PVA) aqueous solution with a water-soluble bio-based macromolecule solution, filling nitrogen, driving oxygen, stirring and mixing uniformly, adding an inorganic acid solution and a glutaraldehyde solution at 0-5 ℃, stirring and mixing uniformly to obtain a homogeneous reaction solution A, cooling to-30-10 ℃ within 10-30 min, reacting for 8-24 h, and melting and washing to obtain the PVA and water-soluble bio-based macromolecule crosslinked network polymer.
Preferably, in the step (2), the water-soluble bio-based macromolecule is one or more of Chitosan (CS), chitosan quaternary ammonium salt (ACS), gelatin (GA), agar (AG) and kappa-carrageenan (kappa-CG) with a deacetylation degree of 80% -95%, and more preferably, the water-soluble bio-based macromolecule is CS and/or GA.
Preferably, in the step (2), the mass fraction of the PVA aqueous solution is 8 to 15%.
Preferably, in the step (2), the mass fraction of the water-soluble bio-based macromolecule solution is 5-15%. Preferably, in the step (2), the inorganic acid solution is one or more of hydrochloric acid, sulfuric acid and phosphoric acid solution, and the mass fraction of the inorganic acid solution is 1-10%.
Preferably, in the step (2), the mass fraction of the glutaraldehyde solution is 5-20%.
Preferably, in the step (2), in the homogeneous reaction solution a, the mass fraction of PVA is 1% -10%, the mass fraction of the water-soluble bio-based macromolecule is 7% -15%, the mass fraction of the inorganic acid is 0.05% -0.5%, and the mass fraction of glutaraldehyde is 0.2% -1%.
(3) Second, third Polymer network preparation
Mixing tetraethoxysilane with H 2 O under continuous stirring to obtain sol B; mixing hydrophilic vinyl monomer, PAO aqueous solution, sol B, cross-linking agent, water-soluble oxidant C and H 2 O in nitrogen atmosphere, adding reducer D at-5-0 deg.C, stirring and mixing to obtain mixture E; dissolving Aniline (ANI) in HCl solution under continuous stirring, and adding oxidant C' at-5-0 ℃ to obtain solution F; maintaining the temperature at-5 ℃ to 0 ℃, and adding the solution F into the mixture solution E under continuous stirring to obtain a mixture solution G; mixing the mixed solution G with the network polymer, cooling to-30 to-10 ℃ within 5 to 20min, reacting for 10 to 24 hours, cooling to-80 to-50 ℃ within 20 to 60min, reacting for 24 to 48 hours, immersing into saturated salt solution for salting out after the reaction is finished, wherein the salting-out temperature is-10 to 0 ℃ and the salting-out time is 48 to 96 hours, and washing with water after the salting-out is finished, so as to obtain the high-strength three-dimensional continuous ultra-macroporous uranium adsorption hydrogel. The second network polymer is mainly a flexible polymer network formed by free radical initiation polymerization of a linear polymer PAO and a vinyl monomer; the third polymer network is a PANI polymer network, and after the second polymer network is formed, aniline (ANI) is better and independently loaded on the surface of the second polymer network to form a Polyaniline (PANI) polymer network which is uniformly and densely distributed. The interpenetrating multi-network polymer structure endows the uranyl ion adsorbent with excellent mechanical properties. In the process of cooling and crystallizing the mixed solution G, solvent water is crystallized into a pore-forming agent, and the redox initiator initiates vinyl monomer polymerization and crosslinking, and linear PAO interpenetrates in a crosslinked polymer gel phase, so that the chain extension of the PAO is realized to form a space three-dimensional network structure of continuous pores. After the reaction is finished, the polymerization system is salted out at a low temperature, ice crystals of the polymerization system are gradually melted to leave a pore structure which is continuously distributed, and meanwhile, strong hydrogen bonding action is formed between side groups in the first and second net polymer chains by salting out synergistic effect, so that the mechanical property of the hydrogel material is improved.
Preferably, in the step (3), the mass fraction of the tetraethoxysilane in the sol B is 10% -50%.
Preferably, in the step (3), the hydrophilic vinyl monomer is one or more of Acrylic Acid (AA), methacrylic acid (MAA), maleic Acid (MA), hydroxyethyl methacrylate (HEM), fumaric Acid (FA), vinylsulfonic acid (ESA), itaconic acid (MSA) and 2-acrylamido-2-methylpropanesulfonic Acid (AMPS).
Preferably, in the step (3), the crosslinking agent is one or more of N-methylolacrylamide (NMA), N' -Methylenebisacrylamide (MBA), ethylene Glycol (EG), glycerol (GG), polyethylene glycol (PEG), polypropylene glycol (PPG) and propylene glycol (MPD). More preferably, the cross-linking agent is preferably MBA and/or NMA.
Preferably, in the step (3), the water-soluble oxidant C is H 2O2 and/or potassium Permanganate (PHG).
Preferably, in the step (3), the reducing agent is ascorbic acid (Vc) and/or oxalic acid (EA).
Preferably, in the step (3), the mass fraction of the vinyl monomer in the mixture solution E is 1% -10%, the mass fraction of the sol B is 1% -5%, the mass fraction of the crosslinking agent is 0.01% -2%, the mass fraction of the water-soluble oxidant C is 0.2% -5%, the mass fraction of the PAO is 3% -10%, and the mass fraction of the reducing agent is 0.1% -2%.
Preferably, in the step (3), the mass fraction of the HCl solution is 2% -6%.
Preferably, in the step (3), the oxidant C' is one or more of Ammonium Persulfate (APS), potassium persulfate (KPS) and Sodium Persulfate (SPS).
Preferably, in the step (3), the mass fraction of HCl in the solution F is 2% -10%, the mass fraction of ANI is 5% -15%, and the mass fraction of the oxidizing agent C' is 1% -10%.
Preferably, in the step (3), the saturated salt solution is a saturated solution of more than one of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate at 20 ℃.
Advantageous effects
The invention provides a high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, which takes water-soluble bio-based macromolecules and PVA (polyvinyl alcohol) as a matrix to prepare a first network structure, wherein a second network has the characteristics of a flexible molecular chain and specific functional groups, and a third network uniformly distributes rigid macromolecular weight PANI on the surface of the second network by a self-assembly method. The hydrogel is analyzed from the molecular level, and shows an interpenetrating structure of a rigid polymer network and a flexible polymer network, so that the mechanical property of the hydrogel material is promoted by the strong hydrogen bonding action among the cooperated salting-out molecular chains; from the analysis of the hydrogel macrostructure, the crystallization pore-forming can generate a three-dimensional continuous ultra-large pore structure from the hydrogel wall surface to the inside by low-temperature dissolution; the three-dimensional continuous pore size is 10-200 mu m; the tensile strength of the wet sample is 1-5 MPa, and the compressive strength of the wet sample is 5-20 MPa; in addition, the introduction of the third network pANI enables the hydrogel to have good conductive property, and the conductivity is 1-5S/m. The hydrogel provided by the invention has the characteristics of high medium flux, low resistance and high strength. The three-dimensional continuous superporous hydrogel can rapidly realize selective adsorption of uranyl ions in water bodies containing the uranyl ions, and the adsorption capacity of the uranyl ions can reach 200-1000 mg/g under different adsorption conditions.
The invention provides a preparation method of high-strength three-dimensional continuous super-macroporous uranium adsorption hydrogel, which comprises the steps of firstly synthesizing a high molecular weight linear polymer-Polyamidoxime (PAO) with adsorption sites, and preparing the three-dimensional continuous super-macroporous structure high-strength uranium adsorption hydrogel by taking the PAO as a raw material through the processes of crosslinking, chain extension, molding and the like. Specifically, in the preparation process, the hydrogel takes polyvinyl alcohol (PVA) and water-soluble bio-based macromolecules as raw materials to form a first network through a low-temperature crystallization polymerization crosslinking strategy; based on the first network, forming a second network by cross-linking a linear polymer formed by random copolymerization of PAO and hydrophilic vinyl monomer serving as a raw material; and meanwhile, forming a third network structure on the second network surface by self-assembling Polyaniline (PANI) in an oxidation initiation mode. The three-network polymerization technology adopts low-temperature crystallization polymerization, and ice crystals are used as pore-forming agents, so that the hydrogel obtains a space three-dimensional continuous pore structure; the mechanical properties of the hydrogel are synergistically improved through salting-out effect after low-temperature crystallization. The introduction of the second network makes the surface of the hydrogel rich in a large amount of 'amidoxime' groups and other functional groups, such as carboxyl, amido, sulfonic acid groups and the like, so that uranium elements are efficiently and rapidly captured in a mode of synergistic chelation of the amidoxime groups with the carboxyl, sulfonic acid groups, amine groups, hydroxyl groups and other functional groups in biological macromolecules. The method combines a low-temperature freezing pore-forming technology, a redox initiation free radical polymerization technology and a self-assembly surface oxidation polymerization technology, and can realize large-scale preparation; the problem of poor mechanical strength of the gel material is mainly solved, and particularly, the engineering application problem that the larger the pore is, the worse the mechanical property is. Forming a three-dimensional continuous pore structure and a three-network interpenetrating structure in a gel phase, introducing nano SiO 2 into a network, and then enabling hydrogen bonds between a rigid macromolecular chain and a flexible macromolecular chain to cooperate through salting-out so as to greatly improve the mechanical property of the gel; the polyaniline surface self-assembled polymerization, which can improve the mechanical capability of the hydrogel and simultaneously endow the hydrogel with conductivity.
The invention provides a preparation method of high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, which is characterized in that amidoxime groups are optimal uranyl ion complexing groups, but acrylonitrile belongs to slightly water-soluble monomers, and random copolymer containing nitrile groups is difficult to obtain by directly adopting an aqueous solution polymerization method, the invention utilizes the weak solubility of acrylonitrile in water, preparing a low-concentration polymerization monomer polymerization system, crystallizing a solvent at a low temperature, and initiating polymerization of a monomer in an amorphous area, so that random copolymerization of acrylonitrile and other acid monomers is realized, nitrile groups are successfully introduced into the hydrogel, amidoxime functional groups of the nitrile groups are further realized, and high adsorption capacity of the hydrogel to uranyl ions is effectively realized; the method successfully realizes the polymerization of the acrylonitrile monomer in the aqueous solution, and abandons the use of organic solvents such as dimethyl sulfoxide, N, N' -dimethylformamide and the like.
Drawings
Fig. 1 is an EDS spectrum and surface element analysis result of the hydrogel described in example 1 after uranium adsorption.
Fig. 2 is an EDS spectrum and surface element analysis result after uranium adsorption of the hydrogel described in example 2.
Fig. 3 is an EDS spectrum and surface element analysis result after uranium adsorption by the hydrogel described in example 3.
Fig. 4 is an EDS spectrum and surface element analysis result after uranium adsorption of the hydrogel described in example 4.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
Preparing AANa and AN into aqueous solution, filling nitrogen and driving oxygen for 20min, cooling the aqueous solution to 0 ℃ in refrigeration equipment in AN ethanol atmosphere, adding H 2O2 and ascorbic acid (Vc), uniformly stirring, cooling the reaction system to-20 ℃ within 30min, maintaining the temperature for reaction for 18H, and taking out to melt at room temperature to obtain P (AANa-co-AN) aqueous solution; adding a mixed solution of hydroxylamine hydrochloride and sodium carbonate into a P (AANa-co-AN) polymer aqueous solution, reacting for 12 hours at 70 ℃, pouring the reacted mixed solution into a dialysis bag, dialyzing for 4days under the condition of pure water, replacing water every 6 hours, and finally concentrating to obtain a PAO aqueous solution with the mass fraction of 15% for later use; wherein, in the reaction system, the mass fraction of AANa is 4.2%, the mass fraction of AN is 4.8%, the mass fraction of H 2O2 is 0.12%, the mass fraction of Vc is 0.07%, the mass fraction of hydroxylamine hydrochloride is ensured to be 15.2%, and the mass fraction of sodium carbonate is 15.4%.
Dissolving PVA with the polymerization degree of 2400 in water at 90 ℃ and preparing into PVA aqueous solution with the mass fraction of 10% for later use; dissolving solid CS with acetic acid with mass fraction of 2% and preparing CS acetic acid solution with mass fraction of 10% for standby.
Under the protection of nitrogen filling, adding the CS solution and the PVA solution into a three-neck flask, continuously stirring for 1h, then transferring to a refrigeration device, cooling to 0 ℃, adding 3% of HCl solution and 10% of glutaraldehyde solution by mass fraction, and continuously stirring at 0 ℃ for 30min to form a homogeneous reaction solution A, wherein in the homogeneous reaction solution A, the CS mass fraction is 5.8%, the HCl mass fraction is 0.3%, the glutaraldehyde mass fraction is 0.3%, and the PVA mass fraction is 8.3%; pouring the homogeneous reaction solution A into freezing equipment with the size of phi (inner diameter) multiplied by d (height) =60 mm multiplied by 1mm in ethanol atmosphere in a silica gel mold, reducing the temperature of the system to-20 ℃ within 15min, at this time, the system has solvent water crystallization phenomenon, PVA and CS begin to carry out cross-linking reaction with glutaraldehyde under the action of HCl, after the reaction time is 12h, taking out PVA and CS cross-linked network polymer which are in a20 ℃ environment and are melted by ice crystals to leave three-dimensional continuous ultra-large pores, namely the first network polymer, and cleaning the first network polymer with deionized water for later use.
Ethyl orthosilicate (TOSi) was mixed with H 2 O under magnetic stirring in a beaker and stirred continuously for 1H to form a TOSi sol with a mass fraction of 25%. Adding AA, MAA, TOSi sol, MBA, H 2O2, the PAO aqueous solution and deionized water into a three-port reactor in sequence under the condition of continuously introducing N 2, continuously stirring for 1H, transferring into a refrigeration device, cooling to-5 ℃, adding Vc into the three-port reactor at the moment, and uniformly stirring and mixing to obtain a mixture solution E; wherein the mass fraction of the mixture liquid E, AA is 3.34%, the mass fraction of AN is 4.56%, the mass fraction of MAA is 2.45%, the mass fraction of TOSi is 2.45%, the mass fraction of MBA is 0.5%, the mass fraction of H 2O2 is 0.64%, the mass fraction of PAO is 8.54%, the mass fraction of Vc is 0.3%, and stirring is continued for 30min; simultaneously adding a HCl solution with a certain mass fraction of 4% and ANI into another three-port reactor under a continuous stirring state, stirring until the ANI is completely dissolved, transferring to a freezing device in an ethanol atmosphere, cooling to 0-minus 5 ℃, and adding APS into the ANI solution to obtain a solution F, wherein in the solution F, the mass fraction of HCl is 3%, the mass fraction of ANI is 9%, and the mass fraction of APS is 1.5%; maintaining the temperature at-5 ℃, pouring the solution F into the mixture E, continuously stirring for 5min, pumping into the first network polymer, cooling the system to-20 ℃ within 10min, continuously cooling the system to-70 ℃ within 30min after the reaction time is 20h, maintaining the temperature for 30h, taking out after the reaction is finished, directly immersing into saturated sodium chloride aqueous solution for salting out, taking out after the salting out temperature is 0 ℃ and the salting out time is 72h, pumping deionized water into a pore canal through a peristaltic pump to wash out unreacted substances and water soluble salt and obtain the high-strength three-dimensional continuous ultra-macroporous uranium adsorption hydrogel.
The pore distribution of the three-dimensional continuous oversized pore uranium adsorption hydrogel is 10-150 mu m, the average wet sample tensile strength is 0.42MPa, and the average compressive strength is 1.82MPa; the average adsorption capacity of uranyl ion aqueous solution with the initial concentration of 28mg/L after 48 hours is 447.24mg/g under the conditions of 25 ℃ and pH=6; the average conductivity was 2.35S/cm.
The EDS energy spectrum and the surface element analysis after uranium is adsorbed by the three-dimensional continuous oversized hole uranium adsorption hydrogel are shown in figure 1.
Example 2
Preparing AANa and AN into aqueous solution, charging nitrogen and expelling oxygen for 20min, cooling the aqueous solution to 0 ℃ in refrigeration equipment in AN ethanol atmosphere, adding H 2O2 and ascorbic acid (Vc), uniformly stirring, cooling the reaction system to-20 ℃ within 30min, and maintaining the temperature for reaction for 18H; taking out and melting at room temperature to obtain a P (AANa-co-AN) aqueous solution; adding a mixed solution of hydroxylamine hydrochloride and sodium carbonate into the aqueous solution of the P (AANa-co-AN) polymer, and reacting for 8 hours at 70 ℃; pouring the reacted mixed solution into a dialysis bag, and dialyzing for 4days under the pure water condition, wherein water is replaced every 6 hours, and finally concentrating to obtain PAO aqueous solution with the mass fraction of 15% for later use; wherein, in the reaction system, the mass fraction of AANa is 3.7%, the mass fraction of AN is 4.6%, the mass fraction of H 2O2 is 0.18%, and the mass fraction of Vc is 0.09%; the mass fraction of hydroxylamine hydrochloride is 14.3%, and the mass fraction of sodium carbonate is 14.7%.
Dissolving PVA with the polymerization degree of 2400 in water at 90 ℃ and preparing into PVA aqueous solution with the mass fraction of 10% for later use; preparing GA solution with mass fraction of 10% for standby.
Under the protection of nitrogen charging, adding the GA solution and the PVA solution into a three-port stirrer, continuously stirring for 1h, then transferring to a refrigeration device, cooling to 0 ℃, adding 3% by mass of HCl solution and 10% by mass of glutaraldehyde solution, and continuously stirring at 0 ℃ for 30min to form a homogeneous reaction solution A, wherein in the homogeneous reaction solution A, the GA mass fraction is 6.5%, the inorganic acid HCl mass fraction is 0.25%, the glutaraldehyde mass fraction is 0.3%, and the PVA mass fraction is 7.3%. Pouring the homogeneous reaction solution A into a silica gel mold with the size of phi (inner diameter) x d (height) =60 mm x 1mm, placing the silica gel mold into freezing equipment in an ethanol atmosphere, and reducing the temperature of the system to-20 ℃ within 10min, wherein the system has a solvent water crystallization phenomenon, PVA and GA begin to undergo a crosslinking reaction with glutaraldehyde under the action of HCl for 20h, taking out the PVA and GA crosslinked network polymer which is obtained by melting ice crystals in an environment at 20 ℃ to leave three-dimensional continuous ultra-large pores, and washing the PVA and GA crosslinked network polymer with deionized water for standby.
TOSi water was continuously stirred in a beaker under magnetic stirring for 1h to form a TOSi sol with a mass fraction of 25%. Continuously introducing N 2, adding AMPS, TOSi sol, MBA and H 2O2, the PAO aqueous solution and deionized water into a three-port reactor, continuously stirring for 1H, transferring into a freezing device in an ethanol atmosphere, cooling to-5 ℃, adding Vc into the three-port reactor at the moment, and continuously stirring for 30min to obtain a mixture liquid E, wherein in the mixture liquid E, the mass fraction of AMPS is 8.46%, the mass fraction of TOSi is 4.35%, the mass fraction of MBA is 0.46%, the mass fraction of H 2O2 is 0.84%, the mass fraction of PAO is 9.42%, and the mass fraction of Vc is 0.48%; simultaneously adding HCl solution with the mass fraction of 3.6% and ANI into another three-port reactor under the continuous stirring state, stirring until the ANI is completely dissolved, transferring to a refrigeration device, cooling to-5 ℃, adding KPS into the ANI solution to obtain solution F, wherein the mass fraction of HCl in the solution F is 2.7%, the mass fraction of ANI is 8.4%, the mass fraction of KPS is 1.2%, pouring the solution F into the mixture E at-5 ℃ for continuous stirring for 5min, then pumping into the first network polymer to replace water in the first polymer skeleton, continuously cooling to the temperature of the system for 20h within 15min, maintaining the temperature of the reactant system to-70 ℃ for 36h within 30min, taking out the reactant system after the reaction, directly immersing into saturated potassium chloride aqueous solution for salting out, and pumping deionized water into pore non-reacted substances and water to obtain high-strength three-dimensional super-macroporous adsorption uranium after the salting-out is carried out for 96 h.
The pore distribution of the three-dimensional continuous oversized pore uranium adsorption hydrogel is 10-100 mu m, the average wet sample tensile strength is 0.82MPa, and the average compressive strength is 1.82MPa; the average adsorption capacity of uranyl ion aqueous solution with the initial concentration of 32mg/L after being adsorbed for 48 hours is 386.24mg/g under the adsorption condition of 25 ℃ and pH=6; the average conductivity was 3.21S/cm.
The EDS energy spectrum and the surface element analysis after uranium is adsorbed by the three-dimensional continuous oversized hole uranium adsorption hydrogel are shown in figure 2.
Example 3
Preparing AANa and AN into aqueous solution, charging nitrogen and expelling oxygen for 20min, cooling the aqueous solution to 0 ℃ in refrigeration equipment in AN ethanol atmosphere, adding H 2O2 and ascorbic acid (Vc), uniformly stirring, cooling the reaction system to-20 ℃ within 30min, and maintaining the temperature for reaction for 12H; the mixture was taken out and thawed at room temperature to obtain AN aqueous solution of P (AANa-co-AN). Adding a mixed solution of hydroxylamine hydrochloride and sodium carbonate into the aqueous solution of the P (AANa-co-AN) polymer, and reacting for 10 hours at 70 ℃; pouring the reacted mixed solution into a dialysis bag, and dialyzing for 4days under the pure water condition, wherein water is replaced every 6 hours, and finally concentrating to obtain the PAO aqueous solution with the mass fraction of 15% for later use. In the reaction system, the mass fraction of AANa is 5.8%, the mass fraction of AN is 5.2%, the mass fraction of H 2O2 is 0.18%, the mass fraction of Vc is 0.09%, the mass fraction of hydroxylamine acid is 10.2%, and the mass fraction of sodium carbonate is 11.6%.
Dissolving PVA with the polymerization degree of 2400 in water at 90 ℃ and preparing into PVA aqueous solution with the mass fraction of 10% for later use; dissolving and preparing 10% AG solution for standby at 80 ℃.
Under the protection of nitrogen filling, adding the standby AG solution and PVA solution into a three-port stirrer, continuously stirring for 1h, then transferring to a refrigeration device in an ethanol atmosphere, cooling to 0 ℃, adding 3% by mass of HCl solution and 15% by mass of glutaraldehyde solution, and continuously stirring at 0 ℃ for 30min to form a homogeneous reaction solution A, wherein in the homogeneous reaction solution A, the PVA is 5.7% by mass, the water-soluble bio-based macromolecule is 8.1% by mass, the inorganic acid is 0.12% by mass, and the glutaraldehyde is 0.62% by mass; pouring the homogeneous reaction solution A into a silica gel mold with the size of phi (inner diameter) multiplied by d (height) =60 mm multiplied by 1mm, reducing the temperature of the system to-20 ℃ within 15min, at this time, the system has solvent water crystallization phenomenon, PVA and AG begin to carry out crosslinking reaction with glutaraldehyde under the action of HCl, after the reaction time is 20h, taking out PVA and AG crosslinked network polymer which is obtained by melting ice crystals in an environment of 20 ℃ and is left with three-dimensional continuous ultra-large pores, namely the first network polymer, and cleaning with deionized water for standby.
TOSi water was continuously stirred in a beaker under magnetic stirring for 1h to form a TOSi sol with a mass fraction of 30%. Adding AMPS, AA, TOSi sol, MBA and PHG, the PAO aqueous solution and deionized water into a three-port reactor under the condition of continuously introducing N 2, continuously stirring for 1h, transferring into refrigeration equipment, cooling to-5 ℃, adding EA into the three-port reactor at the moment, and continuously stirring for 30min to obtain a mixture liquid E, wherein the mass fraction of AA in the mixture liquid E is 6.34%, the mass fraction of AMPS is 2.36%, the mass fraction of TOSi is 3.45%, the mass fraction of MBA is 1.2%, the mass fraction of PHG is 0.98%, the mass fraction of PAO is 9.1%, and EA accounts for 0.45%; simultaneously adding a HCl solution with a mass fraction of 3.6% and ANI into another three-port reactor under a continuous stirring state, stirring until the ANI is completely dissolved, transferring to a refrigeration device, cooling to 0 ℃, and adding APS into the ANI solution to obtain a solution F, wherein in the solution F, the mass fraction of HCl is 3.2%, the mass fraction of ANI is 9.6%, and the mass fraction of APS is 1.7%; maintaining the temperature of 0 ℃ and mixing the solution F and the mixture E, continuously stirring for 5min, pumping into the first network polymer to replace water in a first polymer skeleton, reducing the temperature of the system to minus 25 ℃ within 15min, continuously reducing the temperature of a reaction system to minus 80 ℃ within 30min for 40h after the reaction time is 18h, taking out after the reaction, directly immersing into saturated sodium chloride aqueous solution for salting out, taking out the salting-out temperature is 0 ℃, salting-out for 72h, pumping deionized water into a pore canal through a peristaltic pump to wash out unreacted substances and water-soluble salt, and obtaining the high-strength three-dimensional continuous super-macroporous uranium adsorption hydrogel.
The pore distribution of the three-dimensional continuous oversized pore uranium adsorption hydrogel is 10-150 mu m, the average wet sample tensile strength is 2.3MPa, and the average compressive strength is 5.6MPa; the average adsorption capacity of uranyl ion aqueous solution with the initial concentration of 32mg/L after being adsorbed for 48 hours is 512.45mg/g under the adsorption condition of 25 ℃ and pH=6; the average conductivity was 2.49S/cm.
The EDS energy spectrum and the surface element analysis after uranium is adsorbed by the three-dimensional continuous oversized hole uranium adsorption hydrogel are shown in figure 3.
Example 4
Preparing AANa and AN into aqueous solution, charging nitrogen and expelling oxygen for 20min, cooling the aqueous solution to 0 ℃ in refrigeration equipment in AN ethanol atmosphere, adding H 2O2 and ascorbic acid (Vc), uniformly stirring, cooling the reaction system to-20 ℃ within 30min, and maintaining the temperature for reaction for 18H; taking out, melting at room temperature to obtain AN aqueous solution of P (AANa-co-AN), adding a mixed solution of hydroxylamine hydrochloride and sodium carbonate into the aqueous solution of P (AANa-co-AN) polymer, and reacting at 75 ℃ for 8 hours. Pouring the reacted mixed solution into a dialysis bag, dialyzing for 4days under the pure water condition, replacing water every 6 hours during the period, and finally concentrating to obtain PAO aqueous solution with the mass fraction of 15% for later use; in the reaction system, the mass fraction of AANa is 3.4%, the mass fraction of AN is 6.8%, the mass fraction of H 2O2 is 0.22%, the mass fraction of Vc is 0.11%, the mass fraction of hydroxylamine hydrochloride is 15.2%, and the mass fraction of sodium carbonate is 15.2%.
Dissolving PVA with the polymerization degree of 2400 in water at 90 ℃ and preparing into a pVA aqueous solution with the mass fraction of 10% for later use; preparing kappa-CG solution with the mass fraction of 12% for standby.
Under the protection of nitrogen filling, adding the standby kappa-CG solution and PVA solution into a three-port stirrer, continuously stirring for 1h, then transferring to a refrigeration device in an ethanol atmosphere, cooling to-5 ℃, adding 3% by mass of HCl solution and 10% by mass of glutaraldehyde solution, and continuously stirring at 0 ℃ for 30min to form a homogeneous reaction solution A, wherein in the homogeneous reaction solution A, the mass fraction of PVA is 4.7%, the mass fraction of kappa-CG is 8.7%, the mass fraction of inorganic acid is 0.23%, and the mass fraction of glutaraldehyde is 0.81%; pouring the reaction solution into a silica gel mold with the size of phi (inner diameter) x d (height) =60 mm x 1mm, and reducing the temperature of the system to-20 ℃ within 15min, wherein the system is subjected to solvent water crystallization, PVA and kappa-CG undergo cross-linking reaction with glutaraldehyde under the action of starting HCl, after the reaction time is 20h, taking out the PVA and kappa-CG cross-linked network polymer which is obtained by melting ice crystals in an environment of 20 ℃ to leave three-dimensional continuous oversized pores, namely the first network polymer, and washing with deionized water for later use.
TOSi water was continuously stirred in a beaker under magnetic stirring for 1h to form a TOSi sol with a mass fraction of 35%. Adding AA, MAA, AMPS, TOSi sol, MBA and H 2O2, the PAO aqueous solution and deionized water into a three-port reactor under the condition of continuously introducing N 2, continuously stirring for 1H, transferring into a freezing device in an ethanol atmosphere, cooling to-5 ℃, adding Vc into the three-port reactor at the moment, and continuously stirring for 30min to obtain a mixture liquid E, wherein in the mixture liquid E, the mass fraction of AA is 4.21%, the mass fraction of MAA is 1.44%, the mass fraction of AMPS is 2.05%, the mass fraction of PAO is 7.45%, the mass fraction of TOSi is 4.12%, the mass fraction of MBA is 0.25%, the mass fraction of H 2O2 is 0.72%, and the mass fraction of Vc is 0.35%; simultaneously adding an HCl solution with a certain mass fraction of 4% and ANI into another three-port reactor under the condition of continuous stirring, stirring until the ANI is completely dissolved, transferring to a refrigeration device, cooling to-5 ℃, adding KPS into the ANI solution to obtain a solution F, wherein the mass fraction of HCl in the solution F is 3.7%, the mass fraction of ANI is 8.8%, the mass fraction of KPS is 1.7%, maintaining the temperature of-5 ℃ to mix the solution F with the mixture solution E, continuously stirring for 5min, then pumping into the first network polymer to replace water in a first polymer skeleton, reducing the system temperature to-25 ℃ within 10min, continuously reducing the reaction time to 20h within 30min, reducing the temperature of a reactant system to-70 ℃ for 40h, taking out, directly immersing into a saturated sodium chloride aqueous solution for salting out after the salting-out temperature is 0 ℃, pumping deionized water into a pore canal for unreacted substance and water washing out after the salting-out time is 90h, and obtaining the high-strength three-dimensional super-macroporous uranium adsorption hydrogel.
The pore distribution of the three-dimensional continuous oversized pore uranium adsorption hydrogel is 10-150 mu m, the average wet sample tensile strength is 3.6MPa, and the average compressive strength is 8.4MPa; the average adsorption capacity of uranyl ion aqueous solution with the initial concentration of 50mg/L after being adsorbed for 48 hours is 627.67mg/g under the adsorption condition of 25 ℃ and pH=6; the average conductivity was 1.98S/cm.
The EDS energy spectrum and the surface element analysis after uranium is adsorbed by the three-dimensional continuous oversized hole uranium adsorption hydrogel are shown in figure 4.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.
Claims (10)
1. The utility model provides a three-dimensional super macroporous uranium adsorption hydrogel in succession of high strength which characterized in that: the hydrogel comprises a first polymer network formed by low-temperature crystallization polymerization crosslinking of polyvinyl alcohol and water-soluble bio-based macromolecules, a second polymer network formed by random copolymerization crosslinking of polyamidoxime and hydrophilic vinyl monomers on the basis of the first network, and a third polymer network formed by self-assembled polyaniline on the surface of the second network, wherein nano silicon dioxide is uniformly distributed in a gel phase of the hydrogel; the hydrogel has a three-dimensional continuous open super macroporous structure, the pore size is 10-200 mu m, the tensile strength is 1-5 MPa, the compressive strength is 5-20 MPa, and the conductivity is 1S/m-5S/m;
wherein the water-soluble bio-based macromolecule is more than one of chitosan, chitosan quaternary ammonium salt, gelatin, agar and kappa-carrageenan with the deacetylation degree of 80% -95%.
2. A method for preparing the high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) Dissolving sodium acrylate and acrylonitrile in H 2 O, charging nitrogen, driving oxygen, adding H 2O2 and ascorbic acid at-5-0 ℃, uniformly stirring, cooling to-30-10 ℃ for reaction for 10-20H, and melting after the reaction is finished to obtain a high-viscosity linear random copolymer P (AANa-co-AN) aqueous solution; adding hydroxylamine hydrochloride and sodium carbonate into the P (AANa-co-AN) aqueous solution, reacting for 3-12 hours at 60-80 ℃, dialyzing in pure water after the reaction is finished, and concentrating to obtain a linear polyamidoxime aqueous solution with the mass fraction of 10% -20%;
(2) Mixing a polyvinyl alcohol aqueous solution with a water-soluble bio-based macromolecule solution, filling nitrogen, driving oxygen, stirring and mixing uniformly, adding an inorganic acid solution and a glutaraldehyde solution at 0-5 ℃, stirring and mixing uniformly to obtain a homogeneous reaction solution A, cooling to-30-10 ℃ within 10-30 min, reacting for 8-24 h, melting and washing to obtain a polyvinyl alcohol and water-soluble bio-based macromolecule crosslinked network polymer;
(3) Mixing tetraethoxysilane with H 2 O under continuous stirring to obtain sol B; mixing a hydrophilic vinyl monomer, the polyamidoxime aqueous solution, sol B, a cross-linking agent, a water-soluble oxidant C and H 2 O in a nitrogen atmosphere, adding a reducing agent D at a temperature of-5-0 ℃, and stirring and uniformly mixing to obtain a mixture solution E; dissolving aniline in an HCl solution under continuous stirring, and adding an oxidant C' at-5-0 ℃ to obtain a solution F; maintaining the temperature at-5-0 ℃, and adding the solution F into the mixture solution E under continuous stirring to obtain a mixture solution G; mixing the mixed solution G with the network polymer, cooling to-30 to-10 ℃ within 5 min-20 min, reacting for 10 to 24h, cooling to-80 to-50 ℃ within 20 min-60 min, reacting for 24 to 48h, immersing into a saturated salt solution for salting out after the reaction is finished, wherein the salting-out temperature is-10 to 0 ℃, the salting-out time is 48 to 96h, and washing with water after the salting-out is finished, so as to obtain the high-strength three-dimensional continuous super-macroporous uranium adsorption hydrogel.
3. The method for preparing the high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, as claimed in claim 2, is characterized by comprising the following steps: in the reaction system in the step (1), the mass fraction of sodium acrylate is 1-10%, the mass fraction of acrylonitrile is 2-10%, and the total mass fraction of sodium acrylate and acrylonitrile is 7-15%; the mass fraction of H 2O2 is 0.08% -0.4%, and the mass fraction of ascorbic acid is 0.05% -0.3%; the mass fraction of hydroxylamine hydrochloride is 3-20%, and the mass fraction of sodium carbonate is 2-20%.
4. The method for preparing the high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, as claimed in claim 2, is characterized by comprising the following steps: in the step (2), the water-soluble bio-based macromolecule is more than one of chitosan, chitosan quaternary ammonium salt, gelatin, agar and kappa-carrageenan with the deacetylation degree of 80% -95%;
the inorganic acid solution is one or more of hydrochloric acid, sulfuric acid and phosphoric acid solution.
5. The method for preparing the high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, as claimed in claim 4, is characterized by comprising the following steps: in the step (2), the water-soluble bio-based macromolecule is chitosan and/or gelatin.
6. A method for preparing a high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel according to claim 4 or claim 5, wherein the method comprises the following steps: in the step (2), the mass fraction of the polyvinyl alcohol aqueous solution is 8-15%; the mass fraction of the water-soluble bio-based macromolecule solution is 5-15%; the mass fraction of the inorganic acid solution is 1-10%; the mass fraction of the glutaraldehyde solution is 5-20%;
In the homogeneous reaction liquid A, the mass fraction of the polyvinyl alcohol is 1% -10%, the mass fraction of the water-soluble bio-based macromolecule is 7% -15%, the mass fraction of the inorganic acid is 0.05% -0.5%, and the mass fraction of the glutaraldehyde is 0.2% -1%.
7. The method for preparing the high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, as claimed in claim 2, is characterized by comprising the following steps: in the step (3), the hydrophilic vinyl monomer is one or more of acrylic acid, methacrylic acid, maleic acid, hydroxyethyl methacrylate, fumaric acid, vinylsulfonic acid, itaconic acid and 2-acrylamido-2-methylpropanesulfonic acid.
8. The method for preparing the high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, as claimed in claim 2, is characterized by comprising the following steps: in the step (3), the cross-linking agent is more than one of N-methylol acrylamide, N' -methylene bisacrylamide, ethylene glycol, glycerol, polyethylene glycol, polypropylene glycol and propylene glycol;
The water-soluble oxidant C is H 2O2 and/or potassium permanganate;
The reducing agent is ascorbic acid and/or oxalic acid;
the oxidant C' is more than one of ammonium persulfate, potassium persulfate and sodium persulfate;
the saturated salt solution is one or more of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate at 20 ℃.
9. A method for preparing a high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel according to claim 7 or 8, wherein: in the step (3), the mass fraction of the ethyl orthosilicate in the sol B is 10% -50%;
In the mixture liquid E, the mass fraction of vinyl monomers is 1% -10%, the mass fraction of sol B is 1% -5%, the mass fraction of crosslinking agents is 0.01% -2%, the mass fraction of water-soluble oxidizing agents C is 0.2% -5%, the mass fraction of polyamidoxime is 3% -10%, and the mass fraction of reducing agents is 0.1% -2%;
the mass fraction of the HCl solution is 2% -6%;
In the solution F, the mass fraction of HCl is 2% -10%, the mass fraction of ANI is 5% -15%, and the mass fraction of the oxidant C' is 1% -10%.
10. The method for preparing the high-strength three-dimensional continuous oversized hole uranium adsorption hydrogel, as claimed in claim 9, is characterized by comprising the following steps: the cross-linking agent is N, N' -methylene bisacrylamide and/or N-methylol acrylamide.
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