CN101961605B - Preparation process for diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and resin - Google Patents
Preparation process for diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and resin Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 70
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 70
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 60
- 239000012528 membrane Substances 0.000 title claims abstract description 56
- 238000000926 separation method Methods 0.000 title claims abstract description 46
- RAZLJUXJEOEYAM-UHFFFAOYSA-N 2-[bis[2-(2,6-dioxomorpholin-4-yl)ethyl]azaniumyl]acetate Chemical compound C1C(=O)OC(=O)CN1CCN(CC(=O)O)CCN1CC(=O)OC(=O)C1 RAZLJUXJEOEYAM-UHFFFAOYSA-N 0.000 title claims abstract 17
- 238000002360 preparation method Methods 0.000 title claims description 27
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000126 substance Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000005516 engineering process Methods 0.000 claims abstract description 35
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000012546 transfer Methods 0.000 claims abstract description 21
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 17
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract 8
- 229960003330 pentetic acid Drugs 0.000 claims abstract 2
- 238000005266 casting Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 37
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 6
- 239000003513 alkali Substances 0.000 claims 2
- 230000009920 chelation Effects 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 239000012510 hollow fiber Substances 0.000 claims 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000007872 degassing Methods 0.000 claims 1
- 238000009987 spinning Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 18
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 abstract 1
- 238000001471 micro-filtration Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 14
- 239000012670 alkaline solution Substances 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 11
- 238000009413 insulation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
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- 239000000356 contaminant Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000003113 alkalizing effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004064 recycling 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明提供一种以二乙烯三胺五乙酸二酐、氢氧化钠、硼氢化钠、四丁基溴化铵、对甲苯磺酸、N，N-二甲基乙酰胺、聚乙烯吡咯烷酮等试剂为原料，应用化学共混/相转移技术制备二乙烯三胺五乙酸二酐改性聚偏氟乙烯分离膜和树脂的工艺，该工艺具有操作简单、共混均匀等优点。该技术在聚偏氟乙烯分离膜和树脂中均匀共混了二乙烯三胺五乙酸多氨基多羧酸化合物，改善了聚偏氟乙烯微滤分离膜和树脂的亲水性能，实现了聚偏氟乙烯分离膜和树脂对废水中络合态重金属离子的去除，提高了聚偏氟乙烯分离膜和树脂对饮用水净化的效率，推进了工业废水中重金属污染物的去除和资源化利用，拓展了聚偏氟乙烯分离膜和树脂在水处理领域中的应用。The invention provides a reagent that uses diethylenetriaminepentaacetic dianhydride, sodium hydroxide, sodium borohydride, tetrabutylammonium bromide, p-toluenesulfonic acid, N,N-dimethylacetamide, polyvinylpyrrolidone, etc. Using chemical blending/phase transfer technology as raw material to prepare polyvinylidene fluoride separation membrane and resin modified by diethylene triamine pentaacetic acid dianhydride, the process has the advantages of simple operation and uniform blending. This technology evenly blends diethylenetriaminepentaacetic acid polyaminopolycarboxylic acid compound in polyvinylidene fluoride separation membrane and resin, improves the hydrophilic performance of polyvinylidene fluoride microfiltration separation membrane and resin, and realizes polyvinylidene fluoride separation membrane and resin. The removal of complexed heavy metal ions in wastewater by vinyl fluoride separation membranes and resins has improved the efficiency of polyvinylidene fluoride separation membranes and resins in drinking water purification, and promoted the removal and resource utilization of heavy metal pollutants in industrial wastewater. The application of polyvinylidene fluoride separation membrane and resin in the field of water treatment.
Description
Technical field
The present invention relates to the improved properties of Kynoar macromolecular material; Particularly relate to a kind of employing diethylene triamine pentacetic acid (DTPA) dianhydride, NaOH, sodium borohydride, TBAB, p-methyl benzenesulfonic acid, N; Reagent such as N-dimethylacetylamide are raw material; Applied chemistry blend/phase transfer of technology, the preparation technology that polyvinylidene fluoride separation membrane and resin are carried out modification.
Background technology
The polyvinylidene fluoride separation membrane technology has normal-temperature operation, do not have phase-state change, obvious energy-saving effect is arranged, and filtering accuracy is high, and production is polluted little, the advantage that water yield is big, matter is good.Through the screening and the crown_interception of film, suspended particulate in the water body and colloidal state pollutant there is good removal effect.Polyvinylidene fluoride separation membrane anti-pollution, anti-chemical oxidation function admirable can effectively be removed suspended particulate and colloid pollution thing in the water body, but conventional polyvinylidene fluoride separation membrane can not be realized the removal to water-soluble heavy metal ion.For effectively realizing that polyvinylidene fluoride separation membrane and resin to the removal of free state in the water body and organic complex attitude heavy metal contaminants, tackle it and carry out modification, will have in the functional group introducing diffusion barrier and resin of chelating coordination.
In the heavy metal pollution treatment process, there is the high and secondary pollution important disadvantages of processing cost in widely used chemical precipitation disposal technology.Absorption method comprises ion-exchange and absorption, is the control measures of heavy metal pollution in a kind of potential solution water body with application prospect, but conventional sorbing material such as active carbon, flyash etc. have the shortcoming that adsorption capacity is low, the rate of adsorption is slow.Thereby research and development and application has even aperture distribution, specific area is big, adsorption capacity is high, the rate of adsorption is fast, and the stable novel absorption material of physical and chemical performance is the important behave that solves heavy metal pollution of water body.Polyvinylidene fluoride separation membrane and resin have antipollution, chemically-resistant oxidation, to the stable advantage of microbial action, and mechanical performance is good, physical and chemical performance is stable.But conventional polyvinylidene fluoride separation membrane and resin can not be realized the removal to water-soluble heavy metal contaminants in the water body.
The diffusion barrier of function admirable and the research and development of novel absorption material are the emphasis of polymeric material field research always, just are being devoted to the research and development of novel diffusion barrier and sorbing material both at home and abroad.For heavy metal pollution improvement, wastewater treatment and reuse field, good, the anti-chemical agent oxidation of the diffusion barrier of Kynoar material and resin anti-fouling performance causes people's attention day by day.At present, the emphasis of tackling key problems for polyvinylidene fluoride material is surface graft modification research, the particularly improvement of polyvinylidene fluoride separation membrane and resin hydrophilicity.Improving the hydrophilicity of polyvinylidene fluoride separation membrane and resin, improve the handling property of diffusion barrier and resin, will be the difficult point and the emphasis of each developer and institute tackling key problem.Reagent such as many scholar's using polythene alcohol, acrylic acid, acrylamide and polyacrylic acid; Adopt technology such as radiation-induced, plasma-induced, ozone oxidation; Carried out the research of polyvinylidene fluoride separation membrane and resin surface hydrophilic modifying; At the hydroxy-acid group and the oh group of its surface grafting possess hydrophilic property ability, effectively improved the water-wet behavior of polyvinylidene fluoride separation membrane and resin, realized the absorption of free state heavy metal contaminants is removed.But surface graft modification can produce harmful effect to the physical property of diffusion barrier and resin; As change the microcellular structure and the pore-size distribution of diffusion barrier and resin surface; The hydrophilic radical of grafting can come off, and the polyvinylidene fluoride separation membrane of grafted propylene acid polymer and functional group of sulfonic acid and resin are low to complex state removal of heavy metal ions efficient in the water body.In addition; Adopt diethylene triamine pentacetic acid (DTPA) and melamine that polyvinylidene fluoride separation membrane and resin are carried out modification; Can realize with the polyamino polycarboxylic acid functional group blend of chelating coordination and be grafted to polyvinylidene fluoride separation membrane and resin in; But reaction often needs the high temperature more than 160 ℃, and reaction condition control requires very strict.The existence of these problems will influence the performance of polyvinylidene fluoride separation membrane and resin, finally limit the application in water treatment field of polyvinylidene fluoride separation membrane and resin.
Summary of the invention
In order to overcome the above-mentioned deficiency that prior art exists; The present invention provides the preparation technology of a kind of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane and resin; Through chemical blend/phase transfer of technology, even doping diethylene triamine pentacetic acid (DTPA) polyamino multi-carboxylic acid compounds in polyvinylidene fluoride separation membrane and resin, make in polyvinylidene fluoride separation membrane and the resin even blend possess hydrophilic property can with the polyamino polycarboxylic acid functional group of chelating coordination property; Improved the hydrophilicity of diffusion barrier and resin; Realize the removal of free state and complex state heavy metal ion in the water body, further improved drinking water quality, removed and reclaimed the heavy metal ion in the industrial wastewater; Efficiently solve the heavy metal pollution of water environment, advanced the recycling of heavy metal contaminants.
The preparation technology of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane and resin is:
1) the Kynoar preparation of used chemical liquids of alkalizing:
150～180g NaOH and 3～7g TBAB are joined in the 1L deionized water successively, and stirring and making its whole dissolvings, deionization electrical conductivity of water is 5～10 μ s/cm;
2) basification of Kynoar:
A. after treating that each component is all dissolved in the chemical alkaline solution; Its temperature slowly being raise, treat that temperature is increased to 80 ℃, is that 0.05mm, quality are that 400g Kynoar particle joins in the chemical alkaline solution with average grain diameter; Keeping solution temperature is 75～85 ℃, and the basification time is 8h;
B. alkalize behind the 8h, the Kynoar particle is taken out from chemical alkaline solution, it is cleaned with deionized water, dry down at 60～80 ℃;
3) adopting chemical blend/phase transfer of technology to prepare the blend casting liquid that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane adopted consists of:
A. diethylene triamine pentacetic acid (DTPA) dianhydride 120～200g/L, sodium borohydride 4～7g/L, the Kynoar 120～150g/L of basification, p-methyl benzenesulfonic acid 1～3g/L, polyvinylpyrrolidone 30～50g/L;
B. solvent for use is N, the N-dimethylacetylamide;
C. the addition sequence of each reagent is: at first adding sodium borohydride, is the Kynoar of basification then, secondly is p-methyl benzenesulfonic acid, is diethylene triamine pentacetic acid (DTPA) dianhydride and polyvinylpyrrolidone at last successively;
4) adopt chemical blend/phase transfer of technology to prepare the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane:
A. adopt chemical blend/phase transfer of technology to prepare diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane, in three-neck flask, sodium borohydride is joined N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃; When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the basification is joined in the solvent, keeping the casting liquid temp is 118～122 ℃, and reaction 3h will adopt condensing reflux from solvent begins to be heated to the whole process of insulation reaction 3h; Behind the insulation 3h, will cast liquid temp and reduce to 40～50 ℃, and successively p-methyl benzenesulfonic acid and diethylene triamine pentacetic acid (DTPA) dianhydride joined in the above-mentioned casting liquid, stirring reaction 2h begins to join the whole process of stirring reaction 2h from p-methyl benzenesulfonic acid and need lead to nitrogen protection; After leading to nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation makes each components dissolved and abundant blend 6h in the casting liquid; Behind the stirring 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
B. diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride flat sheet membrane is at the medical scraper system film of smooth usefulness on glass; Film forming in water condensation is bathed then; Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride hollow-fibre membrane is to draw with spinning-drawing machine; Core liquid is 5% ethanol water, and flow velocity is 1.2～1.8ml/min; Casting liquid rate of extrusion is 1.3～1.5ml/min, and the filament length that per minute makes is 35 meters, and condensation is bathed and is deionized water, and its electrical conductivity is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃;
C. diethylene triamine pentacetic acid (DTPA) two anhydride modification vinylidene hollow-fibre membranes and flat sheet membrane are at first soaked 48h with deionized water; Be immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution;
5) adopting chemical blend/phase transfer of technology to prepare the blend casting liquid that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin adopted consists of:
A. diethylene triamine pentacetic acid (DTPA) dianhydride 150～230g/L, sodium borohydride 4～7g/L, the Kynoar 100～130g/L of basification, p-methyl benzenesulfonic acid 1～3g/L, polyvinylpyrrolidone 30～50g/L;
B. solvent for use is N, the N-dimethylacetylamide;
C. the addition sequence of each reagent is: at first adding sodium borohydride, is the Kynoar of basification then, secondly is p-methyl benzenesulfonic acid, is diethylene triamine pentacetic acid (DTPA) dianhydride and polyvinylpyrrolidone at last successively;
6) adopt chemical blend/phase transfer of technology to prepare the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin:
A. adopt chemical blend/phase transfer of technology to prepare diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin, in three-neck flask, sodium borohydride is joined N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃; When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the basification is joined in the solvent, keeping the casting liquid temp is 118～122 ℃, and reaction 3h will adopt condensing reflux from solvent begins to be heated to the whole process of insulation reaction 3h; Behind the insulation 3h, will cast liquid temp and reduce to 40～50 ℃, and successively p-methyl benzenesulfonic acid and diethylene triamine pentacetic acid (DTPA) dianhydride joined in the above-mentioned casting liquid, stirring reaction 2h begins to join the whole process of stirring reaction 2h from p-methyl benzenesulfonic acid and need lead to nitrogen protection; After leading to nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation makes each components dissolved and abundant blend 6h in the casting liquid; Behind the stirring 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
B. the preparation process of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin is: dropwise join in the deionized water with dropper the casting liquid after the deaeration of " a " step; And slowly stir; The deionization electrical conductivity of water is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃; Last casting liquid such as casting drop acceleration can not be too fast, and is necessary get in the deionized water, and could drip next drips casting liquid, and the granularity of resin microsphere is 1.2～1.7mm, and the average pore size of resin surface micropore is 0.18 μ m;
C. diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin at first soaks 48h with deionized water, is immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, and taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution.
The present invention is to adopting diethylene triamine pentacetic acid (DTPA) dianhydride, NaOH, sodium borohydride, TBAB, p-methyl benzenesulfonic acid, N; Reagent such as N-dimethylacetylamide are raw material; Applied chemistry blend/phase transfer of technology, it is suitable equally to carry out polysulfones diffusion barrier, polyethersulfone separating membrane, the modification of polyacrylonitrile diffusion barrier.
The invention has the beneficial effects as follows: this in Kynoar in diffusion barrier and the resin evenly the doping possess hydrophilic property can and chemical graft blend/phase transfer of technology of the polyamino multi-carboxylic acid compounds of chelating coordination property; Have advantages such as simple to operate, that blend is even; Improved the hydrophilicity of conventional polyvinylidene fluoride separation membrane and resin, realized its removal heavy metal contaminants in the water body.This invention has realized the removal to complex state heavy metal ion in the water body of polyvinylidene fluoride separation membrane and resin; Improved microfiltering separation film of polyvinylidene fluoride and resin efficient to drink water purifying; Realize the removal and the recycling of heavy metal contaminants in the industrial wastewater, expanded the application in water treatment field of polyvinylidene fluoride separation membrane and resin.
The specific embodiment
Following mask body combines embodiment, specifies the preparation technology of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane and resin.
Embodiment
1, chemical blend/phase transfer of technology prepares the technology of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane
1) the Kynoar preparation of used chemical liquids of alkalizing:
170g NaOH and 5g TBAB are joined in the 1L deionized water successively, and stirring and making its whole dissolvings, deionization electrical conductivity of water is 5～10 μ s/cm;
2) Kynoar basification:
After treating that each component is all dissolved in the chemical alkaline solution, its temperature is slowly raise;
Treating that the alkaline solution temperature is increased to 80 ℃, is that 0.05mm, quality are that 400g Kynoar particle joins and carries out basification in the chemical alkaline solution with average grain diameter, and keeping solution temperature is 75～85 ℃, and the basification time is 8h;
Behind the basification 8h, the Kynoar particle is taken out from chemical alkaline solution, it is cleaned with deionized water, dry down at 60～80 ℃;
3) adopt chemical blend/phase transfer of technology to prepare the blend casting liquid preparation that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane is adopted:
In three-neck flask, the 0.5g sodium borohydride is joined 100g N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃;
When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the 13g basification is joined in the solvent, keeping the casting liquid temp is 118～122 ℃, and reaction 3h will adopt condensing reflux from solvent begins to be heated to the whole process of insulation reaction 3h;
Behind the insulation 3h; To cast liquid temp and reduce to 40～50 ℃; Successively 0.2g p-methyl benzenesulfonic acid and 150g diethylene triamine pentacetic acid (DTPA) dianhydride are joined in the above-mentioned casting liquid, stirring reaction 2h, the whole process that begins to join stirring reaction 2h from p-methyl benzenesulfonic acid need be led to nitrogen protection;
Behind the logical nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation 6h makes each components dissolved and fully blend in the casting liquid;
Behind the 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
4) preparation of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane:
Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride flat sheet membrane is at the medical scraper system film of smooth usefulness on glass, then film forming in water condensation is bathed; The modified hollow tunica fibrosa is to draw with spinning-drawing machine, and core liquid is 5% ethanol water, and flow velocity is 1.2～1.8mL/min; Casting liquid rate of extrusion is 1.3～1.5mL/min, and the filament length that per minute makes is 35 meters, and condensation is bathed and is deionized water, and its electrical conductivity is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃;
5) processing of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinylidene fluoride separation membrane and preservation:
Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride hollow-fibre membrane, flat sheet membrane; At first soak 48h with deionized water; Be immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution.
2, chemical blend/phase transfer of technology prepares the technology of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin
(1) the Kynoar preparation of used chemical liquids of alkalizing:
170g NaOH and 5g TBAB are joined in the 1L deionized water successively, and stirring and making its whole dissolvings, deionization electrical conductivity of water is 5～10 μ s/cm;
(2) Kynoar basification:
After treating that each component is all dissolved in the chemical alkaline solution, its temperature is slowly raise;
Treating that the alkaline solution temperature is increased to 80 ℃, is that 0.05mm, quality are that 400g Kynoar particle joins and carries out basification in the chemical alkaline solution with average grain diameter, and keeping solution temperature is 75～85 ℃, and the basification time is 8h;
Behind the basification 8h, the Kynoar particle is taken out from chemical alkaline solution, it is cleaned with deionized water, dry down at 60～80 ℃;
(3) adopt chemical blend/phase transfer of technology to prepare the blend casting liquid preparation that diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin is adopted:
In three-neck flask, the 0.5g sodium borohydride is joined 100g N, in the N-dimethylacetamide solvent, make solvent temperature slowly be increased to 120 ℃;
When treating that solvent temperature is increased to 120 ℃, rapidly the Kynoar after the 11g basification is joined in the solvent, keeping the casting liquid temp is 118～122 ℃, and reaction 3h begins to heat the whole process with insulation reaction 3h from solvent and will adopt condensing reflux;
Behind the insulation 3h; To cast liquid temp and reduce to 40～50 ℃; Successively 0.2g p-methyl benzenesulfonic acid and 180g diethylene triamine pentacetic acid (DTPA) dianhydride are joined in the above-mentioned casting liquid, stirring reaction 2h, the whole process that begins to join stirring reaction 2h from p-methyl benzenesulfonic acid need be led to nitrogen protection;
Behind the logical nitrogen 2h, stop logical nitrogen, polyvinylpyrrolidone is joined in the blend casting liquid, stirring and dissolving is finally controlled temperature at 70 ℃～80 ℃, and magnetic agitation 6h makes each components dissolved and fully blend in the casting liquid;
Behind the 6h liquid is cast in blend and placed water-bath deaeration 6～9h, bath temperature is 50 ℃～60 ℃;
(4) preparation of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin:
Casting liquid after the deaeration is dropwise joined in the deionized water with dropper, and slowly stir, the deionization electrical conductivity of water is 20～30 μ s/cm, and water temperature is 40 ℃～50 ℃;
Last casting liquid such as casting drop acceleration can not be too fast, and is necessary get in the deionized water, and could drip next drips casting liquid, and the granularity of mixed microsphere is 1.2～1.7mm, and the average pore size of resin surface micropore is 0.18 μ m;
(5) processing and the preservation of diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin:
Diethylene triamine pentacetic acid (DTPA) dianhydride modified polyvinilidene fluoride resin at first soaks 48h with deionized water, is immersed in 24h in the hydrochloric acid solution of 0.1～0.5mol/L then, and taking out and being immersed in volume ratio after cleaning is to preserve in 0.5～2% the aqueous hydrogen peroxide solution.
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| CN103611434B (en) * | 2013-12-03 | 2015-04-08 | 燕山大学 | Preparation method of tetrabutyl titanate-ethylenediamine tetra(methylenephosphonic acid)/polyvinylidene fluoride chelated film |
| CN106040020B (en) * | 2016-07-04 | 2018-06-08 | 燕山大学 | A kind of preparation method for the Kynoar functional membrane for carrying chelation group |
| CN110038536B (en) * | 2019-04-12 | 2020-03-24 | 燕山大学 | Preparation method of chemical grafting modified polyvinylidene fluoride separation membrane |
| CN110066037A (en) * | 2019-05-20 | 2019-07-30 | 上海烟草集团有限责任公司 | A kind of reconstituted tobacco plain boiled water processing method and system |
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