CN102585420B - 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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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 63
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 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
- 239000000203 mixture Substances 0.000 claims description 56
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 55
- 229920002554 vinyl polymer Polymers 0.000 claims description 55
- 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 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 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
- 239000000725 suspension Substances 0.000 claims description 10
- 239000000017 hydrogel 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
- 238000002156 mixing Methods 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007870 radical polymerization initiator Substances 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012454 non-polar solvent Substances 0.000 claims description 5
- 229910052604 silicate mineral Inorganic materials 0.000 claims description 5
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- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
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- 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
- 238000012545 processing Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical group CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-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
- 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
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001455 metallic ions Chemical class 0.000 abstract 2
- 238000005204 segregation Methods 0.000 abstract 2
- 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 235000019394 potassium persulphate Nutrition 0.000 description 9
- 239000004159 Potassium persulphate Substances 0.000 description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920000136 polysorbate Polymers 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
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000002994 raw material Substances 0.000 description 3
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
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- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 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 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 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
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910001448 ferrous ion Inorganic materials 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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- 229910052708 sodium Inorganic materials 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
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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.In recent years development proves that swelling behavior material has the superpower adsorptive power of selectivity and super large loading capacity to metal ion as heavy metal ion etc., so swelling behavior material becomes again swollen absorbent material.Chinese Patent Application No. 201010284643 and 200710072462 Patent Application Publications taking hydrogel as template, taking Fe(III), Fe(II) prepare the method for ferriferrous oxide nano-particle as raw material.Obvious this method is to prepare magnetic particle by there is chemical reaction after absorption iron ion, but not magnetic hydrogel, and there is the restriction that molecule internal adsorption group is saturated by iron, adsorptive capacity is little, be difficult to hydrogel magnetic power significantly to be adjusted, preparation manipulation complexity, condition is difficult to control, and the application of using it for enrichment and separating metal ion 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 object of the present invention, the technical solution used in the present invention is:
A kind of magnetic expansion adsorption composite material, it is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts and the linking agent of 0.1～2.0 part and be composited by polyreaction by comprising weight part.
In such scheme, described magnetic powder chosen from Fe magnetic mineral or by processing after become the material of magnetic mineral or iron ion be adsorbed in hydrogel, powdery magnetic substance prepared by original position, the median size of described magnetic powder is 0.1～150 μ m.
In such scheme, the median size of described magnetic powder is 1.0-100 μ m.
In such scheme, described non-metallic mineral powder is selected from the silicate minerals powder that median size is 1.0～150 μ m, and described silicate minerals is selected from any one in zeolite, diatomite, wilkinite, attapulgite or kaolin.
In such scheme, the weight part of described water-soluble vinyl unsaturated monomer is 40.0～70.0 parts.
In such scheme, described water-soluble vinyl unsaturated monomer is 2-acrylamide-2-methylpro panesulfonic acid, and acrylamide, or mixing in vinylformic acid one or any two kinds, mix with arbitrary proportion when mixing.
In such scheme, described linking agent comprises that per molecule is at least containing two polymerisable unsaturated groups, and described linking agent is N, N '-methylene-bisacrylamide.
A method of preparing magnetic expansion adsorption composite material, it comprises the following steps:
1) weight part is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, the linking agent of 0.1～2.0 part, the initiator of 0.05～10.0 part and water and mix, obtain mixture, wherein, water and water-soluble vinyl unsaturated monomer are mixed to get the aqueous solution of water-soluble vinyl unsaturated monomer, the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～40%, and described mixture is disperseed;
2) make mixture after above-mentioned dispersion in 10～80 DEG C of heating 1～3 hour, then temperature to the 70～90 DEG C reaction that raises carries out slaking in 1～5 hour, obtain gluey polymerisate;
3) by above-mentioned gluey polymerisate chopping, dry, after pulverizing the magnetic expansion adsorption composite material of granular or powdery.
A method of preparing magnetic expansion adsorption composite material, it comprises the following steps:
1) weight part is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, the linking agent of 0.1～2.0 part, the initiator of 0.05～10.0 part and water and mix, obtain mixture, wherein, water and water-soluble vinyl unsaturated monomer are mixed to get the aqueous solution of 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 DEG C, described mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in non-polar solvent, the mass percentage concentration of described suspension dispersive agent is 0.1%～10%, and then deoxygenation forms oil phase;
4) by step 2) aqueous mixture that obtains is added drop-wise in above-mentioned oil phase, stirs, at 10～80 DEG C, react 2～7 hours;
5) above-mentioned reaction product is filtered, is washed, is drying to obtain described magnetic expansion adsorption composite material.
In such scheme, described initiator is water-soluble radical polymerization initiator or water soluble oxidized reduction initiator, and described water-soluble radical polymerization initiator comprises persulphate.
A method of preparing magnetic expansion adsorption composite material, is characterized in that, it comprises the following steps:
1) weight part is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, the linking agent of 0.1～2.0 part and water and mix, obtain mixture, wherein, water and water-soluble vinyl unsaturated monomer are mixed to get the aqueous solution of water-soluble vinyl unsaturated monomer, the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～35%, and described mixture is disperseed;
2) at room temperature, the mixture after above-mentioned dispersion is reacted after 2～3 hours under ultraviolet light irradiation, then temperature to the 70～90 DEG C reaction that raises carries out slaking in 1～3 hour, obtain gluey polymerisate;
3) by above-mentioned gluey polymerisate chopping, dry, after pulverizing the magnetic expansion adsorption composite material of granular or powdery.
A method of preparing magnetic expansion adsorption composite material, is characterized in that, it comprises the following steps:
1) weight part is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, the linking agent of 0.1～2.0 part and water and mix, obtain mixture, wherein, water and water-soluble vinyl unsaturated monomer are mixed to get the aqueous solution of 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 DEG C, described mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in non-polar solvent, the mass percentage concentration of described suspension dispersive agent is 0.1%～10%, and then deoxygenation forms oil phase;
4) by step 2) aqueous mixture that obtains is added drop-wise in above-mentioned oil phase, stirs, and under ultraviolet light irradiation, reacts after 2～3 hours, stops irradiation, then temperature to the 40～90 DEG C reaction 2～7 hours that raises;
5) above-mentioned reaction product is filtered, is washed, is drying to obtain described magnetic expansion adsorption composite material.
The invention has the beneficial effects as follows: metal ion existing hydrogel network Semi-polarity group and network expansion are strengthened to the function of adsorbing, there is again the function of highly surface activated mineral to adsorption of metal ions simultaneously, expansion loading capacity large (high adsorption capacity), magnetic power is adjustable, gel-strength is high, can carry out adsorption and enrichment to metal ion as heavy metal ion etc. in water body or in soil or in solid-liquid suspension (mixing) system, have easily by magnet or magnetic separation machinery from water body simultaneously, soil, in solid-liquid suspension system, separate, manufacture method is simple, cost is low, turgidity is high, can be widely used in the advantage that thermopnore or preparation equipment carry out automatization mass metal ion isolation, be suitable for environment protection, Pollution abatement, bioseparation, the adsorption and enrichment separation function magnetic expansion adsorption composite material of the sector applications such as ore dressing.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
First introduce in detail related magnetic powder, non-metallic mineral powder, water-soluble vinyl unsaturated monomer, linking agent, initiator, reaction medium and auxiliary agent in the following all embodiment of the present invention below.
1. magnetic powder
Magnetic powder mainly refers to powder, the iron powder containing ferromagnetic mineral, or by becoming the material of magnetic mineral after processing, as: rhombohedral iron ore is reduced to the magnetic product that obtains etc.Median size is 0.1～150 μ m, is preferably 1.0-100 μ m.Ferromagnetic mineral itself has stronger magnetic, and under outside magnetic field effect, the specific magnetising moment is very large, and magnetite is typical ferromagnetic mineral.Regulate magnetic powder content how many adjustable magnetic hydrogel magnetic power, its addition is that weight part is greater than zero and be less than or equal to 50 parts, is preferably 1.0～30.0 parts.
2. non-metallic mineral powder
Described non-metallic mineral powder, refer to specific surface area large, to the particularly silicate minerals powder of large, the high adsorption capacity of heavy metal ion adsorbed capacity of metal ion, as zeolite, diatomite, wilkinite, attapulgite, the 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
Water-soluble vinyl unsaturated monomer is the main body that forms hydrogel, is also 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 derivative thereof; Typical nonionic monomers is: acrylamide and derivative thereof.Wherein preferably water-soluble vinyl unsaturated monomer is 2-acrylamide-2-methylpro panesulfonic acid (hereinafter to be referred as AMPS), acrylamide (hereinafter to be referred as AM), vinylformic acid (hereinafter to be referred as AA) is one, two or more these monomer mixture wherein, if when 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
In cross-linker molecules, at least containing two polymerisable unsaturated groups, these linking agents make hydrogel form in mutually and be cross-linked or lightly crosslinked three-dimensional net structure at body, regulate adjustable its gel-strength of its consumption and water-retaining capacity.Typical linking agent has: N, and N '-methylene-bisacrylamide, consumption is 0.1～2.0 part of weight part.
5. initiator
The water-soluble radical polymerization initiator that is applicable to water solution polymerization process or via Inverse-Phase Suspension Polymerization is persulphate, as: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, these water soluble starters can mix use.Also can as fitting in redox system, ferrous ion, sodium bisulfite, S-WAT etc. use with reducing substances.While being used in conjunction with, each proportioning components is determined by the quantitative relation of chemical equation.Initiator amount is 0.05～10.0 part of weight part, preferably 0.1～2.0 part.Kick off temperature is 10 DEG C～80 DEG C, preferably 65 DEG C～75 DEG C of single initiators, and the preferred temperature of redox initiator is 20 DEG C～50 DEG C.
6. reaction medium and auxiliary agent
While adopting water solution polymerization process, reaction medium is water; While adopting via Inverse-Phase Suspension Polymerization, reaction medium is non-polar solvent, as hexanaphthene or kerosene etc.Add tensio-active agent as op simultaneously, this dish, tweens etc. do suspension dispersive agent and carry out suspended dispersed, and addition is mass percentage concentration 0.1%～10.0%.
The dispersing method of mentioning in all embodiment below can be selected homogenizer to carry out dispersed with stirring or disperse with colloidal mill, or adopts ultrasonic wave to carry out ultrasonic dispersion.
In the present invention, adopt the turgidity that measurement and calculation is inhaled distilled water, tap water and physiological saline with the following method:
The granulated material taking after 0.5～1.0g drying treatment is placed in 500-1000ml beaker, add 450～900ml distilled water or tap water or take granulated material after 0.5～1.0g drying treatment and be placed in 150ml beaker and add 100ml 0.9%NaCl solution, leave standstill after 24 hours, with 100 order mesh screens by unnecessary water elimination, weigh up gel quality affects, be calculated as follows turgidity:
Turgidity=(gel quality affects-xerogel quality)/xerogel quality
In the present invention, according to different metal ions, adopt different analysis test methods to measure concentration of metal ions and change, by adsorptive capacity (mg/g dried resin) sign adsorptive power.
The magnetic expansion polymeric adsorbent of being prepared by the present invention, has 10～300 times of turgiditys, to Cu(II), Cd(II), Pb(II), Zn(II), Cr(III), Hg(II), As(III) etc. have strong adsorptive power, easy-to-use magnetic technology separates.
embodiment 1:
In 1000ml beaker, add the each 50g of AMPS and AM, add water and be mixed with the aqueous solution that mass percentage concentration is 40% water-soluble vinyl unsaturated monomer, under stirring, add N, 0.05 gram of N '-methylene-bisacrylamide (linking agent) 0.1g, Potassium Persulphate, stirring and dissolving, then the diatomite that 1.0g median size 10.0 μ m, grade are greater than TFe50% magnetite powder and 1.0g median size 20.0 μ m is added wherein, 75 DEG C of dispersed with stirring 5 minutes; Mixture after above-mentioned dispersion was cooled to 10 DEG C of reactions after 3 hours, then was increased to 80 DEG C of reactions 1 hour, obtained gel (gluey polymerisate); The gel generating shreds to 2～10mm, be less than 10wt% in dry 5 hours of lower 40 DEG C of vacuum condition to water content, 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), Cr(III) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 2:
In 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, under stirring, add N, N '-methylene-bisacrylamide 2.0g, Potassium Persulphate 1.0g, sodium bisulfite 1.0g, stirring and dissolving, then the wilkinite that 50g median size 100.0 μ m, grade are greater than TFe20% magnetite powder and 30.0g median size 10.0 μ m is added wherein, 70 DEG C of dispersed with stirring 15 minutes; Mixture after above-mentioned dispersion was cooled to 50 DEG C of reactions after 3 hours, then was increased to 70 DEG C of reactions 3 hours, obtained gel (gluey polymerisate); The gel generating shreds to 2～10mm, 80 DEG C of vacuum-drying 3 hours to water content 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), Pb(II) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 3:
In 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, under stirring, add N, 10.0 grams of N '-methylene-bisacrylamide 1.0g, Sodium Persulfates, stirring and dissolving, the attapulgite that again 30.0g median size 80.0 μ m, grade is greater than to TFe30% magnetite powder and 15g median size 2.0 μ m adds wherein, 70 DEG C of supersound process 15 minutes, are down to room temperature and cross colloidal mill powder is disperseed; Mixture after above-mentioned dispersion was warming up to 50 DEG C of reactions after 3 hours, then was increased to 90 DEG C of reactions 5 hours, obtained gel (gluey polymerisate); The gel generating shreds to 2～10mm, 70 DEG C are less than 10wt% to water content in dry 4 hours, 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), Pb(II) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 4:
In 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, under stirring, add N, 5.0 grams of N '-methylene-bisacrylamide 1.5g, ammonium persulphates, stirring and dissolving, the zeolite that again 5.0g median size 1.0 μ m, grade is greater than to TFe50% magnetite powder and 1g median size 45.0 μ m adds wherein, 70 DEG C of dispersed with stirring 15 minutes; Mixture after above-mentioned dispersion was cooled to 65 DEG C of reactions after 3 hours, then was increased to 70 DEG C of reactions 3 hours, obtained gel (gluey polymerisate); The gel generating shreds to 2～10mm, 120 DEG C are less than 10wt% to water content in dry 3 hours, 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), Pb(II) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 5:
In 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, under stirring, add N, 5.0 grams of N '-methylene-bisacrylamide 1.5g, Potassium Persulphates, stirring and dissolving, then the zeolite that 5.0g median size 40.0 μ m, grade are greater than TFe50% magnetite powder and 1g median size 150.0 μ m is added wherein, 70 DEG C of dispersed with stirring 15 minutes; Mixture after above-mentioned dispersion was warming up to 75 DEG C of reactions after 3 hours, then was increased to 90 DEG C of reactions 3 hours, obtained gel (gluey polymerisate); The gel generating shreds to 2～10mm, 120 DEG C are less than 10wt% to water content in dry 3 hours, 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), Pb(II) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 6:
By median size 48.0 μ m, TFe60% iron fine powder (rhombohedral iron ore) 20g carries out magnetizing roasting at 400～600 DEG C after mixing with enough powdered carbons (C powder), obtains magnetite powder.
In 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, under stirring, add N, 0.1 gram of N '-methylene-bisacrylamide 1.0g, Potassium Persulphate, stirring and dissolving, then 10.0g magnetite powder standby upper legal system and 20g median size 100.0 μ m kaolin are added wherein, 70 DEG C of dispersed with stirring 15 minutes; Mixture after above-mentioned dispersion was cooled to 50 DEG C of reactions after 3 hours, then was increased to 70 DEG C of reactions 3 hours, obtained gel (gluey polymerisate); The gel generating shreds to 2～10mm, 120 DEG C are less than 10wt% to water content in dry 3 hours, 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), Pb(II) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 7:
In 1000ml beaker, add 30g AMPS, 10g AM, 10gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 35% water-soluble vinyl unsaturated monomer, under stirring, add N, N '-methylene-bisacrylamide 0.6g, stirring and dissolving, the zeolite that again 5.0g median size 150.0 μ m, grade is greater than to TFe50% magnetite powder and 1g median size 45.0 μ m adds wherein, after stirring and dissolving, in room temperature, mixture is penetrated 2 hours by 40w UV illumination, stopped irradiation, be increased to 70 DEG C of reactions 3 hours, obtain gel (gluey polymerisate); The gel generating shreds to 2～10mm; 90 DEG C are less than 10wt% to water content in dry 8 hours, 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, to Zn(II), Cr(III), Hg(II), As(III) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 8:
Under room temperature nitrogen protection, in 1000ml beaker, add 30g AMPS, 10g AM, 10gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 25% water-soluble vinyl unsaturated monomer, under stirring, add N, N '-methylene-bisacrylamide 0.6g, stirring and dissolving, then the zeolite of iron(ic) chloride and the each 2.5g of ferrous sulfate and 1g median size 45.0 μ m is added wherein, after stirring and dissolving, in room temperature, solution is penetrated 2 hours by 40w UV illumination, stop irradiation, then be increased to 70 DEG C of reactions 3 hours, obtain gel (gluey polymerisate); The gel generating shreds to 2～10mm, adding mass percentage concentration is that 2% alkali lye 400ml soaks 12 hours, leach gel, 90 DEG C are less than 10wt% to water content in dry 8 hours, through mechanical disintegration to 0.1～5.0mm, finally obtain particulate state magnetic expansion adsorption composite material finished product, its turgidity is 20～30, to Zn(II), Cr(III), Hg(II), As(III) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 9:
3g Span-60 is scattered in hexanaphthene, and the mass percentage concentration of this Span-60 is 0.1%.Be warming up to 75 DEG C, logical nitrogen flooding is removed oxygen wherein, opens to stir Span-60 is dissolved completely, forms oil phase.
In 100ml beaker, add 6.0g AMPS, 2.0g AM, 2.0gAA, adds water and is mixed with the aqueous solution that mass percentage concentration is 30% water-soluble vinyl unsaturated monomer, adds 0.2g N under stirring, N '-methylene-bisacrylamide, 0.2 gram of Potassium Persulphate, stirring and dissolving, then the wilkinite that 1.0g median size 20.0 μ m, grade are greater than TFe30% magnetite powder and 3.0g median size 10.0 μ m is added wherein, 70 DEG C of dispersed with stirring 15 minutes aqueous mixture.
Again aqueous mixture is added drop-wise in above-mentioned oil phase, stirs polymerization 2h at 70 DEG C.Treat that temperature is down to room temperature, filter to obtain partical, by washing with alcohol, be less than 10wt% in 80 DEG C of vacuum-drying to water content and obtain particulate state magnetic expansion adsorption composite material finished product, its turgidity is 80～100, to Cd(II), Cu(II), Pb(II) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 10:
3g op-10 is scattered in 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 100ml beaker, add 3.0g AMPS, 1.0g AM, 1.0gAA, adds water and is mixed with the aqueous solution that mass percentage concentration is 15% water-soluble vinyl unsaturated monomer, adds 0.01g N under stirring, N '-methylene-bisacrylamide, 0.005 gram of Potassium Persulphate, stirring and dissolving, then the wilkinite that 0.1g median size 0.1 μ m, grade are greater than TFe30% magnetite powder and 3.0g median size 0.1 μ m is added wherein, 80 DEG C of dispersed with stirring 15 minutes aqueous mixture.
Again aqueous mixture is added drop-wise in above-mentioned oil phase, stirs polymerization 5h at 80 DEG C.Treat that temperature is down to room temperature, filter to obtain partical, by methanol wash, be less than 10wt% in 120 DEG C of vacuum-drying to water content and obtain particulate state magnetic expansion adsorption composite material finished product, its turgidity is 100～120, to Cd(II), Cu(II), Pb(II) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 11:
By 3g tween be scattered in 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 100ml beaker, add 3.0g AMPS, 2.0g AM, 2.0gAA, adds water and is mixed with the aqueous solution that mass percentage concentration is 20% water-soluble vinyl unsaturated monomer, adds 0.1g N under stirring, N '-methylene-bisacrylamide, 0.5 gram of Potassium Persulphate, stirring and dissolving, then the wilkinite that 3.0g median size 20.0 μ m, grade are greater than TFe30% magnetite powder and 3.0g median size 10.0 μ m is added wherein, 50 DEG C of dispersed with stirring 15 minutes aqueous mixture.
Again aqueous mixture is added drop-wise in above-mentioned oil phase, stirs polymerase 17 h at 40 DEG C.Treat that temperature is down to room temperature, filter to obtain partical, by washing with alcohol, be less than 10% in 80 DEG C of vacuum-drying to water content and obtain particulate state magnetic expansion adsorption composite material finished product, its turgidity is 250～260, to Cd(II), Cu(II), Pb(II) adsorptive capacity be 20～400mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
embodiment 12:
By 3g tween be scattered in 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 100ml beaker, add 3.0g AMPS, 3.0g AM, 3.0gAA, adds water and is mixed with the aqueous solution that mass percentage concentration is the water-soluble vinyl unsaturated monomer of 20 %, adds 0.2g N under stirring, N '-methylene-bisacrylamide, 1 gram of Potassium Persulphate, stirring and dissolving, then the wilkinite that 2.0g median size 20.0 μ m, grade are greater than TFe30% magnetite powder and 3.0g median size 10.0 μ m is added wherein, 40 DEG C of dispersed with stirring 15 minutes aqueous mixture.Again aqueous mixture is added drop-wise in above-mentioned oil phase, stirs, suspension is penetrated 2 hours by 40w UV illumination, stop irradiation, be warming up to polymerization 5h at 50 DEG C.Treat that temperature is down to room temperature, filter to obtain partical, by washing with alcohol, be less than 10% in 80 DEG C of vacuum-drying to water content and obtain particulate state magnetic expansion adsorption composite material finished product, its turgidity is 290～300, to Cd(II), Cu(II), Pb(II) adsorptive capacity be 20～300mg/g dried resin, illustrate that turgidity is high, high adsorption capacity.
Each raw material that the present invention is cited, and the bound of the each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, concentration etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (10)
1. a magnetic expansion adsorption composite material, it is characterized in that, it is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts by comprising weight part, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, and the linking agent of 0.1～2.0 part is composited by polyreaction, described non-metallic mineral powder is selected from the silicate minerals powder that median size is 1.0～150 μ m, described silicate minerals is selected from zeolite, wilkinite, attapulgite, or any one in kaolin, described water-soluble vinyl unsaturated monomer is 2-acrylamide-2-methylpro panesulfonic acid, acrylamide, or one or any two or more mixing in vinylformic acid, when mixing, mix with arbitrary proportion, described linking agent is N, N '-methylene-bisacrylamide.
2. magnetic expansion adsorption composite material according to claim 1, it is characterized in that, described magnetic powder chosen from Fe magnetic mineral or by processing after become the material of magnetic mineral or iron ion be adsorbed in hydrogel, powdery magnetic substance prepared by original position, the median size of described magnetic powder is 0.1～150 μ m.
3. magnetic expansion adsorption composite material according to claim 2, is characterized in that, the median size of described magnetic powder is 1.0-100 μ m.
4. magnetic expansion adsorption composite material according to claim 1, is characterized in that, the weight part of described water-soluble vinyl unsaturated monomer is 40.0～70.0 parts.
5. a method of preparing magnetic expansion adsorption composite material as claimed in claim 1, is characterized in that, it comprises the following steps:
1) weight part is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, the linking agent of 0.1～2.0 part, the initiator of 0.05～10.0 part and water and mix, obtain mixture, wherein, water and water-soluble vinyl unsaturated monomer are mixed to get the aqueous solution of water-soluble vinyl unsaturated monomer, the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～40%, and described mixture is disperseed;
2) make mixture after above-mentioned dispersion in 10～80 DEG C of heating 1～3 hour, then temperature to the 70～90 DEG C reaction that raises carries out slaking in 1～5 hour, obtain gluey polymerisate;
3) by above-mentioned gluey polymerisate chopping, dry, after pulverizing the magnetic expansion adsorption composite material of granular or powdery.
6. a method of preparing magnetic expansion adsorption composite material as claimed in claim 1, is characterized in that, it comprises the following steps:
1) weight part is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, the linking agent of 0.1～2.0 part, the initiator of 0.05～10.0 part and water and mix, obtain mixture, wherein, water and water-soluble vinyl unsaturated monomer are mixed to get the aqueous solution of 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 DEG C, described mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in non-polar solvent, the mass percentage concentration of described suspension dispersive agent is 0.1%～10%, and then deoxygenation forms oil phase;
4) by step 2) aqueous mixture that obtains is added drop-wise in above-mentioned oil phase, stirs, at 10～80 DEG C, react 2～7 hours;
5) above-mentioned reaction product is filtered, is washed, is drying to obtain described magnetic expansion adsorption composite material.
7. according to the preparation method of magnetic expansion adsorption composite material described in claim 5 or 6, it is characterized in that, described initiator is water-soluble radical polymerization initiator, and described water-soluble radical polymerization initiator comprises persulphate.
8. the preparation method of magnetic expansion adsorption composite material according to claim 7, is characterized in that, described water-soluble radical polymerization initiator is water soluble oxidized reduction initiator.
9. a method of preparing magnetic expansion adsorption composite material as claimed in claim 1, is characterized in that, it comprises the following steps:
1) weight part is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, the linking agent of 0.1～2.0 part and water and mix, obtain mixture, wherein, water and water-soluble vinyl unsaturated monomer are mixed to get the aqueous solution of water-soluble vinyl unsaturated monomer, the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～35%, and described mixture is disperseed;
2) at room temperature, the mixture after above-mentioned dispersion is reacted after 2～3 hours under ultraviolet light irradiation, then temperature to the 70～90 DEG C reaction that raises carries out slaking in 1～3 hour, obtain gluey polymerisate;
3) by above-mentioned gluey polymerisate chopping, dry, after pulverizing the magnetic expansion adsorption composite material of granular or powdery.
10. a method of preparing magnetic expansion adsorption composite material as claimed in claim 1, is characterized in that, it comprises the following steps:
1) weight part is respectively and is greater than zero and be less than or equal to the magnetic powder of 50 parts, the non-metallic mineral powder of 1.0～30.0 parts, the water-soluble vinyl unsaturated monomer of 30.0～100.0 parts, the linking agent of 0.1～2.0 part and water and mix, obtain mixture, wherein, water and water-soluble vinyl unsaturated monomer are mixed to get the aqueous solution of 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 DEG C, described mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in non-polar solvent, the mass percentage concentration of described suspension dispersive agent is 0.1%～10%, and then deoxygenation forms oil phase;
4) by step 2) aqueous mixture that obtains is added drop-wise in above-mentioned oil phase, stirs, and under ultraviolet light irradiation, reacts after 2～3 hours, stops irradiation, then temperature to the 40～90 DEG C reaction 2～7 hours that raises;
5) above-mentioned reaction product is filtered, is washed, is drying to obtain described magnetic expansion adsorption composite material.
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| 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 |
| CN104017233B (en) * | 2014-05-27 | 2017-01-04 | 哈尔滨工业大学 | The preparation method of magnetotactic bateria cellulose aerogels oil absorption material |
| CN104826600B (en) * | 2015-05-05 | 2018-03-02 | 济南大学 | A kind of magnetic kleit preparation method |
| CN106732453A (en) * | 2016-12-12 | 2017-05-31 | 墨宝股份有限公司 | A kind of adsorption composite material of magnetic expansion and preparation method thereof |
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Effective date of registration: 20151030 Address after: 430206 East Lake high tech Development Zone, Hubei Province, high and new avenue, No. 999, No. Patentee after: WUHAN INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE OF GEO-RESOURES ENVIRONMENT Co.,Ltd. Patentee after: Fan Liren Address before: 430074 Wuhan Road, Hongshan, Shandong Province, Lu Lu Road, No. 388, No. Patentee before: Wuhan in the big asset management Co.,Ltd. Patentee before: Fan Liren |
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Effective date of registration: 20151202 Address after: 430206 East Lake high tech Development Zone, Hubei Province, high and new avenue, No. 999, No. Patentee after: CUG (WUHAN) GOLDEN SHIELD ENVIRONMENTAL TECHNOLOGY Co.,Ltd. Address before: 430206 East Lake high tech Development Zone, Hubei Province, high and new avenue, No. 999, No. Patentee before: WUHAN INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE OF GEO-RESOURES ENVIRONMENT Co.,Ltd. Patentee before: Fan Liren |
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