CN102631899B - 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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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 24
- 229910001385 heavy metal Inorganic materials 0.000 title abstract description 37
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 title abstract 2
- 239000003463 adsorbent Substances 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000012153 distilled water Substances 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
- 239000000126 substance Substances 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 230000005855 radiation Effects 0.000 claims description 37
- 238000005303 weighing Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 26
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- 238000000502 dialysis Methods 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
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- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000006392 deoxygenation reaction Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000010907 mechanical stirring Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
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- 238000010894 electron beam technology Methods 0.000 claims description 6
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- 238000010908 decantation Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 39
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 43
- 238000000034 method Methods 0.000 description 42
- 239000000243 solution Substances 0.000 description 29
- 239000011651 chromium Substances 0.000 description 25
- 238000011068 loading method Methods 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 16
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
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- 230000000274 adsorptive effect Effects 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
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- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-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
- 238000004566 IR spectroscopy Methods 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation 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
- 230000031018 biological processes and functions Effects 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
- 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
- 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
- 239000000839 emulsion Substances 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 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
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- 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
- 239000012716 precipitator Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 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 ferric 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 enter 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 contamination has been classified as the emphasis of " 12 " prevention and cure of pollution work by country.Chromium and lead are the heavy metals of serious environment pollution, the pollution ubiquity that causes, and be difficult to eliminate, cause serious harm for environment and HUMAN 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.), biological process, evaporation concentration, electrolytic process, ion exchange method, absorption method, membrane separation process etc.Wherein reason is most widely used chemical precipitation method because reduced investment, running cost be low etc., but the processing degree of depth of heavy metal contaminants is on the low side, effluent quality is subjected to factor affecting fluctuations such as raw wastewater variation water quality, pH control, sedimentation time, agitation condition bigger, is prone to the phenomenon that exceeds standard; Though evaporation concentration, electrolytic process even depth treatment technology have better performance at treatment effect, and be still higher on facility investment and processing cost, is difficult to realize large-scale promotion application; Coagulation, biological treatment, redox etc. often do not reach the heavy metal wastewater thereby emission standard; Membrane separation technique overall process effects such as reverse osmosis, ultrafiltration, nanofiltration are better, but operational conditions is had relatively high expectations, water outlet and reclamation rate instability, and investment is higher with running cost.Be subjected to environment circle researchist's attention and absorption method is with low cost because of it, method is simple.At present, sorbent material commonly used mainly contains gac, zeolite, ion exchange resin and resin etc., and it is less relatively to adopt copolymerization method to prepare the research of sorbent material.
Existing studies show that, groups such as amino, sulfonic group are owing to introduced higher nitrogen, the sulphur atom of cloud density, and therefore easy and metal ion generation ligand complex has the good adsorption performance to heavy metal ion.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 multipolymer.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, by with AM/AMPS multipolymer generation photochemical reaction, make it to be converted into the method for the material with reactive behavior.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 that preparing amphiphilic polymers-poly-(acrylamide/2-acrylamido-2-methyl propane sulfonic acid/vinyl-amine) by chemical process reaches Cu
2+Absorption, people such as Xie Jianjun (functional polymer journal,, acrylic acid series High hydrophilous resin inverse suspension polymerization method preparation and adsorptivity thereof in 2008) have reported employing inverse suspension polymerization method preparation poly-(vinylformic 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 dispersity, the strong absorption ultraviolet ray, have good fast light, heat, soda acid, corrosive gases and good magnetic are extensively various industrial, the method for preparing nano-sized iron oxide has a lot, as hydrothermal method, the forced hydrolysis method, sol-gel method, 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 Superparamagnetic Iron Oxide nano particle, application number is 201010139529.3 to disclose trace amounts of phosphorus in a kind of removal water body, the nano-compound adsorbent of arsenic and antimony, number of patent application are 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 adsorption of arsenic) adopt the precipitator 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 method 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+Adsorption; 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 aforesaid method great majority are chemical polymerization, its preparation process often needs to add initiator, the macromolecular material purity that causes preparing descends, beam methods then adopts high dosage electron beam irradiation single stage method directly to prepare nano-sized iron oxide, the polymkeric substance that adopts preparation Adsorption of Heavy Metal Ions earlier is loaded with nano ferric oxide and then preparation nano-sized iron oxide hydrogel again, strengthens the method for its absorption heavy metal adsorptive power.
The main chemical process that adopts of existing polymkeric substance research and preparation, wherein the part Study achievement is used to heavy metal absorption.But chemical polymerization method great majority need to add initiator in 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 polymkeric substance, can prepare a kind of organic high molecular polymer with functional groups such as sulfonic groups, can make functional group active adsorption chelating heavy metal ion in the polymkeric substance; Further, carried magnetic nano iron is to increase adsorption effect on the polymkeric substance that has prepared, the preparation method is simple, easy handling, and product has increased the adsorption effect of nano-sized iron oxide on the basis of original polymkeric substance adsorptive power, product has certain mechanical strength, can increase the service life.
Technical solution of the present invention is, has sulfonic polymer-based nano ferric oxide, comprises the polymkeric substance of 2-acrylamido-2-methyl propane sulfonic acid and Hydroxyethyl acrylate copolymerization, polymkeric substance loaded with nano ferric oxide; Wherein, the mol ratio of 2-acrylamido-2-methyl propane sulfonic acid and Hydroxyethyl acrylate is 1: 1～9.
Ferric 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, Hydroxyethyl acrylate and distilled water are mixed by a certain percentage; 2-acrylamido-2-methyl propane sulfonic acid adds Hydroxyethyl 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 Hydroxyethyl acrylate is 1: (1～9);
(2) can be through 10 ± 3min ultrasonication after the mixing;
(3) in the mixture of (1), charge into rare gas element, to guarantee anaerobic state;
(4) in-63～-95 ℃ of temperature ranges, adopting radiation dose is 1 * 10
4～1 * 10
8The high-energy ray irradiation polymerization of Gy forms polymkeric substance.Described energetic ray is
60The Co-gamma-rays,
137Cs-gamma-rays or electron beam.
Rare gas element is nitrogen, argon gas or helium.
Described polymkeric substance loaded with nano ferric oxide method is characterized in that may further comprise the steps:
(1) polymkeric substance for preparing is cut into 0.5-2cm
3Fritter.
(2) take by weighing the polymkeric substance for the treatment of 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 works, bubbling leads to the rare gas element 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 stirring regulate pH to 8-9, stops to drip, and continues normal-temperature reaction.
(4) the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, with deionized water dialysis 24～48h of 1.5L.
The polymer-based nano ferric oxide may further comprise the steps the adsorption method of heavy metal ion in the water body:
(1) the polymer-based nano ferric oxide for preparing is placed in the triangular flask;
(2) the polymer-based nano ferric 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 ferric oxide is removed Cr in water treatment
3+And Pb
2+The application of heavy metal ion.Polymer-based nano ferric oxide Cr
3+And Pb
2+24 hours products of heavy metal ion are to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 199mg/g, 213mg/g.The polymer-based nano ferric oxide is reused behind weak acid scrubbing.
The invention has the beneficial effects as follows: by the method for application of radiation technology preparation, prepare a kind of organic high molecular polymer with functional groups, can make functional group active adsorption chelating heavy metal ion in the polymkeric substance; And on the polymkeric substance that has prepared carried magnetic nano iron, goods of the present invention are to increase adsorption effect, the preparation method is simple, easy handling, and product has increased the adsorption effect of nano-sized iron oxide, long service life on the basis of original polymkeric substance adsorptive power.
Description of drawings
Fig. 1 polymer-based nano ferric oxide is to Cr in the water body
3+Adsorption effect.
Fig. 2 polymer-based nano ferric oxide is to Pb in the water body
2+Adsorption effect.
Embodiment
The present invention further specifies by 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4～1 * 10
8Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polymkeric substance.
3. after the polymkeric substance 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 polymkeric substance for the treatment of 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 works, 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 stirring, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, 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 spectroscopy 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4～1 * 10
8Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano ferric oxide.
7. take by weighing the dried product of polymer-based nano ferric 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 absorbs with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference by ion before and after the absorption can calculate this product to the loading capacity of each ion.After measured, product is to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 199mg/g, 213mg/g.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4～1 * 10
8Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring, up to pH=9, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano ferric oxide.
7. take by weighing the dried product of polymer-based nano ferric 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 absorbs with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference by ion before and after the absorption can calculate this product to the loading capacity of each ion.After measured, product is to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 187mg/g, 199mg/g.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4～1 * 10
8Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works 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 stirring, up to pH=9, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano ferric oxide.
7. take by weighing the dried product of polymer-based nano ferric 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 absorbs with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference by ion before and after the absorption can calculate this product to the loading capacity of each ion.After measured, product is to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 201mg/g, 224mg/g.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano ferric oxide.
7. take by weighing the dried product of polymer-based nano ferric 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 absorbs with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference by ion before and after the absorption can calculate this product to the loading capacity of each ion.After measured, product is to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 173mg/g, 188mg/g.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 24h with 1.5L obtains the polymer-based nano ferric oxide.
7. take by weighing the dried product of polymer-based nano ferric 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 absorbs with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference by ion before and after the absorption can calculate this product to the loading capacity of each ion.After measured, product is to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 135mg/g, 147mg/g.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
7Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 24h with 1.5L obtains the polymer-based nano ferric oxide.
7. take by weighing the dried product of polymer-based nano ferric 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 absorbs with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference by ion before and after the absorption can calculate this product to the loading capacity of each ion.After measured, product is to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 124mg/g, 149mg/g.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
8Gy adopts energetic ray (electron beam) radiation polymerization to form polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano ferric oxide.
7. take by weighing the dried product of polymer-based nano ferric 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 absorbs with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference by ion before and after the absorption can calculate this product to the loading capacity of each ion.After measured, product is to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 153mg/g, 174mg/g.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4～1 * 10
8Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano ferric oxide.
7. take by weighing the dried product of polymer-based nano ferric 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 absorbs with absorption after concentration.Measuring method is used atomic absorption method for the dilution back.Concentration difference by ion before and after the absorption can calculate this product to the loading capacity of each ion.After measured, product is to Cr
3+, Pb
2+The loading capacity of two metal ion species is respectively: 119mg/g, 137mg/g.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4～1 * 10
8Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring, up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano ferric oxide.
7. certain electroplating wastewater contains a large amount of heavy metal ion, wherein Cr
3+Content be about 560mg/L.Through after certain pre-treatment, adopt the polymer-based nano ferric oxide of preparation to handle this electroplating wastewater.In the waste water of 1L, add 2g polymer-based nano ferric 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 ferric oxide product makes it to arrive 10g/L, Cr
3+Clearance can arrive (Fig. 1) more than 93%.The polymer-based nano ferric 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 Hydroxyethyl 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 radiation dose scope is 1 * 10
4～1 * 10
8Gy adopts energetic ray (electron beam) radiation polymerization to form polymkeric substance.
3. after radiation post polymerization thing 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 polymkeric substance 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 works, 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 stirring up to pH=8, stops to drip, and continues normal-temperature reaction 2h.
6. the product magnetic with gained separates, and inclines to considering and cleans for several times, pours in the dialysis tubing, and the deionized water dialysis 48h with 1.5L obtains the polymer-based nano ferric oxide.
7. certain farming is irritated well water because of contiguous certain plumbous smeltery, is subjected to Lead contamination, wherein Pb
2+Content be about 10mg/L.With this well water collecting part water sample, through after certain pre-treatment, adopt the polymer-based nano ferric oxide of preparation to handle.The ratio of polymer-based nano ferric 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+Density loss to 0.2mg/L, clearance reaches 96% (Fig. 2).The polymer-based nano ferric oxide is reused behind weak acid scrubbing.
Claims (1)
1. the preparation method who has sulfonic polymer-based nano ferric oxide is characterized in that comprising the polymkeric substance of 2-acrylamido-2-methyl propane sulfonic acid and Hydroxyethyl acrylate copolymerization, polymkeric substance loaded with nano ferric oxide; Wherein, the mol ratio of 2-acrylamido-2-methyl propane sulfonic acid and Hydroxyethyl acrylate monomer is 1:1～9, and described nano-sized iron oxide comprises ferrous and ferric iron, wherein Fe
2+/ Fe
3+Ratio be 1:1.2～1:2.5mol/mol;
The preparation method may further comprise the steps:
(1) 2-acrylamido-2-methyl propane sulfonic acid, Hydroxyethyl acrylate and distilled water are mixed by a certain percentage; 2-acrylamido-2-methyl propane sulfonic acid adds Hydroxyethyl acrylate: the volume ratio of water is 1～7:7～1, and the mol ratio of 2-acrylamido-2-methyl propane sulfonic acid and Hydroxyethyl acrylate is 1:1～9;
(2) can be through 10 ± 3min ultrasonication after the mixing;
(3) in the mixture of (1), charge into rare gas element, to guarantee anaerobic state; Described rare gas element is nitrogen, argon gas or helium;
(4) in-63～-95 ℃ of temperature ranges, adopting radiation dose is 1 * 10
4～1 * 10
8The high-energy ray irradiation polymerization of Gy forms polymkeric substance; Described energetic ray is
60The Co-gamma-rays,
137Cs-gamma-rays or electron beam;
(5) the above-mentioned polymkeric substance for preparing is cut into 0.5-2cm
3Fritter;
(6) take by weighing the polymkeric substance for the treatment of 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 works, bubbling leads to the rare gas element deoxygenation;
(7) with Fe
2+/ Fe
3+Ratio be the FeSO of 1:1.2～1:2.5mol/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 stirring regulate pH to 8-9, stops to drip, and continues normal-temperature reaction;
(8) the product magnetic with gained separates, and decantation is cleaned for several times, pours in the dialysis tubing, dialyses 24～48 hours with the deionized water of 1.5L.
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