CN102631899A - Preparation method and application of sulfonyl polymer-based nanometer ferric oxide heavy metal adsorbent - Google Patents
Preparation method and application of sulfonyl polymer-based nanometer ferric oxide heavy metal adsorbent Download PDFInfo
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- CN102631899A CN102631899A CN2012101328137A CN201210132813A CN102631899A CN 102631899 A CN102631899 A CN 102631899A CN 2012101328137 A CN2012101328137 A CN 2012101328137A CN 201210132813 A CN201210132813 A CN 201210132813A CN 102631899 A CN102631899 A CN 102631899A
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- iron oxide
- acrylamido
- nano iron
- heavy metal
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229920000642 polymer Polymers 0.000 title claims abstract description 112
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 24
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title abstract description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 title abstract 2
- 239000003463 adsorbent Substances 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000012153 distilled water Substances 0.000 claims abstract description 43
- 150000002500 ions Chemical class 0.000 claims abstract description 42
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims abstract description 30
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 43
- 238000001179 sorption measurement Methods 0.000 claims description 34
- 238000005303 weighing Methods 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 230000005855 radiation Effects 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 13
- 230000005587 bubbling Effects 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000006392 deoxygenation reaction Methods 0.000 claims description 13
- 238000000502 dialysis Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 51
- 239000000243 solution Substances 0.000 description 29
- 239000011651 chromium Substances 0.000 description 25
- 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 12
- 239000002253 acid Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 238000005201 scrubbing Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 241000894007 species Species 0.000 description 9
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 235000020681 well water Nutrition 0.000 description 2
- 239000002349 well water Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 241000399119 Spio Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000012777 commercial manufacturing Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses sulfonyl polymer-based nanometer ferric oxide, comprising a polymer obtained through the copolymerization of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate, and nanometer ferric oxide is loaded on the polymer; and the molar ratio of the 2-acrylamido-2-methylpropanesulfonic acid to the hydroxyethyl acrylate is 1:(1-9). The nanometer ferric oxide comprises ferrous iron and ferric iron. The nanometer ferric oxide is prepared through the following steps of: uniformly mixing the 2-acrylamido-2-methylpropanesulfonic acid, the hydroxyethyl acrylate and distilled water according to a certain proportion, wherein the volume ratio of the sum of the 2-acrylamido-2-methylpropanesulfonic acid and the hydroxyethyl acrylate to the distilled water is (1-7):(7-1), and the molar ratio of the 2-acrylamido-2-methylpropanesulfonic acid to the hydroxyethyl acrylate is 1:(1-9); carrying out irradiating polymerizing by utilizing high-energy ray with the irradiation dosage of 1*10<4> Gy to 1*10<8> Gy within the temperature range from -63 DEG C to -95 DEG C to form the polymer; and absorbing heavy metal ions in a water body.
Description
Technical field
The invention belongs to the environmentally conscious materials technical field, relate to the preparation of polymer-based nano iron oxide and the application that the heavy metal wastewater thereby deep purifying is handled thereof.
Background technology
In recent years; Because it is human increasing to exploitation, smelting, processing and the commercial manufacturing activities of heavy metal; The heavy metal that produces quantitatively with on the kind all increases greatly; Cause heavy metal to get in a large number in soil, the water body, cause that not only serious environmental is polluted and the wasting of resources, and the mankind healthy produced very big threat.In addition, heavy metal and heavy metal ion all have great harm to aquatic biology, plant and environment etc.So control heavy metal pollution has been classified as the emphasis of " 12 " prevention and cure of pollution work by country.Chromium is the heavy metal of serious environment pollution with lead, the pollution ubiquity that causes, and be difficult to eliminate, cause serious harm for environment and health.Therefore, the processing research of carrying out heavy metal contaminants has important practical sense.
The heavy metal containing wastewater treatment technology mainly comprises chemical method (chemical precipitation, redox, ferrite process etc.), bioanalysis, evaporation and concentration, electrolysis, ion-exchange, absorption method, membrane separation process etc.Wherein chemical precipitation method is used the most extensive because of reasons such as reduced investment, operating cost are low; But the processing degree of depth of heavy metal contaminants is on the low side; Effluent quality receives factor affecting fluctuations such as raw wastewater variation water quality, pH control, sedimentation time, stirring condition bigger, is prone to the phenomenon that exceeds standard; Though evaporation and concentration, electrolysis even depth treatment technology have better performance on treatment effect, still higher on equipment investment and processing cost, are difficult to realize large-scale promotion application; Coagulation, biological treatment, redox etc. often do not reach the heavy metal wastewater thereby discharge standard; Membrane separation technique overall process effects such as counter-infiltration, ultrafiltration, nanofiltration are better, but service condition is had relatively high expectations, and water outlet and reclamation rate are unstable, and investment is higher with running cost.Receive environment circle researcher's attention and absorption method is with low cost because of it, method is simple.At present, adsorbent commonly used mainly contains active carbon, zeolite, ion exchange resin and chelating resin etc., and it is less relatively to adopt copolymerization method to prepare the research of adsorbent.
Existing research shows that groups such as amino, sulfonic group are prone to and metal ion generation ligand complex owing to introduced higher nitrogen, the sulphur atom of cloud density, therefore heavy metal ion are had the good adsorption performance.2-acrylamido-2-methyl propane sulfonic acid (AMPS) is owing to have the value that sulfonic group has becomes the Adsorption of Heavy Metal Ions copolymer.Number of patent application is 200710009066 to have announced the preparation method of 2-acrylamido-2-methyl propane sulfonic acid; Number of patent application is 02103930 to have announced under action of ultraviolet light; Through with AM/AMPS copolymer generation photochemical reaction, make it to be converted into the method for material with reactivity.Number of patent application is 200810143887 to disclose the preparation method of a kind of polyacrylic acid/2-acrylamido-2-methyl propane sulfonic acid.In addition, people such as Zhang Baoliang (journal of Shandong university (engineering version),, the Hofmann of Poly (AM/AMPS) reversed-phase emulsion degraded and removing Cu in 2011
2+The application of aspect) reported through chemical method and prepared amphiphilic polymers-gather (acrylamide/2-acrylamido-2-methyl propane sulfonic acid/vinylamine) and Cu
2+Absorption, people such as Xie Jianjun (functional polymer journal,, acrylic acid series high hydroscopic resin inverse suspension polymerization method preparation and adsorptivity thereof in 2008) have reported that the preparation of employing inverse suspension polymerization method gathers (acrylic acid/2-acrylamido-2-methyl propane sulfonic acid) and to Cu
2+, Cr
3+Absorption property.
In recent years; Nano-sized iron oxide is because good dispersion; The strong absorption ultraviolet ray; Have in good fast light, hot, soda acid, corrosive gas and the good extensive various industry of magnetic; The method for preparing nano-sized iron oxide has a lot, and like hydro-thermal method, force water solution, sol-gel process, solid phase method, microwave method, micro emulsion method etc., application number is 200910095739.4 to disclose a kind of preparation method of polyvinyl pyrrolidon modified SPIO nano particle; Application number is 201010139529.3 to disclose a kind of nano-compound adsorbent of removing trace amounts of phosphorus in the water body, arsenic and antimony, and number of patent application is 200510023582.6 to disclose a kind of method that adopts the electron beam irradiation legal system to be equipped with nano-sized iron oxide.In addition, the Liang Meina of Tongji University, Liu Hailing etc. (applied chemistry, 2007, PREPARATION OF NANO FERRIC OXIDE and to the suction-operated of arsenic) adopt the precipitation method to prepare nano-sized iron oxide, studied preparation condition, and product characterized.The Zheng Yana of University Of Ji'nan, what luxuriant strong grade (University Of Ji'nan's journal, 2010, Pb
2+Absorption behavior in the rare earth mixing with nano iron oxide surface) the employing sol-gel process prepares the nano-sized iron oxide of rare earth element (La, Ce) doping vario-property, has studied to prepare it to heavy metal ion Pb
2+Suction-operated; Li Guangchuan, Hu Jun etc. (Guangdong chemical industry, 2011, nano-sized iron oxide is applied to the absorption of cadmium in the water (II)) have studied novel nano Fe
2O
3Material is to Cd in the water
2+The Static Adsorption performance, investigated the principal element that influences adsorption and desorption.But the said method great majority are chemical polymerization; Its preparation process often need be added initator; The macromolecular material purity that causes preparing descends; Beam methods then adopts high dose electron beam irradiation one-step method directly to prepare nano-sized iron oxide, and the polymer that adopts preparation Adsorption of Heavy Metal Ions earlier is loaded with nano iron oxide and then preparation nano-sized iron oxide hydrogel again, strengthens the method for its absorption heavy metal adsorption capacity.
The main chemical method that adopts of existing polymer research and preparation, wherein the part achievement in research is used to heavy metal absorption.But chemical polymerization method great majority need to add initator in the preparation process, thereby the macromolecular material purity that causes preparing descends the function reduction.
Summary of the invention
The present invention seeks to, propose the method that a kind of application of radiation technology prepares polymer, can prepare a kind of organic high molecular polymer, can make that the functional group in the polymer effectively adsorbs the chelating heavy metal ion with functional groups such as sulfonic group; Further; Carried magnetic nano iron is to increase adsorption effect on the polymer that has prepared; The preparation method is simple, easy operating, and product has increased the adsorption effect of nano-sized iron oxide on the basis of original polymer adsorption capacity; Product has certain mechanical strength, can increase the service life.
Technical scheme of the present invention is, has sulfonic polymer-based nano iron oxide, comprises the polymer of 2-acrylamido-2-methyl propane sulfonic acid and hydroxy-ethyl acrylate copolymerization, polymer loaded with nano iron oxide; Wherein, the mol ratio of 2-acrylamido-2-methyl propane sulfonic acid and hydroxy-ethyl acrylate is 1: 1～9.
Iron oxide comprises ferrous and ferric iron, wherein Fe
2+/ Fe
3+Ratio be 1: 1.2～1: 2.5 (mol/mol).
The preparation method may further comprise the steps:
(1) 2-acrylamido-2-methyl propane sulfonic acid, hydroxy-ethyl acrylate and distilled water are mixed by a certain percentage; 2-acrylamido-2-methyl propane sulfonic acid adds hydroxy-ethyl acrylate: the volume ratio of distilled water is (1～7): (7～1), and the mol ratio of 2-acrylamido-2-methyl propane sulfonic acid and hydroxy-ethyl acrylate is 1: (1～9);
(2) can be after the mixing through 10 ± 3min ultrasonic Treatment;
(3) in the mixture of (1), charge into inert gas, to guarantee anaerobic state;
(4) in-63～-95 ℃ of temperature ranges, adopting dose of radiation is 1 * 10
4～1 * 10
8The high-energy ray irradiation polymerization of Gy forms polymer.Said high-energy ray does
60The Co-gamma-rays,
137Cs-gamma-rays or electron beam.
Inert gas is nitrogen, argon gas or helium.
Described polymer loaded with nano iron oxide method is characterized in that may further comprise the steps:
(1) polymer for preparing is cut into 0.5-2cm
3Fritter.
(2) take by weighing the polymer of treating modification in right amount and pack in the three-necked bottle, get a certain amount of distilled water and join in the three-necked bottle with condensing unit, bubbling leads to the inert gas deoxygenation.
(3) with Fe
2+/ Fe
3+Ratio be the FeSO of 1: 1.2～1: 2.5 (mol/mol)
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water, and above-mentioned solution is joined in the three-necked bottle, and the ammoniacal liquor of slow dropping 3%～20% or the NaOH of 0.01～0.1mol/L under the mechanical agitation regulate pH to 8-9, stops to drip, and continues normal-temperature reaction.
(4) the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, with deionized water dialysis 24～48h of 1.5L.
The polymer-based nano iron oxide may further comprise the steps the adsorption method of heavy metal ion in the water body:
(1) the polymer-based nano iron oxide for preparing is placed in the triangular flask;
(2) the polymer-based nano iron oxide is repeatedly washed with deionized water;
(3) under 25 ± 5 ℃ of conditions, different types of heavy metal ion is adsorbed.
Especially described polymer-based nano iron oxide is removed Cr in water treatment
3+And Pb
2+The application of heavy metal ion.Polymer-based nano iron oxide Cr
3+And Pb
2+24 hours products of heavy metal ion are to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 199mg/g, 213mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
The invention has the beneficial effects as follows: through the method for application of radiation technology preparation, prepare a kind of organic high molecular polymer, can make that the functional group in the polymer effectively adsorbs the chelating heavy metal ion with functional groups; And on the polymer that has prepared carried magnetic nano iron, goods of the present invention are to increase adsorption effect, the preparation method is simple, easy operating, and product has increased the adsorption effect of nano-sized iron oxide, long service life on the basis of original polymer adsorption capacity.
Description of drawings
Fig. 1 polymer-based nano iron oxide is to Cr in the water body
3+Adsorption effect.
Fig. 2 polymer-based nano iron oxide is to Pb in the water body
2+Adsorption effect.
The specific embodiment
The present invention further specifies through embodiment, but the present invention is not limited to following examples.
Embodiment 1:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 1: 2 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 5 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control dose of radiation scope is 1 * 10
4～1 * 10
8Gy, the employing high-energy ray (
60The Co-gamma-rays) irradiation polymerization forms polymer.
3. after the polymer that forms after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing the polymer of treating modification in right amount and pack in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 2 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 240r/min) slowly drips 10% ammoniacal liquor under the mechanical agitation, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, with deionized water dialysis 24～48h of 1.5L.
7. product is carried out the sign of structure and composition, comprise and use SEM to carry out the composition that the infrared spectrum analysis product was observed and used to pore structure.The result of SEM shows that the polymer-based nano ferric oxide particles of preparation is spherical, is uniformly dispersed, and is suitable for ion is adsorbed, and is particularly suitable for the absorption to heavy metal ion.
Embodiment 2:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 2: 3 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 5 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control dose of radiation scope is 1 * 10
4～1 * 10
8Gy, the employing high-energy ray (
137The Cs-gamma-rays) irradiation polymerization forms polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 2 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 240r/min) slowly drips 3% ammoniacal liquor under the mechanical agitation, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano iron oxide.
7. take by weighing the dried product of polymer-based nano iron oxide 0.1g and place the 100ml triangular flask respectively for two parts, add the Cr of 50ml 1g/L then respectively
3+, Pb
2+Two kinds of single solution place triangular flask and carry out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorption with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference through ion before and after the absorption can calculate the adsorption capacity of this product to each ion.Through measuring, product is to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 199mg/g, 213mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 3:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 1: 1 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 5 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-95 ℃ temperature, control dose of radiation scope is 1 * 10
4～1 * 10
8Gy, the employing high-energy ray (
60The Co-gamma-rays) irradiation polymerization forms polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to argon gas deoxygenation 20min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 1.5 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 200r/min) slowly drips 15% ammoniacal liquor under the mechanical agitation, up to pH=9, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano iron oxide.
7. take by weighing the dried product of polymer-based nano iron oxide 0.1g and place the 100ml triangular flask respectively for two parts, add the Cr of 50ml 1g/L then respectively
3+, Pb
2+Two kinds of single solution place triangular flask and carry out constant temperature absorption under 20 ℃ of the constant temperature oscillators, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorption with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference through ion before and after the absorption can calculate the adsorption capacity of this product to each ion.Through measuring, product is to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 187mg/g, 199mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 4:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 3: 7 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 3 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-63 ℃ temperature, control dose of radiation scope is 1 * 10
4～1 * 10
8Gy, the employing high-energy ray (
137The Cs-gamma-rays) irradiation polymerization forms polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml and has in the three-necked bottle of condensing unit bubbling helium injection gas deoxygenation 20min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 1.2 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 300r/min) slowly drips 20% ammoniacal liquor under the mechanical agitation, up to pH=9, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano iron oxide.
7. take by weighing the dried product of polymer-based nano iron oxide 0.1g and place the 100ml triangular flask respectively for two parts, add the Cr of 50ml 1g/L then respectively
3+, Pb
2+Two kinds of single solution place triangular flask and carry out constant temperature absorption under 30 ℃ of the constant temperature oscillators, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorption with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference through ion before and after the absorption can calculate the adsorption capacity of this product to each ion.Through measuring, product is to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 201mg/g, 224mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 5:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 1: 4 (v/v) mixes as component C by (A+B): C, and wherein A: B is 1: 1 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-63 ℃～-95 ℃ temperature, control dose of radiation scope is 1 * 10
4Gy, the employing high-energy ray (
60The Co-gamma-rays) irradiation polymerization forms polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 1.7 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 280r/min) slowly drips 8% ammoniacal liquor under the mechanical agitation, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano iron oxide.
7. take by weighing the dried product of polymer-based nano iron oxide 0.1g and place the 100ml triangular flask respectively for two parts, add the Cr of 50ml 1g/L then respectively
3+, Pb
2+Two kinds of single solution place triangular flask and carry out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorption with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference through ion before and after the absorption can calculate the adsorption capacity of this product to each ion.Through measuring, product is to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 173mg/g, 188mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 6:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 3: 2 (v/v) mixes as component C by (A+B): C, and wherein A: B is 1: 5 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-63 ℃～-95 ℃ temperature, control dose of radiation scope is 1 * 10
4Gy, the employing high-energy ray (
137The Cs-gamma-rays) irradiation polymerization forms polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 2 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 280r/min) slowly drips the NaOH of 0.01mol/L under the mechanical agitation, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 24h with 1.5L obtains the polymer-based nano iron oxide.
7. take by weighing the dried product of polymer-based nano iron oxide 0.1g and place the 100ml triangular flask respectively for two parts, add the Cr of 50ml 1g/L then respectively
3+, Pb
2+Two kinds of single solution place triangular flask and carry out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorption with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference through ion before and after the absorption can calculate the adsorption capacity of this product to each ion.Through measuring, product is to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 135mg/g, 147mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 7:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 7: 3 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 5 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-63 ℃～-95 ℃ temperature, control dose of radiation scope is 1 * 10
7Gy, the employing high-energy ray (
60The Co-gamma-rays) irradiation polymerization forms polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 2.5 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 280r/min) slowly drips the NaOH of 0.05mol/L under the mechanical agitation, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 24h with 1.5L obtains the polymer-based nano iron oxide.
7. take by weighing the dried product of polymer-based nano iron oxide 0.1g and place the 100ml triangular flask respectively for two parts, add the Cr of 50ml 1g/L then respectively
3+, Pb
2+Two kinds of single solution place triangular flask and carry out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorption with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference through ion before and after the absorption can calculate the adsorption capacity of this product to each ion.Through measuring, product is to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 124mg/g, 149mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 8:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 4: 1 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 3 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-63 ℃～-95 ℃ temperature, control dose of radiation scope is 1 * 10
8Gy adopts high-energy ray (electron beam) irradiation polymerization to form polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 2.3 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 280r/min) slowly drips the NaOH of 0.08mol/L under the mechanical agitation, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano iron oxide.
7. take by weighing the dried product of polymer-based nano iron oxide 0.1g and place the 100ml triangular flask respectively for two parts, add the Cr of 50ml 1g/L then respectively
3+, Pb
2+Two kinds of single solution place triangular flask and carry out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorption with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference through ion before and after the absorption can calculate the adsorption capacity of this product to each ion.Through measuring, product is to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 153mg/g, 174mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 9:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 1: 1.5 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 3 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control dose of radiation scope is 1 * 10
4～1 * 10
8Gy, the employing high-energy ray (
60The Co-gamma-rays) irradiation polymerization forms polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 2 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 280r/min) slowly drips the NaOH of 0.1mol/L under the mechanical agitation, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano iron oxide.
7. take by weighing the dried product of polymer-based nano iron oxide 0.1g and place the 100ml triangular flask respectively for two parts, add the Cr of 50ml 1g/L then respectively
3+, Pb
2+Two kinds of single solution place triangular flask and carry out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorption with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference through ion before and after the absorption can calculate the adsorption capacity of this product to each ion.Through measuring, product is to Cr
3+, Pb
2+The adsorption capacity of two metal ion species is respectively: 119mg/g, 137mg/g.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 10:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 1: 2 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 3 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control dose of radiation scope is 1 * 10
4～1 * 10
8Gy, the employing high-energy ray (
137The Cs-gamma-rays) irradiation polymerization forms.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 2 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and (rotating speed 280r/min) slowly drips the NaOH of 0.1mol/L under the mechanical agitation, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano iron oxide.
7. certain electroplating wastewater contains a large amount of heavy metal ion, wherein Cr
3+Content be about 560mg/L.Through after certain preliminary treatment, adopt the polymer-based nano iron oxide of preparation to handle this electroplating wastewater.In the waste water of 1L, add 2g polymer-based nano iron oxide desciccate and handle.Behind the 24h, the Cr in the waste water
3+Decline to a great extent, when the amount of increase polymer-based nano iron oxide product makes it to arrive 10g/L, Cr
3+Clearance can arrive (Fig. 1) more than 93%.The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Embodiment 11:
1. the 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS) that takes by weighing certain mass is dissolved in the deionized water; Fully dissolving mixes as component A; Get a certain amount of hydroxy-ethyl acrylate monomer (being called for short HEA) as B component, component A is added in the B component, fully mix; Distilled water is that 1: 1.5 (v/v) mixes as component C by (A+B): C, and wherein A: B is 2: 3 (mol/mol).Using ultrasonic wave that mixture is handled to make mixes.
2. behind the inflated with nitrogen, under-63 ℃ temperature, control dose of radiation scope is 1 * 10
4～1 * 10
8Gy adopts high-energy ray (electron beam) irradiation polymerization to form polymer.
3. after polymer after the radiation being cut into 1cm * 1cm * 1cm fritter and being placed in the triangular flask repeatedly washing, under 40 ℃ of temperature, dry.
4. take by weighing 10g and treat that the polymer of modification packs in the three-necked bottle, the distilled water of measuring 400ml with the graduated cylinder of 1000ml joins 1000ml to have in the three-necked bottle of condensing unit, and bubbling leads to nitrogen deoxygenation 30min.
5. with FeSO
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water according to 1: 2 (mol/mol), and above-mentioned solution is joined in the three-necked bottle, and the ammoniacal liquor of (rotating speed 280r/min) slow Dropwise 5 % under the mechanical agitation up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano iron oxide.
7. certain farming is irritated well water because of contiguous certain plumbous smeltery, receives lead contamination, wherein Pb
2+Content be about 10mg/L.With this well water collecting part water sample,, adopt the polymer-based nano iron oxide of preparation to handle through after certain preliminary treatment.The ratio of polymer-based nano iron oxide with 2g/L added to water sample, after 24h absorption, the Pb in the water sample
2+Be reduced to below the 2mg/L.When dosage increases to 8mg/L, Pb in the water sample after the processing
2+Concentration drop to below the 0.2mg/L, clearance reaches 96% (Fig. 2).The polymer-based nano iron oxide is reused behind weak acid scrubbing.
Claims (7)
1. have sulfonic polymer-based nano iron oxide, it is characterized in that comprising the polymer of 2-acrylamido-2-methyl propane sulfonic acid and hydroxy-ethyl acrylate copolymerization, polymer loaded with nano iron oxide; Wherein, the mol ratio of 2-acrylamido-2-methyl propane sulfonic acid and hydroxy-ethyl acrylate is 1: 1～9.
2. according to claim 1 have a sulfonic polymer-based nano iron oxide, it is characterized in that nano-sized iron oxide comprises ferrous and ferric iron, wherein Fe
2+/ Fe
3+Ratio be 1: 1.2～1: 2.5mol/mo).
3. according to claim 1 have a sulfonic polymer-based nano iron oxide preparation method, it is characterized in that may further comprise the steps:
(1) 2-acrylamido-2-methyl propane sulfonic acid, hydroxy-ethyl acrylate and distilled water are mixed by a certain percentage; 2-acrylamido-2-methyl propane sulfonic acid adds hydroxy-ethyl acrylate: the volume ratio of distilled water is 1～7: 7～1, and the mol ratio of 2-acrylamido-2-methyl propane sulfonic acid and hydroxy-ethyl acrylate is 1: 1～9;
(2) can be after the mixing through 10 ± 3min ultrasonic Treatment;
(3) in the mixture of (1), charge into inert gas, to guarantee anaerobic state;
(4) in-63～-95 ℃ of temperature ranges, adopting dose of radiation is 1 * 10
4～1 * 10
8The high-energy ray irradiation polymerization of Gy forms polymer; Said high-energy ray does
60The Co-gamma-rays,
137Cs-gamma-rays or electron beam.
4. according to claim 3 have a sulfonic polymer-based nano iron oxide preparation method, it is characterized in that inert gas is nitrogen, argon gas or helium.
5. describedly have a sulfonic group polymer loaded with nano iron oxide method according to claim 3 or 4, it is characterized in that may further comprise the steps:
(1) polymer for preparing is cut into 0.5-2cm
3Fritter.
(2) take by weighing the polymer of treating modification in right amount and pack in the three-necked bottle, get a certain amount of distilled water and join in the three-necked bottle with condensing unit, bubbling leads to the inert gas deoxygenation.
(3) with Fe
2+/ Fe
3+Ratio be the FeSO of 1: 1.2～1: 2.5 (mol/mol)
4.7H
2O and FeCl
3.6H
2O is dissolved in respectively in the 10ml distilled water, and above-mentioned solution is joined in the three-necked bottle, and the ammoniacal liquor of slow dropping 3%～20% or the NaOH of 0.01～0.1mol/L under the mechanical agitation regulate pH to 8-9, stops to drip, and continues normal-temperature reaction;
(4) the product magnetic with gained separates, and the worry cleaning many times of inclining is poured in the bag filter, with deionized water dialysis 24～48h of 1.5L.
6. according to the described adsorption method of one of claim 3-5, it is characterized in that may further comprise the steps with sulfonic group polymer-based nano iron oxide to heavy metal ion:
(1) the polymer-based nano iron oxide is repeatedly washed with deionized water;
(2) under 25 ± 5 ℃ of conditions, different types of heavy metal ion is adsorbed.
7. the adsorption method with sulfonic group polymer-based nano iron oxide to heavy metal ion according to claim 6 is characterized in that removing in the water treatment Cr
3+And Pb
2+The application of heavy metal ion.
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| CN106362713A (en) * | 2016-11-02 | 2017-02-01 | 湖北工业大学 | Magnetic adsorbent containing sodium polystyrene sulfonate and preparation method |
| CN108998040A (en) * | 2018-05-28 | 2018-12-14 | 上海环科环境评估咨询有限公司 | Arsenic in soil and pollution of chromium based on organic clay load nanometer iron-series repair medicament |
| CN111285965A (en) * | 2020-03-10 | 2020-06-16 | 刘翠芬 | Slow-release concrete water-retaining agent and preparation method thereof |
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