CN115501763A - Preparation and application method of high-permeability and selectivity ion separation membrane - Google Patents
Preparation and application method of high-permeability and selectivity ion separation membrane Download PDFInfo
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- CN115501763A CN115501763A CN202211168817.0A CN202211168817A CN115501763A CN 115501763 A CN115501763 A CN 115501763A CN 202211168817 A CN202211168817 A CN 202211168817A CN 115501763 A CN115501763 A CN 115501763A
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- Prior art keywords
- membrane
- acid
- hydrochloric acid
- separation ratio
- separation
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Links
- 238000000926 separation method Methods 0.000 title claims abstract description 404
- 239000012528 membrane Substances 0.000 title claims abstract description 208
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 210000004379 membrane Anatomy 0.000 claims abstract description 194
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 66
- 239000002253 acid Substances 0.000 claims abstract description 59
- 239000002351 wastewater Substances 0.000 claims abstract description 47
- 239000011148 porous material Substances 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 150000002500 ions Chemical class 0.000 claims abstract description 35
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003204 osmotic effect Effects 0.000 claims abstract description 6
- 238000012643 polycondensation polymerization Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 614
- 239000000243 solution Substances 0.000 claims description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 99
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- 239000012074 organic phase Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000000502 dialysis Methods 0.000 claims description 37
- 230000002378 acidificating effect Effects 0.000 claims description 33
- 239000012071 phase Substances 0.000 claims description 33
- 238000009792 diffusion process Methods 0.000 claims description 30
- 238000011084 recovery Methods 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- OJUDFURAIYFYBP-UHFFFAOYSA-N (dihydrazinylmethylideneamino)azanium;chloride Chemical group Cl.NNC(NN)=NN OJUDFURAIYFYBP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001299 aldehydes Chemical class 0.000 claims description 15
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 9
- 229920002530 polyetherether ketone Polymers 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims description 8
- HAZRIBSLCUYMQP-UHFFFAOYSA-N 1,2-diaminoguanidine;hydron;chloride Chemical compound Cl.NN\C(N)=N/N HAZRIBSLCUYMQP-UHFFFAOYSA-N 0.000 claims description 7
- FEUATHOQKVGPEK-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarbaldehyde Chemical compound OC1=CC=C(C=O)C=C1C=O FEUATHOQKVGPEK-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- XMOLQZRXGOOMRJ-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3-dicarbaldehyde Chemical compound OC1=CC(O)=C(C=O)C(O)=C1C=O XMOLQZRXGOOMRJ-UHFFFAOYSA-N 0.000 claims description 4
- PIWMYUGNZBJTID-UHFFFAOYSA-N 2,5-dihydroxyterephthalaldehyde Chemical compound OC1=CC(C=O)=C(O)C=C1C=O PIWMYUGNZBJTID-UHFFFAOYSA-N 0.000 claims description 4
- JJOPQMAMJLOGFB-UHFFFAOYSA-N 2-hydroxybenzene-1,3-dicarbaldehyde Chemical compound OC1=C(C=O)C=CC=C1C=O JJOPQMAMJLOGFB-UHFFFAOYSA-N 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- AYZFTYFURGCPEJ-UHFFFAOYSA-N 2,4-dihydroxybenzene-1,3-dicarbaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1C=O AYZFTYFURGCPEJ-UHFFFAOYSA-N 0.000 claims description 3
- ZBOUXALQDLLARY-UHFFFAOYSA-N 2-hydroxy-5-methylbenzene-1,3-dicarbaldehyde Chemical compound CC1=CC(C=O)=C(O)C(C=O)=C1 ZBOUXALQDLLARY-UHFFFAOYSA-N 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 238000009292 forward osmosis Methods 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 3
- DFIOBSJHIZBUCE-UHFFFAOYSA-N 2-hydroxyterephthalaldehyde Chemical compound OC1=CC(C=O)=CC=C1C=O DFIOBSJHIZBUCE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 claims 1
- 230000035699 permeability Effects 0.000 claims 1
- 150000001768 cations Chemical class 0.000 abstract description 27
- 150000001450 anions Chemical class 0.000 abstract description 26
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000002585 base Substances 0.000 description 89
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 52
- 239000008367 deionised water Substances 0.000 description 52
- 229910021641 deionized water Inorganic materials 0.000 description 52
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 38
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 38
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 36
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 36
- 239000001103 potassium chloride Substances 0.000 description 26
- 235000011164 potassium chloride Nutrition 0.000 description 26
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 19
- 229960002089 ferrous chloride Drugs 0.000 description 19
- 239000003014 ion exchange membrane Substances 0.000 description 19
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 19
- 229910001629 magnesium chloride Inorganic materials 0.000 description 19
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 18
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 18
- 239000004327 boric acid Substances 0.000 description 18
- 239000001110 calcium chloride Substances 0.000 description 18
- 229910001628 calcium chloride Inorganic materials 0.000 description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 18
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 18
- 229940071870 hydroiodic acid Drugs 0.000 description 18
- 239000011780 sodium chloride Substances 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 17
- 238000004626 scanning electron microscopy Methods 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 230000003068 static effect Effects 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000012527 feed solution Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- AYARGAAVUXXAON-UHFFFAOYSA-N 2-hydroxybenzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(O)C(C(O)=O)=C1 AYARGAAVUXXAON-UHFFFAOYSA-N 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the field of treating and recycling acid wastewater by a membrane separation technology, and aims to provide a preparation and application method of a high-permeability and selectivity ion separation membrane. The ion separation membrane takes an ultramicro filter membrane with the pore canal size of 5-1000 nm as a basal membrane; the surface of the basement membrane is provided with a Covalent Organic Framework (COF) separation layer formed by condensation polymerization of aldehyde monomers and amine monomers containing guanidine groups, and the size of a pore channel of the COF separation layer is 0.5-5 nm. The invention realizes the simultaneous separation of anions and cations based on a mixing mechanism, has high osmotic selectivity when being used for treating the acid wastewater, realizes the simultaneous separation of anions and cations, and further achieves the purposes of treating the acid wastewater and selectively recycling acid. The membrane preparation method is simple and stable, and the prepared membrane is stable in acid wastewater, so that the acid wastewater can be treated and recovered in an environment-friendly manner with low energy consumption.
Description
Technical Field
The invention relates to the field of treating and recycling acid wastewater by using a membrane separation technology, in particular to a preparation and application method of a high-permeability selective ion separation membrane. Can be simultaneously used for separating hydrogen ions from other cations and separating monobasic acid from anions of dibasic acid and polybasic acid, thereby realizing the selective recovery of acid.
Background
In the industries of steel processing, mining, ion exchange resin regeneration, metallurgy, electroplating and the like, a large amount of wastewater containing high-concentration salt and acid is generated. The acidic waste water has biological toxicity and strong corrosivity, can not only corrode industrial equipment, but also pollute the environment and destroy the ecological balance if not properly treated, threatens the life health of human beings and animals, and causes immeasurable loss. With the development of industry, the pressure of acidic waste water on environment is increasing, and how to treat acidic waste water containing metal ions in a harmless way and recover acid becomes a research hotspot of researchers.
Common methods for treating acidic wastewater currently include neutralization, crystallization, solvent extraction, and membrane technologies. The principle of the neutralization method is to neutralize the acidic wastewater by using an alkaline substance so as to remove hydrogen ions in the wastewater, and the method is a mature technology and has the advantages of low cost, simple and efficient operation, stable treatment result and the like. However, the neutralization method consumes a large amount of alkali in the treatment process, and the production of the alkali consumes a large amount of energy and resources, so the neutralization method is only suitable for being used as a main treatment method of acidic wastewater in the extensive development period of industry. The crystallization method is a technology for separating salt substances from acidic wastewater crystals in a low-temperature environment by utilizing the principle that the solubility of salts in water is reduced along with the reduction of temperature so as to realize the treatment of the acidic wastewater. Although this process is simple to operate, it does not allow recovery of the acid and has a very high energy consumption. The solvent extraction method is a method for separating acid from salts by utilizing the larger solubility difference of the acid and the salts in certain solvents. The method has the advantage of high recovery rate. However, this method is expensive due to the specific selectivity of the solvent and can be used only in specific fields.
Diffusion dialysis is a well-established membrane separation method and is widely used for the recovery of hydrochloric acid, sulfuric acid, nitric acid and mixed acids due to its advantages of low energy consumption, environmental friendliness and continuous operation. During diffusion dialysis, metal ions, protons and counter ions are transferred from the high concentration side to the low concentration side thereof due to the concentration gradient existing on both sides of the ion exchange membrane. Ion exchange membranes used in acidic wastewater treatment can screen protons and other cations by size screening effect or southeast rejection. In general, recovered acid is available on the lower concentration side, while salt ions are enriched on the higher concentration side.
Most of the current diffusion dialysis ion separation membranes cannot combine high flux and high separation ratio, and the ion separation membranes can only realize the separation of hydrogen ions and other cations but cannot realize the separation of anions. For example, chinese patent application (CN 103962020) provides an anion exchange membrane for use in diffusion dialysis. The film consists of an organic phase and an inorganic phase, wherein the organic phase is mainly polyvinyl alcohol (PVA) grafted epoxy ammonium salt, and the inorganic phase is an alkoxy silane compound with amino. The membrane has an acid dialysis coefficient of 0.018-0.021 mh -1 However, H thereof + /Fe 2+ The separation factor reaches 18.6-21. Chinese invention patent (CN 114618307) UiO-66- (COOH) 2 The MOF nano particles are used as fillers, and the fillers are added into a quaternized QPPO film matrix and then blended to prepare a mixed matrix film for diffusion dialysis. H of the film + /Fe 2+ The separation factor reached 399, however, the acid dialysis coefficient was only 0.0064 mh -1 . Thus, these membranes do not recover a single type of acid at high purity.
For the reasons, the high-permeability selective ion separation membrane for acid selective recovery has important practical significance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation and application method of a high-permeability selective ion separation membrane.
In order to solve the technical problem, the solution of the invention is as follows:
providing a high-permeability selective ion separation membrane, wherein the ion separation membrane takes an ultramicro filter membrane with a pore passage size of 5-1000 nm as a base membrane; the surface of the basement membrane is provided with a Covalent Organic Framework (COF) separation layer formed by condensation polymerization of aldehyde monomers and amine monomers containing guanidine groups, and the size of a pore channel of the COF separation layer is 0.5-5 nm.
The invention also provides a preparation method of the ion separation membrane with high osmotic selectivity, which comprises the following steps:
(1) Using an ultramicro filter membrane with the aperture of 5-1000 nm as a basement membrane, and removing the water-retaining agent contained in the basement membrane;
(2) Taking an aqueous solution of an amine monomer containing a guanidine group and an acid catalyst as an aqueous phase solution, and taking an organic solution containing an aldehyde monomer as an oil phase solution; filtering the water phase solution and the oil phase solution, and filling the water phase solution and the oil phase solution into two sides of the basement membrane respectively, wherein the organic phase is in contact with a hydrophobic layer or a compact side of the basement membrane; reacting for 1-30 days at 10-100 ℃, and generating a covalent organic framework separation layer formed by aldehyde monomers and amine monomers containing guanidine groups on the surface of the side, facing the organic phase, of the substrate;
(3) And taking out the base membrane after reaction, and sequentially washing the base membrane with ethanol, methanol and water to remove residual monomers, acid catalysts and organic solvents to obtain the ion separation membrane with high permeation selectivity.
In a preferred embodiment of the present invention, the ultrafiltration membrane is any one of: polyacrylonitrile (PAN) membrane, polysulfone (PSF) membrane, polyvinylidene fluoride (PVDF) membrane, polyethylene (PE) membrane, polypropylene (PP) membrane, polyethersulfone (PES) membrane, polyetheretherketone (PEEK) membrane, sulfonated Polysulfone (SPSF) membrane, sulfonated Polyethersulfone (SPES) membrane, sulfonated Polyetheretherketone (SPEEK) membrane, aluminum oxide (Al) membrane 2 O 3 ) Ceramic material, titanium dioxide (TiO) 2 ) A ceramic material.
In a preferred embodiment of the present invention, the amine monomer is triaminoguanidine hydrochloride (Tag) or 1, 3-diaminoguanidine hydrochloride (Dgm), and the structural formula is shown as follows:
in a preferred embodiment of the present invention, the aldehyde monomer is any one of the following: trialdehyde phloroglucinol (Tp), 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde (Btd), 2-hydroxy-1, 3, 5-trimesic aldehyde (Hb), trimesic aldehyde (Tb), terephthalaldehyde (Bda), 2, 5-dihydroxy-terephthalaldehyde (Dha), 2-hydroxybenzene-1, 4-dimethaldehyde (Hbd), 4, 6-dialdehyde pyrogallol (Pd), 2, 4-diformyl-phloroglucinol (Dpg), 2, 4-dihydroxy-isophthalaldehyde (Dbda), 2-hydroxy-isophthalaldehyde (Hp), 2, 6-diformyl-4-methylphenol (Hmb), or 4-hydroxy-isophthalaldehyde (Dp); the structural formula is as follows:
in a preferred embodiment of the present invention, the acid catalyst is any one of: hydrochloric acid, sulfuric acid, nitric acid, acetic acid, p-toluenesulfonic acid, scandium trifluoromethanesulfonate, or trifluoroacetic acid.
In a preferred embodiment of the present invention, the concentration of the aqueous solution is 1 to 100mmol L -1 The concentration of the oil phase solution is 1-100 mmol L -1 (ii) a And the aqueous phase solution and the oil phase solution were filtered using a 0.45 μm filter head.
In a preferred embodiment of the present invention, the ion separation membrane obtained is further processed into a hollow fiber membrane, a flat sheet membrane or a tubular membrane.
The invention also provides an application method of the high-permeability selective ion separation membrane, which is characterized in that the ion separation membrane is used for treating acid wastewater in a diffusion dialysis mode; the method specifically comprises the following steps:
(1) Pretreating the acidic wastewater, removing slightly soluble inorganic compounds, and removing large particles and colloidal substances in an ultrafiltration mode;
(2) And the ion separation membrane is used for carrying out diffusion dialysis treatment on the acidic wastewater to realize selective recovery of acid.
As a preferable scheme of the invention, the ion separation membrane is used for constructing any one of the following acid separation systems for diffusion dialysis treatment: a forward osmosis system, a reverse osmosis system, a nanofiltration system, a diffusion dialysis system, or an electrodialysis system.
Compared with the prior art, the invention has the beneficial effects that:
1. the high-permeability selective ion separation membrane takes an ultramicro filter membrane as a base membrane, and a Covalent Organic Framework (COF) separation layer with the pore channel size of 0.5-5 nm is arranged on the surface of the ultramicro filter membrane, so that cations can be separated by using a size sieving effect. The pore channel of the COF separation layer contains a guanidine group, so that a charge-assisted hydrogen bond can be formed with different acid molecules, and the anion separation can be realized based on the difference of the strength of the hydrogen bond. Therefore, the invention realizes the simultaneous separation of anions and cations based on the mixing mechanism.
2. The ion separation membrane provided by the invention has high osmotic selectivity, and when the ion separation membrane is used for treating acid wastewater, certain acid can be selectively recovered from the acid wastewater containing various salt ions, and other cations and polyvalent anions except hydrogen ions are intercepted, so that the simultaneous separation of anions and cations is realized, and the purposes of treating the acid wastewater and selectively recovering the acid are further achieved.
3. The membrane preparation method is simple and stable, and the prepared membrane is stable in acid wastewater, so that the acid wastewater can be treated and recovered in an environment-friendly manner with low energy consumption.
Drawings
FIG. 1 is a schematic view of an interfacial polymerization process used in the present invention.
Fig. 2 to 9 are SEM images of the membrane surface (left) and the membrane cross-section (right) of the high permselective ion separation membranes prepared in examples 1 to 8, respectively.
Detailed Description
The following describes an embodiment of the present invention with reference to the drawings.
Example 1
In order to realize the oriented growth of the COF separation layer on the substrate, the COF separation layer is prepared by adopting an interfacial polymerization method. Firstly, the PAN base membrane with the pore size of 250nm is put into deionized water, and the water-retaining agent in the base membrane is removed. The untreated basement membrane soaked in water can generate dense bubbles and a hydrophobic layer attached to the basement membraneAnd replacing the deionized water on the surface and in the middle for many times, and placing the base film in the deionized water for later use after bubbles are not generated on the surface of the base film. The aqueous solution (concentration 10mmol L) -1 1M aqueous acetic acid solution of triaminoguanidine hydrochloride (Tag)) and oil phase solution (concentration of 10mmol L -1 Trialdehyde phloroglucinol (Tp) in ethyl acetate) is filled on both sides of the PAN membrane, with the organic phase contacting the hydrophobic layer of the base membrane. In order to prevent the minute amount of insoluble particles present in the solution from affecting the flatness of interfacial polymerization, the prepared solution needs to be filtered through a filter head (0.45 μm). After 30 days at 10 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in turn to remove residual monomers, catalysts and organic solvents.
The COF film structure in this example is as follows:
after preparing the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 50nm by N 2 The pore diameter of the COF film obtained by adsorption is 0.75nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: hydrochloric acid solution and potassium chloride solution with concentration of 0.25M are respectively used as feed solution, deionized water is used as water, the solution is statically diffused for 1 hour, and the acid dialysis coefficient of the membrane reaches 8 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 380. Hydrochloric acid solution and sodium chloride solution with the concentration of 0.25M are respectively used as feeding liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the sodium chloride can reach 450. Hydrochloric acid solution and lithium chloride solution with the concentration of 0.25M are respectively used as feed solution, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the lithium chloride can reach 580. Hydrochloric acid solution and lithium chloride solution with concentration of 0.25M are respectively used as feeding liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the magnesium chloride can reach 1350. At a concentration of 0.25MThe hydrochloric acid and the calcium chloride solution are respectively used as feeding liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid and the calcium chloride can reach 1230. Hydrochloric acid with the concentration of 0.25M and ferrous chloride solution are respectively used as feeding liquid, deionized water is used as water, the hydrochloric acid and the ferrous chloride are statically diffused for 1 hour, and the separation ratio of the hydrochloric acid to the ferrous chloride can reach 4545. Hydrochloric acid solution and aluminum chloride solution with the concentration of 0.25M are respectively used as feeding liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 8000.
Regarding the anion separation performance of the membrane: hydrochloric acid and acetic acid solutions with the concentration of 0.25M are respectively used as feed liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the acetic acid can reach 10. Hydrochloric acid and hydrofluoric acid solutions with the concentration of 0.25M are respectively used as feed liquid, deionized water is used as water, the hydrochloric acid and the hydrofluoric acid are statically diffused for 1 hour, and the separation ratio of the hydrochloric acid to the hydrofluoric acid can reach 13. The hydrochloric acid and the hydrobromic acid with the concentration of 0.25M are respectively taken as feed liquid, deionized is taken as water production, and the feed liquid and the water production are statically diffused for 1 hour, so that the separation ratio of the hydrochloric acid to the hydrobromic acid can reach 14. The separation ratio of hydrochloric acid and hydroiodic acid can reach 16 by using 0.25M hydrochloric acid and hydroiodic acid solution as feed solution and deionized water as water for static diffusion for 1 hour. Hydrochloric acid and nitric acid solutions with the concentration of 0.25M are respectively used as feeding liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the nitric acid can reach 21. Hydrochloric acid and nitrous acid solutions with the concentration of 0.25M are respectively used as feed liquid, deionized water is used as water for production, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the nitrous acid can reach 30. Hydrochloric acid and carbonic acid solutions with the concentration of 0.25M are respectively used as feed liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the carbonic acid can reach 50. Hydrochloric acid and sulfurous acid solutions with the concentration of 0.25M are respectively used as feeding liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the sulfurous acid can reach 58. Hydrochloric acid and sulfuric acid solutions with the concentration of 0.25M are respectively used as feed solutions, deionized water is used as produced water, the produced water is statically diffused for 1 hour, and the separation ratio of the hydrochloric acid to the sulfuric acid can reach 63. Hydrochloric acid and phosphoric acid solutions with the concentration of 0.25M are respectively used as feed solutions, deionized water is used as water, the feed solutions are statically diffused for 1 hour, and the separation ratio of the hydrochloric acid to the phosphoric acid can reach 220. Hydrochloric acid solution and boric acid solution with the concentration of 0.25M are respectively used as feed liquid, deionized water is used as water, the static diffusion is carried out for 1 hour, and the separation ratio of the hydrochloric acid to the boric acid can reach 180.
Example 2
Firstly, putting a PSF base membrane with a pore passage size of 200nm into deionized water, and removing the water-retaining agent in the base membrane. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 1mmol L) -1 1M aqueous hydrochloric acid solution of triaminoguanidine hydrochloride (Tag)) and oil phase solution (concentration of 1mmol L -1 A solution of 2, 4-dihydroxy-1, 3, 5-mesitylene-trioxaldehyde (Btd) in o-dichlorobenzene) was impregnated on both sides of the PSF film, wherein the organic phase contacted the hydrophobic layer of the base film. The prepared solution needs to be filtered through a filter head (0.45 μm). After 28 days at 20 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparing the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 57nm, by N 2 The pore diameter of the COF film obtained by adsorption is 0.79nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 10 mh -1 The separation ratio of hydrochloric acid to potassium chloride can reach 25, the separation ratio of hydrochloric acid to sodium chloride can reach 41, the separation ratio of hydrochloric acid to lithium chloride can reach 76, the separation ratio of hydrochloric acid to magnesium chloride can reach 109, the separation ratio of hydrochloric acid to calcium chloride can reach 97, the separation ratio of hydrochloric acid to ferrous chloride can reach 361, and the separation ratio of hydrochloric acid to aluminum chloride can reach 76Up to 422.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 10, the separation ratio of hydrochloric acid to hydrofluoric acid can be 12, the separation ratio of hydrochloric acid to hydrobromic acid can be 14, the separation ratio of hydrochloric acid to hydroiodic acid can be 16, the separation ratio of hydrochloric acid to nitric acid can be 18, the separation ratio of hydrochloric acid to nitrous acid can be 21, the separation ratio of hydrochloric acid to carbonic acid can be 56, the separation ratio of hydrochloric acid to sulfurous acid can be 65, the separation ratio of hydrochloric acid to sulfuric acid can be 73, the separation ratio of phosphoric acid can be 160, and the separation ratio of hydrochloric acid to boric acid can be 150.
Example 3
Firstly, the PEEK base film with the pore size of 150nm is put into deionized water, and the water-retaining agent in the base film is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 5mmol L) -1 2M aqueous p-toluenesulfonic acid solution of triaminoguanidine hydrochloride (Tag) and an oil phase solution (concentration of 5mmol L) -1 Xylene solution of 2-hydroxy-1, 3, 5-benzenetricarboxylic acid (Hb) filled both sides of the PEEK film, wherein the organic phase contacted the dense side of the base film. The prepared solution needs to be filtered through a filter head (0.45 μm). After 26 days of reaction at 30 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in turn to remove residual monomers, catalysts and organic solvents. The COF film structure in this embodiment is shown in the figure:
after preparation of the film, the thickness of the film was measured by Scanning Electron Microscopy (SEM) to be 68nm by N 2 The pore diameter of the COF film obtained by adsorption is 0.85nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 8.2 mh -1 Hydrochloric acid, hydrochloric acidThe separation ratio of the potassium chloride to the potassium chloride can reach 290, the separation ratio of the sodium chloride to the sodium chloride can reach 680, the separation ratio of the magnesium chloride to the lithium chloride can reach 1070, the separation ratio of the magnesium chloride to the magnesium chloride can reach 1230, the separation ratio of the calcium chloride to the calcium chloride can reach 1120, the separation ratio of the ferrous chloride to the 6710 and the separation ratio of the aluminum chloride to the 7660.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be up to 13, the separation ratio of hydrochloric acid to hydrofluoric acid can be up to 14, the separation ratio of hydrochloric acid to hydrobromic acid can be up to 16, the separation ratio of hydrochloric acid to hydroiodic acid can be up to 18, the separation ratio of hydrochloric acid to nitric acid can be up to 20, the separation ratio of hydrochloric acid to nitrous acid can be up to 23, the separation ratio of hydrochloric acid to carbonic acid can be up to 59, the separation ratio of hydrochloric acid to sulfurous acid can be up to 65, the separation ratio of hydrochloric acid to sulfuric acid can be up to 73, the separation ratio of hydrochloric acid to phosphoric acid can be up to 165, and the separation ratio of hydrochloric acid to boric acid can be up to 145.
Example 4
Firstly, putting the SPSF basal membrane with the pore size of 100nm into deionized water, and removing the water-retaining agent in the basal membrane. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 15mmol L) -1 2M aqueous trifluoromethanesulfonic acid solution of triaminoguanidine hydrochloride (Tag) and an oil phase solution (concentration of 15mmol L) -1 Petroleum ether solution of trimesic aldehyde (Tb) fills both sides of the SPSF membrane, wherein the organic phase contacts the hydrophobic layer of the base membrane. The prepared solution was filtered through a filter head (0.45 μm). After 24 days at 40 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 75nm, as measured byN 2 The pore diameter of the COF film obtained by adsorption was 0.9nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 7.8 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 67, the separation ratio of the hydrochloric acid to the sodium chloride can reach 87, the separation ratio of the hydrochloric acid to the lithium chloride can reach 131, the separation ratio of the hydrochloric acid to the magnesium chloride can reach 147, the separation ratio of the hydrochloric acid to the calcium chloride can reach 143, the separation ratio of the hydrochloric acid to the ferrous chloride can reach 862, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 973.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be up to 10, the separation ratio of hydrochloric acid to hydrofluoric acid can be up to 12, the separation ratio of hydrochloric acid to hydrobromic acid can be up to 14, the separation ratio of hydrochloric acid to hydroiodic acid can be up to 16, the separation ratio of hydrochloric acid to nitric acid can be up to 17, the separation ratio of hydrochloric acid to nitrous acid can be up to 18, the separation ratio of hydrochloric acid to carbonic acid can be up to 43, the separation ratio of hydrochloric acid to sulfurous acid can be up to 47, the separation ratio of hydrochloric acid to sulfuric acid can be up to 68, the separation ratio of hydrochloric acid to phosphoric acid can be up to 134, and the separation ratio of hydrochloric acid to boric acid can be up to 125.
Example 5
Firstly, the SPES base membrane with the pore size of 50nm is put into deionized water, and the water-retaining agent in the base membrane is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 20mmol L) -1 Triaminoguanidine hydrochloride (Tag) in a 3M scandium trifluoromethanesulfonate aqueous solution and an oil phase solution (concentration of 20mmol L) -1 Terephthalaldehyde (Bda) in hexane) is impregnated into both sides of the SPES membrane, wherein the organic phase contacts the hydrophobic layer of the base membrane. The prepared solution needs to be filtered through a filter head (0.45 μm). After 20 days at 50 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 83nm by N 2 The pore diameter of the COF film obtained by adsorption is 5nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 7.6 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 121, the separation ratio of the hydrochloric acid to the sodium chloride can reach 196, the separation ratio of the hydrochloric acid to the lithium chloride can reach 273, the separation ratio of the hydrochloric acid to the magnesium chloride can reach 487, the separation ratio of the hydrochloric acid to the calcium chloride can reach 381, the separation ratio of the hydrochloric acid to the ferrous chloride can reach 1027, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 1337.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 12, the separation ratio of hydrochloric acid to hydrofluoric acid can be 12, the separation ratio of hydrochloric acid to hydrobromic acid can be 15, the separation ratio of hydrochloric acid to hydroiodic acid can be 19, the separation ratio of hydrochloric acid to nitric acid can be 22, the separation ratio of hydrochloric acid to nitrous acid can be 25, the separation ratio of hydrochloric acid to carbonic acid can be 63, the separation ratio of hydrochloric acid to sulfurous acid can be 68, the separation ratio of hydrochloric acid to sulfuric acid can be 79, the separation ratio of phosphoric acid can be 178, and the separation ratio of hydrochloric acid to boric acid can be 162.
Example 6
Firstly, the SPEEK basement membrane with the pore size of 20nm is put into deionized water, and the water-retaining agent in the basement membrane is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 25mmol L) -1 3M scandium trifluoromethanesulfonate aqueous solution of triaminoguanidine hydrochloride (Tag) and oil phase solution (concentration of 25mmol L) -1 Hexane solution of 2, 5-dihydroxy terephthalaldehyde (Dha) was impregnated into the SPEEK membrane on both sides, with the organic phase contacting the dense side of the membrane. The prepared solution needs to be filtered through a filter head (0.45 μm). At 60 deg.CAfter 15 days of reaction, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 74nm by N 2 The pore diameter of the COF film obtained by adsorption is 3nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 6.5 mh -1 The separation ratio of hydrochloric acid to potassium chloride can reach 157, the separation ratio of hydrochloric acid to sodium chloride can reach 232, the separation ratio of hydrochloric acid to lithium chloride can reach 286, the separation ratio of hydrochloric acid to magnesium chloride can reach 576, the separation ratio of hydrochloric acid to calcium chloride can reach 481, the separation ratio of hydrochloric acid to ferrous chloride can reach 1273, and the separation ratio of hydrochloric acid to aluminum chloride can reach 1622.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 12, the separation ratio of hydrochloric acid to hydrofluoric acid can be 12, the separation ratio of hydrochloric acid to hydrobromic acid can be 13, the separation ratio of hydrochloric acid to hydroiodic acid can be 16, the separation ratio of hydrochloric acid to nitric acid can be 16, the separation ratio of hydrochloric acid to nitrous acid can be 17, the separation ratio of hydrochloric acid to carbonic acid can be 52, the separation ratio of hydrochloric acid to sulfurous acid can be 57, the separation ratio of hydrochloric acid to sulfuric acid can be 58, the separation ratio of hydrochloric acid to phosphoric acid can be 121, and the separation ratio of hydrochloric acid to boric acid can be 105.
Example 7
Firstly, putting the PVDF basement membrane with the pore canal size of 15nm into deionized water, and removing the water-retaining agent in the basement membrane. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 30mmol L) -1 Triaminoguanidine hydrochloride (Tag) in 4M aqueous trifluoroacetic acid solution and an oil phase solution (concentration of 30mmol L) -1 A solution of 2-hydroxybenzene-1, 4-dicarboxaldehyde (Hbd) in acetonitrile) on both sides of the PVDF membrane, where the organic phase contacts the dense side of the base membrane. The prepared solution was filtered through a filter head (0.45 μm). After 10 days at 70 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 83nm by N 2 The pore diameter of the COF film obtained by adsorption is 4.2nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 6.7 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 183, the separation ratio of the hydrochloric acid to the sodium chloride can reach 267, the separation ratio of the hydrochloric acid to the lithium chloride can reach 302, the separation ratio of the hydrochloric acid to the magnesium chloride can reach 873, the separation ratio of the hydrochloric acid to the calcium chloride can reach 761, the separation ratio of the hydrochloric acid to the ferrous chloride can reach 1573, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 1899.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be up to 15, the separation ratio of hydrochloric acid to hydrofluoric acid can be up to 18, the separation ratio of hydrochloric acid to hydrobromic acid can be up to 19, the separation ratio of hydrochloric acid to hydroiodic acid can be up to 21, the separation ratio of hydrochloric acid to nitric acid can be up to 25, the separation ratio of hydrochloric acid to nitrous acid can be up to 27, the separation ratio of hydrochloric acid to carbonic acid can be up to 62, the separation ratio of hydrochloric acid to sulfurous acid can be up to 69, the separation ratio of hydrochloric acid to sulfuric acid can be up to 78, the separation ratio of hydrochloric acid to phosphoric acid can be up to 175, and the separation ratio of hydrochloric acid to boric acid can be up to 155.
Example 8
The PE basal membrane with the pore size of 10nm is firstly put into deionized water, and the water-retaining agent in the basal membrane is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 35mmol L) -1 Triaminoguanidine hydrochloride (Tag) in 4M nitric acid aqueous solution) and oil phase solution (concentration of 35mmol L) -1 4, 6-dialdehyde pyrogallol (Pd) in methylene chloride) was impregnated on both sides of the PE membrane, wherein the organic phase contacted the dense side of the base membrane. The prepared solution was filtered through a filter head (0.45 μm). After 5 days of reaction at 80 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparing the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 79nm, by N 2 The pore diameter of the COF film obtained by adsorption is 0.5nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 6.1 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 196, the separation ratio of the hydrochloric acid to the sodium chloride can reach 274, the separation ratio of the hydrochloric acid to the lithium chloride can reach 313, the separation ratio of the hydrochloric acid to the magnesium chloride can reach 917, the separation ratio of the hydrochloric acid to the calcium chloride can reach 891, the separation ratio of the hydrochloric acid to the ferrous chloride can reach 1893, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 2134.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 10, the separation ratio of hydrochloric acid to hydrofluoric acid can be 11, the separation ratio of hydrochloric acid to hydrobromic acid can be 13, the separation ratio of hydrochloric acid to hydroiodic acid can be 14, the separation ratio of hydrochloric acid to nitric acid can be 16, the separation ratio of hydrochloric acid to nitrous acid can be 16, the separation ratio of hydrochloric acid to carbonic acid can be 65, the separation ratio of hydrochloric acid to sulfurous acid can be 66, the separation ratio of hydrochloric acid to sulfuric acid can be 78, the separation ratio of phosphoric acid can be 125, and the separation ratio of hydrochloric acid to boric acid can be 111.
Example 9
Putting the PP basal membrane with the pore passage size of 5nm into deionized water, and removing the water-retaining agent in the basal membrane. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 40mmol L) -1 Triaminoguanidine hydrochloride (Tag) in 5M acetic acid in water) and an oil phase solution (40 mmol L in concentration) -1 A mesitylene solution of 2, 4-diformylphloroglucinol (Dpg) impregnated on both sides of the PP membrane, wherein the organic phase contacts the dense side of the base membrane. The prepared solution needs to be filtered through a filter head (0.45 μm). After 3 days at 90 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in turn to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was 89nm as measured by Scanning Electron Microscopy (SEM) and by N 2 The pore diameter of the COF film obtained by adsorption is 0.65nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 5.8 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 234, the separation ratio of the hydrochloric acid to the sodium chloride can reach 261, the separation ratio of the hydrochloric acid to the lithium chloride can reach 325, the separation ratio of the hydrochloric acid to the magnesium chloride can reach 974, the separation ratio of the hydrochloric acid to the calcium chloride can reach 907, the separation ratio of the hydrochloric acid to the ferrous chloride can reach 2341, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 3176.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 13, the separation ratio of hydrochloric acid to hydrofluoric acid can be 15, the separation ratio of hydrochloric acid to hydrobromic acid can be 16, the separation ratio of hydrochloric acid to hydroiodic acid can be 16, the separation ratio of hydrochloric acid to nitric acid can be 15, the separation ratio of hydrochloric acid to nitrous acid can be 21, the separation ratio of hydrochloric acid to carbonic acid can be 50, the separation ratio of hydrochloric acid to sulfurous acid can be 58, the separation ratio of hydrochloric acid to sulfuric acid can be 61, the separation ratio of phosphoric acid can be 132, and the separation ratio of hydrochloric acid to boric acid can be 104.
Example 10
Firstly, al with the pore size of 300nm 2 O 3 And putting the base film into deionized water, and removing the water-retaining agent in the base film. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 45mmol L) -1 Triaminoguanidine hydrochloride (Tag) in a 5M sulfuric acid aqueous solution) and an oil phase solution (concentration of 45mmol L) -1 A solution of 2, 4-dihydroxyisophthalaldehyde (Dbda) in o-dichlorobenzene) was impregnated with Al 2 O 3 On both sides of the membrane, the organic phase of which contacts the dense side of the base membrane. The prepared solution was filtered through a filter head (0.45 μm). After 1 day of reaction at 100 c, a yellowish COF layer was observed on the organic phase side of the base film. And taking down the prepared ion exchange membrane, and sequentially cleaning the membrane with ethanol, methanol and water to remove residual monomers, catalysts and organic solvents and fill the pore passages with chloride ions. The COF film structure in this example is shown by the following formula:
after preparation of the film, the thickness of the film was measured by Scanning Electron Microscopy (SEM) to be 68nm by N 2 The pore diameter of the COF film obtained by adsorption is 0.8nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 5.6 mh -1 Hydrochloric acid and chlorineThe separation ratio of potassium chloride can reach 257, the separation ratio of potassium chloride to sodium chloride can reach 275, the separation ratio of potassium chloride to lithium chloride can reach 332, the separation ratio of potassium chloride to magnesium chloride can reach 1187, the separation ratio of potassium chloride to calcium chloride can reach 911, the separation ratio of potassium chloride to ferrous chloride can reach 3437, and the separation ratio of potassium chloride to aluminum chloride can reach 4128.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be up to 15, the separation ratio of hydrochloric acid to hydrofluoric acid can be up to 17, the separation ratio of hydrochloric acid to hydrobromic acid can be up to 19, the separation ratio of hydrochloric acid to hydroiodic acid can be up to 21, the separation ratio of hydrochloric acid to nitric acid can be up to 23, the separation ratio of hydrochloric acid to nitrous acid can be up to 26, the separation ratio of hydrochloric acid to carbonic acid can be up to 52, the separation ratio of hydrochloric acid to sulfurous acid can be up to 61, the separation ratio of hydrochloric acid to sulfuric acid can be up to 65, the separation ratio of hydrochloric acid to phosphoric acid can be up to 122, and the separation ratio of hydrochloric acid to boric acid can be up to 104.
Example 11
TiO with pore canal of 350nm 2 And putting the base film into deionized water, and removing the water-retaining agent in the base film. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 50mmol L) -1 Triaminoguanidine hydrochloride (Tag) in 6M acetic acid aqueous solution) and an oil phase solution (concentration of 50mmol L) -1 Ethyl acetate solution of 2-hydroxyisophthalaldehyde (Hp) impregnated with TiO 2 On both sides of the membrane, the organic phase of which contacts the dense side of the base membrane. The prepared solution was filtered through a filter head (0.45 μm). After 6 days at 15 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparing the film, the film thickness was measured by Scanning Electron Microscopy (SEM)At 77nm, by N 2 The pore diameter of the COF film obtained by adsorption is 0.79nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 5 mh -1 The separation ratio of hydrochloric acid to potassium chloride can reach 261, the separation ratio of hydrochloric acid to sodium chloride can reach 281, the separation ratio of hydrochloric acid to lithium chloride can reach 352, the separation ratio of hydrochloric acid to magnesium chloride can reach 1267, the separation ratio of hydrochloric acid to calcium chloride can reach 933, the separation ratio of hydrochloric acid to ferrous chloride can reach 3673, and the separation ratio of hydrochloric acid to aluminum chloride can reach 4217.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 11, the separation ratio of hydrochloric acid to hydrofluoric acid can be 12, the separation ratio of hydrochloric acid to hydrobromic acid can be 12, the separation ratio of hydrochloric acid to hydroiodic acid can be 12, the separation ratio of hydrochloric acid to nitric acid can be 13, the separation ratio of hydrochloric acid to nitrous acid can be 14, the separation ratio of hydrochloric acid to carbonic acid can be 52, the separation ratio of hydrochloric acid to sulfurous acid can be 55, the separation ratio of hydrochloric acid to sulfuric acid can be 57, the separation ratio of phosphoric acid can be 112, and the separation ratio of hydrochloric acid to boric acid can be 98.
Example 12
Firstly, the PAN base membrane with the pore size of 400nm is placed in deionized water, and the water-retaining agent in the base membrane is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 55mmol L) -1 6M aqueous hydrochloric acid solution of triaminoguanidine hydrochloride (Tag)) and oil phase solution (concentration of 55mmol L -1 Xylene solution of 2, 6-diformyl-4-methylphenol (Hmb) is impregnated on both sides of the PAN membrane, wherein the organic phase contacts the hydrophobic layer of the base membrane. The prepared solution needs to be filtered through a filter head (0.45 μm). After 14 days at 20 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 92nm by N 2 The pore diameter of the COF film obtained by adsorption is 0.95nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 5.3 mh -1 The separation ratio of hydrochloric acid to potassium chloride can reach 251, the separation ratio of hydrochloric acid to sodium chloride can reach 261, the separation ratio of hydrochloric acid to lithium chloride can reach 321, the separation ratio of hydrochloric acid to magnesium chloride can reach 1103, the separation ratio of hydrochloric acid to calcium chloride can reach 865, the separation ratio of hydrochloric acid to ferrous chloride can reach 3445, and the separation ratio of hydrochloric acid to aluminum chloride can reach 4138.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 11, the separation ratio of hydrochloric acid to hydrofluoric acid can be 12, the separation ratio of hydrochloric acid to hydrobromic acid can be 15, the separation ratio of hydrochloric acid to hydroiodic acid can be 17, the separation ratio of hydrochloric acid to nitric acid can be 19, the separation ratio of hydrochloric acid to nitrous acid can be 20, the separation ratio of hydrochloric acid to carbonic acid can be 68, the separation ratio of hydrochloric acid to sulfurous acid can be 87, the separation ratio of hydrochloric acid to sulfuric acid can be 85, the separation ratio of phosphoric acid can be 171, and the separation ratio of hydrochloric acid to boric acid can be 154.
Example 13
The PES basement membrane with the pore size of 450nm is placed into deionized water, and the water-retaining agent in the basement membrane is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 60mmol L) -1 Triaminoguanidine hydrochloride (Tag) in a 7M aqueous acetic acid solution) and an oil phase solution (concentration of 60mmol L) -1 4-hydroxyisophthalaldehyde (Dp) in dichloromethane) is filled on both sides of the PES membrane, wherein the organic phase contacts the hydrophobic layer of the base membrane. The prepared solution was filtered through a filter head (0.45 μm). In thatAfter 16 days at 25 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was 42nm as measured by Scanning Electron Microscopy (SEM) and by N 2 The COF pore diameter obtained by adsorption was 0.9nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 5.8 mh -1 The separation ratio of hydrochloric acid to potassium chloride can reach 242, the separation ratio of hydrochloric acid to sodium chloride can reach 257, the separation ratio of hydrochloric acid to lithium chloride can reach 316, the separation ratio of hydrochloric acid to magnesium chloride can reach 1078, the separation ratio of hydrochloric acid to calcium chloride can reach 853, the separation ratio of hydrochloric acid to ferrous chloride can reach 3217, and the separation ratio of hydrochloric acid to aluminum chloride can reach 4037.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be up to 15, the separation ratio of hydrochloric acid to hydrofluoric acid can be up to 16, the separation ratio of hydrochloric acid to hydrobromic acid can be up to 18, the separation ratio of hydrochloric acid to hydroiodic acid can be up to 21, the separation ratio of hydrochloric acid to nitric acid can be up to 25, the separation ratio of hydrochloric acid to nitrous acid can be up to 27, the separation ratio of hydrochloric acid to carbonic acid can be up to 66, the separation ratio of hydrochloric acid to sulfurous acid can be up to 69, the separation ratio of hydrochloric acid to sulfuric acid can be up to 78, the separation ratio of hydrochloric acid to phosphoric acid can be up to 177, and the separation ratio of hydrochloric acid to boric acid can be up to 148.
Example 14
Firstly, the PEEK base film with the pore size of 500nm is put into deionized water, and the water-retaining agent in the base film is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 70mmol L) -1 1, 3-diaminoguanidine hydrochloride (Dgm) in 7M aqueous acetic acid and an oil phase solution (concentration 70mmol L) -1 Trialdehyde phloroglucinol (Tp) in ethyl acetate) fills both sides of the PEEK film, with the organic phase contacting the dense side of the base film. The prepared solution needs to be filtered through a filter head (0.45 μm). After 18 days at 28 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 60nm by N 2 The pore diameter of the COF film obtained by adsorption is 1.2nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 6.7 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 235, the separation ratio of the hydrochloric acid to the sodium chloride can reach 247, the separation ratio of the hydrochloric acid to the lithium chloride can reach 293, the separation ratio of the hydrochloric acid to the magnesium chloride can reach 987, the separation ratio of the hydrochloric acid to the calcium chloride can reach 901, the separation ratio of the hydrochloric acid to the ferrous chloride can reach 3061, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 3981.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 18, the separation ratio of hydrochloric acid to hydrofluoric acid can be 21, the separation ratio of hydrochloric acid to hydrobromic acid can be 23, the separation ratio of hydrochloric acid to hydroiodic acid can be 25, the separation ratio of hydrochloric acid to nitric acid can be 28, the separation ratio of hydrochloric acid to nitrous acid can be 29, the separation ratio of hydrochloric acid to carbonic acid can be 75, the separation ratio of hydrochloric acid to sulfurous acid can be 87, the separation ratio of hydrochloric acid to sulfuric acid can be 89, the separation ratio of hydrochloric acid to phosphoric acid can be 180, and the separation ratio of hydrochloric acid to boric acid can be 167.
Example 15
Firstly, putting the SPSF basal membrane with the pore size of 700nm into deionized water, and removing the water-retaining agent in the basal membrane. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 80mmol L) -1 1, 3-diaminoguanidine hydrochloride (Dgm) in 8M acetic acid in water) and an oil phase solution (concentration 80mmol L) -1 A mesitylene solution of 2, 4-dihydroxy-1, 3, 5-mesitylene-triformal (Btd) is impregnated on both sides of the SPSF film, wherein the organic phase contacts the hydrophobic layer of the base film. The prepared solution needs to be filtered through a filter head (0.45 μm). After 20 days of reaction at 30 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparing the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 58nm, by N 2 The pore diameter of the COF film obtained by adsorption is 1.5nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 6.9 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 223, the separation ratio of the hydrochloric acid to the sodium chloride can reach 233, the separation ratio of the hydrochloric acid to the lithium chloride can reach 277, the separation ratio of the hydrochloric acid to the magnesium chloride can reach 954, the separation ratio of the hydrochloric acid to the calcium chloride can reach 831, the separation ratio of the hydrochloric acid to the ferrous chloride can reach 2817, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 3437.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be up to 13, the separation ratio of hydrochloric acid to hydrofluoric acid can be up to 14, the separation ratio of hydrochloric acid to hydrobromic acid can be up to 16, the separation ratio of hydrochloric acid to hydroiodic acid can be up to 18, the separation ratio of hydrochloric acid to nitric acid can be up to 20, the separation ratio of hydrochloric acid to nitrous acid can be up to 23, the separation ratio of hydrochloric acid to carbonic acid can be up to 58, the separation ratio of hydrochloric acid to sulfurous acid can be up to 66, the separation ratio of hydrochloric acid to sulfuric acid can be up to 72, the separation ratio of hydrochloric acid to phosphoric acid can be up to 164, and the separation ratio of hydrochloric acid to boric acid can be up to 148.
Example 16
Firstly, the SPES base membrane with the pore size of 900nm is put into deionized water, and the water-retaining agent in the base membrane is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 90mmol L) -1 8M aqueous acetic acid solution of 1, 3-diaminoguanidine hydrochloride (Dgm) and an oil phase solution (concentration of 90mmol L) -1 Cyclohexane solution of 2-hydroxy-1, 3, 5-benzenetricarboxylic acid (Hb) fills both sides of the SPES membrane, wherein the organic phase contacts the hydrophobic layer of the base membrane. The prepared solution was filtered through a filter head (0.45 μm). After a reaction time of 22 days at 35 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 73nm by N 2 The pore diameter of the COF film obtained by adsorption was 1.7nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 7.8 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 188, the separation ratio of the hydrochloric acid to the sodium chloride can reach 206, the separation ratio of the hydrochloric acid to the lithium chloride can reach 267, the separation ratio of the hydrochloric acid to the magnesium chloride can reach 843, the separation ratio of the hydrochloric acid to the calcium chloride can reach 736, the separation ratio of the hydrochloric acid to the ferrous chloride can reach 2117, and the separation ratio of the hydrochloric acid to the aluminum chloride can reach 3234.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 10, the separation ratio of hydrochloric acid to hydrofluoric acid can be 11, the separation ratio of hydrochloric acid to hydrobromic acid can be 12, the separation ratio of hydrochloric acid to hydroiodic acid can be 14, the separation ratio of hydrochloric acid to nitric acid can be 15, the separation ratio of hydrochloric acid to nitrous acid can be 16, the separation ratio of hydrochloric acid to carbonic acid can be 51, the separation ratio of hydrochloric acid to sulfurous acid can be 57, the separation ratio of hydrochloric acid to sulfuric acid can be 59, the separation ratio of phosphoric acid can be 99, and the separation ratio of hydrochloric acid to boric acid can be 87.
Example 17
Firstly, the SPEEK basement membrane with the pore size of 1000nm is put into deionized water, and the water-retaining agent in the basement membrane is removed. And after bubbles are not generated on the surface of the base film, placing the base film in deionized water for later use. The aqueous solution (concentration 100mmol L) -1 1, 3-diaminoguanidine hydrochloride (Dgm) in 9M aqueous acetic acid and an oil phase solution (concentration of 100mmol L) -1 A dichloromethane solution of trimesic aldehyde (Tb) fills both sides of the SPEEK membrane, wherein the organic phase contacts the hydrophobic layer of the base membrane. The prepared solution needs to be filtered through a filter head (0.45 μm). After 24 days at 45 c, a yellowish COF layer was observed on the organic phase side of the base film. The prepared ion exchange membrane is taken down and washed by ethanol, methanol and water in sequence to remove residual monomers, catalysts and organic solvents. The COF film structure in this example is shown by the following formula:
after preparation of the film, the film thickness was measured by Scanning Electron Microscopy (SEM) to be 62nm by N 2 The pore diameter of the COF film obtained by adsorption was 1.9nm. This membrane was then used to perform a simulated acidic wastewater recovery experiment.
Regarding the cation separation performance of the membrane: according to the experimental conditions of example 1, the acid dialysis coefficient of the membrane reached 7.8 mh -1 The separation ratio of the hydrochloric acid to the potassium chloride can reach 176, and the hydrochloric acid to the potassium chloride are mixedThe separation ratio of sodium can reach 198, the separation ratio of sodium to lithium chloride can reach 252, the separation ratio of sodium to magnesium chloride can reach 712, the separation ratio of sodium to calcium chloride can reach 687, the separation ratio of sodium to ferrous chloride can reach 1873, and the separation ratio of sodium to aluminum chloride can reach 2673.
Regarding the anion separation performance of the membrane: according to the experimental conditions of example 1, the separation ratio of hydrochloric acid to acetic acid can be 11, the separation ratio of hydrochloric acid to hydrofluoric acid can be 12, the separation ratio of hydrochloric acid to hydrobromic acid can be 13, the separation ratio of hydrochloric acid to hydroiodic acid can be 15, the separation ratio of hydrochloric acid to nitric acid can be 17, the separation ratio of hydrochloric acid to nitrous acid can be 19, the separation ratio of hydrochloric acid to carbonic acid can be 67, the separation ratio of hydrochloric acid to sulfurous acid can be 69, the separation ratio of hydrochloric acid to sulfuric acid can be 83, the separation ratio of hydrochloric acid to phosphoric acid can be 173, and the separation ratio of hydrochloric acid to boric acid can be 135.
In a specific practical application, the ion separation membrane prepared by the invention can be further processed into a hollow fiber membrane, a flat plate membrane or a tubular membrane form for assembling an acid separation system. The acid separation system may be in the form of any one of the following: a forward osmosis system, a reverse osmosis system, a nanofiltration system, a diffusion dialysis system, or an electrodialysis system.
In an acid separation system, an ion separation membrane is used for treating acid wastewater in a diffusion dialysis mode; the method specifically comprises the following steps: (1) Pretreating the acidic wastewater, removing slightly soluble inorganic compounds, and removing large particles and colloidal substances in an ultrafiltration mode; (2) The ion separation membrane is used for carrying out diffusion dialysis treatment on the acidic wastewater, so that the selective recovery of acid is realized.
It can be seen from the relevant experimental data of the above examples that the ion separation membrane for diffusion dialysis prepared by the interfacial polymerization method of the present invention has high osmotic selectivity. Because rich guanidyl groups are regularly arranged on the nano/sub-nano channel, the separation of anions and cations can be realized at the same time. The membrane has excellent stability and acid resistance, can meet the requirements of practical industrial application, and has a large-scale application prospect in the field of diffusion dialysis acid recovery.
Claims (10)
1. The ion separating membrane with high permeability and selectivity is characterized in that the ion separating membrane takes an ultramicro filter membrane with the pore canal size of 5-1000 nm as a base membrane; the surface of the basement membrane is provided with a covalent organic framework separation layer formed by condensation polymerization of aldehyde monomers and amine monomers containing guanidine groups, and the size of a pore channel of the covalent organic framework separation layer is 0.5-5 nm.
2. A method of making a high permselectivity ion separation membrane according to claim 1, comprising:
(1) Using an ultramicro filter membrane with the aperture of 5-1000 nm as a basement membrane, and removing a water-retaining agent contained in the basement membrane;
(2) Taking an aqueous solution of an amine monomer containing a guanidine group and an acid catalyst as an aqueous phase solution, and taking an organic solution containing an aldehyde monomer as an oil phase solution; filtering the water phase solution and the oil phase solution, and filling the water phase solution and the oil phase solution into two sides of the basement membrane respectively, wherein the organic phase is in contact with a hydrophobic layer or a compact side of the basement membrane; reacting for 1-30 days at 10-100 ℃, and generating a covalent organic framework separation layer formed by aldehyde monomers and amine monomers containing guanidine groups on the surface of the side, facing the organic phase, of the substrate;
(3) And taking out the base membrane after reaction, and sequentially cleaning the base membrane with ethanol, methanol and water to remove residual monomers, acid catalysts and organic solvents to obtain the ion separation membrane with high osmotic selectivity.
3. The method according to claim 2, wherein the ultrafiltration membrane is any one of: polyacrylonitrile membrane, polysulfone membrane, polyvinylidene fluoride membrane, polyethylene membrane, polypropylene membrane, polyethersulfone membrane, polyetheretherketone membrane, sulfonated polysulfone membrane, sulfonated polyethersulfone membrane, sulfonated polyetheretherketone membrane, aluminum oxide ceramic material and titanium dioxide ceramic material.
4. The method of claim 1, wherein the amine monomer is triaminoguanidine hydrochloride or 1, 3-diaminoguanidine hydrochloride.
5. The method according to claim 1, wherein the aldehyde monomer is any one of: trialdehyde phloroglucinol, 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde, 2-hydroxy-1, 3, 5-benzenetricarboxylic aldehyde, trimesic aldehyde, terephthalaldehyde, 2, 5-dihydroxy terephthalaldehyde, 2-hydroxybenzene-1, 4-dicarbaldehyde, 4, 6-dialdehyde pyrogallol, 2, 4-diformyl phloroglucinol, 2, 4-dihydroxy isophthalaldehyde, 2-hydroxy isophthalaldehyde, 2, 6-diformyl-4-methylphenol, or 4-hydroxy isophthalaldehyde.
6. The method of claim 1, wherein the acid-based catalyst is any one of: hydrochloric acid, sulfuric acid, nitric acid, acetic acid, p-toluenesulfonic acid, scandium trifluoromethanesulfonate or trifluoroacetic acid.
7. The method according to claim 2, wherein the concentration of the aqueous phase solution is 1 to 100mmol L -1 The concentration of the oil phase solution is 1-100 mmol L -1 (ii) a And the aqueous phase solution and the oil phase solution were filtered using a 0.45 μm filter head.
8. The method of claim 2, wherein the resulting ion separation membrane is further processed into a hollow fiber membrane, a flat sheet membrane, or a tubular membrane.
9. The method for using the ion separation membrane with high osmotic selectivity as claimed in claim 1, wherein the ion separation membrane is used for treating acidic wastewater in a diffusion dialysis mode; the method specifically comprises the following steps:
(1) Pretreating the acidic wastewater, removing slightly soluble inorganic compounds, and removing large particles and colloidal substances in an ultrafiltration mode;
(2) The ion separation membrane is used for carrying out diffusion dialysis treatment on the acidic wastewater to realize selective recovery of acid.
10. The method according to claim 9, wherein the ion separation membrane is used to build any one of the following acid separation systems for diffusion dialysis treatment: a forward osmosis system, a reverse osmosis system, a nanofiltration system, a diffusion dialysis system, or an electrodialysis system.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105461525A (en) * | 2015-12-23 | 2016-04-06 | 华南理工大学 | Preparation of 1,3,5-tri-formyl trihydroxybenzene and reuse method of trifluoroacetic acid in preparation process |
| CN108889139A (en) * | 2018-07-31 | 2018-11-27 | 南京工业大学 | Method for preparing high-flux covalent organic framework nanofiltration membrane based on interfacial polymerization |
| WO2019034994A1 (en) * | 2017-08-16 | 2019-02-21 | 3M Innovative Properties Company | Polymeric ionomer separation membranes and methods of use |
| CN113234326A (en) * | 2021-05-03 | 2021-08-10 | 浙江大学 | Preparation and application of ionic membrane material with nanometer/sub-nanometer pore canal |
| CN114471177A (en) * | 2022-01-30 | 2022-05-13 | 天津大学 | Anion exchange driven cation selective separation hybrid membrane and preparation and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461525A (en) * | 2015-12-23 | 2016-04-06 | 华南理工大学 | Preparation of 1,3,5-tri-formyl trihydroxybenzene and reuse method of trifluoroacetic acid in preparation process |
| WO2019034994A1 (en) * | 2017-08-16 | 2019-02-21 | 3M Innovative Properties Company | Polymeric ionomer separation membranes and methods of use |
| CN108889139A (en) * | 2018-07-31 | 2018-11-27 | 南京工业大学 | Method for preparing high-flux covalent organic framework nanofiltration membrane based on interfacial polymerization |
| CN113234326A (en) * | 2021-05-03 | 2021-08-10 | 浙江大学 | Preparation and application of ionic membrane material with nanometer/sub-nanometer pore canal |
| CN114471177A (en) * | 2022-01-30 | 2022-05-13 | 天津大学 | Anion exchange driven cation selective separation hybrid membrane and preparation and application thereof |
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