CN103318997A - Preparation method and application of nano iron-based polyether sulfone (PES) organic-inorganic composite material - Google Patents
Preparation method and application of nano iron-based polyether sulfone (PES) organic-inorganic composite material Download PDFInfo
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- CN103318997A CN103318997A CN2013102591815A CN201310259181A CN103318997A CN 103318997 A CN103318997 A CN 103318997A CN 2013102591815 A CN2013102591815 A CN 2013102591815A CN 201310259181 A CN201310259181 A CN 201310259181A CN 103318997 A CN103318997 A CN 103318997A
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- pes
- aqueous solution
- millipore filtration
- iron
- deionized water
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 110
- 229910003471 inorganic composite material Inorganic materials 0.000 title claims abstract 5
- 238000002360 preparation method Methods 0.000 title claims description 42
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 title abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract description 56
- 239000007864 aqueous solution Substances 0.000 claims abstract description 48
- 244000269722 Thea sinensis Species 0.000 claims abstract description 31
- 235000009569 green tea Nutrition 0.000 claims abstract description 31
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005342 ion exchange Methods 0.000 claims abstract description 20
- -1 iron ions Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 103
- 238000001914 filtration Methods 0.000 claims description 81
- 239000008367 deionised water Substances 0.000 claims description 62
- 229910021641 deionized water Inorganic materials 0.000 claims description 59
- 239000011147 inorganic material Substances 0.000 claims description 48
- 229910010272 inorganic material Inorganic materials 0.000 claims description 47
- 238000007306 functionalization reaction Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 125000000524 functional group Chemical group 0.000 claims description 17
- 230000008859 change Effects 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 8
- 125000001246 bromo group Chemical group Br* 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 229960003511 macrogol Drugs 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 2
- 239000004695 Polyether sulfone Substances 0.000 abstract description 95
- 229920006393 polyether sulfone Polymers 0.000 abstract description 95
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 239000012528 membrane Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 230000001603 reducing effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000001471 micro-filtration Methods 0.000 abstract 4
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 229940088710 antibiotic agent Drugs 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 32
- 239000011159 matrix material Substances 0.000 description 23
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 12
- 229960000282 metronidazole Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 238000005067 remediation Methods 0.000 description 8
- 230000006870 function Effects 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 239000012982 microporous membrane Substances 0.000 description 7
- FAXWFCTVSHEODL-UHFFFAOYSA-N 2,4-dibromophenol Chemical compound OC1=CC=C(Br)C=C1Br FAXWFCTVSHEODL-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 101100489867 Mus musculus Got2 gene Proteins 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 241000220324 Pyrus Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000005297 material degradation process Methods 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000021017 pears Nutrition 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- 239000002689 soil Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing a nano iron-based polyether sulfone (PES) organic-inorganic composite material. The method comprises the following steps: (1) pretreating a PES microfiltration membrane; (2) functionalizing the PES microfiltration membrane through methacrylic acid (MA); (3) respectively performing sodium ion exchange and iron ion exchange on the functionalized PES microfiltration membrane; (4) completely soaking the PES microfiltration membrane containing iron ions in an aqueous solution of green tea, so as to form the nano iron-based PES organic-inorganic composite material through the reducing action of the aqueous solution of the green tea. By utilizing the reducing action of the materials, wastewater containing antibiotics, bromate ions, bromo-organic matters and chloro-organic matters is respectively repaired under room temperature conditions. The method is low in process cost, and easy to operate and has the environment-friendly effects, the prepared organic-inorganic composite material is high in degradation capacity, high in stability and long in service cycle, and the composite material can effectively fix iron nanoparticles, is easy to recover and regenerate, belongs to an environment-friendly functional material and is suitable for industrial production.
Description
Technical field
The invention belongs to the environment functional material technical field, relate to a kind of nanometer iron-based PES composite organic-inorganic material environment-friendly preparation method thereof, and this matrix material is applied to the processing of microbiotic in the waste water, bromate ion, bromo organism and chlorinatedorganic.
Background technology
Nano zero valence iron is the most widely engineering nano material of a kind of utilization of repairing contaminated underground water and soil, as a kind of efficient reductive agent, nano zero valence iron has less size, high specific surface area, reactive behavior is good, with low cost and the characteristics such as environmental friendliness, therefore is widely used in removing heavy metal in the underground water and soil, chlorinatedorganic, macromole dyestuff, inorganic anion etc.Yet because high reactive behavior, specific surface area and self the intrinsic magnetic of nano zero valence iron; when nano zero valence iron is applied in the environment remediation; reunion and very easily oxidized usually can occur; make it reduce reactive behavior, reduced the migration distance in underground water and increased loss of pressure head; an engineering difficult problem that exists in order to overcome the nano zero valence iron technology, domestic and international many scholars or the method by surface modification or the technology by load obtain stable performance, have the nano zero valence iron based composites of persistent high efficiency degradation capability.
The immobilized surface at inorganic or organic materials of Nanoscale Iron being alleviated the reunion of nano iron particles and increase its repair ability by physical and chemical adsorption or ion-exchange becomes the study hotspot that the Nanoscale Iron technology is used in environment remediation.The people such as domestic Zhao Zong mountain are with the immobilized ability that increases Water by Nano-iron dissolubility azoic dyestuff at Zeo-karb of nano iron particles.Nanjing University had applied for " composite cationic ion-exchange resin supporting iron-series duplex metal nano granules and preparation method thereof " (application number: 200910028414.4) in 2009, this application utilizes the ion exchange of sulfonic acid, carboxylic acid and phosphonyl group of resin with the immobilized internal surface at resin cation (R.C.) of nano particle, solved the problem that loss of pressure head was large when nano iron particles was directly used in environment remediation, transport property is poor and the reactive behavior persistence is poor, for deep purifying and the safety control of environmental pollutant provides better technical support.In addition, application number is that 200810207760.4 " in-situ preparation method of functional zeroth order iron/polyelectrolyte composite fibrofelt " announced the principle of utilizing electrostatic spinning and prepared the Zero-valent Iron nanofiber mats, the Zero-valent Iron size is between 2-10 nm in the fiber, agglomeration does not occur in the Nanoscale Iron ion of preparation, and fibrefelt is nano iron particles effectively fixedly, and guaranteeing can efficient recovery when nano iron particles applies to environment remediation.
At present, using the aqueous reaction reduction method of borohydride salts is that the laboratory prepares the most common method of nano iron particles, the advantage of this method is that easy handling and security are good, yet, keep away when using borohydride salts reduction preparation nano iron particles unavoidable also can be with serving negative benefit (as causing that environmental pollution and preparation cost are high).Therefore, the method of a kind of green and cheap synthesis of nano metallic particles is arisen at the historic moment, the human tea-polyphenol such as external Smuleac are reductive agent, load Nanoscale Iron and palladium/iron double metal particle have been synthesized by the iron ion green that in-situ reducing loads on the organic millipore filtration of polyvinylidene difluoride (PVDF), than the synthetic Nanoscale Iron matrix material of borohydride salts, pollution-free by ability and preparation process with high stability and lasting degraded environmental pollutant that tea-polyphenol is synthetic.
Literature search is the result show: take the organic filter membrane of polyethersulfone as carrier, methacrylic acid as function monomer and the green tea aqueous solution as green reducing agent synthesis of nano iron-based PES composite organic-inorganic material environment-friendly preparation method thereof and application there is not yet report.In addition, the present invention has also announced the application of metronidazole in the nanometer iron-based PES composite organic-inorganic material degradation water first.
Summary of the invention
Primary and foremost purpose of the present invention provides a kind of nanometer iron-based PES composite organic-inorganic material environment-friendly preparation method thereof, the method belongs to nano composite material green preparation process field, can solve problem that nano particle is difficult to reclaim and regenerates, can be effectively fixing nano iron particles and improve the ability of nano zero valence iron particle repairing environment, for advanced treatment and the purification that contains various pollutent waste water provides better technical support; The composite organic-inorganic material that makes by the inventive method is comprised of the fixing inorganic nano zero-valent iron particle of organic PES millipore filtration and its surface, easy oxidation when this nanometer iron-based PES composite organic-inorganic material can effectively solve the nano zero-valence iron base metallic particles and is directly used in environmental pollution improvement and environment remediation, poor stability and the problem of easily reuniting.
Preparation method of the present invention carries out functionalization take methacrylic acid (MA) as monomer to commercially available polyethersulfone (PES) millipore filtration, (COOH) functional group loads on iron ion in the surface or hole of millipore filtration, forms this matrix material with the iron ion on the green tea aqueous solution reduction film thereafter with PES microporous membrane surface carboxylic acid again.
Nanometer iron-based PES composite organic-inorganic material environment-friendly preparation method thereof comprises the steps:
(1) the PES millipore filtration is carried out pre-treatment
Soak PES millipore filtration 48～72 h with deionized water, per 12 h change a deionized water, to remove the impurity between striping surface and hole and to make millipore filtration reach the contraction balance;
(2) the PES millipore filtration is carried out functionalization
The PES millipore filtration is immersed in the MA functionalization solution behind 5～15 min fully, take out millipore filtration and place 60～80 ℃ of vacuum drying oven oven dry, and then soak 24～60 h with deionized water, per 12 h change a deionized water, with except the unreacted function monomer of striping surface attachment and other unnecessary compositions, this step is for obtaining to contain-the PES millipore filtration of COOH functional group;
(3) the PES millipore filtration of functionalization carried out the sodium ion exchange
To contain-the PES millipore filtration of COOH functional group immerses sodium-salt aqueous solution fully and carries out the sodium ion exchange, takes out behind 24～48 h, and with rinsed with deionized water 2～3 times, and acquisition contains-the PES millipore filtration of COONa functional group;
(4) to contain-the PES millipore filtration of COONa carries out the iron ion exchange
To contain-the PES millipore filtration of COONa functional group immerses molysite aqueous solution fully and carries out the iron ion exchange, takes out behind 24～48 h, and with rinsed with deionized water 2～3 times;
(5) will contain Fe
2+And Fe
3+Or Fe
3+The PES millipore filtration immerse fully in the green tea aqueous solution behind 60～240 min, use respectively rinsed with deionized water 2～3 times, after be stored in the deionized water, for subsequent use, finish the preparation of nanometer iron-based PES composite organic-inorganic material.
The acid functionalization of methacrylic described in the present invention solution refers to comprise the methacrylic acid of 10～35 wt%, the Macrogol 200 of 2～8 wt% and the mixed aqueous solution of 0.5～1 wt% ammonium persulphate.
Sodium-salt aqueous solution described in the present invention is that pH=9～11, concentration are the Na of 0.2～2 M
2CO
3, NaNO
3Or NaHCO
3The aqueous solution.
Molysite aqueous solution described in the present invention is that concentration is the Fe (NO of 10～80 mM
3)
3, Fe (NO
3)
2, Fe
2(SO
4)
3, FeCl
3A kind of in the aqueous solution.
The aqueous solution of green tea described in the present invention is the ratio of adding 20～80 g green tea in every premium on currency solution, and green tea is added boiling 45～120 min in the boiling water, is cooled to room temperature and filtration, and gained filtrate is settled to the initial aqueous solution volume, namely gets the green tea aqueous solution.
Another purpose of the present invention provides a kind of nanometer iron-based PES composite organic-inorganic material, organic materials is the organic millipore filtration carrier of hydrophilic polyethersulfone in this nanometer iron-based PES composite organic-inorganic material, contain methacrylic functional group on the carrier, by ion exchange, this functional group can effectively be fixed on iron ion the surfaces externally and internally of millipore filtration; Inorganic materials is the Zero-valent Iron nano particle that loads on the filter membrane.
Another object of the present invention is nanometer iron-based PES composite organic-inorganic material to be applied in contain microbiotic, bromate ion, in the environment remediation of bromo organism or chlorinatedorganic waste water, utilize composite organic-inorganic material that the present invention makes respectively to containing microbiotic, bromate ion, the simulated wastewater of bromo organism or chlorinatedorganic is repaired, test result shows: freshly prepd nanometer iron-based PES composite organic-inorganic material is to microbiotic in the waste water, bromate ion, bromo organism or chlorinatedorganic clearance are all more than 95%, and nanometer iron-based PES composite organic-inorganic material is to microbiotic in the water after the regeneration, bromate ion, the removal efficient of bromo organism and chlorinatedorganic is respectively 96%, 92%, 93% and 91%, this explanation above-mentioned functions material all has higher repair ability to the different pollutents in the waste water.
Beneficial effect of the present invention is as follows:
(1) method of functionalization PES millipore filtration provided by the invention is simple to operate and cost is low, belongs to green preparation process;
(2) nanometer iron-based PES composite organic-inorganic material environment-friendly preparation method thereof simple possible provided by the present invention, with low cost and environmental protection;
(3) preparation method provided by the invention can fix and dispersed iron nanoparticles effectively, solved the nano zero valence iron granule stability poor, be easy to reunite and the problem of oxidation, improved the repair ability of nano zero valence iron particle;
(4) preparation method provided by the invention has solved when the nano zero valence iron particle is directly used in environmental pollution improvement and environment remediation and has easily run off, has been difficult to the problem that reclaims and regenerate, reduced the ecological risk that runs off and cause into environment water because of nano particle, improve the life cycle of nano zero valence iron particle, thereby reduced the running cost of repairing environment;
(5) nanometer iron-based PES composite organic-inorganic material provided by the invention all has the repair ability of persistent high efficiency to the water body that polluted by microbiotic, bromate ion, bromo organism and chlorinatedorganic, for environmental pollution improvement and environment remediation provide technical support.
Description of drawings
Fig. 1 is field emission scanning electron microscope (FE-SEM) figure of the nano zero valence iron particle of not load;
Fig. 2 is PES millipore filtration FE-SEM schematic diagram, wherein: (a) be the PES millipore filtration FE-SEM figure of not functionalization; (b) be the PES millipore filtration FE-SEM figure of MA functionalization; (c) be that the PES millipore filtration carries the FE-SEM figure behind the nano zero valence iron;
Fig. 3 is metronidazole curve synoptic diagram in the nanometer iron-based PES composite organic-inorganic material degradation water for preparing of the present invention.
Embodiment
Below by drawings and Examples the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1: the preparation method of nano zero valence iron particle, this embodiment is the controlled trial of the inventive method, particular content is as follows:
(1) weighing 8.3406 gram FeSO
4.7H
2Change over to behind the O powder and fill in the clean beaker of deionized water, magnetic agitation makes it abundant dissolving, is mixed with the FeSO that volumetric molar concentration is 0.15 M
4Solution 200 mL, for subsequent use;
(2) weighing 9.711 restrains KBH in addition
4Powder is dissolved in the deionized water, with glass stick stirred for several minute, and is configured to the KBH that volumetric molar concentration is 0.9 M
4Solution 200 mL, after be transferred in the 250 mL pears type separating funnels, for subsequent use;
(3) solution and the material requested of step (1) and (2) configuration are put into anaerobic box in the lump, and will fill KBH
4The pears type separating funnel of solution is fixed on the iron stand, and logical nitrogen 60 min to be removing oxygen wherein first, after with the KBH of 200 mL volumetric molar concentrations, 0.9 M
4Solution dropwise adds the FeSO that volumetric molar concentration is 0.15 M
4Solution; stir while dripping; dropwise rear time-delay and stir 30 min; with gained suspension liquid vacuum filtration, after clean respectively 3 times with deionized water and dehydrated alcohol successively, drain; after the gained powder is placed vacuum-drying under the room temperature; after gained nano zero valence iron particle grinds under nitrogen protection, preserve with the serum bottle sealing, for subsequent use.
(4) Nanoscale Iron of the present embodiment preparation is carried out field emission scanning electron microscope (FE-SEM) the sign (see figure 1), test result shows: serious reunion has occured in the nano iron particles of the not load of the present embodiment preparation, and some particle has been agglomerated into bulk, illustrates that the nano iron particles of the present embodiment preparation has relatively poor dispersiveness.
Embodiment 2: this nanometer iron-based PES composite organic-inorganic material preparation method, particular content is as follows:
(1) get first a PES millipore filtration (diameter, aperture and thickness are respectively 5 cm, 0.45 μ m and 100 μ m) and put into clean beaker immersion 60 h that fill deionized water, per 12 h change a deionized water;
(2) the MA functionalization solution that formed by the mixed aqueous solution of 25 wt% MA, 4 wt% Macrogol 200s and 0.8 wt% ammonium persulphate of configuration, after take out after pretreated PES millipore filtration immersed above-mentioned functions solution 8 min fully, and millipore filtration sent into 75 ℃ vacuum drying oven oven dry, after the PES millipore filtration of functionalization is soaked 36 h with deionized water, per 12 h change a deionized water, and this purpose is unreacted monomer and other residues that adhere to for removing the PES microporous membrane surface;
(3) the PES millipore filtration of functionalization is put into the Na that concentration is 0.8 M
2CO
3Solution (pH=10) allows Na
+With the PES microporous membrane surface-COOH carries out behind ion-exchange 30 h with rinsed with deionized water 3 times;
(4) measure the Fe that concentration is 60 mM
2(SO
4)
3Solution, after put into and contain-millipore filtration of COONa functional group, allow Fe
3Carry out behind ion-exchange 38 h with rinsed with deionized water 3 times with-COONa;
(5) take by weighing the commercially available green tea of 8 g and add boiling 90 min in the 200 mL boiling water, be cooled to room temperature and filtration, gained filtrate is transferred in the 200 mL volumetric flasks and with deionized water is diluted to scale, namely get the green tea aqueous solution;
(6) measure the green tea aqueous solution of 50 mL, will contain Fe
3+The PES millipore filtration immerse fully, allow green tea aqueous solution reductase 12 00 min, use afterwards the rinsed with deionized water millipore filtration 3 times, be stored in the deionized water freshly prepd nanometer iron-based PES composite organic-inorganic material for subsequent use;
(7) matrix material of the present embodiment preparation is carried out field emission scanning electron microscope (FE-SEM) the sign (see figure 2), FE-SEM test result: Fig. 2 (a) is the PES millipore filtration carrier of not functionalization, filter membrane is the structure of porous as can be seen from the figure, and this vesicular structure can play to the nano particle that is easy to reunite the effect of dispersion.Fig. 2 (b) is the PES millipore filtration of MA functionalization, and with respect to former film, the membrane pore size after the functionalization diminishes, and this explanation MA monomer has been functionalized in the PES fenestra and the surface; Fig. 2 (c) is the PES millipore filtration behind the nano zero valence iron that carries of the present embodiment preparation, can be found out between microporous membrane surface and hole by bar-shaped nanometer iron staff particle covering by this figure, can find out from scale, the diameter of nanometer iron staff particle is 20～50 nm, and high dispersing is on the surface of millipore filtration, this is the size of nanometer iron staff particle have been played the cause of control action kou owing to having introduced the containing of the low polymerization degree-polymethyl acrylic acid of COOH functional group during MA functionalization PES millipore filtration on the film surface, comparative example 1 characterization result as can be known, in PES millipore filtration introducing-COOH functional group and be equipped with ion exchange process and can fundamentally control the nano iron particles agglomeration traits, simultaneously also for the recycling of nano zero valence iron based composites and recovery provide may.
Embodiment 3: metronidazole in nanometer iron-based PES composite organic-inorganic material study on the stability and the degradation water, particular content is as follows:
(1) stability of the nanometer iron-based PES composite organic-inorganic material of investigation: prepare nanometer iron-based PES composite organic-inorganic material by method described in the embodiment 2, after be placed in the deionized water of pH=3, and the color of record film this moment, interval 10 days, 20 days, observed once afterwards and kept a record in 30 days and 60 days, the gained observed result shows: the composite material film color is compared when just inserting in the deionized water, interval 10 days, 20 days, the color on 30 days and 60 days caudacoria surfaces does not almost change, all be black, and that the nano zero valence iron particle of pressing the described preparation method's preparation of embodiment 1 soaks in above-mentioned deionized water behind 2 h is just all oxidized, this explanation has high oxidation-resistance with the matrix material of green tea aqueous solution reduction preparation in the water surrounding of meta-acid, thereby provides possible for the utilization of this matrix material in actual engineering of water treatment;
(2) contrast nano zero valence iron particle and nanometer iron-based PES composite organic-inorganic material are removed the ability of metronidazole in the water: configuring starting point concentration with deionized water is the metronidazole aqueous solution (making pH=5.4) of 40 mg/L, measure respectively 50 mL concentration and be the metronidazole aqueous solution of 40 mg/L in 4 clean reaction flasks, the rear PES millipore filtration (pressing the described step preparation in (1) among the embodiment 2-(3)) that adds respectively a MA functionalization, a nanometer iron-based PES composite organic-inorganic material (containing 4.5 mg Fe) (pressing the preparation of method described in the embodiment 2) and 4.5 mg nano zero valence iron particles (pressing the preparation of method described in the embodiment 1), do not add any degradable material (control sample) in last reaction flask, place 25 ℃ of room temperature reaction 120 min, the interval certain hour is got 2 mL water samples and is analyzed;
(3) the data obtained is depicted as degradation curve figure, as shown in Figure 3, by the prepared matrix material of embodiment 2 can be with water in 120 min in metronidazole all remove, and only be 32% by the clearance of the prepared nano zero valence iron particle of embodiment 1, in addition, the PES millipore filtration of MA functionalization is almost 0 to the clearance of metronidazole in the water, this illustrates that nanometer iron-based PES composite organic-inorganic material has the ability of high degraded metronidazole than the nano zero valence iron particle of load not, also illustrates what this matrix material was mainly realized by the reduction process that loads on the nano zero valence iron particle on the PES millipore filtration the degradation process of metronidazole in the water simultaneously;
(4) reacted nanometer iron-based PES composite organic-inorganic material in the present embodiment step (2) is regenerated by step (6) among the embodiment 2, matrix material after the regeneration carries out the metronidazole degradation experiment by the present embodiment step (2), gained degradation curve figure as shown in Figure 3, composites after the regeneration has high degradation capability as we know from the figure, the clearance of metronidazole is 96% in the water in 120 min, this illustrates that nanometer iron-based PES composite organic-inorganic material has good renewable, thereby processing has reduced running cost to actual waste water.
Embodiment 4: bromate ion in the preparation method of nanometer iron-based PES composite organic-inorganic material and the degradation water, particular content is as follows:
(1) PES millipore filtration (diameter, aperture and thickness are respectively 6 cm, 0.45 μ m and 100 μ m) is put into clean beaker immersion 48 h that fill deionized water and carried out pre-treatment, per 12 h change a deionized water; And the MA functionalization solution that formed by the mixed aqueous solution of 10 wt% MA, 2 wt% Macrogol 200s and 0.5 wt% ammonium persulphate of configuration, after take out after pretreated PES millipore filtration immersed above-mentioned functions solution 5 min fully, and millipore filtration sent into 60 ℃ vacuum drying oven oven dry, after the PES millipore filtration of functionalization is soaked 24 h with deionized water, per 12 h change a deionized water;
(2) the PES millipore filtration of functionalization is put into the NaNO that concentration is 0.2 M
3Solution (pH=9) allows Na
+With the PES microporous membrane surface-COOH carries out behind ion-exchange 24 h with rinsed with deionized water 3 times, after measure the Fe (NO that concentration is 10 mM
3)
3Solution, after put into and contain-millipore filtration of COONa functional group, allow Fe
3+Carry out behind ion-exchange 24 h with rinsed with deionized water 3 times with-COONa;
(3) take by weighing the commercially available green tea of 4 g and add boiling 45 min in the 200 mL boiling water, be cooled to room temperature and filtration, gained filtrate is transferred in the 200mL volumetric flask and with deionized water is diluted to scale, namely get the green tea aqueous solution; Measure the 50 mL green tea aqueous solution, the rear immersion fully contained Fe
3+The PES millipore filtration, allow the green tea aqueous solution reduce 60 min, use afterwards the rinsed with deionized water millipore filtration 3 times, be stored in the deionized water freshly prepd nanometer iron-based PES composite organic-inorganic material for subsequent use;
(4) measuring 50 mL concentration is that the bromate aqueous solution of 40 mg/L is in clean reaction flask, the freshly prepd nanometer iron-based PES composite organic-inorganic material of rear adding, place 25 ℃ of room temperature reaction 90 min, the interval certain hour is got 2 mL water samples and is analyzed, after reacting 90 min, bromate concentration is reduced to 0.46 mg/L in the water, and this illustrates that freshly prepd matrix material has higher removal ability to bromate ion in the water;
(5) with after the used matrix material usefulness washed with de-ionized water 3 times, carry out manipulation of regeneration by the present embodiment step (3), the gained regenerated composite material carries out degradation experiment by the present embodiment step (4).After reacting 90 min, the nanometer iron-based PES composite organic-inorganic material of the 2nd activating and regenerating is 95.8% to the clearance of bromate ion in the water, even after the 5th activation, remove efficient and still can reach 92%, illustrate that this matrix material has the ability of bromate ion in the good removal water.
Embodiment 5: in nanometer iron-based PES composite organic-inorganic material preparation method and the degradation water 2, the experiment of 4-dibromophenol, particular content is as follows:
(1) get first a PES millipore filtration (diameter, aperture and thickness are respectively 9 cm, 0.45 μ m and 100 μ m) and put into clean beaker immersion 72 h that fill deionized water, per 12 h change a deionized water, and the pre-treatment of film is finished in rear taking-up;
(2) the MA functionalization solution that formed by the mixed aqueous solution of 35 wt% MA, 8 wt% Macrogol 200s and 1 wt% ammonium persulphate of configuration, after take out after pretreated PES millipore filtration immersed above-mentioned functions solution 15 min fully, and millipore filtration sent into 80 ℃ vacuum drying oven oven dry, after the PES millipore filtration of functionalization is soaked 60 h with deionized water, per 12 h change a deionized water;
(3) the PES millipore filtration of functionalization is put into the NaHCO that concentration is 2 M
3Solution (pH=11) allows Na
+With the PES microporous membrane surface-COOH carries out behind ion-exchange 48 h with rinsed with deionized water 2 times, after measure the FeCl that concentration is 80 mM
3Solution, after put into and contain-filter membrane of COONa functional group, allow Fe
3+Carry out behind ion-exchange 48 h with rinsed with deionized water 3 times with-COONa;
(4) take by weighing the commercially available green tea of 16 g and add boiling 120 min in the 200 mL boiling water, be cooled to room temperature and filtration, gained filtrate is transferred in the 200mL volumetric flask and with deionized water is diluted to scale, namely get the green tea aqueous solution; Measure the green tea aqueous solution of 50 mL, the rear immersion fully contained Fe
3+The PES millipore filtration, allow green tea aqueous solution reductase 12 40 min, use afterwards the rinsed with deionized water millipore filtration 2 times, be stored in the deionized water freshly prepd nanometer iron-based PES composite organic-inorganic material for subsequent use;
(5) measuring 50 mL concentration is 2 of 80 mg/L, the 4-dibromophenol aqueous solution is in 2 clean reaction flasks, rear freshly prepd nanometer iron-based PES composite organic-inorganic material (containing 10.2 mg Fe) and the 10.2 mg nano zero valence iron particles (pressing embodiment 1 described method preparation) of adding respectively, place 25 ℃ of room temperature reaction 100 min, the interval certain hour is got 2 mL water samples and is analyzed, after reacting 100 min, in the water that matrix material is processed 2,4-dibromophenol concentration is reduced to 2.3 mg/L, and 2 in the water after the nano zero valence iron particle disposal, 4-dibromophenol concentration is 46.3 mg/L, the freshly prepd matrix material of this explanation the present embodiment has in the high degradation water 2 than the nano zero valence iron particle of load not, the ability of 4-dibromophenol, after used matrix material usefulness washed with de-ionized water 2 times, carry out manipulation of regeneration by the present embodiment step (4), the gained regenerated composite material is carried out degradation experiment by the present embodiment step (5), after reacting 100 min, matrix material after the 2nd regeneration is in the water 2, the clearance of 4-dibromophenol is 95.3%, behind the 6th activating and regenerating, matrix material is in the water 2, the removal efficient of 4-dibromophenol still can reach 93%, illustrate that matrix material prepared in the present embodiment has in the good removal water 2,4-dibromophenol and renewable.
Embodiment 6: the application of 2,4 dichloro phenol in the preparation method of nanometer iron-based PES composite organic-inorganic material and the degradation water, particular content is as follows:
(1) first a PES millipore filtration (diameter, aperture and thickness are respectively 4.7 cm, 0.45 μ m and 100 μ m) is put into clean beaker immersion 65 h that fill deionized water and carried out pre-treatment, per 12 h change a deionized water; The MA functionalization solution that configuration is comprised of the mixed aqueous solution of 20 wt% MA, 6 wt% Macrogol 200s and 0.7wt% ammonium persulphate, and take out after pretreated PES millipore filtration immersed above-mentioned functions solution 12 min fully, and millipore filtration sent into 65 ℃ vacuum drying oven oven dry, after the PES millipore filtration of functionalization is soaked 48 h with deionized water, per 12 h change a deionized water;
(2) the PES millipore filtration of functionalization is put into the Na that concentration is 1 M
2CO
3Solution (pH=10) allows Na
+With the PES microporous membrane surface-COOH carries out behind ion-exchange 36 h with rinsed with deionized water 2 times, after measure the Fe (NO that concentration is 20 mM
3)
2Solution, after put into and contain-filter membrane of COONa functional group, allow Fe
2+And Fe
3+Carry out behind ion-exchange 36 h with rinsed with deionized water 3 times with-COONa;
(3) take by weighing the commercially available green tea of 12 g and add boiling 100 min in the 200 mL boiling water, be cooled to room temperature and filtration, gained filtrate is transferred in the 200mL volumetric flask and with deionized water is diluted to scale, namely get the green tea aqueous solution; Measure the green tea aqueous solution of 50 mL, the rear immersion fully contained Fe
2+And Fe
3+The PES millipore filtration, allow the green tea aqueous solution reduce 120 min, use afterwards the rinsed with deionized water millipore filtration 3 times, be stored in the deionized water freshly prepd nanometer iron-based PES composite organic-inorganic material for subsequent use;
(4) measuring 50 mL concentration is 2 of 40 mg/L, the 4-chlorophenesic acid aqueous solution is in clean reaction flask, the freshly prepd nanometer iron-based PES composite organic-inorganic material of rear adding places 25 ℃ of room temperature reaction 200 min, and the interval certain hour is got 2 mL water samples and analyzed.After reacting 200 min, in the water 2,4-dibromophenol concentration is reduced to 1.8 mg/L,, the freshly prepd matrix material of this explanation the present embodiment is 2,4 dichloro phenol in the degradation water effectively;
(5) with after the used matrix material usefulness washed with de-ionized water 2 times, carry out manipulation of regeneration by the present embodiment step (3), the gained regenerated composite material is carried out degradation experiment by the present embodiment step (4).After reacting 200 min, the matrix material of the 2nd regeneration is in the water 2, the clearance of 4-chlorophenesic acid is 94.6%, behind the 5th activating and regenerating, matrix material is 91% to the removal efficient of 2,4 dichloro phenol in the water, illustrate this matrix material can effectively dewater in 2, the 4-chlorophenesic acid, and renewable is strong.
Claims (7)
1. nanometer iron-based PES composite organic-inorganic material preparation method is characterized in that the method may further comprise the steps:
(1) first the PES millipore filtration is immersed fully and soak 48～72 h in the deionized water and carry out pre-treatment, per 12 h change a deionized water;
(2) pretreated PES millipore filtration is immersed fully in the methacrylic acid functionalization solution behind 5～15 min, after the taking-up millipore filtration places 60～80 ℃ of lower oven dry, gained functionalization millipore filtration is immersed 24～60 h in the deionized water fully, per 12 h change a deionized water, make to contain-the functionalization PES millipore filtration of COOH functional group;
(3) will contain-the PES millipore filtration of COOH functional group immerses carry out in the sodium-salt aqueous solution taking out behind sodium ion exchange 24～48 h fully, with rinsed with deionized water millipore filtration 2～3 times, obtains to contain-the PES millipore filtration of COONa functional group;
(4) will contain again-the PES millipore filtration of COONa functional group immerses carry out in the molysite aqueous solution taking out behind iron ion exchange 24～48 h fully, with rinsed with deionized water millipore filtration 2～3 times;
(5) will contain Fe
2+And Fe
3+Or Fe
3+The PES millipore filtration immerse reduce in the green tea aqueous solution behind 60～240 min fully, take out with rinsed with deionized water millipore filtration 2～3 times, after be stored in the deionized water, for subsequent use, namely obtain nanometer iron-based PES composite organic-inorganic material.
2. the preparation method of described nanometer iron-based PES composite organic-inorganic material according to claim 1, it is characterized in that: methacrylic acid functionalization solution refers to comprise the methacrylic acid of 10～35 wt%, the Macrogol 200 of 2～8 wt% and the mixed aqueous solution of 0.5～1 wt% ammonium persulphate.
3. the described preparation method that nanometer iron-based PES machine-inorganic composite materials is arranged according to claim 1, it is characterized in that: sodium-salt aqueous solution is that pH=9～11, concentration are the Na of 0.2～2 M
2CO
3, NaNO
3Or NaHCO
3The aqueous solution.
4. the preparation method of described nanometer iron-based PES composite organic-inorganic material according to claim 1, it is characterized in that: molysite aqueous solution is that concentration is the Fe (NO of 10～80 mM
3)
3, Fe (NO
3)
2, Fe
2(SO
4)
3, FeCl
3A kind of in the aqueous solution.
5. the preparation method of described nanometer iron-based PES composite organic-inorganic material according to claim 1, it is characterized in that: the green tea aqueous solution is the ratio of adding 20～80 g green tea in every premium on currency solution, green tea is added boiling 45～120 min in the boiling water, be cooled to room temperature and filtration, gained filtrate is settled to the initial aqueous solution volume, namely gets the green tea aqueous solution.
6. the nanometer iron-based PES composite organic-inorganic material that makes of the preparation method of the described nanometer iron-based PES composite organic-inorganic material of claim 1.
7. the described nanometer iron-based PES composite organic-inorganic material of claim 1 contains application in microbiotic, bromate ion, bromo organism or the chlorinatedorganic waste water in processing.
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