CN102585420A - Magnetic expansion adsorption composite material and preparation method thereof - Google Patents
Magnetic expansion adsorption composite material and preparation method thereof Download PDFInfo
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- CN102585420A CN102585420A CN2012100451295A CN201210045129A CN102585420A CN 102585420 A CN102585420 A CN 102585420A CN 2012100451295 A CN2012100451295 A CN 2012100451295A CN 201210045129 A CN201210045129 A CN 201210045129A CN 102585420 A CN102585420 A CN 102585420A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 65
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 36
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 26
- 239000011707 mineral Substances 0.000 claims abstract description 26
- 239000006247 magnetic powder Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 55
- 229920002554 vinyl polymer Polymers 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 47
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- -1 iron ion Chemical class 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000017 hydrogel Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000012454 non-polar solvent Substances 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 5
- 229910052604 silicate mineral Inorganic materials 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical group OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000006194 liquid suspension Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000001455 metallic ions Chemical class 0.000 abstract description 3
- 239000002689 soil Substances 0.000 abstract description 3
- 238000002955 isolation Methods 0.000 abstract description 2
- 238000007885 magnetic separation Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 230000010339 dilation Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 19
- 230000000274 adsorptive effect Effects 0.000 description 17
- 235000010755 mineral Nutrition 0.000 description 16
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004159 Potassium persulphate Substances 0.000 description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 9
- 235000019394 potassium persulphate Nutrition 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000136 polysorbate Polymers 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000005294 ferromagnetic effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000003350 kerosene Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
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- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a magnetic expansion adsorption composite material and a preparation method thereof. The composite material comprises the following components in parts by weight: more than 0 and less than or equal to 50 parts of magnetic powder, 1.0-30.0 parts of a non-metallic mineral powder body, 50.0-100.0 parts of water solubility Ethylene class unsaturated monomer and 0.1-2.0 parts of cross-linking agent, and is prepared by compounding the components through a polymerization reaction. According to the invention, the obtained magnetic expansion absorption composite material has a function of adsorbing and enriching heavy metal ions of metallic ions in a water body or soil or a stereo-liquid suspension (compound) system; meanwhile, the magnetic expansion absorption composite material has the characteristic of being easy to extract through a magnet or a magnetic separation machine, the manufacturing method is simple, the cost is low, the dilation is high, and the magnetic expansion absorption composite material is broadly used for a fluid bed or cleaning plant to carry out metallic ion segregation, and provides a good adsorbing material for sublimate automatization and large-scale production; and the magnetic expansion adsorption composite material and the preparation method are suitable for adsorption, enrichment and isolation application in industries such as environmental protection, pollution administration, biology segregation and mineral separation.
Description
Technical field
The invention belongs to functional high molecule material and functional composite material technical field, relate in particular to a kind of magnetic expansion adsorption composite material and preparation method thereof.
Background technology
The equal function of dominant macromolecular material of polymeric adsorbent and swelling resin.Recent Development proof swelling behavior material has superpower adsorptive power of selectivity and super large loading capacity to metals ion such as heavy metal ion etc., so the swelling behavior material becomes swollen absorbent material again.It is template that one Chinese patent application number 201010284643 and 200710072462 patented claims disclose with the hydrogel, is the method for feedstock production ferriferrous oxide nano-particle with Fe (III), Fe (II).Obvious this method is to prepare magnetic particle through behind the absorption iron ion chemical reaction taking place; And non magnetic hydrogel; And have the restriction that the intramolecularly adsorption group is saturated by iron, adsorptive capacity is little, be difficult to hydrogel magnetic power is significantly adjusted, preparation manipulation is complicated; Condition is difficult to control, uses it for the application of enrichment and separating metal ionic and is restricted.
Summary of the invention
The object of the present invention is to provide a kind of turgidity high, magnetic expansion adsorption composite material of high adsorption capacity and preparation method thereof.
In order to realize the object of the invention, the technical scheme that the present invention taked is:
A kind of magnetic expansion adsorption composite material, it by comprise weight part be respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts the water-soluble vinyl unsaturated monomer, and 0.1～2.0 part linking agent be composited through polyreaction.
In the such scheme, said magnetic powder chosen from Fe magnetic mineral or through becoming the material of magnetic mineral or iron ion is adsorbed in the hydrogel after the processing, the powdery magnetic of in-situ preparing, the median size of said magnetic powder is 0.1～150 μ m.
In the such scheme, the median size of said magnetic powder is 1.0-100 μ m.
In the such scheme, said non-metallic mineral powder is selected from the silicate minerals powder that median size is 1.0～150 μ m, and said silicate minerals is selected from any one in zeolite, zeyssatite, wilkinite, attapulgite or the kaolin.
In the such scheme, the weight part of said water-soluble vinyl unsaturated monomer is 40.0～70.0 parts.
In the such scheme, said water-soluble vinyl unsaturated monomer is 2-acrylamido-2-methyl propane sulfonic acid, and acrylic amide, or the mixing in the vinylformic acid one or any two kinds mix with arbitrary proportion during mixing.
In the such scheme, said linking agent comprises that per molecule contains two polymerisable unsaturated groups at least, and said linking agent is N, N '-methylene-bisacrylamide.
A kind of method for preparing magnetic expansion adsorption composite material, it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent, 0.05～10.0 part initiator and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer; The mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～40%, and said mixture is disperseed;
2) make mixture after the above-mentioned dispersion in 10～80 ℃ of heating 1～3 hour, elevated temperature to 70～90 a ℃ reaction was carried out slaking in 1～5 hour again, obtained gluey polymerisate;
3) with getting granular or powdered magnetic expansion adsorption composite material after above-mentioned gluey polymerisate chopping, drying, the pulverizing.
A kind of method for preparing magnetic expansion adsorption composite material, it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent, 0.05～10.0 part initiator and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～30%;
2) at 10～80 ℃ said mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in the non-polar solvent, the mass percentage concentration of said suspension dispersive agent is 0.1%～10%, and deoxygenation then forms oil phase;
4) with step 2) aqueous mixture that obtains is added drop-wise in the above-mentioned oil phase, stirs, 10～80 ℃ of reactions 2～7 hours down;
5) said magnetic expansion adsorption composite material is filtered, washed, is drying to obtain to above-mentioned reaction product.
In the such scheme, said initiator is water-soluble radical polymerization initiator or water soluble oxidized reduction initiator, and said water-soluble radical polymerization initiator comprises persulphate.
A kind of method for preparing magnetic expansion adsorption composite material is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer; The mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～35%, and said mixture is disperseed;
2) at room temperature, the mixture after the above-mentioned dispersion was reacted after 2～3 hours under ultraviolet light irradiation, elevated temperature to 70～90 a ℃ reaction was carried out slaking in 1～3 hour again, obtained gluey polymerisate;
3) with getting granular or powdered magnetic expansion adsorption composite material after above-mentioned gluey polymerisate chopping, drying, the pulverizing.
A kind of method for preparing magnetic expansion adsorption composite material is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～30%;
2) at 10～80 ℃ said mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in the non-polar solvent, the mass percentage concentration of said suspension dispersive agent is 0.1%～10%, and deoxygenation then forms oil phase;
4) with step 2) aqueous mixture that obtains is added drop-wise in the above-mentioned oil phase, stirs, and reaction stopped irradiation after 2～3 hours under ultraviolet light irradiation, and ℃ reacted 2～7 hours elevated temperature to 40～90 again;
5) said magnetic expansion adsorption composite material is filtered, washed, is drying to obtain to above-mentioned reaction product.
The invention has the beneficial effects as follows: metals ion existing hydrogel network Semi-polarity group and network expansion are strengthened the function of adsorbing; The function of highly surface activated mineral to adsorption of metal ions arranged again simultaneously, expansion loading capacity big (high adsorption capacity), the magnetic power is adjustable; Gel-strength is high; Can carry out adsorption and enrichment to metals ion such as heavy metal ion etc. in water body or in the soil or in solid-liquid suspension (mixing) system, have simultaneously easily and separated from water body, soil, solid-liquid suspension system by magnet or magnetic separation machinery, method of manufacture is simple; Cost is low; Turgidity is high, can be widely used in the advantage that thermopnore or preparation equipment carry out robotization mass metal ion isolation, is suitable for the adsorption and enrichment separation function magnetic expansion adsorption composite material of sector applications such as environment protection, Pollution abatement, bioseparation, ore dressing.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Introduce related magnetic powder, non-metallic mineral powder, water-soluble vinyl unsaturated monomer, linking agent, initiator, reaction medium and auxiliary agent among following all embodiment of the present invention below at first in detail.
1. magnetic powder
Magnetic powder mainly refers to contain powder, the iron powder of ferromagnetic mineral, or through becoming the material of magnetic mineral after the processing, as: the magnetic product that the rhombohedral iron ore reduction is obtained etc.Median size is 0.1～150 μ m, is preferably 1.0-100 μ m.Ferromagnetic mineral itself has stronger magnetic, and the specific magnetising moment is very big under the outside magnetic field effect, and magnetite is typical ferromagnetic mineral.It is strong and weak to regulate how many adjustable magnetic hydrogel magnetic of magnetic powder content, its addition be weight part greater than zero and smaller or equal to 50 parts, be preferably 1.0～30.0 parts.
2. non-metallic mineral powder
Described non-metallic mineral powder refers to that specific surface area is big, big to the particularly heavy metal ion adsorbed capacity of metals ion, the silicate minerals powder of high adsorption capacity, as: zeolite, zeyssatite, wilkinite, attapulgite, powders such as kaolin.Median size is 1～150 μ m.1.0～30.0 parts of its addition preferred weight parts.
3. water-soluble vinyl unsaturated monomer
The water-soluble vinyl unsaturated monomer is the main body that forms hydrogel, also is to bring adsorption group, produces the main internal cause of absorption property.Typical water-soluble ionic-type vinyl unsaturated monomer is: acrylic or methacrylic acid and verivate thereof; Typical nonionic monomers is: acrylic amide and verivate thereof.Wherein preferably the water-soluble vinyl unsaturated monomer is 2-acrylamido-2-methyl propane sulfonic acid (hereinafter to be referred as AMPS); Acrylic amide (hereinafter to be referred as AM); Wherein a kind in vinylformic acid (hereinafter to be referred as AA), these monomer mixtures more than 2 kinds or 2 kinds, if during mixture, its blending ratio is not limit; Its consumption is 30.0～100.0 parts of weight parts, is preferably 40.0～70.0 parts.
4. linking agent
At least contain two polymerisable unsaturated groups in the cross-linker molecules, these linking agents make hydrogel form crosslinked or lightly crosslinked three-dimensional net structure at body in mutually, regulate its its gel-strength of consumption adjustable and water-retaining capacity.Typical linking agent has: N, N '-methylene-bisacrylamide, consumption are 0.1～2.0 part of weight part.
5. initiator
The water-soluble radical polymerization initiator that is fit to water solution polymerization process or inverse suspension polymerization method is a persulphate, as: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, these water soluble starters can mix use.Also can fit in redox system with reducing substances such as ferrous ion, sodium sulfite anhy 96, S-WAT etc. uses.Each proportioning components is confirmed by the quantitative relation of chemical equation when being used.Initiator amount is 0.05～10.0 part of a weight part, preferred 0.1～2.0 part.Kick off temperature is 10 ℃～80 ℃, preferred 65 ℃～75 ℃ of single initiator, and the preferred temperature of redox initiator is 20 ℃～50 ℃.
6. reaction medium and auxiliary agent
When adopting water solution polymerization process, reaction medium is a water; When adopting the inverse suspension polymerization method, reaction medium is a non-polar solvent, like hexanaphthene or kerosene etc.Add tensio-active agent such as op simultaneously, this dish, tween etc. are done suspension dispersive agent and are carried out suspended dispersed, and addition is a mass percentage concentration 0.1%～10.0%.
Below the dispersing method mentioned among all embodiment can select for use impeller to carry out dispersed with stirring or disperse with colloidal mill, or adopt UW to carry out ultra-sonic dispersion.
Among the present invention, adopt following method to measure and calculate the turgidity of inhaling zero(ppm) water, tap water and saline water:
The granulated material that takes by weighing after 0.5～1.0g drying treatment places the 500-1000ml beaker; Granulated material after adding 450～900ml zero(ppm) water or tap water or taking by weighing 0.5～1.0g drying treatment places the 150ml beaker to add 100ml 0.9%NaCl solution; After leaving standstill 24 hours; With unnecessary water elimination, weigh up gel quality affects with 100 order mesh screens, be calculated as follows turgidity:
Turgidity=(gel quality affects-xerogel quality)/xerogel quality
Among the present invention,, adopt different analysis test methods to measure concentration of metal ions and change, characterize adsorptive power with adsorptive capacity (mg/g dried resin) according to the different metallic ion.
Magnetic expansion polymeric adsorbent by the present invention's preparation has 10～300 times of turgiditys, and Cu (II), Cd (II), Pb (II), Zn (II), Cr (III), Hg (II), As (III) etc. are had strong adsorptive power, and easy-to-use magnetic technology is separated.
Embodiment 1:
In the 1000ml beaker; Add AMPS and each 50g of AM, add water and be mixed with the aqueous solution that mass percentage concentration is 40% water-soluble vinyl unsaturated monomer, stir adding N down; N '-methylene-bisacrylamide (linking agent) 0.1g, Potassium Persulphate 0.05 gram; Stirring and dissolving adds 1.0g median size 10.0 μ m, grade wherein greater than the zeyssatite of TFe50% magnetite powder and 1.0g median size 20.0 μ m again, 75 ℃ of dispersed with stirring 5 minutes; Mixture after the above-mentioned dispersion was cooled to 10 ℃ of reactions after 3 hours, was increased to 80 ℃ of reactions 1 hour again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, in following 40 ℃ of dryings of vacuum condition 5 hours to water cut less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain granular magnetic expansion adsorption composite material finished product, its turgidity is 80～90, to Cd (II); Cu (II); The adsorptive capacity of Cr (III) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 2:
In the 1000ml beaker; Add 10g AMPS and 20g AM, add water and be mixed with the aqueous solution that mass percentage concentration is 20% water-soluble vinyl unsaturated monomer, stir adding N down; N '-methylene-bisacrylamide 2.0g, Potassium Persulphate 1.0g, sodium sulfite anhy 96 1.0g; Stirring and dissolving adds 50g median size 100.0 μ m, grade wherein greater than the wilkinite of TFe20% magnetite powder and 30.0g median size 10.0 μ m again, 70 ℃ of dispersed with stirring 15 minutes; Mixture after the above-mentioned dispersion was cooled to 50 ℃ of reactions after 3 hours, was increased to 70 ℃ of reactions 3 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 80 ℃ of vacuum-drying 3 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain granular magnetic expansion adsorption composite material finished product, its turgidity is 10～30, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 3:
In the 1000ml beaker; Add 20g AMPS, 60g AM and 20g AA; Add water and be mixed with the aqueous solution that mass percentage concentration is 15% water-soluble vinyl unsaturated monomer, stir and add N down, N '-methylene-bisacrylamide 1.0g, Sodium Persulfate 10.0 grams; Stirring and dissolving; 30.0g median size 80.0 μ m, grade are added wherein greater than the attapulgite of TFe30% magnetite powder and 15g median size 2.0 μ m, 70 ℃ of supersound process 15 minutes are reduced to room temperature and are crossed colloidal mill powder is disperseed again; Mixture after the above-mentioned dispersion was warming up to 50 ℃ of reactions after 3 hours, was increased to 90 ℃ of reactions 5 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 70 ℃ of dryings 4 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain granular magnetic expansion adsorption composite material finished product, its turgidity is 200～300, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 4:
In the 1000ml beaker, add 30g AMPS, 40g AM; Add water and be mixed with the aqueous solution that mass percentage concentration is 30% water-soluble vinyl unsaturated monomer; Stir and add N down, N '-methylene-bisacrylamide 1.5g, ammonium persulphate 5.0 grams, stirring and dissolving; Again 5.0g median size 1.0 μ m, grade are added wherein 70 ℃ of dispersed with stirring 15 minutes greater than the zeolite of TFe50% magnetite powder and 1g median size 45.0 μ m; Mixture after the above-mentioned dispersion was cooled to 65 ℃ of reactions after 3 hours, was increased to 70 ℃ of reactions 3 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 120 ℃ of dryings 3 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain granular magnetic expansion adsorption composite material finished product, its turgidity is 20～30, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 5:
In the 1000ml beaker; Add 20g AMPS and 20g AM, add water and be mixed with the aqueous solution that mass percentage concentration is 30% water-soluble vinyl unsaturated monomer, stir adding N down; N '-methylene-bisacrylamide 1.5g, Potassium Persulphate 5.0 grams; Stirring and dissolving adds 5.0g median size 40.0 μ m, grade wherein greater than the zeolite of TFe50% magnetite powder and 1g median size 150.0 μ m again, 70 ℃ of dispersed with stirring 15 minutes; Mixture after the above-mentioned dispersion was warming up to 75 ℃ of reactions after 3 hours, was increased to 90 ℃ of reactions 3 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 120 ℃ of dryings 3 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain granular magnetic expansion adsorption composite material finished product, its turgidity is 100～120, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 6:
With median size 48.0 μ m, smart powder (rhombohedral iron ore) 20g of TFe60% iron mixes the back and carries out magnetizing roasting at 400～600 ℃ with capacity powdered carbon (C powder), obtain magnetite powder.
In the 1000ml beaker; Add 60g AMPS, 20g AM and 20gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 25% water-soluble vinyl unsaturated monomer, stir and add N down; N '-methylene-bisacrylamide 1.0g, Potassium Persulphate 0.1 gram; Stirring and dissolving, the 10.0g magnetite powder that will go up method preparation again and the adding of 20g median size 100.0 μ m kaolin wherein, 70 ℃ of dispersed with stirring 15 minutes; Mixture after the above-mentioned dispersion was cooled to 50 ℃ of reactions after 3 hours, was increased to 70 ℃ of reactions 3 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 120 ℃ of dryings 3 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain granular magnetic expansion adsorption composite material finished product, its turgidity is 100～120, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 7:
In the 1000ml beaker, add 30g AMPS, 10g AM; 10gAA adds water and is mixed with the aqueous solution that mass percentage concentration is 35% water-soluble vinyl unsaturated monomer, stirs to add N down; N '-methylene-bisacrylamide 0.6g, stirring and dissolving add 5.0g median size 150.0 μ m, grade wherein greater than the zeolite of TFe50% magnetite powder and 1g median size 45.0 μ m, after the stirring and dissolving again; In room temperature mixture was penetrated 2 hours with the 40w uv illumination; Stop irradiation, be increased to 70 ℃ of reactions 3 hours, obtain gel (gluey polymerisate); The gel chopping that generates is to 2～10mm; 90 ℃ of dryings 8 hours to water cut is less than 10wt%; Again through mechanical disintegration to 0.1～5.0mm; Finally obtain particulate state magnetic expansion adsorption composite material finished product, its turgidity is 20～30, is 20～400mg/g dried resin to the adsorptive capacity of Zn (II), Cr (III), Hg (II), As (III); Explain that turgidity is high, high adsorption capacity.
Embodiment 8:
Under the room temperature nitrogen protection, in the 1000ml beaker, add 30g AMPS; 10g AM, 10gAA adds water and is mixed with the aqueous solution that mass percentage concentration is 25% water-soluble vinyl unsaturated monomer; Stir adding N down, N '-methylene-bisacrylamide 0.6g, stirring and dissolving, the zeolite with iron(ic)chloride and each 2.5g of ferrous sulfate and 1g median size 45.0 μ m adds wherein again; After the stirring and dissolving, solution was penetrated 2 hours with the 40w uv illumination, stopped irradiation in room temperature; Be increased to 70 ℃ of reactions 3 hours again, obtain gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, adds mass percentage concentration and is 2% alkali lye 400ml and soaked 12 hours, leaches gel; 90 ℃ of dryings 8 hours to water cut through mechanical disintegration to 0.1～5.0mm, finally obtains particulate state magnetic expansion adsorption composite material finished product less than 10wt%; Its turgidity is 20～30; Adsorptive capacity to Zn (II), Cr (III), Hg (II), As (III) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 9:
3g Span-60 is scattered in the hexanaphthene, and the mass percentage concentration of this Span-60 is 0.1%.Be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, opens to stir Span-60 is dissolved fully, forms oil phase.
In the 100ml beaker, add 6.0g AMPS, 2.0g AM; 2.0gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 30% water-soluble vinyl unsaturated monomer, stir and add 0.2g N down; N '-methylene-bisacrylamide, 0.2 gram Potassium Persulphate; Stirring and dissolving adds 1.0g median size 20.0 μ m, grade wherein greater than the wilkinite of TFe30% magnetite powder and 3.0g median size 10.0 μ m again, and 70 ℃ of dispersed with stirring got aqueous mixture in 15 minutes.
Again aqueous mixture is added drop-wise in the above-mentioned oil phase, stirs, at 70 ℃ of following polymerization 2h.Treat that temperature reduces to room temperature, cross and filter partical, use washing with alcohol; Obtain particulate state magnetic expansion adsorption composite material finished product in 80 ℃ of vacuum-drying to water cut less than 10wt%, its turgidity is 80～100, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 10:
3g op-10 is scattered in the kerosene, and the mass percentage concentration of this op-10 is 10%.The oxygen that the logical nitrogen flooding of normal temperature is removed wherein forms oil phase.
In the 100ml beaker, add 3.0g AMPS, 1.0g AM; 1.0gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 15% water-soluble vinyl unsaturated monomer, stir and add 0.01g N down; N '-methylene-bisacrylamide, 0.005 gram Potassium Persulphate; Stirring and dissolving adds 0.1g median size 0.1 μ m, grade wherein greater than the wilkinite of TFe30% magnetite powder and 3.0g median size 0.1 μ m again, and 80 ℃ of dispersed with stirring got aqueous mixture in 15 minutes.
Again aqueous mixture is added drop-wise in the above-mentioned oil phase, stirs, at 80 ℃ of following polymerization 5h.Treat that temperature reduces to room temperature, cross and filter partical, use methanol wash; Obtain particulate state magnetic expansion adsorption composite material finished product in 120 ℃ of vacuum-drying to water cut less than 10wt%, its turgidity is 100～120, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 11:
With the 3g tween be scattered in the hexanaphthene, the mass percentage concentration of this tween is 5%.Stirring and dissolving, the oxygen that logical nitrogen flooding is removed wherein forms oil phase.
In the 100ml beaker, add 3.0g AMPS, 2.0g AM; 2.0gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 20% water-soluble vinyl unsaturated monomer, stir and add 0.1g N down; N '-methylene-bisacrylamide, 0.5 gram Potassium Persulphate; Stirring and dissolving adds 3.0g median size 20.0 μ m, grade wherein greater than the wilkinite of TFe30% magnetite powder and 3.0g median size 10.0 μ m again, and 50 ℃ of dispersed with stirring got aqueous mixture in 15 minutes.
Again aqueous mixture is added drop-wise in the above-mentioned oil phase, stirs, at 40 ℃ of following polymerase 17 h.Treat that temperature reduces to room temperature, cross and filter partical, use washing with alcohol; Obtain particulate state magnetic expansion adsorption composite material finished product in 80 ℃ of vacuum-drying to water cut less than 10%, its turgidity is 250～260, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Embodiment 12:
With the 3g tween be scattered in the hexanaphthene, the mass percentage concentration of this tween is 6%.Stirring and dissolving, the oxygen that logical nitrogen flooding is removed wherein forms oil phase.
In the 100ml beaker, add 3.0g AMPS, 3.0g AM; 3.0gAA, add water and be mixed with the aqueous solution that mass percentage concentration is the water-soluble vinyl unsaturated monomer of 20 %, stir adding 0.2g N down; N '-methylene-bisacrylamide, 1 gram Potassium Persulphate; Stirring and dissolving adds 2.0g median size 20.0 μ m, grade wherein greater than the wilkinite of TFe30% magnetite powder and 3.0g median size 10.0 μ m again, and 40 ℃ of dispersed with stirring got aqueous mixture in 15 minutes.Again aqueous mixture is added drop-wise in the above-mentioned oil phase, stirs, suspension-s was penetrated 2 hours with the 40w uv illumination, stop irradiation, be warming up to 50 ℃ of following polymerization 5h.Treat that temperature reduces to room temperature, cross and filter partical, use washing with alcohol; Obtain particulate state magnetic expansion adsorption composite material finished product in 80 ℃ of vacuum-drying to water cut less than 10%, its turgidity is 290～300, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～300mg/g dried resin, explains that turgidity is high, high adsorption capacity.
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (like temperature, concentration etc.), interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (12)
1. magnetic expansion adsorption composite material; It is characterized in that, it by comprise weight part be respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts the water-soluble vinyl unsaturated monomer, and 0.1～2.0 part linking agent be composited through polyreaction.
2. magnetic expansion adsorption composite material according to claim 1; It is characterized in that; Said magnetic powder chosen from Fe magnetic mineral or through becoming the material of magnetic mineral or iron ion is adsorbed in the hydrogel after the processing; The powdery magnetic of in-situ preparing, the median size of said magnetic powder are 0.1～150 μ m.
3. magnetic expansion adsorption composite material according to claim 2 is characterized in that, the median size of said magnetic powder is 1.0-100 μ m.
4. magnetic expansion adsorption composite material according to claim 1; It is characterized in that; Said non-metallic mineral powder is selected from the silicate minerals powder that median size is 1.0～150 μ m, and said silicate minerals is selected from any one in zeolite, zeyssatite, wilkinite, attapulgite or the kaolin.
5. magnetic expansion adsorption composite material according to claim 1 is characterized in that the weight part of said water-soluble vinyl unsaturated monomer is 40.0～70.0 parts.
6. according to claim 1 or 5 described magnetic expansion adsorption composite materials; It is characterized in that; Said water-soluble vinyl unsaturated monomer is 2-acrylamido-2-methyl propane sulfonic acid; Acrylic amide, or the one or any two or more mixing in the vinylformic acid mix with arbitrary proportion during mixing.
7. magnetic expansion adsorption composite material according to claim 1 is characterized in that, said linking agent comprises that per molecule contains two polymerisable unsaturated groups at least, and said linking agent is N, N '-methylene-bisacrylamide.
8. method for preparing magnetic expansion adsorption composite material as claimed in claim 1 is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent, 0.05～10.0 part initiator and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer; The mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～40%, and said mixture is disperseed;
2) make mixture after the above-mentioned dispersion in 10～80 ℃ of heating 1～3 hour, elevated temperature to 70～90 a ℃ reaction was carried out slaking in 1～5 hour again, obtained gluey polymerisate;
3) with getting granular or powdered magnetic expansion adsorption composite material after above-mentioned gluey polymerisate chopping, drying, the pulverizing.
9. method for preparing magnetic expansion adsorption composite material as claimed in claim 1 is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent, 0.05～10.0 part initiator and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～30%;
2) at 10～80 ℃ said mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in the non-polar solvent, the mass percentage concentration of said suspension dispersive agent is 0.1%～10%, and deoxygenation then forms oil phase;
4) with step 2) aqueous mixture that obtains is added drop-wise in the above-mentioned oil phase, stirs, 10～80 ℃ of reactions 2～7 hours down;
5) said magnetic expansion adsorption composite material is filtered, washed, is drying to obtain to above-mentioned reaction product.
10. according to Claim 8 or the preparation method of 9 said magnetic expansion adsorption composite materials; It is characterized in that; Said initiator is water-soluble radical polymerization initiator or water soluble oxidized reduction initiator, and said water-soluble radical polymerization initiator comprises persulphate.
11. a method for preparing magnetic expansion adsorption composite material as claimed in claim 1 is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer; The mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～35%, and said mixture is disperseed;
2) at room temperature, the mixture after the above-mentioned dispersion was reacted after 2～3 hours under ultraviolet light irradiation, elevated temperature to 70～90 a ℃ reaction was carried out slaking in 1～3 hour again, obtained gluey polymerisate;
3) with getting granular or powdered magnetic expansion adsorption composite material after above-mentioned gluey polymerisate chopping, drying, the pulverizing.
12. a method for preparing magnetic expansion adsorption composite material as claimed in claim 1 is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 1.0～30.0 parts non-metallic mineral powder, 30.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～30%;
2) at 10～80 ℃ said mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in the non-polar solvent, the mass percentage concentration of said suspension dispersive agent is 0.1%～10%, and deoxygenation then forms oil phase;
4) with step 2) aqueous mixture that obtains is added drop-wise in the above-mentioned oil phase, stirs, and reaction stopped irradiation after 2～3 hours under ultraviolet light irradiation, and ℃ reacted 2～7 hours elevated temperature to 40～90 again;
5) said magnetic expansion adsorption composite material is filtered, washed, is drying to obtain to above-mentioned reaction product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817916A (en) * | 2006-03-23 | 2006-08-16 | 中国地质大学（武汉） | Composite materials with high water absorbing and retaining performances containing diatomite and production thereof |
| CN1908057A (en) * | 2006-08-17 | 2007-02-07 | 中国地质大学（武汉） | Polyacrylic acid super absorbent resin containing illite and fly ash and preparation method |
| CN101113022A (en) * | 2007-07-06 | 2008-01-30 | 哈尔滨工业大学 | Chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles |
| CN101935070A (en) * | 2010-09-17 | 2011-01-05 | 东华大学 | Method for synthesizing superparamagnetic ferroferric oxide nano particle in situ by induction of acrylic acid polymer nano hydrogel |
-
2012
- 2012-02-27 CN CN201210045129.5A patent/CN102585420B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817916A (en) * | 2006-03-23 | 2006-08-16 | 中国地质大学（武汉） | Composite materials with high water absorbing and retaining performances containing diatomite and production thereof |
| CN1908057A (en) * | 2006-08-17 | 2007-02-07 | 中国地质大学（武汉） | Polyacrylic acid super absorbent resin containing illite and fly ash and preparation method |
| CN101113022A (en) * | 2007-07-06 | 2008-01-30 | 哈尔滨工业大学 | Chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles |
| CN101935070A (en) * | 2010-09-17 | 2011-01-05 | 东华大学 | Method for synthesizing superparamagnetic ferroferric oxide nano particle in situ by induction of acrylic acid polymer nano hydrogel |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214604A (en) * | 2013-04-27 | 2013-07-24 | 中国地质大学（武汉） | Inorganic-organic compound dispersing agent for suspension polymerization and application of inorganic-organic compound dispersing agent |
| CN103285839A (en) * | 2013-07-02 | 2013-09-11 | 河北工业大学 | Preparation method of calcium-based bentonite-AA (AA-Na) composite granular cadmium ion adsorbent |
| CN103285839B (en) * | 2013-07-02 | 2015-03-11 | 河北工业大学 | Preparation method of calcium-based bentonite-AA (AA-Na) composite granular cadmium ion adsorbent |
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