CN101497051A - Composite cationic ion-exchange resin supporting iron-series duplex metal nano granules as well as preparation method and use thereof - Google Patents
Composite cationic ion-exchange resin supporting iron-series duplex metal nano granules as well as preparation method and use thereof Download PDFInfo
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- CN101497051A CN101497051A CNA2009100284144A CN200910028414A CN101497051A CN 101497051 A CN101497051 A CN 101497051A CN A2009100284144 A CNA2009100284144 A CN A2009100284144A CN 200910028414 A CN200910028414 A CN 200910028414A CN 101497051 A CN101497051 A CN 101497051A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000008187 granular material Substances 0.000 title claims description 40
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 7
- 239000011147 inorganic material Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000002114 nanocomposite Substances 0.000 claims description 37
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910017061 Fe Co Inorganic materials 0.000 claims description 3
- 229910002549 Fe–Cu Inorganic materials 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 229920001429 chelating resin Polymers 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 36
- 238000006731 degradation reaction Methods 0.000 abstract description 36
- 239000000463 material Substances 0.000 abstract description 25
- 239000002245 particle Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 4
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 2
- 238000001179 sorption measurement Methods 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000000805 composite resin Substances 0.000 abstract 1
- 230000007812 deficiency Effects 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 239000012279 sodium borohydride Substances 0.000 abstract 1
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 230000003197 catalytic effect Effects 0.000 description 31
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 30
- 229910001385 heavy metal Inorganic materials 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical class ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 10
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 9
- 229940012189 methyl orange Drugs 0.000 description 9
- 229960002415 trichloroethylene Drugs 0.000 description 9
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 7
- 150000008282 halocarbons Chemical class 0.000 description 7
- 239000002082 metal nanoparticle Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 6
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 description 6
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 4
- XWZDJOJCYUSIEY-UHFFFAOYSA-L disodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O XWZDJOJCYUSIEY-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
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- 230000003335 steric effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The invention discloses a supported ferric bimetallic nanometer composite cation exchange resin, a preparation method and application thereof, which belong to the field of nanometer composite resin. A carrier of the resin is an ionic exchange and adsorption resin with an acidic functional group; a resin frame is styrene series or crylic acid series, and contains a sulfonic group, a carboxylic group or a phosphonic acid group; and a solid supported inorganic material is nanometer iron series bimetallic particles. The preparation method uses the ion exchange and adsorption resin with the acidic functional group as the carrier to be solidly loaded by Fe<2+> or Fe<3+>, is reduced by a NaBH4 or KBH4 solution, and is immersed in a salt solution of the second metal so as to produce the supported ferric bimetallic nanometer composite cation exchange resin. The supported ferric bimetallic nanometer composite cation exchange resin, the preparation method and the application thereof combine Donnan preenrichment effect and high-efficiency catalysis degradation effect into a whole, and improve the degradation speed of the material on a target pollutant while overcoming the deficiencies of easily agglomerated pure nanometer nulvalent iron, unstable chemical property, small particles, large hydraulic loss and the like, thereby having degradation characteristics of high efficiency, fast speed and low cost on an environment micro-pollutant.
Description
Technical field
The present invention relates to a kind of nanocomposite that is used for catalytic degradation environment micropollutants, the composite cationic ion-exchange resin supporting iron-series duplex metal nano granules and its production and application of saying so more specifically.
Background technology
Since the beginning of this century, caused numerous scholars' interest about the research of nano zero valence iron.As a kind of efficient reducing agent, nano zero valence iron has the specific area height, catalytic activity is good, with low cost, many characteristics such as environmental friendliness, be widely used in environmental contaminants, as heavy metal ion, (Li in the catalytic degradation of big molecular dye and halogenated organic matters etc., X.Q., Elliott, D.W., Zhang, W.X.Zero-Valent ironnanoparticles for abatement of environmental pollutants:Materials andengineering aspects.Critical Reviews in Solid State and MaterialsSciences 2006,31:111-122).Shortcoming such as big, the animal migration difference of loss in head when using for the self aggregation effect that overcomes nano zero valence iron, unstable chemcial property (easily oxidized) and engineering, domestic people such as Zhao Zongshan address this problem (Zhao Zongshan with the nano zero valence iron particle is immobilized to cationic ion-exchange resin, Liu Jingfu, Tai is superfine. the carried ion exchange resin zeroth order nanometer iron soluble azo dyes of degrading fast. and Chinese science B: chemistry, 2008,38 (1): 60～66).But immobilized nano zero valence iron particle in the resin inner surface is not ideal enough to the catalytic degradation speed of some difficult degradation pollutants.Form the iron-series duplex metal structure and be not studied the person already and find to significantly improve its degradation rate (Zheng and in the Zero-valent Iron nano particle, introduce second kind of metal difficult degradation pollutants such as trichloro-ethylenes, T.H., Zhan, J.J., He, J.B., et al.Reactivitycharacteristics of nanoscale zerovalent iron-silica composites fortrichloroethylene remediation.Environmental Science ﹠amp; Technology.2008,42:4494-4499).
Nanjing University had applied for " method of resin-base nano hydrated ferric oxide deep purifying heavy metal micro-polluted water body " patent (patent No.: 200710191355.3) in 2007, this patent is that hydrated ferric oxide (iron-series duplex metal) particle is immobilized in the cationic ion-exchange resin inner surface, mainly utilize the collaborative suction-operated of the acidic-group of resin and hydrous iron oxide particle, realize deep purifying heavy metal in the water body to heavy metal.
The result of literature search shows: a kind of composite cationic ion-exchange resin supporting iron-series duplex metal nano granules and preparation method thereof is not seen bibliographical information as yet.
Summary of the invention
1. invent the technical problem that will solve
The invention provides composite cationic ion-exchange resin supporting iron-series duplex metal nano granules and its production and application, the big problem of loss in head when directly using that this nanocomposite can solve the slow and iron-series duplex metal nano particle of Zero-valent iron-carrying nano compound resin catalytic degradation speed, improve the catalytic degradation efficient of nanocomposite, for deep purifying and the security control of environment micropollutants (as heavy metal ion, big molecular dye and halogenated organic matters etc.) provides better technical support.
2. technical scheme
Composite cationic ion-exchange resin supporting iron-series duplex metal nano granules, carrier is ion-exchange and the polymeric adsorbent with acid functional group, resin matrix is polystyrene or acrylic acid series, contains sulfonic group, carboxylic acid group or phosphonate group on the resin matrix, and immobilized inorganic material is the nanometer iron-series bimetal granule.
Above-mentioned carrier is a large hole cation exchanger resin, and resin matrix is polystyrene or acrylic acid series, can contain sulfonic group (SO on the resin matrix
3H), the carboxylic acid group (COOH) or phosphonate group (PO
3H
2) etc., the average pore size of resin is between 1-100nm.These resins can be D001, D113, AmberliteIRA-120, Purolite A-100, NDA100 resin.In this class composite cationic ion-exchange resin supporting iron-series duplex metal nano granules, the content of Fe is 10-250mg/g, and the content of second kind of metal (Al, Cu, Co, Ni, Pd, Re or Zn etc.) is 10-50mg/g, and the iron-series duplex metal nano particle is of a size of 5-100nm.Second kind of metal shifts as electronics and the catalyst of reduction hydrogenation will significantly improve the catalytic degradation speed of this class nanocomposite, and reduces or eliminate the toxicity of reduzate.
The preparation method of composite cationic ion-exchange resin supporting iron-series duplex metal nano granules may further comprise the steps: (A) choose ion-exchange with acid functional group and the polymeric adsorbent carrier as nanocomposite, with Fe
2+Or Fe
3+Ion imports the surfaces externally and internally of resin by ion exchange;
(B) use NaBH
4Or KBH
4Solution will import the Fe of resin surfaces externally and internally
2+Or Fe
3+Ion is reduced to nano zero valence iron;
(C) with the reacted resin of step (B) at N
2Protection is immersed in the soluble-salt solution of second kind of metal A l, Cu, Co, Ni, Pd, Re, Al or Zn down, by washing and dry, promptly obtains a kind of composite cationic ion-exchange resin supporting iron-series duplex metal nano granules again.
Fe in the step (A)
2+Or Fe
3+Ion source is the Fe (NO of 0.1-0.5mol/L in concentration
3)
2Or Fe (NO
3)
3, FeSO
4Or Fe
2(SO
4)
3, FeCl
2Or FeCl
3Deng solution, ion-exchange time is 4-24h.
NaBH in the step (B)
4Or KBH
4The concentration of solution is 0.2～2mol/L, and the character of solution is that the volume ratio of ethanol is 0～50% the aqueous solution, reduction reaction no longer includes bubble in solution emerge till.
The concentration of the salting liquid of the second kind of metal (Al, Cu, Co, Ni, Pd, Re, Zn etc.) in the step (C) is 0.01-1mol/L, and soak time is 4-24h.
The structure of the composite cationic ion-exchange resin supporting iron-series duplex metal nano granules that said method makes can be found out among the transmission electron microscope of tangent plane (TEM) figure in the material from accompanying drawing 1.
Background parts is the skeleton of resin carrier among the figure, and stain is represented nanometer iron-series bimetallic inorganic material, and common nanometer iron-series bimetallic inorganic material can be Fe-Pd, Fe-Cu, Fe-Co, Fe-Ni, Fe-Re, Fe-Al or Fe-Zn etc.From scale as can be seen, inorganic material particle is of a size of nanoscale, and be dispersed in the resin hole, because the stabilized nano grid of holes of carrier structure own, these nano-particle inorganic materials are limited by the steric effect that skeleton nano-pore masterplate causes, suppress its spontaneous gathering, effectively controlled the quick oxidation consumption problem of iron-series duplex metal nano particle simultaneously.The nano-pore masterplate effect of resin has fundamentally solved the stabilization problem of iron-series duplex metal nano particle.
The grain diameter of nanocomposite is 0.5-1.5mm, the excessive problem of loss in head when such particle size can overcome free iron-series duplex metal nano particle and is applied to fluid system.And the acid function base of resin surface has the characteristic of preenrichment for electropositivity pollutants such as the heavy metal ion in the water environment, the big molecules of dyestuff based on Donnan film effect; Resin matrix also has the characteristic of preenrichment for the organic pollution in the water environment based on effects such as hydrophobic effect, micropore fillings.
3. beneficial effect
The invention provides composite cationic ion-exchange resin supporting iron-series duplex metal nano granules and its production and application.The big problem of loss in head when directly using that this nanocomposite has solved the slow and iron-series duplex metal nano particle of Zero-valent iron-carrying nano compound resin catalytic degradation speed, and increase its preenrichment ability for electropositivity pollutant and hydrophobic contaminant in the water environment, crucial is the catalytic degradation efficient that has obviously improved nanocomposite.Based on carry the iron-series duplex metal nano particle to pollutant efficiently, catalytic degradation ability fast, composite cationic ion-exchange resin supporting iron-series duplex metal nano granules provided by the invention is that deep purifying and the security control of environment micropollutants (as heavy metal ion, big molecular dye and halogenated organic matters etc.) provides better technical support.
Figure of description
Fig. 1 is the transmission electron microscope picture (TEM) of tangent plane in the material of the present invention
The specific embodiment
Further specify the present invention by the following examples
Embodiment 1:
5g D001 resin is put into the FeCl of 0.1mol/L
3Exchange 4h in the solution, filter, centrifugal dehydration is with the NaBH of 0.25mol/L
4Aqueous solution reduction is till no longer including bubble emerge in solution.Again reacted resin is immersed the PdCl of 0.01mol/L
24h in the solution.Filter, with the distilled water washing, vacuum drying 24h makes composite cationic ion-exchange resin supporting iron-series duplex metal nano granules (Fe-Pd-D001).The content of Fe is 20mg/g in this nanocomposite, and the content of Pd is 10mg/g, and Fe-Pd duplex metal nano granule particle diameter is 5-100nm.
The Fe-Pd-D001 nanocomposite has extremely strong catalytic degradation ability to heavy metal Cr (VI) and Pb (II).Illustrate, when the concentration of Cr in the water body (VI) and Pb (II) is respectively 10 and during 15mg/L, above-mentioned material can be in 2h be reduced to the concentration of Cr (VI) and Pb (II) respectively 0.02 and below the 0.005mg/L.
The Fe-Pd-D001 nanocomposite has extremely strong catalytic degradation ability to dyestuff sunset yellow and methyl orange.Illustrate, when the concentration of sunset yellow in the water body and methyl orange is respectively 10 and during 20mg/L, above-mentioned material can be in 4h be reduced to the concentration of sunset yellow and methyl orange respectively 0.3 and below the 0.5mg/L.
The Fe-Pd-D001 nanocomposite has extremely strong catalytic degradation ability to halogenated hydrocarbons such as the trichloro-ethylene and the chlorobenzene etc. of trace in the water body.Illustrate, when trichloro-ethylene in the water body and chlorobenzene concentration respectively are 5 and during 2mg/L, above-mentioned material can be in 4h reduces to 0.02 and below the 0.05mg/L respectively with trichloro-ethylene and chlorobenzene concentration.
Embodiment 2:
5g D113 resin is put into the FeCl of 0.2mol/L
3Exchange 8h in the solution, filter, centrifugal dehydration is with the NaBH of 0.5mol/L
4Aqueous solution reduction is till no longer including bubble emerge in solution.Again reacted resin is immersed the AlCl of 0.02mol/L
38h in the solution.Filter, with the distilled water washing, vacuum drying 24h makes composite cationic ion-exchange resin supporting iron-series duplex metal nano granules (Fe-Al-D113).The content of Fe is 40mg/g in this nanocomposite, and the content of Al is 20mg/g, and Fe-Al duplex metal nano granule particle diameter is 5-100nm.
The Fe-Al-D113 nanocomposite has extremely strong catalytic degradation ability to heavy metal Cd (II) and Pb (II).Illustrate, when the concentration of Cd in the water body (VI) and Pb (II) is respectively 10 and during 15mg/L, above-mentioned material can be in 2h be reduced to the concentration of Cr (VI) and Pb (II) respectively 0.003 and below the 0.005mg/L.
The Fe-AI-D113 nanocomposite has extremely strong catalytic degradation ability to gorgeous blue K-3R of dye activity and acid fuchsin.Illustrate, when the concentration of reactive brilliant blue K-3R and acid fuchsin in the water body is respectively 10 and during 20mg/L, above-mentioned material can be in 4h be reduced to the concentration of reactive brilliant blue K-3R and acid fuchsin respectively 0.3 and below the 0.5mg/L.
The Fe-AI-D113 nanocomposite has extremely strong catalytic degradation ability to halogenated hydrocarbons such as the carbon tetrachloride and the tetrachloro-ethylene etc. of trace in the water body.Illustrate, when carbon tetrachloride in the water body and tce concentration respectively are 5 and during 2mg/L, above-mentioned material can be in 4h reduces to 0.02 and below the 0.05mg/L respectively with carbon tetrachloride and tce concentration.
Embodiment 3:
5g Amberlite IRA-120 resin is put into the FeCl of 0.3mol/L
3Exchange 12h in the solution, filter, centrifugal dehydration is with the NaBH of 0.8mol/L
4Aqueous solution reduction is till no longer including bubble emerge in solution.Again reacted resin is immersed the CuCl of 0.05mol/L
28h in the solution.Filter, with the distilled water washing, vacuum drying 24h makes composite cationic ion-exchange resin supporting iron-series duplex metal nano granules (Fe-Cu-IRA120).The content of Fe is 80mg/g in this nanocomposite, and the content of Cu is 30mg/g, and Fe-Cu duplex metal nano granule particle diameter is 5-100nm.
The Fe-Cu-IRA120 nanocomposite has extremely strong catalytic degradation ability to heavy metal Cr (VI) and Pb (II).Illustrate, when the concentration of Cr in the water body (VI) and Pb (II) is respectively 10 and during 15mg/L, above-mentioned material can be in 2h be reduced to the concentration of Cr (VI) and Pb (II) respectively 0.02 and below the 0.005mg/L.
The Fe-Cu-IRA120 nanocomposite has extremely strong catalytic degradation ability to dye activity bright red X-3B and acid purplish red B.Illustrate, when the concentration of reactive brilliant red x-3b in the water body and acid purplish red B is respectively 10 and during 20mg/L, above-mentioned material can be in 4h be reduced to the concentration of reactive brilliant red x-3b and acid purplish red B respectively 0.3 and below the 0.5mg/L.
The Fe-Cu-IRA120 nanocomposite has extremely strong catalytic degradation ability to halogenated hydrocarbons such as the chloroform and the chlorobenzene etc. of trace in the water body.Illustrate, when chloroform in the water body and chlorobenzene concentration respectively are 5 and during 2mg/L, above-mentioned material can be in 4h reduces to 0.02 and below the 0.05mg/L respectively with chloroform and chlorobenzene concentration.
Embodiment 4:
5g Purolite A-100 resin is put into the FeCl of 0.4mol/L
3Exchange 16h in the solution, filter, centrifugal dehydration is with the NaBH of 1.2mol/L
4Aqueous solution reduction is till no longer including bubble emerge in solution.Again reacted resin is immersed the Ni (NO of 0.08mol/L
3)
28h in the solution.Filter, with the distilled water washing, vacuum drying 24h makes composite cationic ion-exchange resin supporting iron-series duplex metal nano granules (Fe-Ni-A100).The content of Fe is 160mg/g in this nanocomposite, and the content of Ni is 40mg/g, and Fe-Ni duplex metal nano granule particle diameter is 5-100nm.
The Fe-Ni-A100 nanocomposite has extremely strong catalytic degradation ability to heavy metal Cd (II) and Pb (II).Illustrate, when the concentration of Cd in the water body (VI) and Pb (II) is respectively 10 and during 15mg/L, above-mentioned material can be in 2h be reduced to the concentration of Cr (VI) and Pb (II) respectively 0.003 and below the 0.005mg/L.
The Fe-Ni-A100 nanocomposite has extremely strong catalytic degradation ability to dyestuff sunset yellow and methyl orange.Illustrate, when the concentration of sunset yellow in the water body and methyl orange is respectively 10 and during 20mg/L, above-mentioned material can be in 4h be reduced to the concentration of sunset yellow and methyl orange respectively 0.3 and below the 0.5mg/L.
The Fe-Ni-A100 nanocomposite has extremely strong catalytic degradation ability to halogenated hydrocarbons such as the trichloro-ethylene and the chlorobenzene etc. of trace in the water body.Illustrate, when trichloro-ethylene in the water body and chlorobenzene concentration respectively are 5 and during 2mg/L, above-mentioned material can be in 4h reduces to 0.02 and below the 0.05mg/L respectively with trichloro-ethylene and chlorobenzene concentration.
Embodiment 5:
5g NDA100 resin is put into the FeCl of 0.5mol/L
3Exchange 24h in the solution, filter, centrifugal dehydration is with the KBH of 2.0mol/L
4Aqueous solution reduction is till no longer including bubble emerge in solution.Again reacted resin is immersed the ZnCl of 1.0mol/L
28h in the solution.Filter, with the distilled water washing, vacuum drying 24h makes composite cationic ion-exchange resin supporting iron-series duplex metal nano granules (Fe-Zn-NDA100).The content of Fe is 240mg/g in this nanocomposite, and the content of Zn is 50mg/g, and Fe-Zn duplex metal nano granule particle diameter is 5-100nm.
The Fe-Al-D113 nanocomposite has extremely strong catalytic degradation ability to heavy metal Cd (II) and Pb (II).Illustrate, when the concentration of Cd in the water body (VI) and Pb (II) is respectively 10 and during 15mg/L, above-mentioned material can be in 2h be reduced to the concentration of Cr (VI) and Pb (II) respectively 0.003 and below the 0.005mg/L.
The Fe-Al-D113 nanocomposite has extremely strong catalytic degradation ability to gorgeous blue K-3R of dye activity and acid fuchsin.Illustrate, when the concentration of reactive brilliant blue K-3R and acid fuchsin in the water body is respectively 10 and during 20mg/L, above-mentioned material can be in 4h be reduced to the concentration of reactive brilliant blue K-3R and acid fuchsin respectively 0.3 and below the 0.5mg/L.
The Fe-Al-D113 nanocomposite has extremely strong catalytic degradation ability to halogenated hydrocarbons such as the carbon tetrachloride and the tetrachloro-ethylene etc. of trace in the water body.Illustrate, when carbon tetrachloride in the water body and tce concentration respectively are 5 and during 2mg/L, above-mentioned material can be in 4h reduces to 0.02 and below the 0.05mg/L respectively with carbon tetrachloride and tce concentration.
Embodiment 6:
5g D001 resin is put into the FeCl of 0.4mol/L
3Exchange 24h in the solution, filter, centrifugal dehydration is with the KBH of 1.6mol/L
4Aqueous solution reduction is till no longer including bubble emerge in solution.Again reacted resin is immersed the CoCl of 0.01mol/L
28h in the solution.Filter, with the distilled water washing, vacuum drying 24h makes composite cationic ion-exchange resin supporting iron-series duplex metal nano granules (Fe-Co-D001).The content of Fe is 160mg/g in this nanocomposite, and the content of Co is 10mg/g, and Fe-Co duplex metal nano granule particle diameter is 5-100nm.
The Fe-Co-D001 nanocomposite has extremely strong catalytic degradation ability to heavy metal Cr (VI) and Pb (II).Illustrate, when the concentration of Cr in the water body (VI) and Pb (II) is respectively 10 and during 15mg/L, above-mentioned material can be in 2h be reduced to the concentration of Cr (VI) and Pb (II) respectively 0.02 and below the 0.005mg/L.
The Fe-Co-D001 nanocomposite has extremely strong catalytic degradation ability to dyestuff sunset yellow and methyl orange.Illustrate, when the concentration of sunset yellow in the water body and methyl orange is respectively 10 and during 20mg/L, above-mentioned material can be in 4h be reduced to the concentration of sunset yellow and methyl orange respectively 0.3 and below the 0.5mg/L.
The Fe-Co-D001 nanocomposite has extremely strong catalytic degradation ability to halogenated hydrocarbons such as the trichloro-ethylene and the chlorobenzene etc. of trace in the water body.Illustrate, when trichloro-ethylene in the water body and chlorobenzene concentration respectively are 5 and during 2mg/L, above-mentioned material can be in 4h reduces to 0.02 and below the 0.05mg/L respectively with trichloro-ethylene and chlorobenzene concentration.
Embodiment 7:
5g D001 resin is put into the FeCl of 0.4mol/L
3Exchange 24h in the solution, filter, centrifugal dehydration is with the KBH of 1.6mol/L
4Aqueous solution reduction is till no longer including bubble emerge in solution.Again reacted resin is immersed the ReCl of 0.01mol/L
28h in the solution.Filter, with the distilled water washing, vacuum drying 24h makes composite cationic ion-exchange resin supporting iron-series duplex metal nano granules (Fe-Re-D001).The content of Fe is 160mg/g in this nanocomposite, and the content of Re is 10mg/g, and Fe-Re duplex metal nano granule particle diameter is 5-100nm.
The Fe-Re-D001 nanocomposite has extremely strong catalytic degradation ability to heavy metal Cd (II) and Pb (II).Illustrate, when the concentration of Cd in the water body (VI) and Pb (II) is respectively 10 and during 15mg/L, above-mentioned material can be in 2h be reduced to the concentration of Cr (VI) and Pb (II) respectively 0.003 and below the 0.005mg/L.
The Fe-Re-D001 nanocomposite has extremely strong catalytic degradation ability to dye activity bright red X-3B and acid purplish red B.Illustrate, when the concentration of reactive brilliant red x-3b in the water body and acid purplish red B is respectively 10 and during 20mg/L, above-mentioned material can be in 4h be reduced to the concentration of reactive brilliant red x-3b and acid purplish red B respectively 0.3 and below the 0.5mg/L.
The Fe-Re-D001 nanocomposite has extremely strong catalytic degradation ability to halogenated hydrocarbons such as the chloroform and the chlorobenzene etc. of trace in the water body.Illustrate, when chloroform in the water body and chlorobenzene concentration respectively are 5 and during 2mg/L, above-mentioned material can be in 4h reduces to 0.02 and below the 0.05mg/L respectively with chloroform and chlorobenzene concentration.
Claims (10)
1. composite cationic ion-exchange resin supporting iron-series duplex metal nano granules, it is characterized in that carrier is ion-exchange and the polymeric adsorbent with acid functional group, resin matrix is polystyrene or acrylic acid series, contain sulfonic group, carboxylic acid group or phosphonate group on the resin matrix, immobilized inorganic material is the nanometer iron-series bimetal granule.
2. composite cationic ion-exchange resin supporting iron-series duplex metal nano granules according to claim 1 is characterized in that carrier is a large hole cation exchanger resin, and the average pore size of resin is between 1-100nm.
3. according to the composite cationic ion-exchange resin supporting iron-series duplex metal nano granules described in the claim 2, it is characterized in that carrier is D001, D113, Amberlite lRA-120, Purolite A-100 or NDA100 resin.
4. according to each described composite cationic ion-exchange resin supporting iron-series duplex metal nano granules in the claim 1～3, it is characterized in that the nanometer iron-series bimetal granule is of a size of 1-100nm.
5. according to each described composite cationic ion-exchange resin supporting iron-series duplex metal nano granules in the claim 1～3, it is characterized in that the nanometer iron-series bimetallic is Fe-Pd, Fe-Cu, Fe-Co, Fe-Ni, Fe-Re, Fe-Al or Fe-Zn, wherein the content of Fe is 10-250mg/g, and the content of other metal is 10-50mg/g.
6. the preparation method of a composite cationic ion-exchange resin supporting iron-series duplex metal nano granules may further comprise the steps:
(A) choose ion-exchange with acid functional group and polymeric adsorbent carrier, with Fe as nanocomposite
2+Or Fe
3+Ion imports the surfaces externally and internally of resin by ion exchange;
(B) use NaBH
4Or KBH
4Solution will import the Fe of resin surfaces externally and internally
2+Or Fe
3+Ion is reduced to nano zero valence iron;
(C) with the reacted resin of step (B) at N
2Protection is immersed in the soluble-salt solution of second kind of metal A l, Cu, Co, Ni, Pd, Re, Al or Zn down, by washing and dry, promptly obtains a kind of composite cationic ion-exchange resin supporting iron-series duplex metal nano granules again.
7. the preparation method of composite cationic ion-exchange resin supporting iron-series duplex metal nano granules according to claim 6 is characterized in that in the step (A) Fe
2+Or Fe
3+Ion source is in the solubility strong acid salt.
8. according to claim 6 or 7 described composite cationic ion-exchange resin supporting iron-series duplex metal nano granules, it is characterized in that in the step (B) NaBH
4Or KBH
4The concentration of solution is 0.2～2mol/L, and solution is that the volume ratio of ethanol is 0～50% the aqueous solution, reduction reaction no longer includes bubble in solution emerge till.
9. according to claim 6 or 7 described composite cationic ion-exchange resin supporting iron-series duplex metal nano granules, it is characterized in that in the step (C), the concentration of the salting liquid of second kind of metal is 0.01-1mol/L, soak time is 4-24h.
10. the application of composite cationic ion-exchange resin supporting iron-series duplex metal nano granules in catalyzing and degrading pollutant.
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