CN118236990B - Polyion liquid gel adsorption material and method for adsorbing and separating heavy metals by using same - Google Patents
Polyion liquid gel adsorption material and method for adsorbing and separating heavy metals by using same Download PDFInfo
- Publication number
- CN118236990B CN118236990B CN202410665719.0A CN202410665719A CN118236990B CN 118236990 B CN118236990 B CN 118236990B CN 202410665719 A CN202410665719 A CN 202410665719A CN 118236990 B CN118236990 B CN 118236990B
- Authority
- CN
- China
- Prior art keywords
- liquid gel
- adsorption material
- gel adsorption
- polyion liquid
- polyion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 104
- 239000007788 liquid Substances 0.000 title claims abstract description 101
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 93
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 239000000499 gel Substances 0.000 claims description 110
- 239000000243 solution Substances 0.000 claims description 49
- 229910052793 cadmium Inorganic materials 0.000 claims description 29
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 29
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 29
- 229910052753 mercury Inorganic materials 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 23
- 229910052748 manganese Inorganic materials 0.000 claims description 23
- 239000011572 manganese Substances 0.000 claims description 23
- -1 oxygen heterocyclic diol Chemical class 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 15
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002460 imidazoles Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000011358 absorbing material Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000010793 electronic waste Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- MOKACWHZOSFWEI-UHFFFAOYSA-N oxetane-2,2-diol Chemical compound OC1(O)CCO1 MOKACWHZOSFWEI-UHFFFAOYSA-N 0.000 claims 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 4
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000012634 fragment Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical group CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J20/28014—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 form
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a polyion liquid gel adsorption material and a method for adsorbing and separating heavy metals, which relate to the technical field of heavy metal adsorption and separation, and are characterized in that a polyion liquid gel adsorption material is prepared by gradient cross-linking reaction, firstly, an inner core of the polyion liquid gel adsorption material is prepared, oxygen heterocycle is introduced to the greatest extent through a sulfur-containing dendritic structure, the inner core presents a dendritic extension space structure, the special space structure determines the chemical activity of a terminal functional group, the regulation and control of a material surface activation site are realized, then imidazole ring structure segments are further cross-linked, the inner core has a special space reticular structure, the displacement of a pi-pi conjugate plane between imidazole ring structures can be realized, and the change of pi-pi conjugate stacking density is realized. The polyion liquid gel adsorption material is used for adsorption separation of heavy metals in wastewater, and high-selectivity adsorption of heavy metal ions is realized through mutual cooperation of imidazole ring structural segments and oxygen atom lone pair electrons in inner core heterocycles.
Description
Technical Field
The invention relates to the technical field of heavy metal adsorption and separation, in particular to a polyion liquid gel adsorption material and a method for adsorbing and separating heavy metals by using the same.
Background
The harm of heavy metal pollution in wastewater to the environment and human health is more and more concerned, and a chemical extraction method is generally adopted to remove heavy metal pollutants, so that the process is easy to operate, and the method is widely applied to the field of remediation of polluted sites, and after chemical extraction, an ion exchange process is adopted to recover heavy metals, so that the recycling-regeneration of the heavy metals is realized. The ion exchange resin has the capability of absorbing heavy metal ions, but the low specific surface area of the ion exchange resin makes the adsorption capability limited, and meanwhile, the selectivity of the ion exchange resin to metal ions is relatively poor, so that the application field of the ion exchange resin is limited. In contrast, the polyionic liquid gel material has the advantages of porous network structure, high capacity and easy mass transfer, and meanwhile, functional monomers can be introduced into the gel adsorbent to enrich the performance of the gel adsorbent.
In recent years, researches on polyion liquid gel adsorption materials mainly focus on imidazole-long carbon crosslinked molecular structures, and although the imidazole-long carbon crosslinked gel adsorption materials expand the application of the gel adsorption materials in the fields of wastewater treatment and the like, certain limitations still exist: (1) The selectivity is poor, complex metal solution can not be satisfied, and in the stage of metal ion adsorption, other adsorbents are required to be used in combination for carrying out the operation of a multistage process; (2) The recycling rate of the material is low, and continuous production of enterprises cannot be realized.
In view of the foregoing, there is a need for an improved polyionic liquid gel adsorption material and a method for adsorbing and separating heavy metals by the same.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyion liquid gel adsorption material and a method for adsorbing and separating heavy metals by the polyion liquid gel adsorption material, wherein the polyion liquid gel adsorption material is prepared by a gradient crosslinking reaction, firstly, an inner core of the polyion liquid gel adsorption material is prepared, oxygen heterocycle is introduced to the greatest extent through a sulfur-containing dendritic structure, the inner core presents a dendritic extending space structure, the special space structure determines the chemical activity of a terminal functional group, the regulation and control of a material surface activation site are realized, and the subsequent further crosslinking of imidazole ring structure fragments is facilitated. The special space reticular structure of the inner core of the polyion liquid gel adsorption material can realize the displacement of pi-pi conjugate planes among imidazole ring structures, realize the change of pi-pi conjugate stacking density, and realize the high-selectivity adsorption of heavy metal ions through the mutual coordination of imidazole ring structure fragments and oxygen atom lone pair electrons in the inner core heterocycle.
In order to achieve the above purpose, the invention provides a polyion liquid gel adsorption material, which has the following structural formula:
；
wherein x is more than 0 and less than or equal to 50, y is more than 0 and less than or equal to 100; Is of the structure of ；Is of the structure ofR is one of hydrogen, methyl and ethyl; representing the site of attachment between functional groups.
As a further improvement of the invention, the preparation method of the polyionic liquid gel adsorption material comprises the following steps:
s1, mixing oxygen heterocyclic dihydric alcohol and 3-bromopropene according to a molar ratio of 1: (3-5) dissolving in ethanol, and adding sodium hydroxide and TBAB, wherein the molar ratio of the oxygen heterocyclic diol to the TBAB is 100: (1-10); heating to 70-100 ℃ and reacting for 4-6 hours; after the reaction is completed, the temperature of the system is reduced to room temperature, methylene dichloride is added to extract a product, an organic phase is dried by anhydrous magnesium sulfate, and an oxygen heterocyclic olefin monomer is obtained by evaporation;
S2, mixing the oxygen heterocyclic olefin monomer obtained in the step S1 with a cross-linking agent according to a molar ratio of (4-9): 1 adding ethanol, ultrasonically dissolving, pouring the mixed solution into a polyethylene bag, degassing with N 2, and sealing;
S3, carrying out electron beam radiation on the polyethylene bag filled with the mixed solution in the step S2 for 5-8 min by using an electron accelerator, so that vinyl groups generate active free radicals for polymerization and cross-linking reaction, and inducing reactant molecular chains to polymerize and cross-link to form a polyion liquid gel inner core;
S4, mixing the polyion liquid gel inner core obtained in the step S3 with imidazole salt according to a molar ratio of 1: (5-20) adding the gel material into a solvent, performing ultrasonic dissolution at 25-85 ℃, pouring the suspension into a silica gel mold, and radiating for 5-8 min at room temperature to obtain the gel material;
s5, drying the gel material obtained in the step S4 to constant weight, soaking in deionized water to remove sol part, and drying again to constant weight to obtain the polyion liquid gel adsorption material.
As a further improvement of the present invention, in step S1, the oxygen heterocyclic diol has the structural formulaThe structural formula of the oxygen heterocyclic olefin monomer is。
As a further improvement of the present invention, in step S2, the crosslinking agent is trimethylolpropane trimethacrylate.
As a further improvement of the invention, 60 Co gamma-rays are adopted for radiation in the step S3 and the step S4, the irradiation voltage is 5-20 MeV, the irradiation dose is 10-300 kGy, and the dose rate is 1-50 kGy/pass.
As a further improvement of the present invention, in step S4, the solvent is one of water, ethanol and DMSO; the structural formula of the imidazole salt isR is one of hydrogen, methyl and ethyl; the concentration of the imidazole salt is 5-80 wt%.
As a further improvement of the invention, in the step S5, the pore diameter of the polyion liquid gel adsorption material is 50-1500 mu m, and the gel fraction is not lower than 50%.
The invention also provides a method for absorbing and separating heavy metals by the polyion liquid gel absorbing material, which adopts the polyion liquid gel absorbing material to absorb and comprises the following steps: adding the polyion liquid gel adsorption material into a solution containing lead, mercury, cadmium and manganese, regulating the pH value of the solution to be 1-7, and adsorbing the lead, mercury, cadmium and manganese in the solution.
The solution containing lead, mercury, cadmium and manganese comprises an ore solution, a catalyst waste liquid, a metallurgical waste liquid and an electronic waste leaching solution, wherein the lead, mercury, cadmium and manganese respectively exist in the form of PbCl 2、HgCl2、CdCl2、MnCl2.
The beneficial effects of the invention are as follows:
(1) The polyion liquid gel adsorption material is prepared through a gradient crosslinking reaction, wherein the gradient crosslinking reaction has the advantages of controllable molecular weight of the material and enrichment of functional group types, firstly, the inner core of the polyion liquid gel adsorption material is prepared, oxygen heterocycle is introduced to the greatest extent through a sulfur-containing dendritic structure, the inner core presents a dendritic extending space structure, the chemical activity of a terminal functional group is determined by the special space structure, the regulation and control of a material surface activation site are realized, and the subsequent further crosslinking of imidazole ring structure fragments is facilitated.
(2) The special space reticular structure of the inner core of the polyion liquid gel adsorption material can realize the displacement of pi-pi conjugate planes among imidazole ring structures, realize the change of pi-pi conjugate stacking density, and realize the high-selectivity adsorption of heavy metal ions through the mutual coordination of imidazole ring structure fragments and oxygen atom lone pair electrons in the inner core heterocycle. In addition, the polyion liquid gel adsorbent has good corrosion resistance, and the applicable conditions of the material are expanded, for example, the polyion liquid gel adsorbent can be used in a high-acid environment.
(3) The method for adsorbing and separating heavy metals by the polyion liquid gel adsorption material provided by the invention is simple to operate, the adsorption rate of lead, mercury, cadmium and manganese in the solution is up to more than 98%, the polyion liquid gel adsorption material can be recycled after regeneration, and the adsorption rate of lead, mercury, cadmium and manganese can be maintained to be more than 95% after 10 times of recycling, so that the efficient selective adsorption of lead, mercury, cadmium and manganese in the solution can be realized.
Drawings
FIG. 1 is a synthetic route diagram of an oxacyclic olefin monomer in a polyionic liquid gel adsorption material provided by the invention.
Fig. 2 is a synthetic route diagram of a polyionic liquid gel core in the polyionic liquid gel adsorption material provided by the invention.
Fig. 3 is a synthetic route diagram of the polyionic liquid gel adsorption material provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a polyion liquid gel adsorption material, which has the following structural formula:
；
wherein x is more than 0 and less than or equal to 50, y is more than 0 and less than or equal to 100; Is of the structure of ；Is of the structure ofR is one of hydrogen, methyl and ethyl; representing the site of attachment between functional groups.
The polyion liquid gel adsorption material is obtained by polymerizing and crosslinking an inner core and an imidazole type ionic liquid monomer through radiation, wherein C=C bonds are induced to generate free radicals, and polymerization and crosslinking between molecular chains of the ionic liquid monomer and a crosslinking agent are further initiated, so that the polyion liquid gel adsorption material is formed, and the preparation method specifically comprises the following steps:
S1, mixing oxygen heterocyclic dihydric alcohol (A) and 3-bromopropene according to a molar ratio of 1: (3-5) dissolving in ethanol, and adding sodium hydroxide and TBAB (tetrabutylammonium bromide), wherein the molar ratio of the oxygen heterocyclic dihydric alcohol to the TBAB is 100: (1-10); heating to 70-100 ℃ and reacting for 4-6 hours; after the completion of the reaction, the temperature of the system was lowered to room temperature, the resultant was extracted with methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate and evaporated to give an oxetane monomer (B).
Specifically, the structural formula of the oxygen heterocyclic diol is; The structural formula of the oxygen heterocyclic olefin monomer isThe synthetic route is shown in FIG. 1.
S2, mixing the oxygen heterocyclic olefin monomer (B) obtained in the step S1 with a cross-linking agent (C) according to a molar ratio of (4-9): 1 into ethanol, after ultrasonic dissolution, pouring the mixed solution into a polyethylene bag, and degassing with N 2 and sealing.
Specifically, the cross-linking agent is trimethylolpropane trimercapto propionate, and the structural formula is。
S3, carrying out electron beam radiation on the polyethylene bag filled with the mixed solution in the step S2 for 5-8 min by using an electron accelerator, so that the vinyl generates active free radicals for polymerization and cross-linking reaction, and the molecular chains of the reactants are induced to polymerize and cross-link to form the polyion liquid gel inner core.
Specifically, 60 Co gamma-rays are adopted for radiation, the irradiation voltage is 5-20 MeV, the irradiation dose is 10-300 kGy, and the dose rate is 1-50 kGy/pass. The structural formula of the polyion liquid gel inner core isThe synthetic route is shown in figure 2, wherein 0< x.ltoreq.50,Is of the structure of；Represents the attachment site between functional groups, hv represents the radiation.
S4, mixing the polyion liquid gel inner core obtained in the step S3 with imidazole salt according to a molar ratio of 1: (5-20) adding the gel material into a solvent, performing ultrasonic dissolution at 25-85 ℃, pouring the suspension into a silica gel mold, and radiating for 5-8 min at room temperature to obtain the gel material.
Specifically, the solvent is one of water, ethanol and DMSO (dimethyl sulfoxide); the structural formula of the imidazole salt isR is one of hydrogen, methyl and ethyl, and the concentration of imidazole salt is 5-80 wt%; the irradiation adopts 60 Co gamma-rays, the irradiation voltage is 5-20 MeV, the irradiation dose is 10-300 kGy, the dose rate is 1-50 kGy/pass, the synthetic route is shown in figure 3, and the obtained gel material has the structural formula of; Wherein x is more than 0 and less than or equal to 50, y is more than 0 and less than or equal to 100; Is of the structure of ；Is of the structure of; R is one of hydrogen, methyl and ethyl,Represents the attachment site between functional groups, hv represents the radiation.
S5, drying the gel material obtained in the step S4 to constant weight, soaking in deionized water to remove a sol part, and drying again to constant weight to obtain the polyion liquid gel adsorption material.
Specifically, the aperture of the polyion liquid gel adsorption material is 50-1500 mu m, and the gel fraction is not lower than 50%.
The invention also provides a method for absorbing and separating heavy metals by the polyion liquid gel absorbing material, which adopts the polyion liquid gel absorbing material to absorb and comprises the following steps: adding the polyion liquid gel adsorption material into a solution containing lead, mercury, cadmium and manganese, regulating the pH value of the solution to be 1-7, and carrying out high-efficiency selective adsorption on the lead, mercury, cadmium and manganese in the solution.
The solution containing lead, mercury, cadmium and manganese comprises ore solution, catalyst waste liquid, metallurgical waste liquid and electronic waste leaching solution, wherein the lead, mercury, cadmium and manganese respectively exist in the form of PbCl 2、HgCl2、CdCl2、MnCl2.
The polyion liquid gel adsorption material and the method for adsorbing and separating heavy metals provided by the invention are described below with reference to specific examples.
Example 1
Example 1 provides a polyionic liquid gel adsorption material, as shown in fig. 1 to 3, and the preparation method comprises the following steps:
S1, mixing 10g of oxygen heterocyclic dihydric alcohol (A) and 3-bromopropene in a molar ratio of 1:3 putting the mixture into a three-neck round-bottom flask, dissolving the reactant into 500mL of absolute ethanol solution, and adding excessive sodium hydroxide and TBAB, wherein the molar ratio of the oxygen heterocyclic diol to the TBAB is 100:5. heated to 70 ℃ and reacted for 4 hours. After the completion of the above reaction, the temperature of the system was lowered to room temperature, the resultant was extracted with an excess of methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate, and evaporated to give the product, the oxa-cyclic olefin monomer (B), in 76% yield.
S2, mixing an oxygen heterocyclic olefin monomer (B) and a crosslinking agent trimethylolpropane trimethacrylic acid ester (C) in a molar ratio of 4:1 into ethanol, after ultrasonic dissolution, pouring the mixed solution into a polyethylene bag, and degassing with N 2 and sealing.
S3, using an electron accelerator to radiate electron beams for 5min, so that vinyl groups generate active free radicals for polymerization crosslinking reaction, and inducing reactant molecular chains to polymerize and crosslink to form the polyion liquid gel inner core. Irradiation conditions: the irradiation voltage is 10MeV, the irradiation dose is 80kGy, and the dose rate is 10kGy/pass.
S4, mixing the polyion liquid gel inner core with imidazole salt according to a molar ratio of 1:10 in DMSO, after ultrasonic dissolution at 35 ℃, pouring the suspension into a silica gel mold (1.8X4 cm), and radiating for 5min at room temperature to obtain a gel material.
S5, drying the obtained gel material to constant weight at 50 ℃, then soaking in deionized water to remove sol part, and drying again to constant weight at 50 ℃ to obtain the polyion liquid gel adsorption material with the gel fraction of 50%.
Example 2
Embodiment 2 provides a method for absorbing and separating heavy metals by using a polyion liquid gel absorbing material, which is prepared by adopting the polyion liquid gel absorbing material prepared by embodiment 1, and comprises the following specific operation steps:
10g of the polyion liquid gel adsorption material of example 1 was weighed, put into 100mL of a solution containing PbCl 2、HgCl2、CdCl2、MnCl2 at room temperature, the pH value of the solution was adjusted to 1, and after adsorption for 24 hours in a water bath oscillator at 25 ℃, clear liquid was taken, and the concentration of lead, mercury, cadmium and manganese in the solution was detected by ICP-OES (inductively coupled plasma atomic emission spectrometer), so that the adsorption rate of the polyion liquid gel adsorption material was calculated, and the results are shown in Table 1.
Examples 3 to 8
Examples 3-8 respectively provide a method for adsorbing and separating heavy metals by using a polyionic liquid gel adsorption material, compared with example 2, the difference is only that the pH value of the solution is different, other experimental parameters and conditions are basically the same as those of example 2, and the detailed description is omitted herein, and the results are shown in Table 1.
As shown in Table 1, the polyion liquid gel adsorption material prepared by the invention can efficiently adsorb lead, mercury, cadmium and manganese, the adsorption rate is more than 98% in a wider pH range, and the material maintains good adsorption capacity under the condition of high acidity (pH=1-2), so that the complete adsorption of manganese in solution can be realized.
Example 9
Embodiment 9 provides a method for adsorbing and separating heavy metals by using a polyion liquid gel adsorption material, which is different from embodiment 2 only in that the solution containing PbCl 2、HgCl2、CdCl2、MnCl2 is an electronic waste leaching solution, the pH value of the solution is adjusted to be 2, other experimental parameters and conditions are basically the same as those of embodiment 2, and the detailed description is omitted herein, and the results are shown in Table 2.
As can be seen from Table 2, the polyion liquid gel adsorption material prepared by the invention can efficiently adsorb lead, mercury, cadmium and manganese in the electronic waste leaching solution, and can realize the complete adsorption separation of mercury, cadmium and manganese.
Example 10
Example 10 provides a kinetic adsorption experiment of a polyionic liquid gel adsorption material, which comprises the following specific operation steps:
Preparing a PbCl 2 solution, a HgCl 2 solution, a CdCl 2 solution and a MnCl 2 solution with the concentration of 100ppm respectively, taking 10mL of the solutions respectively, adding 10mg of the polyion liquid gel adsorption material prepared in example 1 respectively, reacting for 60min, taking out the adsorption material respectively at the reaction time of 1min, 5min, 10min, 20min, 30min and 60min, and detecting the concentration of lead, mercury, cadmium and manganese in the solution by ICP-OES so as to calculate the adsorption rate of the polyion liquid gel adsorption material.
The results show that the polyionic liquid gel adsorption material prepared in the example 1 has equilibrium in 10min on the dynamic adsorption of lead, mercury, cadmium and manganese.
Examples 11 to 13
Examples 11 to 13 respectively provide a method for adsorbing and separating heavy metals by using the polyion liquid gel adsorption material, wherein the polyion liquid gel adsorption material prepared in example 1 is used for adsorbing and separating lead, mercury, cadmium and manganese from a plurality of coexisting ion solutions, and the specific operation steps are as follows:
Preparing a series of blend solutions containing lead, mercury, cadmium, manganese, iron, zinc and tin in different concentration ratios, respectively adding 10mg of polyion liquid gel adsorption material into 10mL of the blend solutions, adsorbing for 24 hours, taking clear liquid, detecting the concentration of each metal ion in the solution by ICP-OES so as to calculate the adsorption rate of the gel material, and the result is shown in Table 3.
As can be seen from Table 3, the polyionic liquid gel adsorption material has excellent adsorption selectivity to lead, mercury, cadmium and manganese, but does not substantially adsorb the rest coexisting metal ions of iron, zinc and tin.
Example 14
Example 14 provides a polyionic liquid gel adsorption material regeneration-circulation experiment, which comprises the following specific operation steps:
10g of the polyion liquid gel adsorption material of example 1 is weighed, put into 100mL of water solution containing PbCl 2、HgCl2、CdCl2、MnCl2 at room temperature, the pH value of the solution is regulated to be 1, and after adsorption is carried out for 24 hours in a water bath oscillator at 25 ℃, clear liquid is taken, and the concentration of lead, mercury, cadmium and manganese in the solution is detected by ICP-OES, so that the adsorption rate of the polyion liquid gel adsorption material is calculated.
And then washing the polyion liquid gel adsorption material by using dilute hydrochloric acid for 3-5 times, soaking in deionized water for 1h, drying to constant weight at 50 ℃ to complete regeneration, putting into 100mL of aqueous solution containing PbCl 2、HgCl2、CdCl2、MnCl2 at room temperature, adjusting the pH value of the solution to be 1, carrying out adsorption test again, calculating the adsorption rate of the polyion liquid gel adsorption material, and completing one cycle of regeneration-circulation, wherein the cycle is marked as C-1. And so on, are designated as C-2, C-3..c-10, and the test results are shown in table 4.
As shown in table 4, the polyion liquid gel adsorption material has good regeneration-circulation effect, and the material keeps the original adsorption performance from regeneration-circulation to the 5 th time; the adsorption performance of the material is not obviously reduced after the material is recycled to the 10 th time, and the adsorption rates of lead, mercury, cadmium and manganese are 95%, 96%, 98% and 98% respectively.
Therefore, the polyion liquid gel adsorption material prepared by the invention realizes the quality change on the adsorption performance of the material through the arrangement of the inner core and outer core imidazole chain segment structures with specific structures and the interaction between functional groups, so that the obtained gel adsorption material has good regeneration-circulation effect when the excellent selective adsorption performance is kept.
In summary, according to the polyion liquid gel adsorption material and the method for adsorbing and separating heavy metals provided by the invention, the inner core of the polyion liquid gel adsorption material introduces oxygen heterocycle to the greatest extent through the sulfur-containing dendritic structure, the inner core presents a dendritic extending space structure, the special space structure determines the chemical activity of the terminal functional group, the regulation and control of the material surface activation site are realized, the subsequent further crosslinking of imidazole ring structure fragments is facilitated, the displacement of pi-pi conjugated planes among imidazole ring structures can be realized, the change of pi-pi conjugated stacking density is realized, and the high-selectivity adsorption of heavy metal ions is realized through the mutual cooperation of the imidazole ring structure fragments and oxygen atom lone pair electrons in the inner core heterocycle.
The method is simple to operate, has high adsorption rate on lead, mercury, cadmium and manganese, and efficiently realizes selective adsorption of lead, mercury, cadmium and manganese. Meanwhile, the polyion liquid gel adsorption material has a good regeneration-circulation effect, can be repeatedly used for many times, and is favorable for market popularization of the material.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The polyion liquid gel adsorption material is characterized by comprising the following structural formula:
；
wherein x is more than 0 and less than or equal to 50, y is more than 0 and less than or equal to 100; Is of the structure of ；Is of the structure ofR is one of hydrogen, methyl and ethyl; representing the site of attachment between functional groups.
2. The polyionic liquid gel adsorption material according to claim 1, wherein the preparation method of the polyionic liquid gel adsorption material comprises the following steps:
s1, mixing oxygen heterocyclic dihydric alcohol and 3-bromopropene according to a molar ratio of 1: (3-5) dissolving in ethanol, and adding sodium hydroxide and TBAB, wherein the molar ratio of the oxygen heterocyclic diol to the TBAB is 100: (1-10); heating to 70-100 ℃ and reacting for 4-6 hours; after the reaction is completed, the temperature of the system is reduced to room temperature, methylene dichloride is added to extract a product, an organic phase is dried by anhydrous magnesium sulfate, and an oxygen heterocyclic olefin monomer is obtained by evaporation;
S2, mixing the oxygen heterocyclic olefin monomer obtained in the step S1 with a cross-linking agent according to a molar ratio of (4-9): 1 adding ethanol, ultrasonically dissolving, pouring the mixed solution into a polyethylene bag, degassing with N 2, and sealing;
S3, carrying out electron beam radiation on the polyethylene bag filled with the mixed solution in the step S2 for 5-8 min by using an electron accelerator, so that vinyl groups generate active free radicals for polymerization and cross-linking reaction, and inducing reactant molecular chains to polymerize and cross-link to form a polyion liquid gel inner core;
S4, mixing the polyion liquid gel inner core obtained in the step S3 with imidazole salt according to a molar ratio of 1: (5-20) adding the gel material into a solvent, performing ultrasonic dissolution at 25-85 ℃, pouring the suspension into a silica gel mold, and radiating for 5-8 min at room temperature to obtain the gel material;
s5, drying the gel material obtained in the step S4 to constant weight, soaking in deionized water to remove sol part, and drying again to constant weight to obtain the polyion liquid gel adsorption material.
3. The polyionic liquid gel adsorption material according to claim 2, wherein in step S1, the structural formula of the oxetane diol isThe structural formula of the oxygen heterocyclic olefin monomer is。
4. The polyionic liquid gel adsorption material according to claim 2, wherein in step S2, the crosslinking agent is trimethylolpropane trimercapto propionate.
5. The polyionic liquid gel adsorption material according to claim 2, wherein in the step S3 and the step S4, 60 Co gamma-rays are adopted for radiation, the irradiation voltage is 5-20 mev, the irradiation dose is 10-300 kgy, and the dose rate is 1-50 kgy/pass.
6. The polyionic liquid gel adsorption material according to claim 2, wherein in step S4, the solvent is one of water, ethanol and DMSO; the structural formula of the imidazole salt isWherein R is one of hydrogen, methyl and ethyl; the concentration of the imidazole salt is 5-80 wt%.
7. The polyionic liquid gel adsorption material according to claim 2, wherein in step S5, the pore size of the polyionic liquid gel adsorption material is 50-1500 μm, and the gel fraction is not lower than 50%.
8. A method for absorbing and separating heavy metals by using the polyion liquid gel absorbing material as defined in any one of claims 1 to 7, comprising the following steps: adding the polyion liquid gel adsorption material into a solution containing lead, mercury, cadmium and manganese, regulating the pH value of the solution to be 1-7, and adsorbing the lead, mercury, cadmium and manganese in the solution.
9. The method for adsorbing and separating heavy metals by using the polyion liquid gel adsorption material according to claim 8, wherein the solution containing lead, mercury, cadmium and manganese comprises an ore solution, a catalyst waste liquid, a metallurgical waste liquid and an electronic waste leaching solution.
10. The method for adsorbing and separating heavy metals by using the polyionic liquid gel adsorption material according to claim 9, wherein the lead, mercury, cadmium and manganese in the solution containing lead, mercury, cadmium and manganese exist in the form of PbCl 2、HgCl2、CdCl2、MnCl2 respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410665719.0A CN118236990B (en) | 2024-05-27 | 2024-05-27 | Polyion liquid gel adsorption material and method for adsorbing and separating heavy metals by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410665719.0A CN118236990B (en) | 2024-05-27 | 2024-05-27 | Polyion liquid gel adsorption material and method for adsorbing and separating heavy metals by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118236990A CN118236990A (en) | 2024-06-25 |
| CN118236990B true CN118236990B (en) | 2024-08-06 |
Family
ID=91558940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410665719.0A Active CN118236990B (en) | 2024-05-27 | 2024-05-27 | Polyion liquid gel adsorption material and method for adsorbing and separating heavy metals by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118236990B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120169329A (en) * | 2025-05-22 | 2025-06-20 | 长春黄金研究院有限公司 | Polyion gel adsorption material and method for separating and purifying complex gold and copper by using polyion gel adsorption material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107805308A (en) * | 2016-09-09 | 2018-03-16 | 翁秋梅 | A kind of dynamic aggregation thing and its application with hybrid cross-linked network |
| CN109666121A (en) * | 2017-10-17 | 2019-04-23 | 翁秋梅 | A kind of hydridization dynamic crosslinking polymer and its application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10464811B2 (en) * | 2009-04-06 | 2019-11-05 | Nanyang Technological University | Method of forming a particulate porous metal oxide or metalloid oxide |
| JP7333239B2 (en) * | 2019-09-30 | 2023-08-24 | 日清紡ホールディングス株式会社 | Composite material |
-
2024
- 2024-05-27 CN CN202410665719.0A patent/CN118236990B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107805308A (en) * | 2016-09-09 | 2018-03-16 | 翁秋梅 | A kind of dynamic aggregation thing and its application with hybrid cross-linked network |
| CN109666121A (en) * | 2017-10-17 | 2019-04-23 | 翁秋梅 | A kind of hydridization dynamic crosslinking polymer and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118236990A (en) | 2024-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Seko et al. | Syntheses of amine-type adsorbents with emulsion graft polymerization of glycidyl methacrylate | |
| CN118236990B (en) | Polyion liquid gel adsorption material and method for adsorbing and separating heavy metals by using same | |
| CN110732306B (en) | Modified covalent organic framework material for adsorbing and separating rhenium and preparation method thereof | |
| Yue et al. | Seawater uranium sorbents: preparation from a mesoporous copolymer initiator by atom‐transfer radical polymerization | |
| CN103304820B (en) | Preparation method of efficient polyethyleneimine modified cellulose-based heavy metal adsorbent | |
| Choi et al. | Adsorption of Pb2+ and Pd2+ on polyethylene membrane with amino group modified by radiation‐induced graft copolymerization | |
| CN114870818B (en) | Method for adsorbing and separating gold, platinum and palladium by using polyion liquid gel adsorbent | |
| CN102294231B (en) | Molecularly imprinted fiber material and preparation method thereof | |
| Sekine et al. | Biodegradable metal adsorbent synthesized by graft polymerization onto nonwoven cotton fabric | |
| CN107002175B (en) | Adsorption and separation materials of rare earth elements | |
| CN106824124B (en) | A kind of nitrogen-containing porous polymer chelating resin and method for preparing and treating uranium-containing wastewater | |
| Yang et al. | Agile construction of porous organic frameworks pending carboxylic acids and imidazolium-based ionic liquids for the efficient fixation of CO2 to cyclic carbonates | |
| CN107537563B (en) | Quaternary phosphonium salt organic polymer catalyst and preparation method and application thereof | |
| CN114783641B (en) | Application method of polyionic liquid gel material in uranium-rhenium adsorption separation | |
| Karimi et al. | Imidazolyl‐Functionalized Ordered Mesoporous Polymer from Nanocasting as an Effective Support for Highly Dispersed Palladium Nanoparticles in the Heck Reaction | |
| JPS6258774B2 (en) | ||
| Ma et al. | A mild method of amine-type adsorbents syntheses with emulsion graft polymerization of glycidyl methacrylate on polyethylene non-woven fabric by pre-irradiation | |
| WO2001029104A1 (en) | Organic polymeric material, process for producing the same, and heavy-metal ion remover comprising the same | |
| Dafader et al. | Preparation and characterization of iminodiacetate group containing nonwoven polyethylene fabrics and its application in chromium adsorption | |
| Madrid et al. | Immobilization of an organophosphorus compound on polypropylene‐g‐poly (glycidyl methacrylate) polymer support and its application in scandium recovery | |
| CN104877059B (en) | A kind of cross-linked polystyrene-polypropylene hydroxamic acid interpenetrating network resin and its preparation method and application | |
| Valentino et al. | Phosphonium Salt/Al‐Porphyrin Copolymer as Bifunctional Heterogeneous Catalyst for CO2 Conversion to Cyclic Carbonates | |
| Wang et al. | Polymeric superabsorbing composite prepared using a glow‐discharge electrolysis plasma for the removal of divalent heavy metal ions from aqueous solutions and its swelling properties | |
| Liu et al. | Hg (II) removal with polyacrylamide grafted crosslinked poly (vinyl chloride) beads via surface‐initiated controlled/“living” radical polymerization | |
| Ma et al. | Crosslinking induced by irradiation raises selectivity of polymeric adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |