CN114643046A - Preparation method of amidoxime microgel adsorbent and application of amidoxime microgel adsorbent in rapid uranium extraction - Google Patents
Preparation method of amidoxime microgel adsorbent and application of amidoxime microgel adsorbent in rapid uranium extraction Download PDFInfo
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- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003463 adsorbent Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 12
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000000605 extraction Methods 0.000 title abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 20
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 claims abstract description 8
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000000502 dialysis Methods 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 11
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 239000000017 hydrogel Substances 0.000 abstract description 16
- 239000000178 monomer Substances 0.000 abstract description 15
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 230000008961 swelling Effects 0.000 abstract description 5
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000007112 amidation reaction Methods 0.000 abstract 1
- IONSZLINWCGRRI-UHFFFAOYSA-N n'-hydroxymethanimidamide Chemical group NC=NO IONSZLINWCGRRI-UHFFFAOYSA-N 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 uranyl ions Chemical class 0.000 description 4
- 230000003203 everyday effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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Abstract
The invention belongs to the technical field of adsorption separation functional materials, and relates to a preparation method of an amidoxime microgel adsorbent and application thereof in rapid uranium extraction. The method comprises the following steps: firstly, preparing microgel rich in carboxyl by using N' N-diethylacrylamide DEA as a skeleton monomer, then modifying diaminomaleonitrile by using amidation reaction, and further reacting nitrile group to form amidoxime group by using hydroxylamine hydrochloride. According to the invention, the DEA is adopted as the skeleton monomer to synthesize the microgel capable of swelling in the organic solvent, so that the hydrogel material can modify amidoxime groups in the organic solvent, a special amidoxime monomer does not need to be synthesized, and the preparation method of the material is greatly simplified; as the microgel material is adopted for adsorbing uranium, the swelling rate of the microgel material is far greater than that of common hydrogel, so that the adsorption rate is greatly improved.
Description
Technical Field
The invention belongs to the technical field of preparation of adsorption separation functional materials, and particularly relates to a preparation method of an amidoxime microgel adsorbent and application thereof in rapid uranium extraction.
Background
Nuclear energy is a mature energy source that can continuously provide electricity on a large scale with extremely high energy density and ultra-low greenhouse gas emissions. Because of the large-scale use of nuclear energy, accidents of nuclear leakage caused by accidental factors of the nuclear energy also sometimes occur. The radioactive elements not only pollute the marine environment, but also accumulate in marine organisms, and cause serious harm to human bodies after being eaten by human beings. Uranium is the major nuclear element and there is a need for an adsorbent that can rapidly treat leaked uranium in an emergency.
The polymer cross-linked network hydrogel draws wide attention in a plurality of application fields due to the universality of the composition, the convenience of preparation and adjustable physical properties. Hydrogels can swell in water and retain a large amount of water while maintaining their chemical structure. In recent years, reports of applying hydrogel materials to adsorption of metal ions have increased, but the problem that the rate of adsorption is slow when hydrogel materials are adsorbed is still urgently needed to be solved. The microgel is hydrogel with the size of 0.5-10 mu m, has the excellent characteristics of hydrogel, and has a swelling water absorption rate which is far greater than that of a common macroscopic hydrogel material because the swelling speed of the hydrogel is inversely proportional to the size of the hydrogel. The microgel material is applied to adsorbing uranium, so that the adsorption rate can be greatly improved.
Due to the special spatial configuration of the amidoxime group, the amidoxime group is matched with the size of U (VI), and the selective adsorption effect on U (VI) can be realized through coordination. On the basis of the method, amidoxime groups can be introduced into the material to endow the material with the selective U (VI) adsorption capacity. When the amidoxime group is modified on the material, an organic solvent is needed, but the common hydrogel material cannot swell in the organic solvent, belongs to a shrinking state, and greatly reduces the reaction efficiency. Therefore, there is a need to develop a hydrogel material that can swell in organic solvents.
In order to avoid the defects, a novel hydrogel material which can swell in an organic solvent to facilitate modification and has a faster adsorption rate is needed to be researched and applied to selective uranium extraction.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to overcome the problems that hydrogel is not easy to modify in an organic solvent and the adsorption rate is low, and provides a preparation method of amidoxime-based microgel. Amidoxime groups are taken as selective ligands, N' N-diethyl acrylamide is taken as a microgel skeleton monomer, and the amidoxime functionalized microgel adsorbent is prepared.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
(1) preparing carboxyl functionalized Microgel (Microgel-COOH);
adding a certain amount of N 'N-Diethylacrylamide (DEA), N' N-dimethylbisacrylamide (Bis), acrylic acid (AAc) and Sodium Dodecyl Sulfate (SDS) to a certain volume of deionized water, and aerating the mixed solution for a period of time t1Then, the mixture is stirred and heated to the temperature T in water bath1Adding a certain amount of potassium persulfate (KPS) to react for a period of time t2. Dialyzing the obtained solution by using a dialysis bag with the molecular weight of 300000, and finally freeze-drying to obtain the product carboxyl microgel.
(2) Preparing nitrile group functionalized Microgel (Microgel-CN);
adding a certain amount of Microgel-COOH, Diaminomaleonitrile (DAMN), 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide (NHS) synthesized in the step (1) into a certain volume of ethanol, and controlling the temperature to be T2The stirring reaction is carried out for a time t3. The resulting solution was dialyzed using a dialysis bag with a molecular weight of 300000 and finally freeze-dried to obtain Microgel-CN.
(3) Preparation of amidoxime functionalized Microgel adsorbent (Microgel-AO):
adding a certain amount of Microgel-CN synthesized in the step (2), sodium hydroxide and hydroxylamine hydrochloride into a mixed solution of ethanol and water, and heating to the temperature T3Stirring the reaction time t4. And dialyzing the reacted solution by using a 300000 dialysis bag, and finally freeze-drying to obtain the amidoxime microgel.
Preferably, in the step (1), the dosage ratio of DEA, Bis, AAc, SDS, deionized water and KPS is: 0.5-2.5 g: 0.01-0.08 g: 0.05-0.2 g: 0.005-0.02 g: 50-120 mL; 0.02-0.1g, reaction temperature T1At 65-90 deg.C for t110-60min, reaction time t2Is 2-8 h.
Preferably, in the step (2), the amount of Microgel-COOH, DAMN, EDC, NHS and ethanol synthesized in the step (1) is 0.5-2 g: 0.1-0.3 g: 0.2-0.53 g: 0.1-0.33 g: 80-150mL, reaction temperature T2At 4-40 deg.C for a reaction time t3Is 6-24 h.
Preferably, in the step (3), the amount ratio of the mixed solution of the Microgel-CN, the hydroxylamine hydrochloride, the NaOH and the ethanol water synthesized in the step (2) is 0.5-2 g: 0.5-10 g: 0.5-5 g: 80-150mL, wherein in the ethanol-water mixed solution, the volume ratio of ethanol to deionized water is 7: 3-9: 1. reaction temperature T3At 65-80 deg.C for t4Is 2-12 h.
The amidoxime microgel adsorbent prepared by the invention can be used for selective adsorption and separation of hexavalent uranium in a solution. The specific application method comprises the following steps: at 15-50 ℃, the material is placed in a solution with uranium concentration of 0.1-200mg/L and pH value of 4-9, and after 1-2880min, the adsorption is completed.
The invention has the beneficial effects that:
(1) the amidoxime group is selected as a selective functional unit of U (VI), the microgel with smaller size is taken as a substrate, and the amidoxime functional microgel based adsorbent is prepared, so that the rapid specific adsorption of U (VI) is realized.
(2) According to the invention, the microgel rich in amidoxime groups is obtained through free radical precipitation polymerization and then further modified, and as the gel swelling speed is inversely proportional to the particle size, the microgel adsorbent with smaller particle size greatly improves the adsorption rate; because the microgel skeleton monomer is DEA, the synthesized hydrogel can swell in partial organic solvent, thereby providing convenience for further modifying amidoxime groups of the material, avoiding synthesizing more complex monomers and simplifying the material synthesis steps.
Drawings
FIG. 1 is SEM images (a, b) and DLS data chart (c) of Microgel-AO in example 1.
FIG. 2 is a FI-IR data plot of Microgel-CN and Microgel-AO from example 1.
FIG. 3 is a graph showing the effect of pH on the adsorption capacity of uranyl ions by amidoxime-based microgels prepared in example 1.
FIG. 4 shows adsorption kinetics of the Microgel-AO prepared in example 1 for uranyl ions and a model fitting curve thereof.
FIG. 5 is a graph of the effect of temperature on the adsorption equilibrium of the Microgel-AO on uranyl ions prepared in example 1 and a model fit curve thereof.
FIG. 6 shows the adsorption selectivity of Microgel-AO prepared in example 1.
Detailed Description
The identification performance evaluation in the embodiment of the invention is carried out according to the following method: this was done using static adsorption experiments. Testing the adsorption capacity of U (VI) by 5.0mg of Microgel-AO in the pH range of 4.0-9.0, measuring the content of U (VI) after adsorption by an inductively coupled plasma emission spectrometer, and determining the optimal adsorption pH according to the result; secondly, the influence of adsorption time on the Microgel-AO adsorption capacity is researched, and data are subjected to fitting calculation and analysis by using a Pseudo first-order model, a Pseudo second-order model and the like respectively; to study the maximum adsorption capacity of Microgel-AO, we performed adsorption equilibrium experiments at u (vi) concentrations ranging from 10 to 60ppm, fitted using Langmuir model and Freundlich model, and calculated the adsorption capacity from the results; and other substances with the same structure as uranyl radical ions are selected as competitive adsorbates to participate in the research of the selective adsorption performance of the Microgel-AO.
The invention is further illustrated by the following examples.
Example 1:
(1) preparing Microgel-COOH;
in a flask, 1.66g DEA, 0.0432g Bis, 0.101g AAc and 0.0115g SDS were added to 100mL deionized water and N was passed through2After 30min, the mixture was heated to 70 ℃ with magnetic stirring, 0.081g KPS was added, and the reaction was carried out for 5 h. And after the reaction is finished, dialyzing the reacted solution by using a 300000 dialysis bag, dialyzing in pure water for 7 days, changing water for three times every day to remove the incompletely reacted monomers, and finally freeze-drying to obtain the carboxyl microgel.
(2) Preparing Microgel-CN;
1.5g of Microgel-COOH obtained in step (1), 0.151g of DAMN, 0.268g of EDC and 0.163g of NHS were added to 100mL of ethanol. Heating to 40 ℃ by magnetic stirring, and reacting for 12 h. After the reaction is finished, dialyzing the reacted solution by using a 300000 dialysis bag, dialyzing in pure water for 7 days, changing water for removing incompletely reacted monomers three times a day, and finally freeze-drying to obtain the Microgel-CN.
(3) Preparation of Microgel-AO:
in a flask, 1.5g of Microgel-CN obtained in step (2), 5g of hydroxylamine hydrochloride and 2.2g of NaOH were added to a solution containing ethanol in a ratio of 9: 1, adjusting the pH to 8 by using a 1M sodium hydroxide solution, stirring and heating to 80 ℃, and reacting for 6 hours. And after the reaction is finished, dialyzing the solution by using a 300000 dialysis bag, dialyzing in pure water for 7 days, changing water for three times every day to remove the incompletely reacted monomers, and finally freezing and drying to obtain the amidoxime-based microgel.
As shown in fig. 1, the microgel synthesized in step (1) is substantially spherical and monodisperse; as can be seen from the DLS data chart in FIG. 1c, the particle size of the material is uniform in the aqueous solution environment, the particle size is between 735 and 765nm, and the monodispersion coefficient is smaller and is 0.065;
as shown in FIG. 2, in the FI-IR data chart, Microgel-AO disappeared the characteristic peak of nitrile group around 2230-.
In conclusion, the material has been synthesized successfully.
Example 2:
(1) preparing Microgel-COOH;
in a flask, 0.5g DEA, 0.01g Bis, 0.05g AAc and 0.005g SDS were added to 100mL deionized water and N was passed through2After 30min, heat to 70 ℃ with magnetic stirring, add 0.02g KPS, react for 2 h. And after the reaction is finished, dialyzing the reacted solution by using a 300000 dialysis bag, dialyzing in pure water for 7 days, changing water for three times every day to remove the incompletely reacted monomers, and finally freeze-drying to obtain the carboxyl microgel.
(2) Preparing Microgel-CN;
0.5g of Microgel-COOH obtained in step (1), 0.1g of DAMN, 0.2g of EDC and 0.1g of NHS were added to 100mL of ethanol. Heating to 4 ℃ by magnetic stirring, and reacting for 6 h. After the reaction is finished, dialyzing the reacted solution by using a 300000 dialysis bag, dialyzing in pure water for 7 days, changing water for removing incompletely reacted monomers three times a day, and finally freeze-drying to obtain the Microgel-CN.
(3) Preparation of Microgel-AO:
in a flask, 0.5g of Microgel-CN obtained in step (2), 0.5g of hydroxylamine hydrochloride and 0.5g of NaOH were added to a solution containing ethanol in a ratio of 8: 2, the pH was adjusted to 8 using 1M sodium hydroxide solution, and the mixture was stirred and heated to 65 ℃ to react for 2 hours. And after the reaction is finished, dialyzing the reacted solution by using a 300000 dialysis bag, dialyzing in pure water for 7 days, changing water for removing the incompletely reacted monomers three times a day, and finally freeze-drying to obtain the amidoxime-based microgel.
Example 3:
(1) preparing Microgel-COOH;
in a flask, 2.5g DEA, 0.08g Bis, 0.2g AAc and 0.02g SDS were added to 100mL deionized water and N was passed through2After 30min, heat to 70 ℃ with magnetic stirring, add 0.1g KPS, react for 12 h. After the reaction is finished, dialyzing the reacted solution by using a 300000 dialysis bag for 7 days in pure water, replacing water for removing incompletely reacted monomers three times a day, and finally freeze-drying to obtain the Microgel-COOH.
(2) Preparing Microgel-CN;
2g of Microgel-COOH obtained in step (1), 0.3g of DAMN, 0.53g of EDC and 0.33g of NHS were added to 100mL of ethanol. Heating to 40 ℃ by magnetic stirring, and reacting for 24 h. After the reaction is finished, dialyzing the reacted solution by using a 300000 dialysis bag, dialyzing in pure water for 7 days, changing water for removing incompletely reacted monomers three times a day, and finally freeze-drying to obtain the Microgel-CN.
(3) Preparation of Microgel-AO:
in a flask, 2g of the nitrile-based microgel obtained in step (2), 10g of hydroxylamine hydrochloride and 5g of NaOH were added to a solution containing ethanol in a water ratio of 8: 2, the pH was adjusted to 8 using a 1M sodium hydroxide solution, and the mixture was stirred and heated to 90 degrees, followed by reaction for 2 hours. After the reaction, the reacted solution was dialyzed using a 300000 dialysis bag for 7 days in pure water, water was changed three times a day to remove the incompletely reacted monomers, and finally freeze-dried to obtain Microgel-AO.
And (3) performance testing:
the pH value of the environment has great influence on the adsorption behavior of metal ions; the effect of Microgel-AO on the adsorption capacity of U (VI) in the pH range of 4.0 to 9.0 was therefore investigated. As shown in FIG. 3, the adsorption capacity of the Microgel-AO showed a gradually increasing trend with increasing pH at pH values of not higher than 6.0, and decreased with increasing pH values after pH values of higher than 6.0.
The adsorption kinetics of Microgel-AO at different concentrations U (VI) are shown in FIG. 4. As can be seen from the figure, the adsorption capacity of the Microgel-AO rapidly increased within the first 5min, the maximum adsorption capacity was reached within 10min, and the data were subjected to fitting calculation and analysis using a Pseudo first-order model and a Pseudo second-order model, respectively.
To investigate the maximum adsorption capacity of Microgel-AO, we have a concentration of 10-60 mg.L in U (VI)-1Adsorption equilibrium tests were performed over the range, adsorption data were fitted using Langmuir and Freundlich models, and the effect of temperature on adsorption capacity was explored. As shown in fig. 5, the adsorption capacity increases with increasing temperature over the test temperature range.
The combination of interfering ions and amidoxime groups has great influence on the adsorption capacity of amidoxime microgel for adsorbing U (VI), and VO is selected3-，Co2+，Ni+，Zn2+，Pb2+，Ca2+，Mg2+，K+And Na+As competitive ions of U (VI), the adsorbent in VO was studied3-，Co2+，Ni+，Zn2+，Pb2+，Ca2+，Mg2+，K+，Na+And adsorption behavior in the mixed solution of U (VI). As shown in FIG. 6, in the presence of numerous interfering ions, the Microgel-AO pair U (VI) still has the highest adsorption capacity, much larger than VO3-，Co2+，Ni+，Cu2+，Zn2+，Pb2+And the adsorption capacity corresponding to metal ions with low concentration is equal.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the various embodiments thereof, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (9)
1. The preparation method of the amidoxime microgel adsorbent is characterized by comprising the following steps:
(1) preparing carboxyl functionalized Microgel Microgel-COOH;
adding a certain amount of N 'N-diethylacrylamide DEA, N' N-dimethylbisacrylamide Bis, acrylic acid AAc and sodium dodecyl sulfate SDS into a certain volume of deionized water, and aerating the mixed solution for a period of time t1Then, the mixture is stirred and heated to the temperature T in water bath1Adding a certain amount of potassium persulfate KPS, and reacting for a period of time t2Dialyzing the obtained solution, and finally freeze-drying to obtain a product carboxyl microgel;
(2) preparing nitrile group functionalized Microgel-CN;
adding a certain amount of Microgel-COOH, diaminomaleonitrile DAMN, 1-ethyl- (3-dimethylaminopropyl) carbodiimide EDC and N-hydroxysuccinimide NHS synthesized in the step (1) into a certain volume of ethanol, and controlling the temperature to be T2The stirring reaction is carried out for a time t3Dialyzing the obtained solution, and finally freeze-drying to obtain Microgel-CN;
(3) preparation of amidoxime functionalized Microgel adsorbent (Microgel-AO):
adding a certain amount of Microgel-CN synthesized in the step (2), sodium hydroxide and hydroxylamine hydrochloride into a mixed solution of ethanol and water, and heating to the temperature T3Stirring the reaction time t4(ii) a Dialyzing the reacted solution, and finally freezing and drying to obtain the amidoxime-based microgel.
2. The method according to claim 1, wherein in the step (1), the DEA, Bis, AAc, SDS, deionized water and KPS are used in a ratio of: 0.5-2.5 g: 0.01-0.08 g: 0.05-0.2 g: 0.005-0.02 g: 50-120 mL; 0.02-0.1 g.
3. The method according to claim 1, wherein in the step (1), the reaction temperature T is set to1At 65-90 deg.C for t110-60min, reaction time t2Is 2-8 h.
4. The method according to claim 1, wherein in the step (2), the ratio of the amount of Microgel-COOH, DAMN, EDC, NHS and ethanol is 0.5 to 2 g: 0.1-0.3 g: 0.2-0.53 g: 0.1-0.33 g: 80-150 mL.
5. The method according to claim 1, wherein in the step (2), the reaction temperature T is set to2At 4-40 deg.C for a reaction time t3Is 6-24 h.
6. The production method according to claim 1, wherein in the step (3), the mixed solution of Microgel-CN, hydroxylamine hydrochloride, NaOH and ethanol water is used in a ratio of 0.5 to 2 g: 0.5-10 g: 0.5-5 g: 80-150mL, wherein in the ethanol-water mixed solution, the volume ratio of ethanol to deionized water is 7: 3-9: 1.
7. the method according to claim 1, wherein in the step (3), the reaction temperature T is set to3At 65-80 deg.C for t4Is 2-12 h.
8. The method according to claim 1, wherein in each of the steps (1) to (3), dialysis is carried out using a dialysis bag having a molecular weight of 300000.
9. Use of an amidoxime microgel adsorbent prepared according to any one of claims 1 to 8 for selective adsorption and separation of hexavalent uranium in solution.
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