CN113145081A - Easy-to-detach regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater and preparation method thereof - Google Patents
Easy-to-detach regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater and preparation method thereof Download PDFInfo
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- CN113145081A CN113145081A CN202110149463.4A CN202110149463A CN113145081A CN 113145081 A CN113145081 A CN 113145081A CN 202110149463 A CN202110149463 A CN 202110149463A CN 113145081 A CN113145081 A CN 113145081A
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- CN
- China
- Prior art keywords
- nanofiber membrane
- open chain
- chain cucurbituril
- polyvinyl alcohol
- cucurbituril
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- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 title claims abstract description 147
- 239000000463 material Substances 0.000 title claims abstract description 88
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002121 nanofiber Substances 0.000 claims abstract description 145
- 239000012528 membrane Substances 0.000 claims abstract description 143
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 81
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 81
- 238000001179 sorption measurement Methods 0.000 claims abstract description 72
- 238000003795 desorption Methods 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 30
- 230000008929 regeneration Effects 0.000 claims abstract description 26
- 238000011069 regeneration method Methods 0.000 claims abstract description 26
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 25
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 20
- 239000011630 iodine Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 230000002285 radioactive effect Effects 0.000 claims abstract description 17
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims abstract description 14
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 14
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 11
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 93
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 claims description 22
- 238000001523 electrospinning Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000009987 spinning Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011888 foil Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000007664 blowing Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 241000755266 Kathetostoma giganteum Species 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 8
- 229940071870 hydroiodic acid Drugs 0.000 claims description 8
- 238000010408 sweeping Methods 0.000 claims description 8
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 2
- 240000009087 Crescentia cujete Species 0.000 abstract 1
- 235000005983 Crescentia cujete Nutrition 0.000 abstract 1
- 235000009797 Lagenaria vulgaris Nutrition 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 24
- 239000003344 environmental pollutant Substances 0.000 description 11
- 231100000719 pollutant Toxicity 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
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- 239000000126 substance Substances 0.000 description 9
- 238000011160 research Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 229920000858 Cyclodextrin Polymers 0.000 description 4
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 4
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- 239000002901 radioactive waste Substances 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 238000005025 nuclear technology Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
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- 239000011343 solid material Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- -1 uranyl ions Chemical class 0.000 description 2
- 239000002351 wastewater 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VBWSWBQVYDBVGA-NAHFVJFTSA-N uranium-234;uranium-235;uranium-238 Chemical compound [234U].[235U].[238U] VBWSWBQVYDBVGA-NAHFVJFTSA-N 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to an easy-to-remove regenerated open chain calabash ureido material for treating nuclear industrial wastewater and a preparation method thereof, wherein polyvinyl alcohol and dialdehyde are used as main raw materials for electrostatic spinning, and then the electrostatic spinning is carried out in a strong acid methanol solution to form a film through crosslinking; and grafting and modifying the open chain cucurbituril on the surface of the nanofiber membrane, wherein the open chain cucurbituril is of a structure with a ureido repeat unit of 3. The open chain cucurbit uril-based material prepared by the method has good mechanical property, the tensile strength is 50-80 MPa, and the elastic modulus is 2000-3000 MPa; the material has high adsorbability to radioactive nuclides uranium, thorium, iodine and tellurium, and the maximum adsorption rate reaches more than 95 percent; the material has easy desorption and regeneration, can complete desorption through methanol and water washing, and has the adsorption rate of more than 85 percent after 5 times of adsorption-desorption cycles. The preparation method is efficient and practical; the material prepared by the method has good mechanical property, high adsorbability and easy desorption and regeneration.
Description
Technical Field
The invention belongs to the technical field of nuclear industrial wastewater treatment, and relates to an easily-desorbed regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater and a preparation method thereof.
Background
The rapid, safe and healthy development of the nuclear industry is a global problem in various fields related to energy, economy, civilian life, environment, and the like. With the development of the nuclear industry and other nuclear technologies (such as shaft mining, nuclear power operation, nuclear technology application, etc.), a large amount of radioactive waste is inevitably generated. Due to the special properties of radioactive wastes, the radioactive wastes must be treated to be discharged to the outside.
In nuclear industrial wastewater, radionuclide contaminants can be divided into two categories: one is radioactive metals such as radioactive uranium, thorium, etc., and the other is radioactive non-metals such as radioactive iodine, etc.
Among them, uranium is the most important natural radioactive element and also an important nuclear fuel. Because of the wide application range, uranium and compounds thereof have high toxicity and very long half-life, so that the uranium is naturally an undisputed very important radioactive heavy metal pollutant. Thorium is also an extremely important nuclear fuel in the development of the atomic energy industry, and is a development direction of the future nuclear energy utilization. The main methods for these metal contaminants include adsorption, ion exchange, solvent extraction and separation, chemical precipitation, flotation, biological treatment, and superconducting magnetic separation. Researches find that the solvent extraction separation method has certain limitations on extracting uranium and thorium from low-concentration wastewater, such as complex engineering installation, serious extractant loss and the like; when ion exchange resin is used for experiments, the resin is easy to pollute and destroy active groups on the surface of a material, so that the adsorption capacity of the resin is greatly reduced. The adsorption method is one of the hottest methods for radioactive metal adsorption research at the present stage.
The radioactive iodine is mostly released into the atmosphere in the form of gas, and a small part is organic iodine (CH)3I, etc.) and inorganic iodine (I)-、IO3-Etc.) into a body of water. Common methods for removing radioactive iodine in wastewater include precipitation, ion exchange, membrane separation, adsorption, and the like. Most solid adsorbents are silver-loaded inorganic porous materials, such as molecular sieves, silica gel, alumina, and the like, which adsorb iodine mainly through chemical changes, but the high price and the less-ideal adsorption capacity of noble metals limit their application. The adsorption method is one of the hottest methods for iodine capture at present.
In summary, for radioactive metals and non-metallic substances, the adsorption method has attracted considerable attention due to the advantages of simple preparation, low cost, wide material sources, and the like, and the adsorption material with low preparation cost and good adsorption performance has been the focus of research. The nanofiber membrane is used as a novel material, is small in diameter and large in specific surface area, and compared with the traditional filter material, the nanofiber membrane has the advantages of light weight, high porosity and high permeability, the filtering and adsorption functions of the filter material are well combined together, and the filtering efficiency and the adsorption capacity are remarkably improved.
However, the conventional nanofiber membrane does not have the capability of removing radionuclides by itself due to the limitation of the functional group structure of the polymer itself. The nanofiber membrane is modified by a chemical modification method, and the problem that spinning solution is crosslinked into gel exists, so that a spinning nozzle and a pipeline are blocked in the electrostatic spinning process. Research shows that the mechanical property of the electrostatic spinning chitosan/polyvinyl alcohol (CS/PVA) nanofiber membrane is obviously weakened along with the prolonging of the soaking time. The microporous aromatic skeleton metal-organic framework lac-Zn/PDMS composite membrane has certain stability in a water-containing environment, but the contact angle of the membrane is reduced, part of adsorption sites are blocked by PDMS, and the adsorption capacity for iodine is low.
And for the nano fiber membrane based on the cyclic main body (such as cyclodextrin, crown ether, pillar arene and cucurbituril), various problems such as poor mechanical property, poor adsorption selectivity or poor solubility of the cyclic main body, difficulty in electrostatic spinning and the like exist.
For example, the functional beta-cyclodextrin hydrogel adsorbs U (VI), Th (IV), and the adsorption performance of the adsorbent material mainly comes from the addition of beta-cyclodextrin. The dibenzo-18-crown-6 with different proportions is doped into polyacrylonitrile and is added into a dimethylformamide solution to be dissolved to prepare an electrospinning solution, and the electrospinning solution is spun into fibers by adopting an electrospinning technology, so that the adsorption active sites of the obtained nanofibers are improved, and the adsorption performance is better. However, the chemical structure flexibility of the cyclic main bodies such as cyclodextrin and crown ether leads to poor mechanical properties of the nanofiber membrane, and the surface of the nanofiber membrane subjected to modification treatment is easily polluted and easily influenced by external conditions.
Through an electrostatic spinning technology, a MeP5/PA nano-fiber membrane is prepared from methoxy pillar [5] arene/polyacrylate (MeP5/PA) blended emulsion, and the adsorption behavior of the nano-fiber membrane on four p-nitrobenzene derivatives shows that the addition of pillar arene can improve the adsorption capacity of the nano-fiber membrane. However, because the methoxy pillar [5] arene cavity structure is smaller, the host-object identification is difficult to carry out on organic pollutants with larger molecular sizes, so that the application range of the nano-fiber membrane is weakened, the nano-fiber membrane can only adsorb p-nitrobenzene, and the adjacent and meta-nitrobenzene cannot be adsorbed because the size of the nano-fiber membrane is larger than that of the methoxy pillar [5] arene cavity.
The cucurbituril is a small molecular compound, has poor solubility, is only dissolved in a concentrated acid solution, and cannot meet various conditions required by electrostatic spinning.
Besides, the adsorption capacity and the removal efficiency are only index parameters on the one hand for evaluating the adsorption effect of the modified nanofiber membrane on pollutants, and the regeneration performance of the adsorption material is also paid attention. And when the adsorbent is applied to the actual production process, the adsorbent with high desorption rate is more suitable. Therefore, in order to make the adsorption material more economical and efficient in practical application, it is necessary to pay attention to the desorption process and repetitive research of the material.
Various adsorbents are required to desorb pollutants after adsorbing the pollutants so as to be recycled. Currently, there are two main types of methods for adsorbent desorption treatment:
for solid materials such as activated carbon fibers, glass hollow fiber membranes, pillared aromatic hydrocarbons and the like, the desorption conditions are generally high-temperature calcination, the energy consumption is high, the material repeatability is obviously influenced, and the method is not suitable for the desorption process of the nanofiber membrane material. For example, the column aromatic hydrocarbon sodium is used for selectively adsorbing iodine simple substance, and during repeated performance research, the column aromatic hydrocarbon solid material adsorbing iodine is subjected to vacuum heating at 125 ℃ for 12 hours to achieve complete desorption.
For the nano-fiber and the conventional membrane material, strong acid and strong base solution is generally used for leaching desorption. Although the desorption effect and efficiency of the method are high, the reusability of the material is seriously influenced, and the adsorption performance of a plurality of membrane materials on pollutants is obviously reduced in the second cycle experiment. For example, nitrile group-rich polyacrylonitrile fiber (PAN fiber) is used as a raw material to prepare amidoxime group polyacrylonitrile fiber (PAO fiber) to adsorb low-concentration uranyl ions in a solution, and after comparing desorption effects of various desorbents on PAO materials, desorption effects of 6 desorbents, namely hydrogen peroxide, succinimide, potassium carbonate, potassium bicarbonate, potassium hydroxide and ammonia water, are found to be not ideal; the uranium can be eluted by more than 90% by hydrochloric acid, nitric acid and perchloric acid with the concentration of 0.5 mol/L. However, most of the fibers after desorption except the fibers treated by 0.5mol/L tartaric acid solution are gelatinized and even fade, and the four strong acids destroy the original structure of the fibers, and the higher the concentration of the acids is, the more serious the damage of the materials is, which is very unfavorable for the recycling of the adsorbing materials. After the amphoteric cellulose nanofiber membrane is desorbed in dilute alkali liquor or dilute sulfuric acid, the maximum adsorption capacity is obviously reduced, and the fiber membrane form is damaged. The microporous aromatic skeleton metal-organic framework lac-Zn/PDMS composite membrane continuously passes through an iodine aqueous solution to be adsorbed three times, the lac-Zn/PDMS membrane is subjected to desorption treatment after the iodine aqueous solution is adsorbed each time, and the iodine aqueous solution adsorbed each time is used as the iodine aqueous solution adsorbed next time, so that the reusability of the membrane is found to be poor.
In summary, it is very important to develop and prepare a new type of nanofiber membrane which is easy to desorb and regenerate for treating nuclear industrial wastewater. From the above analysis, the current combination of supramolecular chemistry and nanofiber membrane field is limited to basic research and macrocyclic host, and these nanofiber membranes based on macrocyclic host have various disadvantages, though each has advantages. For example, the macrocyclic hosts lack adaptive selectivity for complex substances in the real environment due to self annular closed structures (the hosts are induced to deform by adding an object); and the host-guest action between the macrocyclic host and the pollutant is relatively strong, so that the nanofiber membrane has the problems of relatively strict conditions, high energy consumption, high desorption difficulty and the like when desorbing the radionuclide, thereby causing relatively poor reusable performance. Therefore, the invention adopts the non-annular main body, namely the open chain cucurbituril graft modification nanofiber membrane, and creatively solves the problems of low radionuclide adsorption capacity, poor product mechanical property, high desorption regeneration difficulty and the like.
Disclosure of Invention
The invention aims to solve the technical problems of poor adsorption performance to radioactive nuclide, poor mechanical property of a product, unstable product quality, narrow application range, poor product regeneration cycle performance caused by radioactive nuclide desorption and the like in the prior art, provides an easy-desorption regeneration open-chain cucurbituril-based material for treating nuclear industrial wastewater and a preparation method thereof, and can endow a nanofiber membrane with unique molecular recognition capability, thereby being applied to the field of adsorption separation of radioactive nuclide. The method solves the problems of poor environmental adaptability, low adsorption quantity, low radionuclide selectivity, poor radionuclide desorption regeneration service performance and the like in the process of separating, adsorbing and desorbing substances of the nanofiber membrane, and has the advantages of simple synthesis procedure, mild conditions and popularization value.
The invention aims to provide an easy-desorption regeneration open-chain cucurbituril carbamido material for treating nuclear industrial wastewater, in particular to an easy-desorption cyclic regeneration nanofiber membrane based on open-chain cucurbituril with molecular recognition capability, which can desorb radionuclide through simple treatment so as to be regenerated and recycled.
The second purpose of the invention is to provide a preparation method of the nanofiber membrane.
The invention relates to an easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater, which is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril;
the structural formula of the hydroxyl-substituted open chain cucurbituril is shown in the specification
The ureido repeat unit is 3, as determined by the size selectivity. The open chain cucurbituril with the pollutant molecular structure size and the cavity structure more matched has stronger binding capacity, so that the nanofiber membrane modified by the more matched open chain cucurbituril has higher adsorption efficiency on corresponding pollutants, and when the ureido repeating unit in the hydroxyl-substituted open chain cucurbituril is 3, the matching performance is best, so that the open chain cucurbituril is more suitable, and the adsorption efficiency and the adsorption quantity are low due to too many or too few repeating units.
In the aspect of material structure performance, the chemical modifiability of the hydroxyl-substituted open-chain cucurbituril enables researchers to easily perform functionalization on the hydroxyl-substituted open-chain cucurbituril according to different application conditions, the application field of the nanofiber membrane is wider by changing the hydrophilic and hydrophobic properties of the hydroxyl-substituted open-chain cucurbituril, and the problem caused when a chemical modification method is used for modifying the nanofiber membrane is avoided; the rigid structure of the open chain cucurbituril can also increase the mechanical property of the nanofiber membrane;
in the aspect of material adsorption of radioactive nuclide, the C-type open chain cucurbituril is added with structural adaptability on the basis of not losing the original carbamido rigid skeleton, so that the introduction of the open chain cucurbituril can greatly enhance the adsorption and separation effects of the nanofiber membrane on different chemical environments and chemical substances of different types and sizes. The cavity structure which can change according to the chemical environment can realize the adsorption of the nanofiber membrane on various types of radioactive nuclides and improve the adsorption quantity, so the application range of the nanofiber membrane is wider.
In the aspect of desorption and regeneration of materials, the nanofiber membrane based on the open chain cucurbituril is desorbed because the open chain cucurbituril is easily changed from a C-shape to an S-shape under a certain condition, so that the desorption condition in the process is mild, the energy consumption is low, and the influence on the reusability of the membrane material is small.
Compared with the previous research work, the combination of the supermolecule chemistry and the nanofiber membrane field is only limited to the application of the macrocyclic main body to the nanofiber membrane. Just because the nanofiber membrane based on the cucurbituril makes up the defects of the currently known nanofiber membrane, the application of the nanofiber membrane in the aspect of water treatment of pollutant adsorption is more important and urgent.
As a preferred technical scheme:
the easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater has the grafting rate of the open chain cucurbituril substituted by hydroxyl on the surface of the nanofiber membrane of 60-80%; the nanofiber membrane is a cross-linked polyvinyl alcohol-based nanofiber membrane, the average diameter of the nanofibers is 200-300 nm, the tensile strength of the nanofiber membrane is 50-80 MPa, and the elastic modulus of the nanofiber membrane is 2000-3000 MPa; the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 40-90%, and a three-dimensional network structure is formed among the polyvinyl alcohol-based nanofibers through aldol condensation chemical crosslinking caused by dialdehyde under a strong acid condition.
The easy-to-detach regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater has the maximum adsorption rate of more than 95% on radionuclides uranium, thorium, iodine and tellurium; the easy-desorption regeneration open-chain cucurbituril-based material for treating nuclear industrial wastewater can complete desorption after being washed by methanol and water after adsorbing the radionuclide, and the adsorption rate is still more than 85 percent after 5 times of adsorption-desorption cycles.
The invention also provides a preparation method of the easy-to-remove regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater, which comprises the steps of completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane into a reaction solution for reaction, taking out and washing to obtain the easy-to-remove regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater;
the preparation method of the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane comprises the following steps:
the method comprises the following steps: dissolving polyvinyl alcohol in deionized water, heating and keeping constant temperature to obtain a uniform solution;
step two: adding dialdehyde to the homogeneous solution;
step three: then carrying out electrostatic spinning to obtain electrospinning;
step four: soaking the electrospinning into a strong acid methanol solution to obtain a crosslinked polyvinyl alcohol electrospinning nanofiber membrane; the strong acid methanol solution can be greatly excessive as long as the soaking can be ensured;
the reaction liquid is an intermediate product obtained by reacting hydroxyl-substituted open chain cucurbituril with isocyanate propyltriethoxysilane in an anhydrous dimethyl sulfoxide solvent;
the structural formula of the hydroxyl-substituted open chain cucurbituril is shown in the specification
The structural formula of the intermediate product is
The mechanism of the in-situ crosslinking process of the polyvinyl alcohol and the dialdehyde is that hydroxyl of the polyvinyl alcohol and aldehyde group of the dialdehyde are subjected to aldol condensation reaction under the condition of strong acid, so that the crosslinking effect is achieved.
As a preferred technical scheme:
in the method, in the first step, the mass fraction of the polyvinyl alcohol is 8-15%, and the heating temperature is 85-95 ℃.
In the method, in the second step, dialdehyde is added and then stirred for 0.5 h; the dialdehyde is glutaraldehyde, hexanedial, heptadialdehyde or octanediol; the mass ratio of the polyvinyl alcohol to the dialdehyde is (2-5): 1.
The method comprises the following steps of: the voltage is 10-20 kV, the aluminum foil is used as a receiving screen, the receiving distance between a needle head and the aluminum foil is 15cm, and the spinning speed is 0.3-0.6 mL.h-1(i.e., using a constant flow injection pump at a rate of 0.3-0.6 mL. h-1The flow rate of (3) to deliver the polymer solution), the inside diameter of the flat-head needle is 0.7 mm; the electrospinning is prepared in an environment with the temperature of 20-30 ℃ and the relative humidity of 30-50%.
In the fourth step, the content of the strong acid in the methanol solution of the strong acid is 8-12 wt%, and the time for soaking the electrospinning fiber in the methanol solution of the strong acid is 7-11 days; the strong acid is hydrochloric acid, sulfuric acid, hydroiodic acid, or hydrobromic acid.
In the above method, the specific preparation method of the reaction solution is as follows: adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide (DMSO), stirring by magnetic force to dissolve completely, adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution for 10-15 hours at the temperature of 70-90 ℃; wherein the mol ratio of the open chain cucurbituril to the isocyanate propyltriethoxysilane is (1-1.5): 1, and the volume ratio of the DMSO to the anhydrous pyridine is (8-10): 1.
In the method, the conditions for completely immersing the crosslinked polyvinyl alcohol electrospun nanofiber membrane into the reaction solution are as follows: oscillating for 4-8 hours at the temperature of 25-35 ℃; the washing is that DMSO, methanol and water are used for washing in sequence, and nitrogen is introduced into a nitrogen blowing instrument for blowing and sweeping after washing.
The mechanism by which the radionuclide moiety is adsorbed in the present invention: the molecular recognition ability is derived from the host-guest recognition ability of the cucurbituril. The open chain cucurbituril forms a C-shaped structure, the internal cavity has hydrophobicity, and the abundant nitrogen and oxygen atoms on the ureido are easy to coordinate with metal ions due to the lone pair electrons, so that the adsorption performance can be improved. Therefore, through chemical modification, due to the effects of halogen bonds, hydrogen bonds, coordination bonds, hydrophobic effects and other factors, the open-chain cucurbituril can complex various radionuclides to form a host-guest complex (namely, a host-guest recognition effect exists between the open-chain cucurbituril and pollutants) and has environment self-adaptability capability (the size of a cavity of the open-chain cucurbituril can be matched with a guest molecule by adjusting the size of the opening of the open-chain cucurbituril). Size of radionuclide-uranium (103pm, often UO)2+And UO2 2+Ion form), thorium (148pm), iodine (220pm), tellurium (221pm), compatible with the open chain cucurbituril cavity. Thus, the existence of the open chain cucurbituril modified on the nanofiber membrane increases the adsorption amount of the radionuclide by the nanofiber membrane.
The mechanism by which the radionuclide moieties are desorbed in the present invention: at present, three methods for desorbing pollutants are mainly adopted, namely, competitive molecules are added to form a new host-guest structure (a method adopted by a macrocyclic host); secondly, the external stimulation mainly destroys the acting force of the high temperature, the illumination, the pH regulation and the like (the method adopted by the macrocyclic main body); third, the change of external conditions changes the shape of host molecules, the sizes of the host and the guest cannot be matched (the method of the invention), and the shape of a macrocyclic host (such as cucurbituril, columnar arene and the like) is difficult to change due to structural limitation, so that the method cannot be adopted. In the invention, on one hand, the open chain cucurbituril can be changed into an S-type structure from a C-type structure under the stimulation of external environment mainly including special solvent, heating and the like, so that the cavity structure of a host is changed, a host-guest complex is damaged, and adsorbed radionuclides are separated; on the other hand, iodine, tellurium and the like have good solubility in methanol, and the adsorbed radioactive non-metallic substances can be separated from the host-guest complex, so that the desorption process is completed.
Has the advantages that:
(1) the easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater has good mechanical properties such as high tensile strength and high modulus;
(2) the easy-desorption regeneration open-chain cucurbituril-based material for treating nuclear industrial wastewater has high adsorbability on radionuclides uranium, thorium, iodine and tellurium, and is easy to desorb, regenerate and recycle;
(3) the preparation method of the easy-to-detach regenerated open-chain cucurbit uril material for treating nuclear industrial wastewater avoids the problem that a ureido structure is difficult to dissolve, and modifies the ureido structure to the surface of a nanofiber membrane by using a grafting modification method; and dialdehyde and polyvinyl alcohol are subjected to chemical crosslinking under the condition of strong acid, so that the crosslinking degree of nanofiber electrospinning is enhanced, and the mechanical property and the stability of the material in water are improved.
Drawings
FIG. 1 is a schematic diagram of a process for grafting and modifying hydroxyl-substituted open chain cucurbituril on the surface of a polyvinyl alcohol nanofiber membrane (PVANF); wherein,
the expression open chain cucurbiturils,
denotes a nanofiber membrane (PVANF).
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The structural formula of the hydroxyl-substituted open chain cucurbituril adopted in the embodiment of the invention is as follows:
the reaction liquid prepared in the embodiment is an intermediate product obtained by the reaction of hydroxyl-substituted open chain cucurbituril and isocyanate propyltriethoxysilane in an anhydrous dimethyl sulfoxide solvent, and the structural formula of the reaction liquid is
Fig. 1 is a schematic diagram of a process of grafting and modifying hydroxyl-substituted open-chain cucurbituril onto a surface of a polyvinyl alcohol nanofiber membrane (PVANF), specifically: reacting hydroxyl-substituted open chain cucurbituril with isocyanate propyltriethoxysilane in DMSO (dimethylsulfoxide), and reacting the obtained product with a polyvinyl alcohol nanofiber membrane (PVANF) in DMSO to obtain the nanofiber membrane with the surface grafted with the hydroxyl-substituted open chain cucurbituril.
Example 1
A preparation method of an easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater specifically comprises the following steps:
(1) preparing a crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane:
(1.1) dissolving polyvinyl alcohol in deionized water, heating to 90 ℃, and mixing at constant temperature to obtain a uniform solution with the mass fraction of 10%;
(1.2) adding glutaraldehyde into the uniform solution, and stirring for 0.5h to obtain a spinning solution; wherein the mass ratio of the polyvinyl alcohol to the glutaraldehyde is 4: 1;
(1.3) Using a constant flow syringe pump, the flow rate of the spinning solution supplied was 0.5 mL. h-1The polymer solution is conveyed, the voltage is set to be 13kV, the aluminum foil is used as a receiving screen, the receiving distance between the needle head and the aluminum foil is 15cm, and the inner diameter of the flat-head needle head is 0.7 mm; electrospinning at 25 deg.C and relative humidity of 40% to obtain electrospun fiber;
(1.4) soaking the obtained electrospun fiber in a methanol solution of hydrochloric acid for 9 days to obtain a crosslinked polyvinyl alcohol electrospun nanofiber membrane; wherein the mass fraction of the hydrochloric acid in the methanol solution of the hydrochloric acid is 10 wt%;
the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 45%; wherein the average diameter of the nanofibers is 220 nm; the tensile strength of the nanofiber membrane is 55MPa, and the elastic modulus of the nanofiber membrane is 2200 MPa;
(2) preparation of reaction solution:
adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide, stirring by magnetic force to fully dissolve, then adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution at 80 ℃ for 12 hours to obtain a reaction solution; wherein, the molar ratio of the hydroxyl-substituted open chain cucurbituril to the isocyanate propyltriethoxysilane is 1.1:1, and the volume ratio of the anhydrous dimethyl sulfoxide to the anhydrous pyridine is 10: 1;
(3) completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane prepared in the step (1) into the reaction liquid prepared in the step (2) to vibrate for 6 hours at the temperature of 30 ℃ for reaction, taking out and washing with anhydrous dimethyl sulfoxide, methanol and water in sequence, and blowing and sweeping with nitrogen by using a nitrogen blower after washing to obtain the easily-desorbed regenerated open-chain cucurbituril urea-based material for treating nuclear industrial wastewater; wherein the mass ratio of the polyvinyl alcohol electrostatic spinning nanofiber membrane to the hydroxyl-substituted open-chain cucurbituril is 34:1 during reaction;
the prepared easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril, and the grafting rate of the hydroxyl substituted open chain cucurbituril is 63%.
The application of the open chain cucurbituril-based polyvinyl alcohol nanofiber membrane in treating nuclear industrial wastewater comprises the following steps:
uranium and iodine are respectively selected as model molecules, and the adsorption effect of the open chain cucurbituril-based polyvinyl alcohol nanofiber membrane on the uranium and the iodine is detected.
Uranium adsorption experiment:
uranium stock solution: accurately weigh 0.211g UO2(NO3)2·6H2And O, diluting the solution with a few drops of diluted HCl in a 100mL volumetric flask to a constant volume, adjusting the pH value to about 3.0, and preparing a 1000mg/L shaft stock solution for later use. Diluting 10mL of the uranium stock solution with 90mL of diluted HCl, placing the diluted solution in a 100mL volumetric flask, adjusting the pH value to about 3.0, and preparing 100mg/L of shaft stock solution for later use. The 10mg nanofiber membrane was added to a 10mL polypropylene tube, followed by the uranium stock solution to form the target mixture, and finally pure water was added to make the total volume 6 mL. All test tubes were shaken at 25 ℃ for 24h and centrifuged at 10000rpm for 30min to separate the solid from the liquid. The supernatant was taken and measured with an ultraviolet-visible spectrophotometer at a wavelength of 652 nm.
Iodine adsorption experiment:
and (3) placing the 10mg nanofiber membrane in a cyclohexane solution with the concentration of 3mg/mL iodine, and testing the concentration of the iodine solution at different times by using an ultraviolet-visible spectrophotometer to calculate and obtain the mass fraction of the adsorbed iodine.
The result shows that the open chain cucurbituril-based polyvinyl alcohol nanofiber membrane has obvious adsorption effect on uranium and iodine, and the maximum adsorption capacity is 95%.
Desorption reproducibility test:
uranium desorption experiment:
the nano-fiber membrane adsorbent adsorbed with uranium is dried to be complete in vacuum at 40 ℃. Methanol solution is used as a desorbent and added into a 10mL centrifugal test tube, and deionized water is used for fixing the volume to 5 mL. Oscillating for 24h in a constant temperature water bath oscillator, centrifuging for 30min, taking supernatant, and measuring absorbance at 652nm by using an ultraviolet-visible spectrophotometer.
Iodine desorption experiment:
and (3) taking a methanol solution as a desorbent, washing the nanofiber membrane adsorbent after absorbing iodine, measuring the mass of the nanofiber membrane adsorbent after vacuum drying at 40 ℃, and calculating the mass fraction of residual iodine.
The result shows that the open-chain cucurbituril-based polyvinyl alcohol nanofiber membrane can recover the adsorption capacity again after being simply cleaned by methanol, the adsorption capacity is not obviously reduced after repeated use for many times, and the adsorption rate is still 87% after 5 times of adsorption-desorption cycles.
Example 2
A preparation method of an easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater specifically comprises the following steps:
(1) preparing a crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane:
(1.1) dissolving polyvinyl alcohol in deionized water, heating to 87 ℃, and mixing at constant temperature to obtain a uniform solution with the mass fraction of 10%;
(1.2) adding adipaldehyde into the uniform solution, and stirring for 0.5h to obtain a spinning solution; wherein the mass ratio of the polyvinyl alcohol to the hexanedial is 3: 1;
(1.3) Using a constant flow syringe pump, the flow rate of the spinning solution supplied was 0.4 mL. h-1The polymer solution is conveyed, the voltage is set to be 13kV, the aluminum foil is used as a receiving screen, the receiving distance between the needle head and the aluminum foil is 15cm, and the inner diameter of the flat-head needle head is 0.7 mm; electrospinning at 22 deg.C and relative humidity of 34% to obtain electrospun fiber;
(1.4) soaking the obtained electrospun fiber in a methanol solution of sulfuric acid for 7 days to obtain a crosslinked polyvinyl alcohol electrospun nanofiber membrane; wherein the mass fraction of the sulfuric acid in the methanol solution of the sulfuric acid is 8 wt%;
the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 40%; wherein the average diameter of the nanofibers is 200 nm; the tensile strength of the nanofiber membrane is 50MPa, and the elastic modulus of the nanofiber membrane is 2000 MPa;
(2) preparation of reaction solution:
adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide, stirring by magnetic force to fully dissolve, then adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution for 15 hours at 70 ℃ to obtain a reaction solution; wherein, the molar ratio of the hydroxyl-substituted open chain cucurbituril to the isocyanate propyltriethoxysilane is 1:1, and the volume ratio of the anhydrous dimethyl sulfoxide to the anhydrous pyridine is 8: 1;
(3) completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane prepared in the step (1) into the reaction liquid prepared in the step (2) to vibrate for 8 hours at the temperature of 23 ℃ for reaction, taking out and washing with anhydrous dimethyl sulfoxide, methanol and water in sequence, and blowing and sweeping with nitrogen by using a nitrogen blower after washing to obtain the easily-desorbed regenerated open-chain cucurbituril urea-based material for treating nuclear industrial wastewater; wherein the mass ratio of the polyvinyl alcohol electrostatic spinning nanofiber membrane to the hydroxyl-substituted open-chain cucurbituril is 38: 1.
The prepared easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril, and the grafting rate of the hydroxyl substituted open chain cucurbituril is 60%;
the easy-desorption regeneration open chain cucurbit urea-based material for treating the nuclear industrial wastewater is applied to the adsorption and desorption of uranium, and the result is as follows: the maximum adsorption rate of the easily-desorbed and regenerated open-chain cucurbituril-based material for treating the nuclear industrial wastewater to uranium reaches 95 percent; the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater can complete desorption after absorbing uranium through methanol and water washing, and the adsorption rate is still 85% after 5 times of adsorption-desorption cycles.
Example 3
A preparation method of an easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater specifically comprises the following steps:
(1) preparing a crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane:
(1.1) dissolving polyvinyl alcohol in deionized water, heating to 90 ℃, and mixing at constant temperature to obtain a uniform solution with the mass fraction of 12%;
(1.2) adding heptanediol into the uniform solution, and stirring for 0.5h to obtain a spinning solution; wherein the mass ratio of the polyvinyl alcohol to the heptanediol is 4: 1;
(1.3) Using a constant flow syringe pump, the flow rate of the spinning solution supplied was 0.5 mL. h-1The polymer solution is conveyed, the voltage is set to be 16kV, the aluminum foil is used as a receiving screen, the receiving distance between the needle head and the aluminum foil is 15cm, and the inner diameter of the flat-head needle head is 0.7 mm; electrospinning at 25 deg.C and relative humidity of 40% to obtain electrospun fiber;
(1.4) soaking the obtained electrospun fiber in a methanol solution of hydroiodic acid for 9 days to obtain a crosslinked polyvinyl alcohol electrospun nanofiber membrane; wherein the mass fraction of the hydroiodic acid in the methanol solution of the hydroiodic acid is 9 wt%;
the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 50%; wherein the average diameter of the nanofibers is 240 nm; the tensile strength of the nanofiber membrane is 58MPa, and the elastic modulus of the nanofiber membrane is 2400 MPa;
(2) preparation of reaction solution:
adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide, stirring by magnetic force to fully dissolve, then adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution for 13 hours at 80 ℃ to obtain a reaction solution; wherein, the molar ratio of the hydroxyl-substituted open chain cucurbituril to the isocyanate propyltriethoxysilane is 1.5:1, and the volume ratio of the anhydrous dimethyl sulfoxide to the anhydrous pyridine is 8: 1;
(3) completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane prepared in the step (1) into the reaction liquid prepared in the step (2) to vibrate for 7 hours at the temperature of 25 ℃ for reaction, taking out and washing with anhydrous dimethyl sulfoxide, methanol and water in sequence, and blowing and sweeping with nitrogen by using a nitrogen blower after washing to obtain the easily-desorbed regenerated open-chain cucurbituril urea-based material for treating nuclear industrial wastewater; wherein the mass ratio of the polyvinyl alcohol electrostatic spinning nanofiber membrane to the hydroxyl-substituted open-chain cucurbituril is 30:1 during reaction.
The prepared easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril, and the grafting rate of the hydroxyl substituted open chain cucurbituril is 66%;
the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater is applied to adsorption and desorption of thorium, and the result is as follows: the maximum adsorption rate of the easy-to-remove regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater to thorium reaches 96 percent; the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater can complete desorption after absorbing thorium through methanol and water washing, and the adsorption rate is still 88% after 5 times of adsorption-desorption cycles.
Example 4
A preparation method of an easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater specifically comprises the following steps:
(1) preparing a crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane:
(1.1) dissolving polyvinyl alcohol in deionized water, heating to 92 ℃, and mixing at constant temperature to obtain a uniform solution with the mass fraction of 15%;
(1.2) adding octanediol into the uniform solution, and stirring for 0.5h to obtain a spinning solution; wherein the mass ratio of the polyvinyl alcohol to the octanediol is 5: 1;
(1.3) Using a constant flow syringe pump, the flow rate of the spinning solution supplied was 0.6 mL. h-1The polymer solution is conveyed, the voltage is set to be 20kV, the aluminum foil is used as a receiving screen, the receiving distance between the needle head and the aluminum foil is 15cm, and the inner diameter of the flat-head needle head is 0.7 mm; electrospinning at 30 deg.C and relative humidity of 50% to obtain electrospun fiber;
(1.4) soaking the obtained electrospun fiber in a methanol solution of hydrobromic acid for 8 days to obtain a crosslinked polyvinyl alcohol electrospun nanofiber membrane; wherein the mass fraction of the hydrobromic acid in the methanol solution of the hydrobromic acid is 10 wt%;
the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 65%; wherein the average diameter of the nanofibers is 260 nm; the tensile strength of the nanofiber membrane is 66MPa, and the elastic modulus of the nanofiber membrane is 2600 MPa;
(2) preparation of reaction solution:
adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide, stirring by magnetic force to fully dissolve, then adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution for 14 hours at 76 ℃ to obtain reaction solution; wherein, the molar ratio of the hydroxyl-substituted open chain cucurbituril to the isocyanate propyltriethoxysilane is 1.4:1, and the volume ratio of the anhydrous dimethyl sulfoxide to the anhydrous pyridine is 9: 1;
(3) completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane prepared in the step (1) into the reaction liquid prepared in the step (2) to vibrate for 6 hours at the temperature of 28 ℃ for reaction, taking out and washing with anhydrous dimethyl sulfoxide, methanol and water in sequence, and blowing and sweeping with nitrogen by using a nitrogen blower after washing to obtain the easily-desorbed regenerated open-chain cucurbituril urea-based material for treating nuclear industrial wastewater; wherein the mass ratio of the polyvinyl alcohol electrostatic spinning nanofiber membrane to the hydroxyl-substituted open-chain cucurbituril is 26:1 during reaction;
the prepared easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril, and the grafting rate of the hydroxyl substituted open chain cucurbituril is 69%.
The easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater is applied to the adsorption and desorption of iodine, and the result is as follows: the maximum adsorption rate of the easily-desorbed and regenerated open-chain cucurbituril-based material for treating the nuclear industrial wastewater to tellurium reaches 97 percent; the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater can complete desorption after absorbing tellurium through methanol and water washing, and the adsorption rate is still 89% after 5 times of adsorption-desorption cycles.
Example 5
A preparation method of an easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater specifically comprises the following steps:
(1) preparing a crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane:
(1.1) dissolving polyvinyl alcohol in deionized water, heating to 95 ℃, and mixing at constant temperature to obtain a uniform solution with the mass fraction of 14%;
(1.2) adding glutaraldehyde into the uniform solution, and stirring for 0.5h to obtain a spinning solution; wherein the mass ratio of the polyvinyl alcohol to the glutaraldehyde is 2: 1;
(1.3) Using a constant flow syringe pump, the flow rate of the spinning solution supplied was 0.3 mL. h-1The polymer solution is conveyed, the voltage is set to be 10kV, the aluminum foil is used as a receiving screen, the receiving distance between the needle head and the aluminum foil is 15cm, and the inner diameter of the flat-head needle head is 0.7 mm; electrospinning at 28 deg.C and relative humidity of 46% to obtain electrospun fiber;
(1.4) soaking the obtained electrospun fiber in a methanol solution of hydrochloric acid for 10 days to obtain a crosslinked polyvinyl alcohol electrospun nanofiber membrane; wherein the mass fraction of the hydrochloric acid in the methanol solution of the hydrochloric acid is 11 wt%;
the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 80%; wherein the average diameter of the nanofibers is 290 nm; the tensile strength of the nanofiber membrane is 75MPa, and the elastic modulus is 2900 MPa;
(2) preparation of reaction solution:
adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide, stirring by magnetic force to fully dissolve, then adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution at 84 ℃ for 12 hours to obtain a reaction solution; wherein, the molar ratio of the hydroxyl-substituted open chain cucurbituril to the isocyanate propyltriethoxysilane is 1.3:1, and the volume ratio of the anhydrous dimethyl sulfoxide to the anhydrous pyridine is 9: 1.
(3) Completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane prepared in the step (1) into the reaction liquid prepared in the step (2) to vibrate for 5 hours at 32 ℃ for reaction, taking out and washing with anhydrous dimethyl sulfoxide, methanol and water in sequence, and blowing and sweeping with nitrogen by using a nitrogen blower after washing to obtain the easily-desorbed regenerated open-chain cucurbituril material for treating nuclear industrial wastewater; wherein the mass ratio of the polyvinyl alcohol electrostatic spinning nanofiber membrane to the hydroxyl-substituted open-chain cucurbituril is 22:1 during reaction;
the prepared easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril, and the grafting rate of the hydroxyl substituted open chain cucurbituril is 77%;
the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater is applied to the adsorption and desorption of tellurium, and the result is as follows: the maximum adsorption rate of the easily-desorbed and regenerated open-chain cucurbituril-based material for treating the nuclear industrial wastewater to tellurium reaches 97 percent; the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater can complete desorption after absorbing tellurium through methanol and water washing, and the adsorption rate is still 91% after 5 times of adsorption-desorption cycles.
Example 6
A preparation method of an easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater specifically comprises the following steps:
(1) preparing a crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane:
(1.1) dissolving polyvinyl alcohol in deionized water, heating to 94 ℃, and mixing at constant temperature to obtain a uniform solution with the mass fraction of 13%;
(1.2) adding adipaldehyde into the uniform solution, and stirring for 0.5h to obtain a spinning solution; wherein the mass ratio of the polyvinyl alcohol to the hexanedial is 3: 1;
(1.3) Using a constant flow syringe pump, the flow rate of the spinning solution supplied was 0.4 mL. h-1The polymer solution is conveyed, the voltage is set to be 15kV, the aluminum foil is used as a receiving screen, the receiving distance between the needle head and the aluminum foil is 15cm, and the inner diameter of the flat-head needle head is 0.7 mm; electrospinning at 24 deg.C and relative humidity of 38% to obtain electrospun fiber;
(1.4) soaking the obtained electrospun fiber in a methanol solution of sulfuric acid for 11 days to obtain a crosslinked polyvinyl alcohol electrospun nanofiber membrane; wherein the mass fraction of the sulfuric acid in the methanol solution of the sulfuric acid is 12 wt%;
the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 90%; wherein the average diameter of the nanofibers is 300 nm; the tensile strength of the nanofiber membrane is 80MPa, and the elastic modulus is 3000 MPa;
(2) preparation of reaction solution:
adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide, stirring by magnetic force to fully dissolve, then adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution for 10 hours at 90 ℃ to obtain reaction solution; wherein, the molar ratio of the hydroxyl-substituted open chain cucurbituril to the isocyanate propyltriethoxysilane is 1.2:1, and the volume ratio of the anhydrous dimethyl sulfoxide to the anhydrous pyridine is 10: 1;
(3) completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane prepared in the step (1) into the reaction liquid prepared in the step (2), oscillating for 4.5 hours at 34 ℃ for reaction, taking out and washing with anhydrous dimethyl sulfoxide, methanol and water in sequence, and blowing with nitrogen by using a nitrogen blowing instrument after washing to obtain the easily-desorbed regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater; wherein the mass ratio of the polyvinyl alcohol electrostatic spinning nanofiber membrane to the hydroxyl-substituted open-chain cucurbituril is 14: 1.
The prepared easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril, and the grafting rate of the hydroxyl substituted open chain cucurbituril is 80%;
the easy-desorption regeneration open chain cucurbit urea-based material for treating the nuclear industrial wastewater is applied to the adsorption and desorption of uranium, and the result is as follows: the maximum adsorption rate of the easily-desorbed and regenerated open-chain cucurbituril-based material for treating the nuclear industrial wastewater to uranium reaches 98 percent; the easy-desorption regeneration open chain cucurbituril-based material for treating the nuclear industrial wastewater can complete desorption after absorbing uranium through methanol and water washing, and the adsorption rate is still 94% after 5 times of adsorption-desorption cycles.
Example 7
A preparation method of an easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater specifically comprises the following steps:
(1) preparing a crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane:
(1.1) dissolving polyvinyl alcohol in deionized water, heating to 89 ℃, and mixing at constant temperature to obtain a uniform solution with the mass fraction of 9%;
(1.2) adding heptanediol into the uniform solution, and stirring for 0.5h to obtain a spinning solution; wherein the mass ratio of the polyvinyl alcohol to the heptanediol is 4: 1;
(1.3) Using a constant flow syringe pump, the flow rate of the feed of the spinning solution was 0.5mL·h-1The polymer solution is conveyed, the voltage is set to be 18kV, the aluminum foil is used as a receiving screen, the receiving distance between the needle head and the aluminum foil is 15cm, and the inner diameter of the flat-head needle head is 0.7 mm; electrospinning at 27 deg.C and relative humidity of 43% to obtain electrospun fiber;
(1.4) soaking the obtained electrospun fiber in a methanol solution of hydroiodic acid for 10 days to obtain a crosslinked polyvinyl alcohol electrospun nanofiber membrane; wherein the mass fraction of the hydroiodic acid in the methanol solution of the hydroiodic acid is 9 wt%;
the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 75%; wherein the average diameter of the nanofibers is 280 nm; the tensile strength of the nanofiber membrane is 70MPa, and the elastic modulus is 2800 MPa;
(2) preparation of reaction solution:
adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide, stirring by magnetic force to fully dissolve, then adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution for 11 hours at 88 ℃ to obtain a reaction solution; wherein, the molar ratio of the hydroxyl-substituted open chain cucurbituril to the isocyanate propyltriethoxysilane is 1.1:1, and the volume ratio of the anhydrous dimethyl sulfoxide to the anhydrous pyridine is 10: 1;
(3) completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane prepared in the step (1) into the reaction liquid prepared in the step (2) to vibrate for 4 hours at 35 ℃ for reaction, taking out and washing with anhydrous dimethyl sulfoxide, methanol and water in sequence, and blowing and sweeping with nitrogen by using a nitrogen blower after washing to obtain the easily-desorbed regenerated open-chain cucurbituril material for treating nuclear industrial wastewater; wherein the mass ratio of the polyvinyl alcohol electrostatic spinning nanofiber membrane to the hydroxyl-substituted open-chain cucurbituril is 18: 1.
The prepared easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril, and the grafting rate of the hydroxyl substituted open chain cucurbituril is 75 percent;
the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater is applied to adsorption and desorption of thorium, and the result is as follows: the maximum adsorption rate of the easy-to-remove regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater to thorium reaches 97 percent; the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater can complete desorption after absorbing thorium through methanol and water washing, and the adsorption rate is still 92% after 5 times of adsorption-desorption cycles.
Claims (10)
1. The easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater is characterized in that: is a nanofiber membrane with the surface grafted with hydroxyl substituted open chain cucurbituril;
the structural formula of the hydroxyl-substituted open chain cucurbituril is shown in the specification
2. The easy-to-detach regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater according to claim 1, wherein the grafting ratio of the hydroxyl-substituted open chain cucurbituril on the surface of the nanofiber membrane is 60-80%; the nanofiber membrane is a cross-linked polyvinyl alcohol-based nanofiber membrane, the average diameter of the nanofibers is 200-300 nm, the tensile strength of the nanofiber membrane is 50-80 MPa, and the elastic modulus of the nanofiber membrane is 2000-3000 MPa; the crosslinking degree of the crosslinked polyvinyl alcohol-based nanofiber membrane is 40-90%.
3. The easy-to-desorb regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater according to claim 1, wherein the maximum adsorption rate of the easy-to-desorb regenerated open chain cucurbituril-based material for treating nuclear industrial wastewater to radionuclide is more than 95%; the easy-desorption regeneration open chain cucurbituril-based material for treating nuclear industrial wastewater can complete desorption after being washed by methanol and water after adsorbing the radionuclide, and the adsorption rate is still more than 85 percent after 5 adsorption-desorption cycles; the radioactive nuclides are uranium, thorium, iodine and tellurium.
4. A preparation method of an easily-desorbed and regenerated open-chain cucurbituril-based material for treating nuclear industrial wastewater is characterized by comprising the following steps: completely immersing the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane into the reaction solution for reaction, taking out and washing to obtain the easily-desorbed regenerated open-chain cucurbituril-based material for treating the nuclear industrial wastewater;
the preparation method of the crosslinked polyvinyl alcohol electrostatic spinning nanofiber membrane comprises the following steps:
the method comprises the following steps: dissolving polyvinyl alcohol in deionized water, heating and keeping constant temperature to obtain a uniform solution;
step two: adding dialdehyde to the homogeneous solution;
step three: then carrying out electrostatic spinning to obtain electrospinning;
step four: soaking the electrospinning into a strong acid methanol solution to obtain a crosslinked polyvinyl alcohol electrospinning nanofiber membrane;
the reaction liquid is an intermediate product obtained by reacting hydroxyl-substituted open chain cucurbituril with isocyanate propyltriethoxysilane in an anhydrous dimethyl sulfoxide solvent;
the structural formula of the hydroxyl-substituted open chain cucurbituril is shown in the specification
The structural formula of the intermediate product is
5. The method according to claim 4, wherein in the first step, the mass fraction of the polyvinyl alcohol is 8-15%, and the heating temperature is 85-95 ℃.
6. The method according to claim 4, wherein in step two, the dialdehyde is added and then stirred for 0.5 h; the dialdehyde is glutaraldehyde, hexanedial, heptadialdehyde or octanediol; the mass ratio of the polyvinyl alcohol to the dialdehyde is (2-5): 1.
7. The method according to claim 4, wherein in the third step, the spinning process of the electrostatic spinning is as follows: the voltage is 10-20 kV, the aluminum foil is used as a receiving screen, the receiving distance between the needle head and the aluminum foil is 15cm, and the spinning speed is 0.3-0.6 mL.h-1The inner diameter of the flat-head needle is 0.7 mm; the electrospinning is prepared in an environment with the temperature of 20-30 ℃ and the relative humidity of 30-50%.
8. The method of claim 4, wherein in the fourth step, the content of the strong acid in the methanol solution of the strong acid is 8 to 12 wt%, and the time for immersing the electrospinning filament in the methanol solution of the strong acid is 7 to 11 days; the strong acid is hydrochloric acid, sulfuric acid, hydroiodic acid, or hydrobromic acid.
9. The method according to claim 4, wherein the reaction solution is prepared by a specific method comprising: adding hydroxyl-substituted open chain cucurbituril into anhydrous dimethyl sulfoxide, stirring by magnetic force to fully dissolve, then adding anhydrous pyridine, and introducing nitrogen for protection; then adding isocyanate propyl triethoxysilane, and reacting the obtained mixed solution for 10-15 hours at the temperature of 70-90 ℃; wherein the molar ratio of the hydroxyl-substituted open chain cucurbituril to the isocyanate propyltriethoxysilane is (1-1.5): 1, and the volume ratio of the anhydrous dimethyl sulfoxide to the anhydrous pyridine is (8-10): 1.
10. The method according to claim 4, wherein the conditions for completely immersing the crosslinked polyvinyl alcohol electrospun nanofiber membrane in the reaction solution are as follows: oscillating for 4-8 hours at the temperature of 25-35 ℃; the washing is that anhydrous dimethyl sulfoxide, methanol and water are used for washing in sequence, and a nitrogen blowing instrument is used for introducing nitrogen for blowing and sweeping after washing.
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