CN117160404A - Porous composite material and preparation method and application thereof - Google Patents
Porous composite material and preparation method and application thereof Download PDFInfo
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- CN117160404A CN117160404A CN202311431938.4A CN202311431938A CN117160404A CN 117160404 A CN117160404 A CN 117160404A CN 202311431938 A CN202311431938 A CN 202311431938A CN 117160404 A CN117160404 A CN 117160404A
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- 239000002131 composite material Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 87
- 150000003839 salts Chemical class 0.000 claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 74
- 239000002184 metal Substances 0.000 claims abstract description 74
- 239000003463 adsorbent Substances 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 141
- 235000002639 sodium chloride Nutrition 0.000 claims description 129
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 96
- 239000012071 phase Substances 0.000 claims description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 239000003795 chemical substances by application Substances 0.000 claims description 63
- 239000008346 aqueous phase Substances 0.000 claims description 58
- 239000002270 dispersing agent Substances 0.000 claims description 54
- 238000005185 salting out Methods 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- 239000011780 sodium chloride Substances 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 42
- 239000012266 salt solution Substances 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 37
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 32
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 29
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 29
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 19
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 19
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 18
- -1 polypropylene acrylate Polymers 0.000 claims description 17
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000003361 porogen Substances 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 4
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 3
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 abstract description 27
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 abstract description 27
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 229910001419 rubidium ion Inorganic materials 0.000 abstract description 10
- 229910052792 caesium Inorganic materials 0.000 abstract description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000005669 field effect Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 60
- 239000008367 deionised water Substances 0.000 description 46
- 229910021641 deionized water Inorganic materials 0.000 description 46
- 239000002245 particle Substances 0.000 description 32
- 238000005406 washing Methods 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 23
- 239000011324 bead Substances 0.000 description 16
- 239000012295 chemical reaction liquid Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 16
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 15
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 15
- 238000002791 soaking Methods 0.000 description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 14
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 8
- 238000011068 loading method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- FAWNVSNJFDIJRM-UHFFFAOYSA-N [Rb].[Cs] Chemical compound [Rb].[Cs] FAWNVSNJFDIJRM-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- NCCSSGKUIKYAJD-UHFFFAOYSA-N rubidium(1+) Chemical compound [Rb+] NCCSSGKUIKYAJD-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a porous composite material, a preparation method and application thereof. The porous composite comprises: a porous crosslinked polymer support and a metal salt supported within the porous crosslinked polymer support; the chemical formula of the metal salt is M x N y Fe(CN) 6 Wherein M represents a divalent metal ion, N represents a metal ion having a valence of trivalent or more, 0 < x < 2, and 0 < y < 1. Wherein, the porous cross-linked polymer carrier has pore canal 'finite field effect' which can wrap metal salt in the pore canal, can effectively prevent the metal salt from losing, greatly improve the load capacity and stability, and cooperate with the synergistic effect of different metal ions, so that the porous composite material has high selectivity and rubidium ion resistanceThe composite material has high adsorption capacity and good separation effect on rubidium/cesium, and can be used as a stable high-selectivity rubidium-extracting adsorbent.
Description
Technical Field
The invention relates to the technical field of adsorbents, in particular to a porous composite material and a preparation method and application thereof.
Background
Rubidium products have wide application in the fields of chemical catalysis, petroleum exploitation and medical science. The rubidium resource in nature exists mainly in the form of salt lake rubidium resource, and then mica ore. The traditional technology for extracting rubidium from salt lakes mainly comprises 5 kinds of technology: (1) solar evaporation, (2) co-precipitation, (3) electrochemical techniques, (4) solvent extraction and (5) ion exchange adsorption, all of which have their own limitations and have complex manufacturing processes that are costly.
Various salt lake rubidium-extracting adsorbents are reported, but the selective adsorption capacity of rubidium and other impurity ions (such as cesium) is still poor, and improvement is needed.
Disclosure of Invention
Based on the above, the porous composite material provided by the invention has high selectivity to rubidium, high adsorption capacity and high stability, and can be used as a rubidium extracting adsorbent with high selectivity, high adsorption capacity and high stability.
The technical proposal is as follows:
a porous composite comprising:
a porous crosslinked polymer support and a metal salt supported within the porous crosslinked polymer support;
the chemical formula of the metal salt is M x N y Fe(CN) 6 Wherein M represents a divalent metal ion, N represents a metal ion having a valence of trivalent or more, 0 < x < 2, and 0 < y < 1.
In one embodiment, 0 < x.ltoreq.1.
In one embodiment, the mass ratio of the porous crosslinked polymer carrier to the metal salt is (0.1-1.5): 1.
In one embodiment, the porous crosslinked polymer support has a porosity of 30.0% to 40.0%.
In one embodiment, the pores of the porous cross-linked polymer carrier comprise micropores and mesopores, and the pore diameter is 1nm to 8nm.
In one embodiment, the porous cross-linked polymer carrier is made of one or more selected from the group consisting of cross-linked polymethyl acrylate, cross-linked polypropylene acrylate, cross-linked polybutyl acrylate, cross-linked polymethyl methacrylate, cross-linked polypropylene methacrylate and cross-linked polybutyl methacrylate.
In one embodiment, M is selected from Zn 2+ 、Co 2+ 、Mg 2+ 、Cu 2+ And Ni 2+ One or more of the following.
In one embodiment, N is selected from Fe 3+ 、Zr 4+ 、Ti 4+ And Mn of 4+ One or more of the following.
The invention also provides a preparation method of the porous composite material, which comprises the following steps:
mixing a monomer, an initiator, a crosslinking agent and a pore-forming agent, and preparing a porous crosslinked polymer carrier through polymerization reaction;
mixing and reacting the M salt, the N salt and the potassium ferrocyanide solution with the porous cross-linked polymer carrier to prepare the porous composite material.
In one embodiment, the method for preparing a porous crosslinked polymer carrier by polymerization by mixing a monomer, an initiator, a crosslinking agent, and a porogen comprises the steps of:
mixing a dispersing agent and a salting-out agent in water to prepare an aqueous phase solution;
mixing a monomer, an initiator, a cross-linking agent and a pore-forming agent to prepare an oil phase solution;
mixing the aqueous phase solution and the oil phase solution, and preparing the porous cross-linked polymer carrier through polymerization reaction.
In one embodiment, the dispersant is selected from one or more of polyvinyl alcohol, polyethylene glycol, hydroxymethyl cellulose, hydroxyethyl cellulose, and methyl hydroxypropyl cellulose.
In one embodiment, the mass content of the dispersing agent in the aqueous phase solution is 0.5% -3.0%.
In one embodiment, the salting-out agent is selected from one or more of sodium chloride, potassium chloride, sodium nitrate and potassium nitrate.
In one embodiment, the mass content of the salting-out agent in the aqueous phase solution is 5% -15%.
In one embodiment, the monomer is selected from one or more of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate, and butyl methacrylate.
In one embodiment, the initiator is selected from one or more of benzoyl peroxide, methyl ethyl ketone peroxide, and azobisisobutyronitrile.
In one embodiment, the mass ratio of the monomer to the initiator is (10-15): 0.2-1.5.
In one embodiment, the cross-linking agent is selected from one or more of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate and allyl isocyanurate.
In one embodiment, the mass ratio of the monomer to the cross-linking agent is (1-3): 2-10.
In one embodiment, the porogen is selected from one or more of toluene, isooctane, aviation gasoline, and n-heptane.
In one embodiment, the mass ratio of the monomer to the porogen is (1-3): 0.5-3.
In one embodiment, the polymerization reaction is two-stage polymerization, wherein the temperature of the first-stage polymerization reaction is 50-70 ℃ for 2-6 h, and the temperature of the second-stage polymerization reaction is 80-95 ℃ for 4-10 h.
In one embodiment, the M-containing salt and the N-salt are each independently one or more of hydrochloride, nitrate, sulfate, acetate, and carbonate.
In one embodiment, the molar ratio of the molar total of the M salt to the N salt to the potassium ferrocyanide is (0.1-3): 1.
in one embodiment, the molar ratio of the M salt to the N salt is (1-25): 1-15.
In one embodiment, the step of mixing and reacting a solution of M salt, N salt, potassium ferrocyanide with the porous cross-linked polymer support to produce the porous composite material comprises:
dissolving M salt and N salt in water to prepare a metal salt solution;
Mixing the porous cross-linked polymer carrier with the metal salt solution to prepare a solid-liquid mixture;
and preparing the porous composite material by a deposition precipitation reaction between the solid-liquid mixture and the potassium ferrocyanide solution.
In one embodiment, the porous cross-linked polymer support is mixed with the metal salt solution for a period of time ranging from 10 hours to 20 hours.
In one embodiment, the temperature of the deposition and precipitation reaction is 20-50 ℃ and the time is 10-20 h.
The invention also provides an adsorbent comprising a porous composite as described above, or a porous composite made according to a method of making a porous composite as described above.
In one embodiment, the adsorbent is a salt lake rubidium-extracted adsorbent.
The invention has at least the following beneficial effects:
the porous composite material provided by the invention comprises: porous cross-linked polymer carrier and metal salt loaded in the porous cross-linked polymer carrier, wherein the chemical formula of the metal salt is M x N y Fe(CN) 6 Wherein M represents a divalent metal ion, N represents a metal ion having a valence of trivalent or more, 0 < x < 2, and 0 < y < 1. The porous cross-linked polymer carrier provides a huge internal specific surface area and pore volume for the metal salt, which is beneficial to improving the loading capacity of the metal salt, and the porous cross-linked polymer carrier has a pore canal 'finite field effect' which can wind the metal salt in the pore canal, can effectively prevent the metal salt from losing, greatly improve the stability of the metal salt and is matched with different metals The synergistic effect between ions makes the porous composite material have high selectivity and adsorption capacity to rubidium ions and good separation effect to rubidium/cesium.
Through tests, the porous composite material provided by the embodiment of the invention is used as a rubidium extracting adsorbent, has high rubidium adsorption selectivity, and can keep the rubidium ion adsorption capacity unchanged basically after being recycled for 20 times, and the porous composite material has excellent stability and can be used as a stable high-selectivity rubidium extracting adsorbent.
In addition, the preparation method of the porous composite material provided by the invention has the advantages of simple and easily-controlled process, simple and convenient operation, less equipment investment, less labor investment, environmental protection, high yield, pure product, easy recovery of the product, controllable quality and easy industrialization.
Drawings
FIG. 1 shows SEM results of the composites prepared in accordance with certain examples of the invention and comparative examples, wherein (a) in FIG. 1 shows the SEM results of the composites of example 3, (b) in FIG. 1 shows the SEM results of the composites of example 6, (c) in FIG. 1 shows the SEM results of the composites of comparative example 1, and (d) in FIG. 1 shows the SEM results of the composites of comparative example 5;
FIG. 2 is a flow chart of a method of preparing a porous composite material according to an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and figures. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, unless a specifically defined term is used, such as "consisting of … … only," etc., another component may be added.
The words "preferably," "more preferably," "more preferably," and the like, refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention. That is, in the present invention, "preferable", "more preferable", etc. are merely description of embodiments or examples that are more effective, but do not limit the scope of the present invention.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, "at least one" means one or more, such as one, two or more. The meaning of "plural" or "several" means at least two, for example, two, three, etc., and the meaning of "multiple" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
All steps of the present invention may be performed sequentially or randomly unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further comprise step (c), meaning that step (c) may be added to the method in any order, e.g., the method may comprise steps (a), (b) and (c), steps (a), (c) and (b), steps (c), (a) and (b), etc.
In the present invention, "above" or "below" includes the present number. E.g., 1 or less, including 1.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations in a range such as + -5 deg.C, + -4 deg.C, + -3 deg.C, + -2 deg.C, + -1 deg.C.
Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
The raw materials, reagent materials, and the like used in the following embodiments are commercially available products unless otherwise specified.
Rubidium products are widely applied in the fields of chemical catalysis, petroleum exploitation and medical medicine, but rubidium resources are very limited, and the rubidium resources in nature mainly exist in the form of salt lake rubidium resources, and then mica ores. Because the rubidium in the salt lake has low grade and complex composition, the exploitation difficulty is extremely high. Therefore, how to develop low-grade rubidium resources in salt lake brine efficiently is significant.
The traditional technology for extracting rubidium from salt lakes mainly comprises 5 kinds of technology: (1) solar evaporation, (2) co-precipitation, (3) electrochemical techniques, (4) solvent extraction and (5) ion exchange adsorption, all of which have their own limitations and have complex manufacturing processes that are costly.
Various salt lake rubidium-extracting adsorbents are reported, but the selective adsorption capacity of rubidium and other impurity ions (such as cesium) is still poor, and improvement is needed.
Based on the above, the porous composite material provided by the invention has high selectivity to rubidium, high adsorption capacity and high stability, and can be used as a rubidium extracting adsorbent with high selectivity, high adsorption capacity and high stability.
The technical proposal is as follows:
a porous composite comprising:
a porous crosslinked polymer support and a metal salt supported within the porous crosslinked polymer support;
The chemical formula of the metal salt is M x N y Fe(CN) 6 Wherein M represents a divalent metal ion, N represents a metal ion having a valence of trivalent or more, 0 < x < 2, and 0 < y < 1.
The porous cross-linked polymer carrier provides a huge internal specific surface area and pore volume for metal salt, is beneficial to improving the loading capacity of the metal salt, and the porous cross-linked polymer carrier has a pore channel 'finite field effect' capable of winding the metal salt in the pore channel, so that the metal salt can be effectively prevented from losing, the stability of the porous cross-linked polymer carrier is greatly improved, and the porous composite material is matched with the synergistic effect of different metal ions, so that the porous composite material has high selectivity on rubidium ions and good separation effect on rubidium/cesium.
In the present invention, 0 < x < 2,0 < y < 1. Preferably, 0 < x.ltoreq.1, 0 < y < 1. Further, x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9. Further, x is more than or equal to 0.1 and less than or equal to 0.8,0.1, and y is more than or equal to 0.8.
In one embodiment, the porous cross-linked polymer support has a porosity of 30.0% to 40.0%, which is more advantageous for supporting metal salts. It is understood that the porosity of the porous crosslinked polymer carrier includes, but is not limited to, 30.0%, 31.0%, 32.0%, 33.0%, 34.0%, 35.0%, 36.0%, 38.0%, 39.039.0%, or 40.0%.
In one embodiment, the pores in the porous cross-linked polymer carrier comprise micropores and mesopores, and the pore diameter is 1nm to 8nm. Further, for the pores in the carrier, the sum of the micropore and mesoporous volume is more than 95 percent, which is favorable for loading metal salt and is precipitatedM formed by precipitation reaction x N y Fe(CN) 6 The "confinement" is within the pores of the porous crosslinked polymer support. Still further, the micropore volume ratio was 20.3%, the mesopore volume ratio was 76.8% and the macropore volume was Kong Zhanbi was 2.9%.
In one embodiment, the mass ratio of the porous cross-linked polymer carrier to the metal salt is (0.1-1.5): 1, which corresponds to the loading of the metal salt of 50% -70%, and the high loading can improve the adsorption capacity of the porous composite material to rubidium ions.
In one embodiment, the porous cross-linked polymer carrier is made of one or more selected from the group consisting of cross-linked polymethyl acrylate, cross-linked polypropylene acrylate, cross-linked polybutyl acrylate, cross-linked polymethyl methacrylate, cross-linked polypropylene methacrylate and cross-linked polybutyl methacrylate.
In the present invention, M represents a divalent metal ion, and in one embodiment M is selected from Zn 2+ 、Co 2+ 、Mg 2+ 、Cu 2+ And Ni 2+ One or more of the following.
In the present invention, N represents a metal ion having a valence of trivalent or more, including but not limited to trivalent metal ion, tetravalent metal ion, pentavalent metal ion, and hexavalent metal ion. Preferably, N represents a metal ion having a valence of trivalent and/or tetravalent. In one embodiment, N is selected from Fe 3+ 、Zr 4+ 、Ti 4+ And Mn of 4+ One or more of the following.
Fig. 1 is an SEM image of a porous composite material according to some embodiments of the present invention and comparative examples, wherein (a) in fig. 1 is an SEM result of a composite material according to example 3, and (b) in fig. 1 is an SEM result of a composite material according to example 6, and it can be seen that the porous composite materials synthesized in examples 3 and 6 according to the present invention have supported metal salts located in the pores of the porous crosslinked polymer carrier, which is advantageous for improving the stability of the supported metal salts.
Referring to fig. 2, the present invention also provides a method for preparing the porous composite material as described above, comprising the steps of:
mixing a monomer, an initiator, a crosslinking agent and a pore-forming agent, and preparing a porous crosslinked polymer carrier through polymerization reaction;
mixing and reacting the M salt, the N salt and the potassium ferrocyanide solution with the porous cross-linked polymer carrier to prepare the porous composite material.
The preparation method of the porous composite material provided by the invention has the advantages of simple and easily-controlled process, simplicity and convenience in operation, less equipment investment, less labor investment, environment friendliness, high yield, purity of products, easiness in recovery of the products, controllable quality and easiness in industrialization.
The method for preparing the porous composite material of the present invention will be described in detail by way of a stepwise description.
And S100, mixing a monomer, an initiator, a crosslinking agent and a pore-forming agent, and preparing the porous crosslinked polymer carrier through polymerization reaction.
In one embodiment, the monomer is selected from one or more of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate, and butyl methacrylate.
In one embodiment, the initiator is selected from one or more of benzoyl peroxide, methyl ethyl ketone peroxide, and azobisisobutyronitrile. Preferably, the initiator is dibenzoyl peroxide.
In one embodiment, the mass ratio of the monomer to the initiator is (10-15): (0.2-1.5), including but not limited to 10:0.2, 10:0.5, 10:0.8, 10:1, 10:1.2, 10:1.5, 11:0.2, 11:0.5, 11:0.8, 11:1, 11:1.2, 11:1.5, 12:0.2, 12:0.5, 12:0.8, 12:1, 12:1.2, 12:1.5, 13:0.2, 13:0.5, 13:0.8, 13:1, 13:1.2, 13:1.5, 14:0.2, 14:0.5, 14:0.8, 14:1, 14:1.2, 14:1.5, 15:0.2, 15:0.5, 15:0.8, 15:1, 15:1.2, or 15:1.5.
In one embodiment, the cross-linking agent is selected from one or more of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate and allyl isocyanurate.
In one embodiment, the mass ratio of the monomer to the crosslinker is (1-3): (2-10), including but not limited to 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:1, 2:3, 2:4, 2:5, 2:6, 2:7, 2:8, 2:9, 3:2, 3:4, 3:5, 3:6, 3:7, 3:8, 3:9, or 3:10.
In one embodiment, the porogen is selected from one or more of toluene, isooctane, aviation gasoline, and n-heptane.
In one embodiment, the mass ratio of the monomer to the porogen is (1-3): (0.5-3), including but not limited to 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 2:0.5, 2:1.5, 2:2, 2:2.5, 2:3, 3:0.5, 3:1, 3:1.5, 3:2, or 3:2.5.
In one embodiment, the polymerization is a two-stage polymerization. Further, the temperature of the first stage polymerization reaction is 50-70 ℃, the time is 2-6 h, the temperature of the second stage polymerization reaction is 80-95 ℃ and the time is 4-10 h. It is understood that the temperature of the first stage polymerization reaction includes, but is not limited to, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃. It is understood that the time of the first stage polymerization reaction includes, but is not limited to, 2h, 3h, 4h, 5h, or 6h. It is understood that the temperature of the second stage polymerization reaction includes, but is not limited to, 80 ℃, 85 ℃, 90 ℃, or 95 ℃. It is understood that the time for the second stage polymerization reaction includes, but is not limited to, 4h, 5h, 6h, 7h, 8h, 9h, or 10h.
In one embodiment, S100, mixing a monomer, an initiator, a crosslinking agent, and a porogen, preparing a porous crosslinked polymer support by polymerization comprises the steps of:
s110, mixing a dispersing agent and a salting-out agent in water to prepare an aqueous phase solution;
s120, mixing a monomer, an initiator, a cross-linking agent and a pore-forming agent to prepare an oil phase solution;
s130, mixing the aqueous phase solution and the oil phase solution, and preparing the porous cross-linked polymer carrier through polymerization reaction.
It will be appreciated that the order of steps S110 and S120 may be replaced in the present invention, and no requirement is made.
In one embodiment, the dispersant is selected from one or more of polyvinyl alcohol, polyethylene glycol, hydroxymethyl cellulose, hydroxyethyl cellulose, and methyl hydroxypropyl cellulose. Further, the polyvinyl alcohol is one or more of PVA 1000, PVA 6000 and PVA 10000; the polyethylene glycol is one or more of PEG 200, PEG 600 and PEG-1000.
In one embodiment, the dispersant is present in the aqueous solution at a level of 0.5% to 3.0% by mass, including but not limited to 0.5%, 1.0%, 1.5%, 2.0%, 2.5% or 3.0%.
In one embodiment, the salting-out agent is selected from one or more of sodium chloride, potassium chloride, sodium nitrate and potassium nitrate.
In one embodiment, the salting-out agent is present in the aqueous solution in an amount of 5% to 15% by mass, including but not limited to 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%.
In one embodiment, mixing the aqueous phase solution and the oil phase solution comprises the steps of:
the aqueous phase solution prepared in the step S110 is added into the oil phase solution prepared in the step S120, and the oil phase is stirred to be dispersed into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase, so that the pore size range and the porosity of the synthesized porous crosslinked polymer carrier can be effectively controlled. .
In one embodiment, after the step of polymerizing, the method further comprises the steps of cooling and washing the reaction solution with water.
S200, mixing and reacting M salt, N salt and potassium ferrocyanide solution with the porous cross-linked polymer carrier to prepare the porous composite material.
In one embodiment, the M-containing salt and the N-salt are each independently one or more of hydrochloride, nitrate, sulfate, acetate, and carbonate.
In one embodiment, the molar ratio of the molar total of the M salt to the N salt to the potassium ferrocyanide is (0.1-3): 1, including but not limited to 0.1:1, 0.2:1, 0.4:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.1:1, 1.4:1, 1.5:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.5:1, 2.6:1, 2.8:1, or 3:1.
In one embodiment, the molar ratio of the M salt to the N salt is (1-25): (1-15), and the selectivity of the rubidium extracting adsorbent can be effectively improved by utilizing the synergistic effect of different metals through regulating the molar ratio of the M salt to the N salt (different metal salts). It is understood that the molar ratio of the M salt to the N salt includes, but is not limited to, 1:15, 1:10, 1:5, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 15:1, 20:1, 25:1, 3:2, 5:2, 8:3, 10:3, 15:7, 20:3, or 25:4. Preferably, the molar ratio of the M salt to the N salt is (1-5): 1-10. Further, the molar ratio of the M salt to the N salt is 1 (5-10).
In one embodiment, S200 mixes and reacts M salt, N salt, potassium ferrocyanide solution with the porous cross-linked polymer carrier, and the step of preparing the porous composite material includes:
s210, dissolving M salt and N salt in water to prepare a metal salt solution;
s220, mixing the porous cross-linked polymer carrier with the metal salt solution to prepare a solid-liquid mixture;
s230, preparing the porous composite material by a deposition precipitation reaction of the solid-liquid mixture and the potassium ferrocyanide solution.
In one embodiment, the volume ratio of the porous cross-linked polymer carrier to the metal salt solution is 1 (0.1-5), which is more favorable for the reaction of potassium ferrocyanide with two metal salt ions to generate the multi-metal precipitation compound with high selectivity to rubidium ions.
In one embodiment, the porous crosslinked polymer support is mixed with the metal salt solution for a period of time ranging from 10h to 20h, such that it includes, but is not limited to, 10h, 12h, 14h, 15h, 16h, 17h, 18h, 19h, or 20h.
In one embodiment, the temperature of the deposition and precipitation reaction is 20-50 ℃ and the time is 10-20 h. It is understood that the temperature of the deposition precipitation reaction includes, but is not limited to, 20 ℃, 30 ℃, 40 ℃, or 50 ℃. Deposition precipitation reaction
In one embodiment, after the step of depositing the precipitation reaction, the method further comprises the steps of solid-liquid separating the reaction liquid to obtain a solid and washing the solid with water.
The invention also provides an adsorbent comprising a porous composite as described above, or a porous composite made according to a method of making a porous composite as described above.
In one embodiment, the adsorbent is a salt lake rubidium-extracted adsorbent.
Further description will be given below with reference to specific examples and comparative examples.
In the comparative examples of the following examples, uniformity coefficient refers to the degree of difference between the sizes of resin particles, and is used to evaluate the degree of uniformity of particle distribution.
Example 1
The embodiment provides a porous composite material and a preparation method thereof, and the porous composite material comprises the following specific steps:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing methyl methacrylate, allyl itaconate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved to obtain a second oil phase solution, wherein the mass ratio of the monomer to the initiator is 10:1;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 30.0%, the particle size of 3.0-5.0 nm and the uniformity coefficient of more than 92%;
6) Adding 3mol of cobalt nitrate and 3mol of zirconium tetrachloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, cobalt nitrate and zirconium tetrachloride to react for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-1.
Example 2
The embodiment provides a porous composite material and a preparation method thereof, and the porous composite material comprises the following specific steps:
1) Adding a dispersing agent PEG-2000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-2000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing propyl methacrylate, allyl methacrylate and toluene according to a molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved to obtain a second oil phase solution, wherein the mass ratio of the monomers to the initiator is 10:1;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 32.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 95%;
6) Adding 3mol of nickel sulfate and 3mol of titanium tetrachloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, nickel sulfate and titanium tetrachloride to react for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-2.
Example 3
The embodiment provides a porous composite material and a preparation method thereof, and the porous composite material comprises the following specific steps:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 98%;
6) Adding 2mol of nickel sulfate and 3mol of ferric trichloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, nickel sulfate and ferric trichloride to react for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-3.
Example 4
The embodiment provides a porous composite material and a preparation method thereof, and the porous composite material comprises the following specific steps:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing methyl acrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-4.0 nm and the uniformity coefficient of more than 93%;
6) Adding 1mol of cobalt sulfate and 4mol of ferric trichloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, nickel sulfate and ferric trichloride to react for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-4.
Example 5
The embodiment provides a porous composite material and a preparation method thereof, and the porous composite material comprises the following specific steps:
1) Adding a dispersing agent PEG-2000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-2000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing methyl acrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 38.0%, the particle size of 3.0-5.0 nm and the uniformity coefficient of more than 95%;
6) Adding 2mol of zirconium tetrachloride and 3mol of ferric trichloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, zirconium tetrachloride and ferric trichloride to react for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-5.
Example 6
The embodiment provides a porous composite material and a preparation method thereof, and the porous composite material comprises the following specific steps:
1) Adding a dispersing agent PVA-100 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PVA-100 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing methyl acrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 33.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 93%;
6) Adding 2mol of zirconium tetrachloride and 2mol of titanium tetrachloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, reacting with zirconium tetrachloride and titanium tetrachloride for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-6.
Example 7
The embodiment provides a porous composite material and a preparation method thereof, and the porous composite material comprises the following specific steps:
1) Adding a dispersing agent PVA-200 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PVA-200 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:1 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1.1, so as to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 33.1%, the particle size of 2.0-6.0 nm and the uniformity coefficient of more than 93%;
6) Adding 2mol of nickel sulfate and 3mol of ferric trichloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100ml of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, nickel sulfate and ferric trichloride to react for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-7.
Comparative example 1
The comparative example provides a porous composite material and a preparation method thereof, and the porous composite material is specifically as follows:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 98%;
6) Adding 2mol of nickel sulfate into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution and nickel sulfate to react for 15 hours at the temperature of 30 ℃, and washing with deionized water to obtain the porous composite material-8.
Comparative example 2
The comparative example provides a porous composite material and a preparation method thereof, and the porous composite material is specifically as follows:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 98%;
6) Adding 4mol of cobalt sulfate into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution and cobalt sulfate to react for 15 hours at the temperature of 30 ℃, and washing with deionized water to obtain the porous composite material-9.
Comparative example 3
The comparative example provides a porous composite material and a preparation method thereof, and the porous composite material is specifically as follows:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 98%;
6) Adding 3mol of ferric trichloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100ml of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution and ferric trichloride to react for 15 hours at the temperature of 30 ℃, and washing with deionized water to obtain the porous composite material-10.
Comparative example 4
The comparative example provides a porous composite material and a preparation method thereof, and the porous composite material is specifically as follows:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 98%;
6) Adding 3mol of zirconium tetrachloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution to completely react with zirconium tetrachloride, and washing with deionized water to obtain the porous composite material-11.
Comparative example 5
The comparative example provides a porous composite material and a preparation method thereof, and the porous composite material is specifically as follows:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.1 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 98%;
6) Adding 2mol of nickel sulfate into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution and nickel sulfate to react for 15 hours at the temperature of 30 ℃, and washing with deionized water to obtain the porous composite material-12.
Comparative example 6
The comparative example provides a porous composite material and a preparation method thereof, and the porous composite material is specifically as follows:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate and diethylene glycol dimethacrylate according to the molar ratio of 1:2 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1, so as to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a cross-linked polymer carrier with the uniformity coefficient of more than 98%;
6) Adding 2mol of nickel sulfate into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution and nickel sulfate to react for 15 hours at the temperature of 30 ℃, and washing with deionized water to obtain the porous composite material-13.
Comparative example 7
The comparative example provides a porous composite material and a preparation method thereof, and the porous composite material is specifically as follows:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 98%;
6) Adding 2mol of zirconium sulfate and 3mol of ferric trichloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, nickel sulfate and ferric trichloride to react for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-14.
Comparative example 8
The comparative example provides a porous composite material and a preparation method thereof, and the porous composite material is specifically as follows:
1) Adding a dispersing agent PEG-1000 and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent PEG-1000 and the salting-out agent NaCl are completely dissolved to obtain a water phase solution; wherein, in the aqueous phase solution, the weight proportion of the dispersing agent is 1.0 percent, and the weight proportion of the salting-out agent NaCl is 10 percent;
2) Uniformly mixing butyl methacrylate, diethylene glycol dimethacrylate and toluene according to the molar ratio of 1:2:0.5 to obtain a first oil phase solution, then adding benzoyl peroxide, and stirring at room temperature until the mixture is completely dissolved, wherein the mass ratio of the monomers to the initiator is 10:1 to obtain a second oil phase solution;
3) Adding the aqueous phase solution prepared in the step 1) into the second oil phase solution prepared in the step 2), and stirring to disperse the oil phase into oil beads with the particle size of 0.3-1.2 mm in the aqueous phase;
4) Heating to 60 ℃, reacting for 5 hours, heating to 85 ℃ and reacting for 10 hours;
5) Cooling and washing the reaction liquid to obtain a porous crosslinked polymer carrier with the porosity of 35.0%, the particle size of 2.0-5.0 nm and the uniformity coefficient of more than 98%;
6) Adding 2mol of ferric sulfate and 3mol of ferric trichloride into 1L of deionized water, and uniformly stirring to form a metal salt solution;
7) Adding 100g of porous crosslinked polymer carrier into 1L of the metal salt solution in the step 6), and soaking for 15h;
8) Adding 1mol of potassium ferrocyanide solution, nickel sulfate and ferric trichloride to react for 15 hours at 30 ℃, and washing with deionized water to obtain the porous composite material-15.
Comparative example 9
The comparative example provides a porous composite material-16 and a method for preparing the same, wherein the second 4 oil phase solution does not contain a cross-linking agent, and the prepared polymer carrier is not a cross-linked polymer carrier, compared with the example 3.
Testing
The porous composite materials obtained in the above examples and comparative examples were tested for adsorption properties by experiments. The specific method comprises the following steps: 10ml of rubidium-extracted adsorbent is loaded into a column, added into 20BV rubidium-cesium-containing brine solution (pH=9.0, [ Rb+ ] =212 ppm, [ Cs+ ] =50.7 ppm, T=293K), and adsorbed at a flow rate of 2BV/h to determine the concentrations of rubidium and cesium in water; then, deionized water was diluted and then tested with AAS, and the adsorption capacity and adsorption selectivity were calculated, and the results are shown in Table 1 below.
TABLE 1
As can be seen from table 1, compared with comparative examples 1 to 9, the porous composite materials according to examples 1 to 7 of the present invention have higher adsorption capacity for rubidium ions and better separation effect for rubidium/cesium, and can be used as a high-selectivity rubidium-extracting adsorbent; and the adsorption capacity of rubidium ions is kept unchanged basically after the experiment process is repeated for 20 times. Experimental results prove that: the porous composite material provided by the invention has high adsorption capacity, high selectivity and high stability on rubidium ions as a rubidium extracting adsorbent, and has a wide application prospect.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art may obtain technical solutions through logic analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (12)
1. A porous composite material, comprising:
a porous crosslinked polymer support and a metal salt supported within the porous crosslinked polymer support;
the chemical formula of the metal salt is M x N y Fe(CN) 6 Wherein M represents a divalent metal ion, and N represents a metal ion having a valence of trivalent or more，0＜x＜2，0＜y＜1。
2. The porous composite according to claim 1, wherein at least one of the following (1) to (3) is satisfied:
(1) The mass ratio of the porous cross-linked polymer carrier to the metal salt is (0.1-1.5): 1;
(2) The porosity of the porous cross-linked polymer carrier is 30.0% -40.0%;
(3) The pores in the porous cross-linked polymer carrier comprise micropores and mesopores, and the pore diameter is 1 nm-8 nm.
3. The porous composite according to claim 1 or 2, wherein the porous cross-linked polymer carrier is selected from one or more of cross-linked polymethyl acrylate, cross-linked polypropylene acrylate, cross-linked polybutyl acrylate, cross-linked polymethyl methacrylate, cross-linked polypropylene acrylate and cross-linked polybutyl methacrylate.
4. The porous composite according to claim 1 or 2, wherein at least one of the following (1) to (2) is satisfied:
(1) M is selected from Zn 2+ 、Co 2+ 、Mg 2+ 、Cu 2+ And Ni 2+ One or more of the following;
(2) N is selected from Fe 3+ 、Zr 4+ 、Ti 4+ And Mn of 4+ One or more of the following.
5. A method of preparing a porous composite according to any one of claims 1 to 4, comprising the steps of:
mixing a monomer, an initiator, a crosslinking agent and a pore-forming agent, and preparing a porous crosslinked polymer carrier through polymerization reaction;
Mixing and reacting the M salt, the N salt and the potassium ferrocyanide solution with the porous cross-linked polymer carrier to prepare the porous composite material.
6. The method for producing a porous composite material according to claim 5, wherein at least one of the following (1) to (3) is satisfied:
(1) The M-containing salt and the N-containing salt are respectively one or more of hydrochloride, nitrate, sulfate, acetate and carbonate;
(2) The molar ratio of the molar total amount of the M salt to the N salt to the potassium ferrocyanide is (0.1-3): 1, a step of;
(3) The molar ratio of the M salt to the N salt is (1-25): 1-15.
7. The method of preparing a porous composite according to claim 6, wherein the step of mixing and reacting a solution of M salt, N salt, potassium ferrocyanide with the porous cross-linked polymer carrier comprises:
dissolving M salt and N salt in water to prepare a metal salt solution;
mixing the porous cross-linked polymer carrier with the metal salt solution to prepare a solid-liquid mixture;
and preparing the porous composite material by a deposition precipitation reaction between the solid-liquid mixture and the potassium ferrocyanide solution.
8. The method for producing a porous composite material according to claim 7, wherein at least one of the following (1) to (2) is satisfied:
(1) The mixing time of the porous cross-linked polymer carrier and the metal salt solution is 10-20 h;
(2) The temperature of the deposition and precipitation reaction is 20-50 ℃ and the time is 10-20 h.
9. The method for producing a porous composite according to any one of claims 5 to 8, wherein at least one of the following (1) to (8) is satisfied:
(1) The monomer is selected from one or more of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate and butyl methacrylate;
(2) The initiator is selected from one or more of benzoyl peroxide, methyl ethyl ketone peroxide and azodiisobutyronitrile;
(3) The mass ratio of the monomer to the initiator is (10-15) (0.2-1.5);
(4) The cross-linking agent is selected from one or more of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate and allyl isocyanurate;
(5) The mass ratio of the monomer to the cross-linking agent is (1-3): 2-10;
(6) The pore-forming agent is selected from one or more of toluene, isooctane, aviation gasoline and n-heptane;
(7) The mass ratio of the monomer to the pore-forming agent is (1-3) (0.5-3);
(8) The polymerization reaction is two-stage polymerization, the temperature of the first-stage polymerization reaction is 50-70 ℃, the time is 2-6 h, the temperature of the second-stage polymerization reaction is 80-95 ℃ and the time is 4-10 h.
10. The method of preparing a porous composite according to any one of claims 5 to 8, wherein the step of mixing a monomer, an initiator, a crosslinking agent and a porogen to prepare a porous crosslinked polymer carrier by polymerization comprises the steps of:
mixing a dispersing agent and a salting-out agent in water to prepare an aqueous phase solution;
mixing a monomer, an initiator, a cross-linking agent and a pore-forming agent to prepare an oil phase solution;
mixing the aqueous phase solution and the oil phase solution, and preparing the porous cross-linked polymer carrier through polymerization reaction.
11. The method for producing a porous composite material according to claim 10, wherein at least one of the following (1) to (4) is satisfied:
(1) The dispersing agent is one or more selected from polyvinyl alcohol, polyethylene glycol, hydroxymethyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose;
(2) In the aqueous phase solution, the mass content of the dispersing agent is 0.5% -3.0%;
(3) The salting-out agent is selected from one or more of sodium chloride, potassium chloride, sodium nitrate and potassium nitrate;
(4) In the aqueous phase solution, the mass content of the salting-out agent is 5-15%.
12. An adsorbent comprising the porous composite of any one of claims 1 to 4 or a porous composite produced according to the method of producing a porous composite of any one of claims 5 to 11.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6558552B1 (en) * | 1997-07-09 | 2003-05-06 | Commissariat A L'energie Atomique | Composite material based on hexacyanoferrates and polymer, method for making it and use |
| CN101041123A (en) * | 2007-03-16 | 2007-09-26 | 清华大学 | Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials |
| CN102836693A (en) * | 2012-09-19 | 2012-12-26 | 清华大学 | Magnetic-nucleus coated type inorganic ion adsorbent used for removing Cs ions in radioactive wastewater, and preparation method of same |
| JP2014048164A (en) * | 2012-08-31 | 2014-03-17 | Japan Atomic Energy Agency | Method for decontaminating cesium and transition metal by ferrocyanide ion |
| US20140151305A1 (en) * | 2011-08-17 | 2014-06-05 | Christian Schrage | Adsorbent precipitated on a carrier, method for producing said adsorbent, and use of said adsorbent |
| CN107735178A (en) * | 2015-07-06 | 2018-02-23 | 朗盛德国有限责任公司 | Caesium selective resin |
| KR20190002028A (en) * | 2017-06-29 | 2019-01-08 | 충남대학교산학협력단 | Polymer gel-Prussian blue complex and its manufacturing method |
| CN109351323A (en) * | 2018-11-09 | 2019-02-19 | 天津碧水源膜材料有限公司 | De- ammonium material of selectivity and the preparation method and application thereof |
| CN112742343A (en) * | 2020-11-13 | 2021-05-04 | 烟台大学 | Copper nickel ferrocyanide/montmorillonite composite material, preparation method and adsorption application thereof |
| CN115703060A (en) * | 2021-08-03 | 2023-02-17 | 中国科学院青海盐湖研究所 | Preparation method and product of magnetic bimetallic MOF rubidium/cesium adsorbent |
| CN116173925A (en) * | 2023-03-31 | 2023-05-30 | 江苏海普功能材料有限公司 | High-adsorption-rate lithium extraction adsorbent and preparation method and application thereof |
-
2023
- 2023-10-31 CN CN202311431938.4A patent/CN117160404B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6558552B1 (en) * | 1997-07-09 | 2003-05-06 | Commissariat A L'energie Atomique | Composite material based on hexacyanoferrates and polymer, method for making it and use |
| CN101041123A (en) * | 2007-03-16 | 2007-09-26 | 清华大学 | Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials |
| US20140151305A1 (en) * | 2011-08-17 | 2014-06-05 | Christian Schrage | Adsorbent precipitated on a carrier, method for producing said adsorbent, and use of said adsorbent |
| JP2014048164A (en) * | 2012-08-31 | 2014-03-17 | Japan Atomic Energy Agency | Method for decontaminating cesium and transition metal by ferrocyanide ion |
| CN102836693A (en) * | 2012-09-19 | 2012-12-26 | 清华大学 | Magnetic-nucleus coated type inorganic ion adsorbent used for removing Cs ions in radioactive wastewater, and preparation method of same |
| CN107735178A (en) * | 2015-07-06 | 2018-02-23 | 朗盛德国有限责任公司 | Caesium selective resin |
| US20180193828A1 (en) * | 2015-07-06 | 2018-07-12 | Lanxess Deutschland Gmbh | Caesium selective resin |
| KR20190002028A (en) * | 2017-06-29 | 2019-01-08 | 충남대학교산학협력단 | Polymer gel-Prussian blue complex and its manufacturing method |
| CN109351323A (en) * | 2018-11-09 | 2019-02-19 | 天津碧水源膜材料有限公司 | De- ammonium material of selectivity and the preparation method and application thereof |
| CN112742343A (en) * | 2020-11-13 | 2021-05-04 | 烟台大学 | Copper nickel ferrocyanide/montmorillonite composite material, preparation method and adsorption application thereof |
| CN115703060A (en) * | 2021-08-03 | 2023-02-17 | 中国科学院青海盐湖研究所 | Preparation method and product of magnetic bimetallic MOF rubidium/cesium adsorbent |
| CN116173925A (en) * | 2023-03-31 | 2023-05-30 | 江苏海普功能材料有限公司 | High-adsorption-rate lithium extraction adsorbent and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 蒋育澄 等: "重稀碱金属铷和铯的分离分析方法进展", 稀有金属, no. 04, 31 July 2002 (2002-07-31), pages 299 - 302 * |
| 闫树旺 等: "卤水中铷铯的分离与提取", 矿物岩石, no. 02, 31 December 1993 (1993-12-31), pages 113 - 119 * |
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