WO2023241689A1 - 一种多孔胺化有机氟胶囊及其制法与应用 - Google Patents
一种多孔胺化有机氟胶囊及其制法与应用 Download PDFInfo
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- WO2023241689A1 WO2023241689A1 PCT/CN2023/100648 CN2023100648W WO2023241689A1 WO 2023241689 A1 WO2023241689 A1 WO 2023241689A1 CN 2023100648 W CN2023100648 W CN 2023100648W WO 2023241689 A1 WO2023241689 A1 WO 2023241689A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organic fluorine
- aminated
- porous
- capsule
- phenolic resin
- Prior art date
Links
- 239000002775 capsule Substances 0.000 title claims abstract description 112
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000011737 fluorine Substances 0.000 title claims abstract description 71
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000002033 PVDF binder Substances 0.000 claims abstract description 26
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 25
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 25
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 52
- 238000001179 sorption measurement Methods 0.000 claims description 45
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 150000004812 organic fluorine compounds Chemical class 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 6
- 230000007423 decrease Effects 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000011549 displacement method Methods 0.000 abstract 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000010586 diagram Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 3
- -1 salt ions Chemical class 0.000 description 3
- 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 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005102 attenuated total reflection Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 1
- QYCPVKMFWNBDPV-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorooctanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(O)=O QYCPVKMFWNBDPV-UHFFFAOYSA-N 0.000 description 1
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PXUULQAPEKKVAH-UHFFFAOYSA-N perfluorohexanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PXUULQAPEKKVAH-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/4816—Wall or shell material
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J3/00—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
- A61J3/07—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use
- A61J3/071—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use into the form of telescopically engaged two-piece capsules
- A61J3/074—Filling capsules; Related operations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J3/00—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
- A61J3/07—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use
- A61J3/071—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use into the form of telescopically engaged two-piece capsules
- A61J3/077—Manufacturing capsule shells
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
Definitions
- PFCs Perfluorinated compounds
- 3M Company Since first synthesized by 3M Company in the late 1940s, PFCs have been widely used in various fields of human production and life due to their hydrophobic and lipophobic properties, high temperature resistance, and strong oxidation resistance. Studies have found that their extensive use and their strong stability make PFCs ubiquitous in the global environment, with concentrations up to 1 mg ⁇ L -1 in surface water and groundwater.
- PFOA has also been included in the priority control list of persistent organic pollutants.
- the health limit concentration of PFOA in drinking water is 70ng ⁇ L -1 .
- the purpose of the invention is to provide a porous aminated organic Fluorine capsules
- another object of the present invention is to provide a preparation method of porous aminated organic fluorine capsules
- yet another object of the present invention is to provide an application of porous aminated organic fluorine capsules in adsorbing perfluorinated compounds.
- the porous aminated organic fluorine capsule of the present invention includes a porous organic fluorine shell, and the inside of the organic fluorine shell is filled with aminated phenolic resin.
- the pore diameter on the porous organic fluorine shell ranges from 28.6 to 330.5 nm, and the pore diameter decreases as the content of aminated phenolic resin in the capsule increases.
- the diameter of the porous aminated organic fluorine capsule is 1.5-1.8 mm.
- the preparation method of the above-mentioned porous aminated organofluorine capsules includes the following steps:
- the mass ratio of ethylenediamine, formaldehyde, and resorcinol is 1 to 3:1 to 3:1 to 2.
- the volume ratio of ethanol to water is 2:5.
- the mass concentration ratio of polyvinylidene fluoride, polyvinylpyrrolidone, and aminated phenolic resin powder is 12:2:4-12.
- the weight average molecular weight of polyvinylidene fluoride is 170,000 to 190,000.
- the weight average molecular weight of polyvinylpyrrolidone is 1,200,000 to 1,400,000.
- the volume ratio of isopropyl alcohol to water in the mixture of water and isopropyl alcohol is 30%.
- the application of the above-mentioned porous aminated organic fluorine capsules in adsorbing perfluorinated compounds is to mix the porous aminated organic fluorine capsules with the perfluorinated compounds and oscillate at a constant temperature of 24 to 26°C.
- the mass concentration ratio is 5 ⁇ 100:1.
- the pH of the porous aminated organic fluorine capsule after mixing with the perfluorinated compound is adjusted to 2 to 9.25, and the adsorption rate of the perfluorinated compound is greater than 95%.
- Adsorption principle Polyvinylidene fluoride, which has a similar structure to perfluorinated compounds, is used as a raw material to strengthen the adhesive.
- the non-polar and lipophobic nature of the capsule shell effectively eliminates the interference of highly polar inorganic substances such as salt ions and lipophilic organic substances such as humic substances, thus improving the selectivity of perfluorinated compounds.
- Aminated phenolic resin can adsorb PFASs in the solution through electrostatic attraction, and the porous organic fluorine shell protects the aminated phenolic resin's adsorption of PFASs from interference.
- the porous organic fluorine capsule material is synthesized through the solvent replacement method.
- the organic fluorine capsule and the internal aminated phenolic resin are used in the capsule.
- the porous aminated organic fluorine capsule material maintains the particle shape of traditional commercial activated carbon and ion exchange resin without reducing the residence time of the capsule in water treatment. At the same time, the particles are large and easy to recycle;
- the size distribution diagram of is the electron microscopy image of AFC-1 under the 200nm scale, i is the surface pore distribution map of AFC-1, j is the electron microscopy image of AFC-2 under the 100 ⁇ m scale, k is the electron microscopy image of AFC-2 under the 200nm scale, l is the surface pore distribution map of AFC-2, m is the electron microscopy image of AFC-3 under the 100 ⁇ m scale, n is the electron microscopy image of AFC-3 under the 200 nm scale, and o is the surface pore distribution map of AFC-3;
- Figure 3 is a specific surface area distribution diagram of the porous aminated organic fluorine capsule material of the present invention.
- Figure 4 is a schematic infrared spectrum diagram of the porous aminated organic fluorine capsule material of the present invention.
- Figure 7 is a comparison chart of the adsorption effects of different adsorption materials of the present invention on PFOA;
- Figure 10 is a diagram showing the influence of coexisting substances in different environments on the adsorption of PFOA by porous aminated organofluorine capsule materials, where a is the influence diagram of AFC-2 adsorbing PFOA, and b is the influence diagram of ANP adsorbing PFOA;
- Figure 11 is a recycling diagram of the porous aminated organic fluorine capsule material of the present invention.
- the weight average molecular weight of polyvinylidene fluoride is 170,000 to 190,000.
- the weight average molecular weight of polyvinylpyrrolidone is 1,200,000 to 1,400,000.
- a method for preparing porous aminated organic fluorine capsule materials includes the following steps:
- a method for preparing porous aminated organic fluorine capsule materials including the following steps:
- a method for preparing porous aminated organic fluorine capsule materials including the following steps:
- a method for preparing porous aminated organic fluorine capsule materials including the following steps:
- a method for preparing porous aminated organic fluorine capsule materials including the following steps:
- a method for preparing porous aminated organic fluorine capsule materials including the following steps:
- ANP is a uniform microsphere with an average diameter of 225.3nm.
- FC containing ANP is a white sphere with a diameter of 1.8 to 2 mm, and AFC-1 to AFC-5 are yellow-brown porous spheres with a diameter of 1.5 to 1.8 mm.
- the FC surface contains pores with an average pore diameter of 5.4 ⁇ m.
- the surface of AFC-1 ⁇ AFC-4 also has abundant and uniform micropores, with the pore diameter ranging from 28.6 to 330.5nm. The pore diameter decreases with the increase of ANP content in the capsule. No voids are observed on the surface of ACF-5. .
- Select powdered ANP, single particle FC and AFC use multiple attenuated total reflection (ATR) mode, and directly test the infrared signal of the selected sample on the solid sample stage.
- ATR attenuated total reflection
- porous aminated organofluorine capsules are characterized by a zeta potential meter. The specific steps are:
- ANP has a very strong adsorption capacity for PFOA, and capsules without amination cannot adsorb PFOA; capsules with different raw material ratios have different adsorption effects on PFOA.
- the general rule is that as the ANP content increases, the capsules have different adsorption effects on PFOA. The adsorption efficiency first increased and then decreased. Among them, AFC-2 has the best adsorption effect on PFOA.
- powdered activated carbon and FC can hardly adsorb PFOA, while AFC-2 and ANP have better adsorption effects on PFOA, and can reduce the concentration of 1 ⁇ gL -1 PFOA to less than 70ngL -1 within the first hour. .
- step (2) Add 5 mg of AFC-2 to the solution obtained in step (1), seal and oscillate using a constant temperature oscillation box, control the reaction temperature at 25 ⁇ 1°C, and take out two portions of the supernatant after 1 hour as Parallel samples were used to determine adsorption efficiency.
- step (2) Add 5 mg of AFC-2 and ANP respectively to the solution obtained in step (1), seal and oscillate using a constant temperature oscillation box, control the reaction temperature at 25 ⁇ 1°C, and take out two portions of the supernatant after 1 hour The liquid was used as a parallel sample to measure the adsorption efficiency.
- step (2) Add 5 mg of AFC-2 and ANP respectively to the solution obtained in step (1), seal and oscillate using a constant temperature oscillation box, control the reaction temperature at 25 ⁇ 1°C, and take out two portions after 1 and 5 hours. The supernatant was used as a parallel sample to determine the adsorption efficiency.
- humic substances SRHA, SRFA
- small molecular acids OA, BA
- salt ions NaCl, CaCl 2
- porous aminated organofluorine capsules have strong recycling and regeneration capabilities, and their adsorption capacity for PFOA remains almost unchanged after five adsorption-desorption cycles.
- S4 Disperse the half-cooked capsules obtained in S3 into pure water, stir for 24 hours, and then vacuum-dry in a vacuum drying oven at 90°C for 12 hours to obtain porous aminated organic fluorine capsules.
- S4 Disperse the half-cooked capsules obtained in S3 into pure water, stir for 24 hours, and then vacuum-dry in a vacuum drying oven at 100°C for 12 hours to obtain porous aminated organic fluorine capsules.
- a method for preparing porous aminated organic fluorine capsule materials including the following steps:
- S4 Disperse the half-cooked capsules obtained in S3 into pure water, stir for 24 hours, and then vacuum-dry in a vacuum drying oven at 95°C for 12 hours to obtain porous aminated organic fluorine capsules.
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Pharmacology & Pharmacy (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
一种多孔胺化有机氟胶囊及其制备方法和应用,包括多孔有机氟外壳,所述有机氟外壳内部填充胺化酚醛树脂。基于常用的膜材料聚偏二氟乙烯、造孔剂聚乙烯吡咯烷酮和胺化酚醛树脂,通过溶剂置换法合成多孔有机氟胶囊材料,在胶囊有机氟外壳和内部胺化酚醛树脂的协同作用下,成功实现对阴离子型全氟化合物的高效选择性去除,且原料廉价易得,制备简便。
Description
本发明属于胶囊及其制法与应用,具体为一种多孔胺化有机氟胶囊及其制法与应用。
全氟化合物(PFCs)是一类人工合成的具有表面活性剂性质的新型氟化物,其以碳氟键组成的烷基链为骨架,离子头部连接不同的官能团,化学通式为F(CF2)n-R。自20世纪40年代末3M公司首次合成以来,PFCs由于具有疏水疏脂性、耐高温、耐强氧化性而被广泛应于人类生产生活的各个领域。研究发现,大量的使用及其自身的强稳定性使得PFCs普遍存在于全球环境中,在地表水和地下水中的浓度最高可达到1mg·L-1。在投入市场的3000多种PFCs中,全氟辛酸(PFOA)最具代表性,其不仅生产使用量巨大,而且是多种PFCs在环境和生物体内转化的最终产物,检出频率和浓度极高。环境中的PFOA主要通过食物和饮用水进入人体,并具有一定的致畸致癌效应。近四十年来,人体血清中PFOA的含量不断上升,最高浓度已达5μg·L-1。
为消除这类污染物对环境和生物体的不良影响,已发布限制销售和使用PFOA的法令,PFOA也被列入持久性有机污染物优先控制名录,饮用水中PFOA的健康限制浓度为70ng·L-1。为了环境和人体健康,都应对PFASs去除技术进行深入研究。
据相关研究表明,基于水和电子的高级还原技术和基于硫酸根自由基的高级氧化技术能够有效处理高浓度PFOA污染废水,但对实际环境水体中痕量PFOA的去除效果较差。因此,若想对水体中的痕量PFOA进行无害化处理,首先要对其进行选择性吸附浓缩。
目前,市面上已有的传统吸附技术(活性炭、交换离子树脂、矿物材料)等对这类污染物的去除效率低,且抗干扰性差。于是研究人员开发出了一系列选择性吸附PFOA的新材料,如共价有机氟骨架材料(COFs)和有机氟改性粘土矿物等,但依然存在着成本高、抗干扰性差、易产生二次污染等问题。
因此,亟需开发出一种低成本、易分离且能够选择性吸附实际环境水体中痕量PFOA的吸附材料。
发明内容
发明目的:为了克服现有技术中存在的不足,本发明目的是提供一种多孔胺化有机
氟胶囊,本发明的另一目的是提供一种多孔胺化有机氟胶囊的制备方法,本发明的再一目的是提供一种多孔胺化有机氟胶囊在吸附全氟化合物中的应用。
技术方案:本发明所述的一种多孔胺化有机氟胶囊,包括多孔有机氟外壳,所述有机氟外壳内部填充胺化酚醛树脂。
进一步地,多孔有机氟外壳上的孔孔径28.6~330.5nm,且孔径随着胶囊中胺化酚醛树脂的含量增加而减小。
进一步地,多孔胺化有机氟胶囊的直径1.5~1.8mm。
上述多孔胺化有机氟胶囊的制备方法,包括以下步骤:
S1,将乙二胺、甲醛和间苯二酚溶于醇水混合液中,25~30℃下搅拌,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤,离心,在90~100℃干燥12~16h,研磨成胺化酚醛树脂粉末;
S2,将聚偏二氟乙烯、聚乙烯吡咯烷酮和胺化酚醛树脂粉末混合,分散于N,N-二甲基甲酰胺溶剂中,在50~60℃下持续搅拌2~4小时,使其分散均匀并排除气泡,获得凝胶态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,在25~30℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌后在90~100℃真空干燥,得到多孔胺化有机氟胶囊。
进一步地,S1中,乙二胺、甲醛、间苯二酚的质量比为1~3:1~3:1~2。醇水混合液中,乙醇和水的体积比为2:5。
进一步地,S2中,聚偏二氟乙烯、聚乙烯吡咯烷酮、胺化酚醛树脂粉末的质量浓度比为12:2:4~12。聚偏二氟乙烯的重均分子量为170000~190000。聚乙烯吡咯烷酮的重均分子量为1200000~1400000。
进一步地,S3中,水和异丙醇的混合液中异丙醇与水的体积比为30%。
上述多孔胺化有机氟胶囊在吸附全氟化合物中的应用,将多孔胺化有机氟胶囊与全氟化合物混合,在24~26℃恒温振荡,多孔胺化有机氟胶囊材料与全氟化合物之间的质量浓度比为5~100:1。
进一步地,多孔胺化有机氟胶囊与全氟化合物混合后的pH调节为2~9.25,全氟化合物的吸附率大于95%。
吸附原理:利用与全氟化合物具有相似结构的聚偏二氟乙烯作为原材料,增强了胶
囊外壳的非极性和疏脂性,有效排除了盐离子等强极性无机物和腐殖质等亲脂性有机物的干扰,进而提高了对全氟化合物的选择性。胺化酚醛树脂可以通过静电吸引作用吸附溶液中的PFASs,多孔有机氟外壳保护胺化酚醛树脂对PFASs的吸附不受干扰。
有益效果:本发明和现有技术相比,具有如下显著性特点:
1、基于常用的膜材料聚偏二氟乙烯、造孔剂聚乙烯吡咯烷酮和自制的胺化酚醛树脂,通过溶剂置换法合成多孔有机氟胶囊材料,在胶囊有机氟外壳和内部胺化酚醛树脂的协同作用下,成功实现了对阴离子型全氟化合物的高效选择性去除,且原料廉价易得,制备过程操作简便;
2、多孔胺化有机氟胶囊材料在宽pH的范围内实现了对全氟化合物的高效选择性吸附,对强酸、强碱环境仍具有良好的适应性,即使在强碱性的条件下,对全氟化合物的吸附率依然能够达到95%以上,可用于极端环境;
3、多孔胺化有机氟胶囊材料,既保持了传统商业活性炭和离子交换树脂的颗粒形态,又不会减少胶囊在水处理中的停留时间,同时颗粒大,易于回收;
4、具有良好的重复利用性,吸附PFOA后的胶囊可以通过甲醇溶液的洗脱恢复吸附能力,重复5次后对PFOA的吸附量几乎不变,具有良好的经济适用性,前景光明。
图1是本发明的合成路径图;
图2是本发明的扫描电镜图和尺寸分布图,其中,a为1μm标尺下的胺化酚醛树脂的电镜图,b为200nm标尺下的胺化酚醛树脂的电镜图,c为胺化酚醛树脂的尺寸分布图,d为100μm标尺下的FC的电镜图,e为2μm标尺下的FC的电镜图,f为FC的表面孔道分布图,g为100μm标尺下的AFC-1的电镜图,h为200nm标尺下的AFC-1的电镜图,i为AFC-1的表面孔道分布图,j为100μm标尺下的AFC-2的电镜图,k为200nm标尺下的AFC-2的电镜图,l为AFC-2的表面孔道分布图,m为100μm标尺下的AFC-3的电镜图,n为200nm标尺下的AFC-3的电镜图,o为AFC-3的表面孔道分布图;
图3是本发明的多孔胺化有机氟胶囊材料的比表面积分布图;
图4是本发明的多孔胺化有机氟胶囊材料的红外光谱示意图;
图5是本发明的多孔胺化有机氟胶囊材料的ζ电位示意图;
图6是本发明的多孔胺化有机氟胶囊材料对PFOA的吸附热力学图,其中,a为ANP对PFOA的吸附热力学图,b为FC、AFC-1、AFC-2、AFC-3、AFC-4、AFC-5对PFOA的吸附热力学图;
图7是本发明的不同吸附材料对PFOA吸附效果的对比图;
图8是本发明的多孔胺化有机氟胶囊材料对不同全氟化合物的吸附动力学图;
图9是本发明pH对多孔胺化有机氟胶囊材料吸附PFOA的影响图;
图10是不同环境共存物质对多孔胺化有机氟胶囊材料吸附PFOA的影响图,其中,a为AFC-2吸附PFOA的影响图,b为ANP吸附PFOA的影响图;
图11是本发明的多孔胺化有机氟胶囊材料的循环再生图。
以下各实施例中,聚偏二氟乙烯的重均分子量为170000~190000。聚乙烯吡咯烷酮的重均分子量为1200000~1400000。
实施例1
如图1,一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将质量比为1:3:2的乙二胺、甲醛和间苯二酚溶于醇水混合液中,乙醇和水的体积比为2:5,在30℃下搅拌24小时,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤5次,离心,洗涤后得到的沉淀物在100℃鼓风干燥箱中干燥12h,研磨成胺化酚醛树脂粉末(ANP);
S2,将聚偏二氟乙烯(PVDF)、聚乙烯吡咯烷酮(PVP)和胺化酚醛树脂粉末(ANP)混合,聚偏二氟乙烯、聚乙烯吡咯烷酮、胺化酚醛树脂粉末的质量浓度比为12:2:4,分散于N,N-二甲基甲酰胺溶剂(DMF)中,在60℃下持续搅拌2小时,获得凝胶态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在25℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌24小时后在100℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊,命名为AFC-1。
实施例2
一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将质量比为1:3:2的乙二胺、甲醛和间苯二酚溶于醇水混合液中,乙醇和水的体积比为2:5,在30℃下搅拌24小时,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤5次,离心,洗涤后得到的沉淀物在100℃鼓风干燥箱中干燥12h,研磨成胺化酚醛树脂粉末;
S2,将PVDF、PVP和ANP混合,聚偏二氟乙烯、聚乙烯吡咯烷酮、胺化酚醛树脂粉末的质量浓度比为12:2:6,分散于DMF中,在60℃下持续搅拌2小时,获得凝胶态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在25℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌24小时后在100℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊,命名为AFC-2。
实施例3
一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将质量比为1:3:2的乙二胺、甲醛和间苯二酚溶于醇水混合液中,乙醇和水的体积比为2:5,在30℃下搅拌24小时,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤5次,离心,洗涤后得到的沉淀物在100℃鼓风干燥箱中干燥12h,研磨成胺化酚醛树脂粉末;
S2,将PVDF、PVP和ANP混合,聚偏二氟乙烯、聚乙烯吡咯烷酮、胺化酚醛树脂粉末的质量浓度比为12:2:8,分散于DMF中,在60℃下持续搅拌2小时,获得凝胶态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在25℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌24小时后在100℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊,命名为AFC-3。
实施例4
一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将质量比为1:3:2的乙二胺、甲醛和间苯二酚溶于醇水混合液中,乙醇和水的体积比为2:5,在30℃下搅拌24小时,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤5次,离心,洗涤后得到的沉淀物在100℃鼓风干燥箱中干燥12h,研磨成胺化酚醛树脂粉末;
S2,将PVDF、PVP和ANP混合,聚偏二氟乙烯、聚乙烯吡咯烷酮、胺化酚醛树脂粉末的质量浓度比为12:2:10,分散于DMF中,在60℃下持续搅拌2小时,获得凝胶
态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在25℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌24小时后在100℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊,命名为AFC-4。
实施例5
一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将质量比为1:3:2的乙二胺、甲醛和间苯二酚溶于醇水混合液中,乙醇和水的体积比为2:5,在30℃下搅拌24小时,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤5次,离心,洗涤后得到的沉淀物在100℃鼓风干燥箱中干燥12h,研磨成胺化酚醛树脂粉末;
S2,将PVDF、PVP和ANP混合,聚偏二氟乙烯、聚乙烯吡咯烷酮、胺化酚醛树脂粉末的质量浓度比为12:2:12,分散于DMF中,在60℃下持续搅拌2小时,获得凝胶态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在25℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌24小时后在100℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊,命名为AFC-5。
对比例
一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将PVDF、PVP和ANP混合,聚偏二氟乙烯、聚乙烯吡咯烷酮的质量浓度比为12:2,分散于DMF中,在60℃下持续搅拌2小时,获得凝胶态混合物;
S2,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在25℃下边搅拌边用注射器将S1得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S3,将S2得到的半熟胶囊分散于纯水中,搅拌24小时后在100℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊,命名为FC。
测试1
将实施例1~5中S1所得ANP用导电胶粘贴在扫描电镜样品台,放入扫描电镜中进行拍摄,如图2,可以得出结论:ANP为平均直径225.3nm的均匀微球,不含ANP的FC为直径1.8~2mm的白色球体,AFC-1~AFC-5为直径1.5~1.8mm的黄褐色多孔球体。FC表面含有平均孔径为5.4μm的孔道。AFC-1~AFC-4表面也具有丰富且均匀的微孔,孔道直径范围为28.6~330.5nm,且孔径随着胶囊中ANP含量的增加而减小,ACF-5表面没有观察到有空隙存在。
测试2
称取相同质量的分别由实施例1~5所制得的多孔胺化有机氟胶囊,在N2吸附脱附仪上选用解控模式测试不同样品的比表面积,测试结果如图3所示。可以得出结论:ANP的比表面积为178.43m2g-1,FC的比表面积为98.89m2g-1,AFC-1、AFC-2、AFC-3、AFC-4和AFC-5的比表面积分别为132.96、160.50、155.22、144.63和128.88m2g-1,比表面积随着胶囊中ANP含量的增加呈现先增大后减小的趋势,其中AFC-2的比表面积最大。
测试3
选取粉末ANP、单颗粒FC和AFC,使用多次衰减全反射(ATR)模式,在固体样品台上直接测试选取样品的红外信号,数据如图4所示。
由此可以得出结论:2853.4和2925.6cm-1处亚甲基(-CH2-)伸缩振动的信号来自于ANP,不同的多孔胺化有机氟胶囊在此处出现较强的信号,且随着ANP含量的提高,信号逐渐增强表明胶囊中ANP的含量逐渐增加。1604.3cm-1处为氨基中N-H键的弯曲振动信号,ANP在此处出现较强信号表明其中含有丰富的氨基,不同的多孔胺化有机氟胶囊在此处的信号随着ANP含量的增加而增强也表明胶囊中氨基的含量不断增加。
测试4
通过ζ电位仪表征多孔胺化有机氟胶囊,其具体步骤为:
(1)分别配置含有1g·L-1的FC(对比例所得)和ANP溶液(实施例1所得),用不同浓度的NaOH调节反应液pH为2~11;
(2)利用ζ电位仪测定步骤(1)中所得溶液的ζ电位。
由此可得出结论:ANP和FC的等电点分别为9.25和6.88,这表示在较宽的pH范围(pH=2~9.25)范围内,ANP均能通过静电作用吸引阴离子型全氟化合物。
测试5
考察多孔胺化有机氟胶囊对PFOA的吸附热力学,其步骤具体为:
(1)准备6组初始浓度为10~200mg·L-1和1组初始浓度10~900mgL-1的PFOA溶
液各5mL,用不同浓度的NaOH调节反应液pH到6,分别加入5mgFC、AFC-1、AFC-2、AFC-3、AFC-4、AFC-5和ANP,密封后利用恒温振荡箱振荡,反应温度控制在25±1℃,在1小时后分别取出两份上清液作为平行样品测定PFOA浓度。
(2)使用langmuir模型拟合对PFOA的吸附等温线,模型为Qe=(KL×Qmax×Ce)/(1+KL×Ce),得到PFOA在ANP、FC和AFC-1~AFC-5上的最大吸附量分别为0.64837、0.00031、0.01038、0.04559、0.04013、0.03322、0.02278mgmg-1,具体结果如图7所示。
由此可以得出结论:ANP对PFOA的吸附能力极强,没有胺化的胶囊不能吸附PFOA;不同原料比例的胶囊对PFOA的吸附效果不同,大致规律为随着ANP含量的增加,胶囊对PFOA的吸附效率先增加后下降。其中AFC-2对PFOA的吸附效果最好。
测试6
考察吸附能力最强的多孔胺化有机氟胶囊AFC-2与其他吸附材料对PFOA吸附,其具体步骤为:
(1)配置含有1μgL-1的PFOA溶液5mL,用不同浓度的NaOH调节反应液pH到6;
(2)在步骤(1)中所得的溶液中分别加入5mg的AFC-2、FC、ANP和粉末活性炭,密封后利用恒温振荡箱振荡,反应温度控制在25±1℃,反应时间为5小时。取样时间分别设置为0、0.1、0.3、0.6、1、5h。每个时间点分别取出两份上清液作为平行样品测定PFOA的吸附率,如图7所示。
由此可以得出结论:粉末活性炭和FC几乎不能吸附PFOA,AFC-2和ANP对PFOA的吸附效果较好,在最初的1小时内就能使1μgL-1PFOA的浓度降低至70ngL-1以下。
测试7
考察多孔胺化有机氟胶囊对不同全氟化合物的吸附动力学图,其具体步骤为:
(1)分别配置含有1μgL-1的三氟乙酸(TFA)、全氟丁酸(PFBA)、全氟己酸(PFHxA)、PFOA、全氟辛烷磺酸(PFOS)、六氟环氧丙烷三聚体酸(HFPO-TA)和全氟辛二酸(PFdiCA)溶液5mL,用不同浓度的NaOH调节反应液pH到6;
(2)在步骤(1)中所得的溶液中分别加入5mg的AFC-2,密封后利用恒温振荡箱振荡,反应温度控制在25±1℃,在1小时后分别取出两份上清液作为平行样品测定吸附效率。
由此可以得出结论:多孔胺化有机氟胶囊对不同全氟化合物的吸附效果不同,对
PFOA、PFOS、HFPO-TA的吸附效果最好,吸附率可达98%以上;对TFA和PFdiCA的吸附效果一般。
测试8
考察pH对多孔胺化有机氟胶囊吸附全氟化合物的影响,其具体步骤为:
(1)配置含有1μgL-1的PFOA溶液5mL,用不同浓度的NaOH调节反应液pH为2、4、6、8、10;
(2)在步骤(1)中所得的溶液中分别加入5mg的AFC-2和ANP,密封后利用恒温振荡箱振荡,反应温度控制在25±1℃,在1小时后分别取出两份上清液作为平行样品测定吸附效率。
由此可以得出结论:当pH<8时,pH对AFC-2和ANP吸附PFOA的过程几乎没有影响,而当pH>8时,pH对ANP吸附PFOA的过程影响较大,对AFC-2吸附PFOA的过程影响较小。
测试9
考察环境共存物质腐殖质(腐殖酸(SRHA)、富里酸(SRFA))、小分子酸(草酸(OA)、苯甲酸(BA))和盐离子(氯化钠(NaCl)、氯化钙(CaCl2))对多孔胺化有机氟胶囊吸附全氟化合物的影响,其具体步骤为:
(1)分别配置含有1μgL-1PFOA和不同浓度的环境共存物质(5mgL-1SRHA、SRFA,5mgL-1NaCl、CaCl2,10mMOA、BA)溶液5mL,用不同浓度的NaOH调节反应液pH到6;
(2)在步骤(1)中所得的溶液中分别加入5mg的AFC-2和ANP,密封后利用恒温振荡箱振荡,反应温度控制在25±1℃,在1和5小时后分别取出两份上清液作为平行样品测定吸附效率。)
由此可以得出结论:腐殖质(SRHA、SRFA)、小分子酸(OA、BA)和盐离子(NaCl、CaCl2)对ANP吸附PFOA的过程有较大影响,对AFC-2吸附PFOA的过程影响较小。
测试10
考察多孔胺化有机氟胶囊的循环再生能力,其具体步骤为:
(1)将吸附饱和的多孔胺化有机氟胶囊置于5mL甲醇中,密封后利用恒温振荡箱振荡,反应温度控制在25±1℃。在10小时后分别取出两份上清液作为平行样品测定解吸效率。
(2)取出解吸后的多孔胺化有机氟胶囊清洗烘干并重新吸附1μgL-1PFOA,重复上
述解吸过程5次,综合评估胶囊材料的循环再生效率。
由此可以得出结论:多孔胺化有机氟胶囊的循环再生能力较强,吸附-解吸5次后对PFOA的吸附能力几乎不变。
实施例6
一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将质量比为1:1:1的乙二胺、甲醛和间苯二酚溶于醇水混合液中,乙醇和水的体积比为2:5,在25~30℃下搅拌24小时,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤5次,离心,洗涤后得到的沉淀物在90℃鼓风干燥箱中干燥12h,研磨成胺化酚醛树脂粉末;
S2,将PVDF、PVP和ANP混合,分散于DMF中,在50℃下持续搅拌2小时,获得凝胶态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在25℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌24小时后在90℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊。
实施例7
一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将质量比为3:3:2的乙二胺、甲醛和间苯二酚溶于醇水混合液中,乙醇和水的体积比为2:5,在25~30℃下搅拌24小时,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤5次,离心,洗涤后得到的沉淀物在100℃鼓风干燥箱中干燥16h,研磨成胺化酚醛树脂粉末;
S2,将PVDF、PVP和ANP混合,分散于DMF中,在60℃下持续搅拌4小时,获得凝胶态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在30℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌24小时后在100℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊。
实施例8
一种多孔胺化有机氟胶囊材料的制备方法,包括以下步骤:
S1,将质量比为2:2:1的乙二胺、甲醛和间苯二酚溶于醇水混合液中,乙醇和水的体积比为2:5,在25~30℃下搅拌24小时,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤5次,离心,洗涤后得到的沉淀物在95℃鼓风干燥箱中干燥14h,研磨成胺化酚醛树脂粉末(ANP);
S2,将PVDF、PVP和ANP混合,分散于DMF中,在55℃下持续搅拌3小时,获得凝胶态混合物;
S3,使用水和异丙醇的混合液作为溶剂交换液,异丙醇与水的体积比为30%,在27℃下边搅拌边用注射器将S2得到的凝胶态混合物滴入溶剂交换液中,持续搅拌2小时,得到半熟胶囊;
S4,将S3得到的半熟胶囊分散于纯水中,搅拌24小时后在95℃的真空干燥箱中真空干燥12小时,得到多孔胺化有机氟胶囊。
Claims (10)
- 一种多孔胺化有机氟胶囊,其特征在于:包括多孔有机氟外壳,所述有机氟外壳内部填充胺化酚醛树脂。
- 根据权利要求1所述的一种多孔胺化有机氟胶囊,其特征在于:所述多孔有机氟外壳上的孔孔径28.6~330.5nm,且孔径随着胶囊中胺化酚醛树脂的含量增加而减小。
- 根据权利要求1所述的一种多孔胺化有机氟胶囊,其特征在于:所述多孔胺化有机氟胶囊的直径1.5~1.8mm。
- 根据权利要求1~3任一所述的一种多孔胺化有机氟胶囊的制备方法,其特征在于,包括以下步骤:S1,将乙二胺、甲醛和间苯二酚溶于醇水混合液中,25~30℃下搅拌,通过聚合反应合成胺化酚醛树脂,用超纯水洗涤,离心,在90~100℃干燥12~16h,研磨成胺化酚醛树脂粉末;S2,将聚偏二氟乙烯、聚乙烯吡咯烷酮和胺化酚醛树脂粉末混合,分散于N,N-二甲基甲酰胺溶剂中,在50~60℃下持续搅拌2~4小时,获得凝胶态混合物;S3,使用水和异丙醇的混合液作为溶剂交换液,在25~30℃下边搅拌边将S2得到的凝胶态混合物滴入溶剂交换液中,得到半熟胶囊;S4,将S3得到的半熟胶囊分散于纯水中,搅拌后在90~100℃真空干燥,得到多孔胺化有机氟胶囊。
- 根据权利要求4所述的一种多孔胺化有机氟胶囊的制备方法,其特征在于:所述S1中,乙二胺、甲醛、间苯二酚的质量比为1~3:1~3:1~2。
- 根据权利要求4所述的一种多孔胺化有机氟胶囊的制备方法,其特征在于:所述S2中,聚偏二氟乙烯、聚乙烯吡咯烷酮、胺化酚醛树脂粉末的质量浓度比为12:2:4~12。
- 根据权利要求4所述的一种多孔胺化有机氟胶囊的制备方法,其特征在于:所述S2中,聚偏二氟乙烯的重均分子量为170000~190000。
- 根据权利要求4所述的一种多孔胺化有机氟胶囊的制备方法,其特征在于:所述S2中,聚乙烯吡咯烷酮的重均分子量为1200000~1400000。
- 根据权利要求1~3任一所述的一种多孔胺化有机氟胶囊在吸附全氟化合物中的应用,其特征在于:将多孔胺化有机氟胶囊与全氟化合物混合,在24~26℃恒温振荡,所述多孔胺化有机氟胶囊材料与全氟化合物之间的质量浓度比为5~100:1。
- 根据权利要求9所述的一种多孔胺化有机氟胶囊在吸附全氟化合物中的应用,其特征在于:所述多孔胺化有机氟胶囊与全氟化合物混合后的pH调节为2~9.25,全氟 化合物的吸附率大于95%。
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