CN115786703B - Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid - Google Patents
Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid Download PDFInfo
- Publication number
- CN115786703B CN115786703B CN202211627574.2A CN202211627574A CN115786703B CN 115786703 B CN115786703 B CN 115786703B CN 202211627574 A CN202211627574 A CN 202211627574A CN 115786703 B CN115786703 B CN 115786703B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- ionic liquid
- porous material
- solution
- inorganic porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 106
- 239000011148 porous material Substances 0.000 title claims abstract description 87
- 150000002500 ions Chemical class 0.000 title claims abstract description 57
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 37
- 239000011707 mineral Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000000605 extraction Methods 0.000 claims abstract description 92
- 239000003960 organic solvent Substances 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims description 137
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 137
- -1 N-hexylpyridine ion Chemical class 0.000 claims description 136
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 87
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 68
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 51
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229940049964 oleate Drugs 0.000 claims description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 11
- 239000004005 microsphere Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- KTUWFYALZIAAGE-UHFFFAOYSA-N 1-methyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C=C1 KTUWFYALZIAAGE-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 229940068492 thiosalicylate Drugs 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000007790 solid phase Substances 0.000 claims 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 161
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 238000001035 drying Methods 0.000 description 27
- 238000011068 loading method Methods 0.000 description 25
- 229910052737 gold Inorganic materials 0.000 description 24
- 239000010931 gold Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- 238000001291 vacuum drying Methods 0.000 description 21
- MKAZOCQEUWHHEE-UHFFFAOYSA-N 14,14-dibutyloctadecylphosphanium;chloride Chemical compound [Cl-].CCCCC(CCCC)(CCCC)CCCCCCCCCCCCC[PH3+] MKAZOCQEUWHHEE-UHFFFAOYSA-N 0.000 description 17
- KXDPICLMJAKLDW-UHFFFAOYSA-N CCCCCCCCCCCCCCP(CCCCCC)(CCCCCC)CCCCCC.Cl Chemical compound CCCCCCCCCCCCCCP(CCCCCC)(CCCCCC)CCCCCC.Cl KXDPICLMJAKLDW-UHFFFAOYSA-N 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 17
- 238000002791 soaking Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- 229910052763 palladium Inorganic materials 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 230000007420 reactivation Effects 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 229910052761 rare earth metal Inorganic materials 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000003517 fume Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- WFIYFFUAOQKJJS-UHFFFAOYSA-N tetraoctylphosphanium Chemical compound CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC WFIYFFUAOQKJJS-UHFFFAOYSA-N 0.000 description 10
- 238000002386 leaching Methods 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- VZEXBFGSXLYLKX-UHFFFAOYSA-N 1-hexyl-2H-pyridine hydrochloride Chemical compound C(CCCCC)N1CC=CC=C1.Cl VZEXBFGSXLYLKX-UHFFFAOYSA-N 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- UEPYVEILIFKOAA-UHFFFAOYSA-N methyl(trioctyl)azanium;nitrate Chemical compound [O-][N+]([O-])=O.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC UEPYVEILIFKOAA-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229960001701 chloroform Drugs 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- NJOSLBYBLJVAMY-UHFFFAOYSA-M methyl(trioctyl)azanium;2-sulfanylbenzoate Chemical compound [O-]C(=O)C1=CC=CC=C1S.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC NJOSLBYBLJVAMY-UHFFFAOYSA-M 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- UNRVFVIZRXNZKT-UHFFFAOYSA-N CCCCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound CCCCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F UNRVFVIZRXNZKT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000007038 hydrochlorination reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229940103494 thiosalicylic acid Drugs 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- FROQVHAYMSVXTG-UHFFFAOYSA-N 1-hexyl-2h-pyridine Chemical compound CCCCCCN1CC=CC=C1 FROQVHAYMSVXTG-UHFFFAOYSA-N 0.000 description 1
- JEOSMYVMLZTQOH-UHFFFAOYSA-M 1-hexylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCC[N+]1=CC=CC=C1 JEOSMYVMLZTQOH-UHFFFAOYSA-M 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GSYYOWFJGPBHCK-UHFFFAOYSA-N CCCCCCCCCCCCCCP(CCCCCC)(CCCCCC)CCCCCC Chemical compound CCCCCCCCCCCCCCP(CCCCCC)(CCCCCC)CCCCCC GSYYOWFJGPBHCK-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- HBAIZOJDXAXWHS-UHFFFAOYSA-M Sodium thiosalicylate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1S HBAIZOJDXAXWHS-UHFFFAOYSA-M 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BJAOWHVROIMDMK-UHFFFAOYSA-N hexyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[PH2+]CCCCCC BJAOWHVROIMDMK-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 229960003703 sodium thiosalicylate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- XJVIPPHGDPEDJL-UHFFFAOYSA-N thiourea;hydrochloride Chemical compound Cl.NC(N)=S XJVIPPHGDPEDJL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B17/00—Obtaining cadmium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/28—Amines
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/34—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing sulfur, e.g. sulfonium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/36—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B43/00—Obtaining mercury
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
A method for extracting mineral ions using an inorganic porous material supported ionic liquid technology, comprising: 1: adding an inorganic porous material into an organic solvent; 2: adding an ionic liquid into an organic solvent; 3: mixing the obtained organic solvent containing the inorganic porous material with the organic solvent containing the ionic liquid, and removing the organic solvent; 4: adding an inorganic porous material containing ionic liquid into an aqueous solution containing extracted mineral substances for extraction; 5: separating the extracted inorganic porous material containing the extracted metal from the aqueous solution to obtain an extracted inorganic porous material containing extracted mineral ions; 6: and separating the extracted mineral ions from the extracted inorganic porous material containing the extracted mineral ions.
Description
Technical Field
The invention belongs to the technical field of mineral separation, and particularly relates to a method for extracting mineral ions by a technology of loading an ionic liquid on an inorganic porous material.
Background
In order to obtain some noble metals or rare earth ions, the current mining technology is that ore is obtained by mining, and after crushing, primary selection and fine selection, the ore is subjected to acid treatment to prepare an aqueous solution of mineral ions containing the required metal, the aqueous solution of mineral ions is extracted by using an organic solvent (grease), an organic phase is separated, and the post treatment is performed to obtain the required metal. Wherein, the steps of oil-water separation and post-treatment for separating the organic phase are complicated, and the organic solvent (grease) is easy to pollute the environment.
The ion exchange extraction method utilizes the ion exchange of anions/cations and metal ions/rare earth ions in the solution on the extractant, thereby realizing the efficient extraction of the ions, and has the advantage of realizing the rapid extraction of the ions under the condition of low-concentration metal ions/rare earth ions. The ionic liquid is used as a novel green solvent, and has a wide application prospect in the field of mineral ion extraction. But its use in the field of mineral extraction is limited due to its high viscosity.
Chinese patent [ application No. 20161081105. X "composite material with ionic liquid supported by porous material, and preparation method and application thereof" discloses that composite material with ionic liquid supported by porous material is used for gas storage or separation, such as H 2,CH4,SO3 CO2, etc. The skeleton code of the molecular sieve used in China patent application No. 201210146337.4, a microporous molecular sieve-functionalized ionic liquid composite material and a preparation method thereof, is FAU/BEA/EMT/MWW, and the field used in the method is the field of capturing and storing CO 2, removing flue gas SO 2 and other acid gas. Chinese patent [ application No. 201510552191. X ] "a porous solid material supported ionic liquid-gold catalyst and preparation and application thereof" is mainly used for preparing the catalyst in the reaction of synthesizing chloroethylene by hydrochlorination of acetylene. The porous solid supported ionic liquid prepared by China patent application No. 201710907328.5 is used for adsorbing HCl gas, and typical application occasions are HCl/C 2H2 mixed gas and HCl adsorbed in industrial tail gas of chloroethylene synthesized by hydrochlorination of acetylene, so that the HCl is enriched or separated and recovered. The method for synthesizing the ionic liquid supported porous material and the application thereof are characterized in that the ionic liquid is synthesized in situ in the porous material, (the supported ionic liquid is bifunctional ionic liquid with two functional groups of amino groups and copper groups, the porous material is respectively immersed into mixed solution of Et 3 NHCl and CuCl 2 to synthesize the ionic liquid in situ, the application field of the bifunctional ionic liquid supported porous material prepared by the method is the removal of hydrogen sulfide gas in mixed gas, the cation of the ionic liquid used in the immobilized ionic liquid and the preparation method thereof is trialkylbenzyl ammonium cation, the anion is deprotonated dialkyl diglycolamine acid, and the carrier used is polymer carrier-resin.
At present, no report on a method for extracting mineral ions by using a technology for loading an ionic liquid on an inorganic porous material is found.
Disclosure of Invention
In order to overcome the shortcomings of the prior art, the invention aims to provide a technology for loading an ionic liquid on an inorganic porous material and using the ionic liquid for extracting mineral ions. In particular, a technique for loading an ionic liquid on an inorganic porous material is used for extracting mineral ions, which comprises the following steps:
step 1: adding the inorganic porous material into an organic solvent, so that the organic solvent can completely infiltrate the pore channels of the inorganic porous material;
step 2: adding the ionic liquid into an organic solvent to enable the ionic liquid to be completely dispersed;
Step 3: mixing and stirring the organic solvent containing the inorganic porous material obtained in the step 1 and the step 2 and the organic solvent containing the ionic liquid, and removing the organic solvent to obtain an extracted inorganic porous material containing the ionic liquid;
Step 4: adding the inorganic porous material containing the ionic liquid into an aqueous solution containing extracted mineral substances for extraction;
Step 5: separating the extracted inorganic porous material containing the extracted metal from the aqueous solution to obtain an extracted inorganic porous material containing extracted mineral ions;
And 6, separating the extracted mineral ions from the extracted inorganic porous material containing the extracted mineral ions by using a conventional technology.
In the present invention, the preparation of the inorganic porous material may be selected according to a conventional technique. Preferably has a stable pore structure, can resist the corrosion of organic solvents and can be recycled for a plurality of times. For example, the porous inorganic solid carrier is selected from porous silica, porous silica microspheres, porous aluminum oxide, porous titanium dioxide, hollow glass and other oxides; one or more of KIT-6, MCM-41, SBA-15, MCM-22, TS-1, SAPO-34, SAPO-11, ZSM-5, ZSM-35, beta, ZSM-23, 3A, 4A, 13X, SBA-15, MCM-48, Y-type molecular sieves and titanium-silicon inorganic solid porous materials.
In the present invention, in steps 1 and 2, the organic solvent includes: one or more of aliphatic alcohol, acetonitrile, toluene, acetone, cyclohexane, DMF, NMP, DMSO, tetrahydrofuran, thiourea, propanethiol, methyl chloride, methylene dichloride, carbon disulfide and the like can be dispersed in the ionic liquid.
Preferably, the organic solvent in step 1 and the organic solvent in step 2 are mutually soluble and may be the same or different.
In the present invention, the choice of ionic liquid is determined by the metal ions to be extracted, and this choice can be made by conventional techniques. For example, for obtaining gold in minerals, the organic extraction solvent can be trihexyl (tetradecyl) phosphine chloride, and the preferred source is abundant and easily available, so that the method is favorable for industrial application.
Specifically, in step 2, the ionic liquid includes: imidazole, pyridine, quaternary phosphorus, pyrrolidine, morpholine, piperidine and quaternary ammonium ionic liquid. Including, without limitation, the following ionic liquids: the cation is N-hexyl pyridine ion, trihexyl (tetradecyl) phosphine ion, (tributyl) N-tetradecyl phosphine ion, tri-N-octyl methyl ammonium ion, 1-hexyl-3-methylimidazole ion, 1-butyl-3-methylimidazole ion, tetraoctyl phosphonium ion, 1-octyl-3-methylimidazole, 1-methyl-3- [ tri- (trimethylsiloxy) ] silylimidazole ion, trioctylmethyl ammonium ion, 1-hexyl-3- (3-methylthioureidopropyl) imidazole ion.
The anions of the ionic liquid are chloride ions, bromide ions, trifluoromethanesulfonyl imide, hexafluorophosphate ions, thiosalicylate ions, di (2-ethylhexyl) phosphate ions and tetrafluoroborate ions
In the present invention, the mineral ions described in step 4 include: au, pd, pt, cu, metal ions such as Fe, mn, al and the like, and one or a mixed solution of a plurality of ions such as Y, eu, ce, co, V, pb, mo, U, th and the like, including a solution of metal ions and rare earth ions in a blending way.
In the present invention, the steps 1 to 4 can be carried out by referring to conventional techniques.
Preferably, the inorganic porous material containing extracted mineral ions in step 5 is separated from the aqueous solution, and the inorganic porous material extractant containing extracted mineral ions can be directly fished out of the extraction tank by using a filter screen or the aqueous phase in the extraction tank can be removed.
The invention can realize the following technical effects:
1) The defect that oil-water separation is needed in the traditional method can be avoided, and the pollution to the environment is reduced;
2) The defect of high viscosity of the ionic liquid can be avoided, and the ionic liquid can be directly used for the extraction reaction in the liquid phase;
3) The advantage of larger specific surface area of the contact porous material can reduce the extraction time to several minutes, and greatly improves the extraction efficiency.
4) The method of the invention can also be used for treating organic pollutants, nitrogen and phosphorus and other pollutants in sewage.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
Fig. 1 is a flow chart of a method for extracting mineral ions using a technique of loading an inorganic porous material with an ionic liquid according to the present invention. In the figure:
step 1: an inorganic porous material having pores impregnated with an organic solvent;
Step 2: an ionic liquid dispersed in an organic solvent;
Step 3: mixing and removing the organic solvent;
Step 4: inorganic porous material loaded with ionic liquid;
Step 5: extracting mineral ions;
and 6, carrying out subsequent treatment.
Detailed Description
Reference will now be made in detail to the exemplary embodiments and clinical examples, the embodiments described in the following exemplary embodiments and clinical examples not being representative of all embodiments consistent with the present invention. Instead, they are merely representative examples of the method of the present invention for extracting mineral ions using an inorganic porous material loaded with an ionic liquid. The excellent technical effects of the present invention can be more emphasized by these exemplary embodiments.
The technical scheme of the invention will be described in detail below by taking industrial extraction of mineral ions as an example.
Example 1
Step 1: spherical porous alumina is selected as a carrier, the particle size is 500 meshes, the specific surface area is 200m 2/g, and the pore volume is 0.3cm 3/g. 500g of the porous alumina is added into dichloromethane solution to obtain dichloromethane-infiltrated alumina inorganic porous material.
Step 2: 250g N-hexyl pyridine chloride ion liquid is added into 10L of dichloromethane, and after stirring is carried out for 1h, dichloromethane solution containing N-hexyl pyridine chloride ion liquid is obtained.
Step 3: adding the porous aluminum oxide soaked in the dichloromethane obtained in the step 1 into the dichloromethane solution of the 10L N-hexyl pyridine chloride salt obtained in the step 2, stirring for 1h, standing for 24 h at room temperature in a fume hood, and obtaining the aluminum oxide loaded by the N-hexyl pyridine chloride salt after the dichloromethane is completely volatilized. Wherein the loading of the ionic liquid is 50%.
Step 4: 500g of the N-hexylpyridinium chloride ionic liquid-supported aluminum oxide prepared in step 3 was added to a solution of 5L of chloroauric acid, wherein the concentration of chloroauric acid ions was 1mg/ml.
Step 5: the N-hexyl pyridine chloride salt loaded aluminum oxide which completes gold ion extraction is separated from the water phase by a 1000 mesh filter screen. In the rest chloroauric acid solution, the solubility of chloroauric acid ions is 0.015mg/ml, and the extraction rate of gold ions is 98.5%.
And 6, adding the N-hexyl pyridine chloride salt loaded aluminum oxide extracted with gold ions obtained in the step 5 into 1L of solution containing thiourea, soaking, and stirring for 1h, wherein the concentration of the thiourea is 1mol/L. The above-mentioned N-hexylpyridine chloride salt-supported aluminum oxide was again separated from the solution by using a 200-mesh sieve. The concentration of gold ions in the solution is 4.8265mg/ml, the back extraction rate is 98%, and the gold ion-containing solution can be used in the next gold ion treatment process.
Step 7: after the back extraction is finished, adding the aluminum oxide loaded by the N-hexyl pyridine chloride salt separated by a filter screen into 10L of 1mol/L HCl solution, soaking for 24 hours, drying in a vacuum drying oven at room temperature for 24 hours, and repeating the extraction process for the steps 4-6 after removing water.
Example 2
Step 1: the SAPO-11 molecular sieve is selected as a carrier, the particle size is 400 meshes, the specific surface area is 400m 2/g, and the pore volume is 0.4cm 3/g. 1000g of the SAPO-11 molecular sieve is added into tetrahydrofuran solution to obtain the SAPO-11 molecular sieve with the pore channel completely infiltrated by tetrahydrofuran.
Step 2: 450g of trihexyl (tetradecyl) phosphine chloride ionic liquid is added into 90L of acetonitrile, and the mixture is stirred for 1h to be dispersed, so as to obtain an acetonitrile solution of the trihexyl (tetradecyl) phosphine chloride ionic liquid.
Step 3: pouring the SAPO-11 molecular sieve obtained in the step 1 and containing 1 g of the SAPO-11 molecular sieve completely infiltrated by the tetrahydrofuran solution into 90L of the trihexyl (tetradecyl) phosphine chloride ionic liquid obtained in the step 2, stirring for 1h, drying in a fume hood at 60 ℃ for 24 hours, and obtaining the SAPO-11 loaded by the trihexyl (tetradecyl) phosphine chloride ionic liquid after the organic solvent mixed by acetonitrile and tetrahydrofuran is completely volatilized. Wherein the loading of the ionic liquid is 45%.
Step 4: 1000g of the trihexyl (tetradecyl) phosphine chloride ionic liquid loaded SAPO-11 molecular sieve prepared in step 3 was added to a 50L solution of chloroauric acid, wherein the concentration of chloroauric acid ions was 2g/L.
Step 5: after stirring for 10 seconds, the three hexyl (tetradecyl) phosphine chloride loaded SAPO-11 molecular sieve which has completed chloroauric acid ion extraction is separated from the water phase by a 1000-mesh filter screen, and the solubility of chloroauric acid in the residual solution is 0.04g/L, and the extraction rate of gold ions is 98%.
Step 6: adding the trihexyl (tetradecyl) phosphine chloride loaded SAPO-11 molecular sieve extracted with chloroauric acid ions into 50L of solution containing thiourea, soaking, and stirring for 1h, wherein the concentration of the thiourea is 1mol/L. The above trihexyl (tetradecyl) phosphine chloride supported SAPO-11 molecular sieve was again separated from the solution using a 800 mesh screen. The concentration of gold ions in the solution is 1.86g/L, the back extraction rate is 94.9%, and the gold ion-containing solution can be used in the next treatment process.
Step 7: after the back extraction is finished, adding the trihexyl (tetradecyl) phosphine chloride loaded SAPO-11 molecular sieve separated by a filter screen into 10L of 1mol/L HCl solution, and soaking for 24 hours, thereby finishing the reactivation of the ionic liquid. Drying in a vacuum drying oven at room temperature for 24 hours, and removing water to obtain the final product for extraction in step 4-6.
Example 3
Step 1: ZSM-23 molecular sieve is selected as a carrier, the particle size is 500 meshes, the specific surface area is 200m 2/ g, and the pore volume is 0.2cm 3/g. 1000g of the ZSM-23 molecular sieve is added into ethanol solution to obtain ZSM-23 molecular sieve which is fully infiltrated by the ethanol solution.
Step 2: 370g of trihexyl (tetradecyl) phosphine chloride ion liquid is added into 7.4L of acetone solution, and the mixture is stirred for 1h for dispersion, so that the acetone solution in which the trihexyl (tetradecyl) phosphine chloride ion liquid is dispersed is obtained.
Step 3: mixing 1000g of ZSM-23 molecular sieve infiltrated by ethanol and 7.4L of 37 g of trihexyl (tetradecyl) phosphine chloride ionic liquid obtained in the step (1) with an acetone solution, stirring for 1h, drying in a fume hood at 80 ℃ for 24 hours, and obtaining the ZSM-23 molecular sieve loaded by the trihexyl (tetradecyl) phosphine chloride ionic liquid after the organic solvent mixed by ethanol and acetone is completely volatilized, wherein the loading amount of the ionic liquid is 37%.
Step 4: 1200g of the trihexyl (tetradecyl) phosphine chloride ionic liquid-supported ZSM-23 molecular sieve prepared in step 3 was added to a 50L solution of chloroauric acid, wherein the concentration of chloroauric acid ions was 2g/L.
Step 5: after stirring for 1min, separating the trihexyl (tetradecyl) phosphine chloride loaded ZSM-23 molecular sieve which has been subjected to gold ion extraction from the water phase by using a 200-mesh filter screen, wherein the solubility of chloroauric acid in the solution is 0.01g/L, and the extraction rate of gold ions is 99.5%.
Step 6: adding the trihexyl (tetradecyl) phosphine chloride loaded ZSM-23 molecular sieve extracted with gold ions into 5L of solution containing thiourea, soaking, and stirring for 1h, wherein the concentration of the thiourea is 1mol/L. The above-mentioned trihexyl (tetradecyl) phosphine chloride-supported ZSM-23 was again separated from the solution using a 200 mesh screen. The concentration of gold ions in the solution is 19.1g/L, the back extraction rate is 96%, and the gold ion-containing solution can be used in the next treatment process.
Step 7: after the back extraction is finished, the trihexyl (tetradecyl) phosphine chloride loaded ZSM-23 molecular sieve separated by a filter screen is treated according to a conventional method, for example: adding the mixture into 10L of 1mol/L HCl solution, and soaking for 24 hours to finish the reactivation of the ionic liquid. Drying in a vacuum drying oven at room temperature for 24 hours, and removing water to obtain the final product for extraction in step 4-6.
Example 4
Step 1: the spherical Beta molecular sieve is selected as a carrier, the particle size is 400 meshes, the specific surface area is 300m 2/g, and the pore volume is 0.3cm 3/g. 500g of the Beta molecular sieve described above was added to a heptane solution to give a Beta molecular sieve fully wetted by heptane.
Step 2: 250g of (tributyl) n-tetradecylphosphine chloride was added to 2L of heptane and stirred for 1 hour to obtain a heptane solution of (tributyl) n-tetradecylphosphine chloride ionic liquid dispersion.
Step 3: pouring the heptane solution containing 500g of Beta molecular sieve in the step 1 into 2L of the heptane solution containing 250g of (tributyl) n-tetradecylphosphine chloride in the step 2, stirring for 1h, drying at room temperature for 24 h, and obtaining the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid after the heptane is completely volatilized, wherein the loading of the ionic liquid is 50%.
Step 4: 220g of Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid prepared in the step 3 is added into 100L of concentrated leaching solution of the waste circuit board, wherein the concentration of gold is 0.5g/L, the concentration of palladium is 0.3g/L, and the concentration of platinum is 0.08g/L.
Step5: after stirring for 10min, the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride and subjected to gold ion extraction is separated from the water phase by a 500-mesh filter screen, so that the Beta molecular sieve containing gold is obtained. In the rest mixed solution, the solubility of gold in the solution is 0.0125g/L, the extraction rate of gold ions is 97.5%, the concentration of palladium is 0.2919g/L, the extraction rate is 2.7%, the concentration of platinum is 0.079g/L, and the extraction rate is 1.25%.
Step 6: 130.8g of the Beta molecular sieve supported by the (tributyl) n-tetradecylphosphine chloride ionic liquid prepared in step 3 was added to the mixed solution remaining in step 5.
Step 7: after stirring for 10min, the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride and subjected to palladium ion extraction is separated from the water phase by a 200-mesh filter screen, so that the Beta molecular sieve containing palladium is obtained. The concentration of palladium in the residual solution was 5X 10 -4 g/L, the extraction rate was 99.83%, the concentration of platinum was 0.0782g/L, and the extraction rate was 1%.
Step 8: 267.7g of the (tributyl) n-tetradecylphosphine chloride ionic liquid-supported Beta molecular sieve prepared in step 3 was added to the mixed solution remaining in step 7.
Step 9: after stirring for 10min, the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid which has been subjected to platinum ion extraction is separated from the water phase by a 500-mesh filter screen, so that the Beta molecular sieve containing platinum is obtained. The concentration of platinum in the residual solution was 0.0013g/L, and the extraction rate was 98.3%.
Step 10: and (3) adding the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid extracted with gold ions obtained in the step (5) into 10L of solution containing thiourea, soaking, and stirring for 1h, wherein the concentration of the thiourea is 1mol/L. And separating the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid from the solution by using a 200-mesh filter screen. The concentration of gold ions in the solution is 4.70g/L, the back extraction rate is 96.4%, and the thiourea solution containing gold ions can be used in the next treatment process.
Step 11: and (3) adding the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid with palladium ions extracted in the step 7 into 10L of solution containing thiourea, soaking, and stirring for 1h, wherein the concentration of the thiourea is 1mol/L. And separating the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid from the solution by using a 200-mesh filter screen. The concentration of palladium ions in the solution is 2.65g/L, the back extraction rate is 91%, and the solution containing the thiourea of the palladium ions can be used in the next treatment process
Step 12: and (3) adding the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid with the platinum ions extracted in the step 9 into 10L of solution containing thiourea, soaking, and stirring for 1h, wherein the concentration of the thiourea is 1mol/L. The Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride ionic liquid is separated from the solution by a 200-mesh filter screen. The concentration of platinum ions in the solution is 0.68g/L, the back extraction rate is 88.75%, and the solution containing platinum ion thiourea can be used in the next treatment process
Step 13: after the back extraction is finished, adding the Beta molecular sieve loaded by the (tributyl) n-tetradecylphosphine chloride separated by a filter screen into 10L of 1mol/L HCl solution, and soaking for 24 hours, thereby finishing the reactivation of the ionic liquid. Drying in a vacuum drying oven at room temperature for 24 hours, and removing water to obtain the final product.
Example 5
Step 1: ZSM-5 molecular sieve with specific surface area of 330m 2/g and particle size of 10 μm is selected. 500g of ZSM-5 molecular sieve was added to the chloroform solution to give a ZSM-5 molecular sieve fully infiltrated by chloroform.
Step 2: 1000g of tri-n-octyl methyl bis (2-ethylhexyl) ammonium phosphate is dissolved in 20L of chloroform solution and stirred to obtain the trichloromethane solution of tri-n-octyl methyl bis (2-ethylhexyl) ammonium phosphate.
Step 3: the chloroform solution containing 500g of ZSM-5 molecular sieve obtained in step 1 was added to the prepared trichloromethane solution of tri-n-octylmethyl bis (2-ethylhexyl) ammonium phosphate in step 2. After stirring for 1h, vacuum drying for 24h at room temperature, and removing the chloroform solution to obtain the tri-n-octyl methyl bis (2-ethylhexyl) ammonium phosphate loaded ZSM-5 molecular sieve extractant. Wherein the loading of the ionic liquid is 50%.
Step 4: 1000g of the tri-n-octylmethyl bis (2-ethylhexyl) ammonium phosphate-supported ZSM-5 molecular sieve extractant obtained in step 3 was added to 200L of the leachate of the old fluorescent bulb. Which contains 1888mg/LY 3+、160mg/L Eu3+、2.12mg/L La3+、2.0mg/L Ce3+ and 160.7mg/L Ca 2+.
Step 5: after stirring for 2min, the above mixed solution was filtered with a filter membrane having a pore size of 0.45 μm, and the tri-n-octylmethyl bis (2-ethylhexyl) ammonium phosphate loaded mesoporous aluminum oxide extractant, from which Y 3+ and Eu 3 + were extracted, was separated from the fluorescent bulb extract. Eu 3+、Y3+、La3+、Ce3+、Ca2+ ion concentration in the leaching solution of the fluorescent lamp is 0.032mg/L,0.19mg/L,2.0mg/L,2.0mg/L and 158mg/L respectively, so that the extraction rate of the tri-n-octyl methyl bis (2-ethylhexyl) ammonium phosphate loaded ZSM-5 molecular sieve extractant to Eu 3+ and Y 3+ is 99.98% and 99.99%, and the extraction rate to Ce 3+ and Ca 2+ is 0%.
Step 6: the ZSM-5 molecular sieve extractant loaded with tri-n-octyl methyl bis (2-ethylhexyl) ammonium phosphate extracted by Y 3+ and Eu 3+ in the step 5 is added into HNO 3 with the concentration of 1M in 200L, and after soaking for 1h, the concentrations of Y 3+ and Eu 3+ in the solution are 1718.1mg/L and 152mg/L, so that the stripping rate is 91% and 95%.
Step 7: and (3) soaking the ZSM-5 molecular sieve extractant loaded with the tri-n-octyl methyl bis (2-ethylhexyl) ammonium phosphate subjected to back extraction in the step (6) with 10L of bis (2-ethylhexyl) phosphoric acid with the concentration of 1M, so as to finish the reactivation of the extractant. The revived tri-n-octyl methyl bis (2-ethylhexyl) ammonium phosphate loaded ZSM-5 molecular sieve extractant can be directly used for extracting rare earth ions Y 3+ and Eu 3+ in the waste fluorescent lamp in the step 4-6.
Example 6
Step 1: selecting SBA-15 molecular sieve, its grain size is 500 meshes, specific surface area is 700cm 3/g, pore diameter is 8nm. 1000g of SBA-15 molecular sieve was added to a mixed solution of acetone and tetrahydrofuran to obtain a molecular sieve containing SBA-15 impregnated with an organic solvent mixed with tetrahydrofuran and acetone.
Step 2: after 750g of 1-hexyl-3-methylimidazole tetrafluoroborate was dissolved in 15L of tetrahydrofuran solution, the solution was stirred for half an hour to completely disperse the ionic liquid in tetrahydrofuran, thereby obtaining a tetrahydrofuran solution of 1-hexyl-3-methylimidazole tetrafluoroborate.
Step 3: the acetone and tetrahydrofuran solution obtained in step 1 containing 1000g of SBA-15 molecular sieves was used. Added to 15L of the tetrahydrofuran solution of 1-hexyl-3-methylimidazole tetrafluoroborate obtained in the step 2, and stirred for 1 hour. Standing for 24 hours in a fume hood at room temperature, and volatilizing the organic solvents tetrahydrofuran and acetone to obtain the SBA-15 molecular sieve extractant loaded with the 1-hexyl-3-methylimidazole tetrafluoroborate, wherein the loading amount of the ionic liquid is 75%.
Step 4: 1000g of the 1-hexyl-3-methylimidazolium tetrafluoroborate loaded SBA-15 molecular sieve extractant with a load of 75% obtained in step 3 was added to 500L copper mine wastewater, wherein the concentration of Cu 2+ was 2g/L.
Step 5: after stirring for 5min, the molecular sieve is separated from the solution by adopting a filtering method, and the concentration of Cu 2+ in the residual solution is 0.1228g/L. Namely, the extraction rate of copper ions was 93.86%.
Step 6: the 1-hexyl-3-methylimidazole tetrafluoroborate loaded SBA-15 molecular sieve which is obtained by filtering in the step 5 and extracts copper ions is soaked in 100L of hydrochloric acid with the concentration of 0.1mol/L, and after stirring for 30min, the concentration of copper ions in the solution is 8.88g/L, namely the back extraction rate of copper ions is 94.6%.
And 7, soaking the 1-hexyl-3-methylimidazole tetrafluoroborate loaded SBA-15 molecular sieve subjected to back extraction in the step 6 in 20L 2M sodium tetrafluoroborate solution for 12 hours, and then completing the reactivation of the 1-hexyl-3-methylimidazole tetrafluoroborate loaded SBA-15 molecular sieve extractant. And (3) drying the mixture in a vacuum drying oven for 24 hours at room temperature, and removing water, wherein the reactivated SBA-15 molecular sieve extractant loaded with the 1-hexyl-3-methylimidazolium tetrafluoroborate can be directly used for extracting Cu 2+ ions in the step 4.
Example 7
Step 1: 1200g of mesoporous titanium dioxide with the grain size of 100nm is calcined in air for 2 hours at the temperature of 300 ℃ to remove residual organic impurities of moisture in the mesoporous titanium dioxide. The specific surface area is 100m 2/g, the aperture is 3nm, and the mesoporous titanium dioxide immersed by the acetone solvent is obtained by dispersing the mesoporous titanium dioxide into 5L of acetone solution.
Step 2: 800g of 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt was dissolved in 16L of acetone, and after stirring, an acetone solution of 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt was obtained.
Step 3: the mesoporous titanium dioxide infiltrated by the acetone solvent obtained in the step 1 and the acetone solution of the-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt obtained in the step 2 are mixed and stirred for 30min, and dried in a vacuum drying oven for 24 hours under the room temperature condition, and the acetone solvent is removed. The mesoporous titanium dioxide extractant loaded by the 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt with the ionic liquid load of 66.7% can be obtained.
And 4, adding 500g of mesoporous titanium dioxide loaded by the 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt with the loading capacity of 66.7% obtained in the step 3 into 200L of rare earth factory wastewater, wherein the concentration of nitric acid is 3mol/L in a nitric acid solution with the concentration of 7mmol/L Ce 4+.
Step 5: after stirring for 7min, a filter membrane with the aperture of 0.25um is used for filtering, and the concentration of Ce 4+ in the residual filtrate is 0.35mmol/L, namely the extraction rate of the mesoporous titanium dioxide loaded by the 1-butyl-3-methylimidazole bistrifluoromethylsulfonylimine salt to Ce 4+ is 95%.
Step 6: and (3) adding the mesoporous titanium dioxide loaded by the 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt, obtained by filtering in the step (5), into 20L of 0.1mol/L oxalic acid, and stirring for 30min, wherein the concentration of cerium ions in the solution is 59.46mmol/L, namely the reextraction rate of cerium ions is 89.41%.
Step 7; and (3) soaking the mesoporous titanium dioxide loaded by the back-extracted 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt in the step (6) in 10L 2M bis (trifluoromethanesulfonyl) imide solution for 12 hours, and then completing the reactivation of the mesoporous titanium dioxide extractant loaded by the 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt. Drying for 24 hours at room temperature in a vacuum drying oven, and removing water, wherein the revived mesoporous titanium dioxide extractant loaded by the 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt can be directly used for extracting cerium ions in the fourth step.
Example 8
Step 1: 2000g of TS-1 molecular sieve was calcined in air at 300℃for 2 hours to remove residual organic impurities from the water. This was added to 12L of methylene chloride to give a molecular sieve containing TS-1 which was impregnated with methylene chloride solvent.
Step 2: 600g of tetraoctyl phosphonium oleate was dissolved in 12L of acetone, and after stirring, an acetone solution of tetraoctyl phosphonium oleate was obtained.
Step 3: the TS-1 molecular sieve soaked in the methylene chloride solvent obtained in the step 1 and the acetone containing tetraoctyl phosphonium oleate in the step 2 are mixed and stirred for half an hour. Drying in a vacuum drying oven for 24 hours, and removing the organic solvent. Thus obtaining the TS-1 molecular sieve extractant loaded by tetraoctyl phosphonium oleate with the ionic liquid loading capacity of 30 percent.
Step 4: 1000g of the TS-1 molecular sieve extractant loaded by tetraoctyl phosphonium oleate with 30% loading capacity obtained in the step 3 is added into the leaching solution of a 500L lithium ion battery, and the leaching solution contains 1g/L Co 2+,1.14g/LMn2+,1.40g/L Ni2+,0.39g/L Li+.
Step 5: after stirring for 3min, filtration was performed using a filter membrane having a pore size of 0.45 μm, the content of Co 2+ in the remaining filtrate was 0.01g/L, the content of Mn was 0.125g/L Ni 2+ and the concentration of Li + was 1.40g/LNi 2+,0.39g/L Li+. Namely, the extraction rate of the TS-1 molecular sieve extractant loaded by tetraoctyl phosphonium oleate to Co 4+ and Mn 2+ ions is 99 percent and 89 percent respectively.
Step 6: the TS-1 molecular sieve loaded by tetraoctyl phosphonium oleate and extracted with Co 4+ and Mn 2+ ions obtained by filtering in the step 5 is soaked in 10L of 1mol/L hydrochloric acid and stirred for 30min, the concentration of cobalt ions in the solution is 47.67g/L, the concentration of manganese ions is 49.61g/L, namely the back extraction rates of Co 4+ and Mn 2+ ions are 96.3 percent and 97.8 percent respectively.
Step 7: and (3) soaking the TS-1 molecular sieve loaded by tetraoctyl phosphonium oleate and subjected to back extraction in the step (6) for 12 hours by using a 20L0.1M sodium oleate solution, and then, reactivating the TS-1 molecular sieve extractant loaded by tetraoctyl phosphonium oleate. Drying in a vacuum drying oven for 24 hours at room temperature, and removing water, wherein the revived TS-1 molecular sieve extractant loaded by tetraoctyl phosphonium oleate can be directly used for extracting cobalt ions and manganese ions in the step 4-6.
Example 9
Step 1: the specific surface area of the selected 13x molecular sieve is 640m 2/g, the pore size is 0.668nm, and the pore volume is 0.242cm 3/g. 1000g of the above molecular sieve was added to DMF to obtain 13x molecular sieve impregnated with DMF.
Step 2: 800g of 1-octyl-3-methylimidazole hexafluorophosphate was dissolved in 16L of DMF and stirred to obtain a DMF solution of 1-octyl-3-methylimidazole hexafluorophosphate.
Step 3: the DMF-impregnated 13x molecular sieve obtained in step 1 was added to the DMF solution of 1-octyl-3-methylimidazolium hexafluorophosphate obtained in step 2. After stirring for 0.5h, freeze drying for 48h, a 1-octyl-3-methylimidazole hexafluorophosphate loaded 13x molecular sieve was obtained. The loading of the ionic liquid is 80%.
Step 4: 200g of the 1-octyl-3-methylimidazolium hexafluorophosphate supported 13x molecular sieve obtained in step 3 was added to 10L of the cerium-containing magnet waste leachate, which contained 0.0275mol/LCe (NO 3)4.
Step 5: after stirring for 5min, the equilibrium of ion exchange was reached. The molecular sieve extracted with cerium is separated from rare earth solution by a filter membrane. The content of rare earth ion cerium in the residual solution is 0.0041mol/L, namely the exchange rate of rare earth ion cerium is 85.1%.
Step 6: adding the 1-octyl-3-methylimidazole hexafluorophosphate loaded 13x molecular sieve extracted with rare earth ions obtained in the step 5 into 10L 5mol/L hydrochloric acid solution, soaking for 12h, wherein the concentration of cerium ions in the solution is 0.023mol/L, namely the back extraction efficiency is 98.1%
Step 7: and (3) adding the 13x molecular sieve loaded by the 1-octyl-3-methylimidazolium hexafluorophosphate subjected to back extraction in the step (6) into 10L of 0.2M KPF 6 solution, so as to finish the reactivation of the 13x molecular sieve loaded by the 1-octyl-3-methylimidazolium hexafluorophosphate. Drying in a vacuum drying oven at room temperature for 24 hours, removing water, and then re-using in the steps 4-6 for extracting rare earth ions.
Example 10
Step 1: 400g of MCM-48 molecular sieve and 400g of MCM-22 are added into the acetone solution to obtain the MCM-48 and MCM-22 which can completely infiltrate the pore canal of the molecular sieve.
Step 2: 200g of 1-methyl-3- [ tris- (trimethylsiloxy) ] cyclopropylimidazole chloride was added to 64L of acetonitrile and stirred to obtain an acetonitrile solution of 1-methyl-3- [ tris- (trimethylsiloxy) ] cyclopropylimidazole chloride.
Step 3: 400g of MCM-48 molecular sieve which is completely infiltrated by acetone and 400g of MCM-22 molecular sieve which is completely infiltrated by acetone solvent are stirred for half an hour with the acetonitrile solution of 1-methyl-3- [ tri- (trimethylsiloxy) ] silapropylimidazole chloride obtained in the step 2. After drying under vacuum at room temperature for 24 hours, the organic solvent was removed. Thus obtaining the MCM-48 and MCM-22 mixture of the 1-methyl-3- [ tri- (trimethylsiloxy) ] silapropylimidazole chloride with the ionic liquid loading of 25 percent.
Step 4: 600g of the 1-methyl-3- [ tris- (trimethylsiloxy) ] cyclopropylimidazole chloride-supported MCM-48/MCM-22 molecular sieve obtained in step 3 was added to 10L of the catalyst leaching solution, wherein the Pd 2+ concentration in the solution was 0.2mmol/L, and the solution was stirred for 1min.
Step 5: the MCM-48/MCM-22 molecular sieve extractant loaded by the 1-methyl-3- [ tri- (trimethylsiloxy) ] silapropylimidazole chloride is separated from the extracting solution of the palladium ions by a filter paper suction filtration method, and the concentration of Pd 2+ in the residual solution is 0.004mol/L, namely the extracting rate of the palladium ions is 98%.
Step 6: adding the 1-methyl-3- [ tri- (trimethylsiloxy) ] silapropylimidazole chloride loaded MCM-48/MCM-22 molecular sieve obtained in the step 5 into 10L of 1M NaCl soaking solution for 1h, wherein the concentration of palladium ions in the solution is 0.1923mmol/L, namely the back extraction efficiency is 98.1%
Step 7: the re-activation of the MCM-48/MCM-22 molecular sieve loaded by the 1-methyl-3- [ tri- (trimethylsiloxy) ] silapropylimidazole chloride after the back extraction in the step 6 can be completed by adding the MCM-48/MCM-22 molecular sieve loaded by the 1-methyl-3- [ tri- (trimethylsiloxy) ] silapropylimidazole chloride into 10L 2M HCl. Drying in a vacuum drying oven at room temperature for 24 hours, removing water, and then, extracting palladium ions in the steps 4-6 again.
Example 11
Step 1: the selected inorganic porous material is titanium-silicon molecular sieve, the specific surface area is 400cm 3/g, the particle size is 70 meshes, and the aperture is 0.57nm. 1000g of titanium silicalite molecular sieve is added into dichloromethane solution to obtain titanium silicalite molecular sieve which is completely infiltrated by dichloromethane into pore channels.
Step 2: 500g of trioctyl methyl ammonium chloride Aliquat 336 was dissolved in 20L of methylene chloride, and after stirring, a methylene chloride solution of trioctyl methyl ammonium chloride was obtained
Step 3: adding the titanium silicalite molecular sieve treated in the step 1 into a dichloromethane solution of trioctyl methyl ammonium chloride, stirring for 60min, standing for 24h in a fume hood, and obtaining the titanium silicalite molecular sieve loaded by trioctyl methyl ammonium chloride with the ionic liquid load of 50% after the dichloromethane is naturally volatilized.
Step 4: 300g of trioctylmethyl ammonium chloride Aliquat 336 ionic liquid loaded titanium-silicon molecular sieve with 50% loading capacity is added into 10L of television circuit board leaching solution, 600mg/L of Cu 2+ is contained, 200g of EDTA is added at the same time, and stirring is carried out for 10min.
Step 5: after filtration by using a filter membrane with the pore diameter of 0.45um, the concentration of Cu 2+ in the residual solution is 67.8mg/L, namely the extraction efficiency of the titanium silicalite molecular sieve extractant loaded by trioctylmethyl ammonium chloride Aliquat 336 ionic liquid to Cu 2+ is 88.7%.
Step 6: the trioctylmethyl ammonium chloride Aliquat 336 ionic liquid loaded titanium silicon molecular sieve extractant extracted with copper ions obtained in the step 5 is added into 10L of 1mol/L NaCl, and after stirring for half an hour, the concentration of Cu 2+ in the water phase is 517.3mg/L, namely the back extraction rate of Cu 2+ is 97.2%.
Step 7: and (3) adding the titanium silicalite molecular sieve loaded by the trioctyl methyl ammonium chloride Aliquat 336 ionic liquid subjected to back extraction in the step (6) into 10L of 2M HCl, and thus, reactivating the titanium silicalite molecular sieve loaded by the trioctyl methyl ammonium chloride Aliquat 336 ionic liquid can be finished. Drying in a vacuum drying oven at room temperature for 24 hours, removing water, and then re-using in the step 4-6 to extract Cu 2+ ions.
Example 12
Step 1: the selected inorganic porous material is SBA-15 molecular sieve, the specific surface area is 700cm 3/g, and the aperture is 8nm. 1000g of SBA-15 molecular sieve is calcined for 2 hours under the condition of 300 ℃ air to remove residual moisture and impurities, and then the residual moisture and impurities are added into tetrahydrofuran solution to obtain the SBA-15 molecular sieve with channels completely infiltrated by tetrahydrofuran.
Step 2: 450g of 1-butyl-3-methylimidazole hexafluorophosphate was dissolved in 15L of tetrahydrofuran, and after stirring, a tetrahydrofuran solution of trioctyl methyl ammonium chloride was obtained
Step 3: adding the SBA-15 molecular sieve completely infiltrated by the tetrahydrofuran in the step 1 into the tetrahydrofuran solution of the 1-butyl-3-methylimidazole hexafluorophosphate obtained in the step 2, stirring for 60min, standing for 24h in a fume hood, and obtaining the SBA-15 molecular sieve of the 1-butyl-3-methylimidazole hexafluorophosphate with 45% ionic liquid load after the tetrahydrofuran is naturally volatilized.
Step 4: 800g of SBA-15 molecular sieve loaded by 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid with 45 percent of load is added into 100L of lead storage battery electrode leaching liquid, wherein the concentration of Pb 2+ is 100mg/L.
Step 5: after stirring for 10min, filtering by a filter membrane with the aperture of 0.45um, and the concentration of Pb 2+ in the residual solution is 17mg/L, namely the extraction efficiency of the SBA-15 molecular sieve extractant loaded by the 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid on Pb 2+ is 83%.
Step 6: the lead-extracted 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid-loaded SBA-15 molecular sieve extractant obtained in the step 5 is added into 50L of 3mol/L HNO 3, and after stirring for half an hour, the concentration of Pb 2+ in the water phase is 161.02mg/L, namely the back extraction rate of Pb 2+ is 97%.
Step 7: and (3) adding the trioctyl methyl ammonium chloride Aliquat 336 ionic liquid loaded SBA-15 molecular sieve subjected to back extraction in the step (6) into 50L of 0.2M KPF 6, so as to complete the reactivation of the 1-butyl-3-methylimidazole hexafluorophosphate loaded SBA-15 molecular sieve. Drying in a vacuum drying oven at room temperature for 24 hours, removing water, and then re-using the dry powder in the step 4-6 to extract Pb 2+ ions.
Example 13
Step 1: the inorganic porous material is selected as SAPO-11 molecular sieve, and the specific surface area of the particle size of 10 mu m is 200cm 3/g. 2000g of SAPO-11 molecular sieve is calcined for 2 hours under the condition of 300 ℃ air to remove residual moisture and impurities, and then added into 10L of NMP solution, and after the NMP solution completely infiltrates the SAPO-11 molecular sieve, the NMF solution containing the SAPO-11 molecular sieve is obtained.
Step 2: 1500g of methyltrioctylammonium thiosalicylate was dissolved in 30L of DMF and stirred to obtain a solution of methyltrioctylammonium thiosalicylate in DMF
Step 3: after adding 2000g of the NMP solution containing SAPO-11 molecular sieve obtained in step 1 to the DMF solution of methyltrioctyl ammonium thiosalicylate, stirring for 60 min. And freeze-drying for 48 hours, and completely removing the mixed solvent to obtain the SAPO-11 molecular sieve loaded with the methyl trioctyl ammonium thiosalicylate, wherein the ionic liquid loading amount of the SAPO-11 molecular sieve is 75%.
Step 4: 1000g of the SAPO-11 molecular sieve loaded by the thiosalicylic acid methyl trioctyl ammonium salt ionic liquid with 75 percent of loading capacity is added into 100L of cadmium smelting factory wastewater, wherein the concentration of Cd 2+ is 100mg/L.
Step 5: after stirring for 10min, filtering by a filter membrane with the aperture of 0.45um, wherein the concentration of Cd 2+ in the residual solution is 0.1mg/L, namely the extraction efficiency of the SAPO-11 molecular sieve extractant loaded by the thiosalicylic acid methyl trioctyl ammonium salt ionic liquid on Cd 2+ is 99.9%.
Step 6: the SAPO-11 molecular sieve extractant loaded by the cadmium extracted methyltrioctylammonium thiosalicylate ionic liquid obtained in the step 5 is added into 50L of 1mol/L HCl, and after stirring for half an hour, the concentration of Cd 2+ in the water phase is 194mg/L, namely the back extraction rate of Cd 2+ is 97%.
Step 7: adding the back-extracted thiotrioctyl ammonium salt ionic liquid loaded SAPO-11 molecular sieve in the step 6 into 50L 1M sodium thiosalicylate, drying for 24 hours at room temperature in a vacuum drying oven, removing water, and then recovering the extraction activity of the thiotrioctyl ammonium salt ionic liquid loaded SAPO-11 molecular sieve, wherein the method can be used for extracting Cd 2+ ions in the step 4-6 again.
Example 14
Step 1: the selected inorganic porous material is a KIT-6 molecular sieve, the specific surface area is 780cm 3/g, the aperture is 9.2nm, and 1500g of the KIT-6 molecular sieve is calcined for 2 hours under the condition of 300 ℃ air to remove residual moisture and impurities. 1000g of the KIT-6 molecular sieve is dispersed into 10L of cyclohexane solution to obtain the KIT-6 molecular sieve containing pore channels which are completely infiltrated by cyclohexane.
Step 2: 420g of methyltrioctyl ammonium chloride was dissolved in 8.4L of cyclohexane, and after stirring, a cyclohexane solution of methyltrioctyl ammonium chloride was obtained.
Step 3: and (3) stirring the cyclohexane solution containing 1000g of the KIT-6 infiltrated by cyclohexane and the methyltrioctylammonium chloride ionic liquid obtained in the step (2) for 60min, standing for 24h in a fume hood, and obtaining the KIT-6 molecular sieve with the ionic liquid load of 42% methyltrioctylammonium chloride after cyclohexane naturally volatilizes.
And 4, adding 230g of KIT-6 molecular sieve loaded by methyltrioctylammonium chloride with the loading capacity of 42% into 10L of nickel-molybdenum ore calcine sulfuric acid leaching solution, wherein the concentration of MoO 4 2- is 0.766g/L, stirring for 30min, filtering by using a filter membrane with the pore diameter of 0.45um, and the concentration of MoO 4 2- in the residual solution is 0.153g/L, namely, the extraction efficiency of the KIT-6 molecular sieve extractant loaded by methyltrioctylammonium chloride on MoO 4 2- is 80%.
Step 5, adding the molybdenum-extracted methyltrioctyl ammonium chloride-loaded KIT-6 molecular sieve extractant obtained in the step 4 into 10L of 1mol/L of NaClO,
Step 6: after stirring the solution in step 5 for half an hour, the concentration of MoO 4 2- ions in the aqueous phase was 0.583g/L, i.e. the stripping rate of MoO 4 2- was 95.1%.
Step 7: and (3) adding the KIT-6 molecular sieve extractant loaded by the methyltrioctyl ammonium chloride and subjected to back extraction in the step (6) into 10L of 1M hydrochloric acid, drying for 24 hours at room temperature in a vacuum drying oven, and removing water to complete the reactivation of the KIT-6 molecular sieve loaded by the methyltrioctyl ammonium chloride. Can be used for the fourth step again for the extraction of MoO4 2- ions.
Example 15
Step 1: selecting an inorganic porous material as a ZSM-5 molecular sieve, and drying 2000g of ZSM-5 molecular sieve for 24 hours under the vacuum condition of 120 ℃. The specific surface area is 500m 2/g, and the pore volume is 0.65cm 3/g. 1000g of the ZSM molecular sieve thus treated was added to 10L of acetone solution to give a ZSM-5 molecular sieve which was completely impregnated with acetone solvent.
Step 2: 360g of trioctyl methyl ammonium chloride Aliquat 336 was dissolved in 20L of acetonitrile to give a cyclohexane solution of trioctyl methyl ammonium chloride.
Step 3: and (3) stirring the ZSM-5 molecular sieve infiltrated by the acetone solvent in the step (1) and the cyclohexane solution of the trioctyl methyl ammonium chloride obtained in the step (2) for half an hour, and drying the mixture in a fume hood for 24 hours to obtain the ZSM-5 molecular sieve loaded by the trioctyl methyl ammonium chloride with 36% ionic liquid load.
Step 4, 800g of the trioctyl methyl ammonium chloride loaded ZSM-5 molecular sieve obtained in the step 3 is used. Added into 10L of rare earth element solution containing lanthanide series and actinide series. The solution contained 2×10 -3 M of U 4+,Th4+,La3+,Nd3+,Y3+,Fe3+, ph=1.4. After stirring for 5min, the ZSM-5 molecular sieve loaded by the trioctyl methyl ammonium chloride is fished out from the solution containing the rare earth elements by using a filter membrane. In the residual solution, the contents of U 4+、Th4+ and Fe 3+ ions are 0, namely the extraction rate of the three elements is 100%. While the extraction rate for the remaining Y 3+,Nd3+ and La 3+ ions was 0%.
Step 5: adding the trioctylmethyl ammonium chloride loaded ZSM-5 molecular sieve extracted with U 4+、Th4+ and Fe 3+ elements obtained in the step 4 into 10L hydrochloric acid with the concentration of 1mol/L to carry out rare earth ion back extraction. After 1h, the contents of U 4+、Th4+ and Fe 3+ elements in the stripping solution were 1.91× -3M、1.96×10-3M、1.88×10-3 M, and the efficiencies were 95.5%,98% and 94%, respectively.
Step 6: and (3) adding the ZSM-5 molecular sieve extractant loaded by the methyltrioctyl ammonium chloride and subjected to back extraction in the step (5) into 10L of 1M hydrochloric acid, drying for 24 hours at room temperature in a vacuum drying oven, and removing water to realize the reactivation of the ZSM-5 molecular sieve extractant loaded by the methyltrioctyl ammonium chloride. Can be used for extracting U 4+、Th4+ and Fe 3+ ions in the step 4-6 again.
Example 16
Step 1: the selected inorganic porous material is diatomite, the specific surface area is 40m 2/g, the pore diameter is 9.2nm, the pore volume is 0.45cm 3/g, 1000g of diatomite molecular sieve is calcined for 2 hours under the condition of 300 ℃ air, residual moisture and impurities are removed, and then the diatomite is added into dichloromethane, so that diatomite completely infiltrated by the dichloromethane is obtained.
Step 2: 430g of 1-cyano-1-octylpyrrole bromide was dissolved in 20L of methylene chloride to obtain a methylene chloride solution of 1-cyano-1-octylpyrrole bromide.
Step 3: 1000g of the diatomaceous earth impregnated with methylene chloride obtained in the step 1 was added to the methylene chloride solution of 1-cyano-1-octylpyrrole bromide obtained in the step 2, and after stirring for half an hour, it was dried in a fume hood for 24 hours to obtain diatomaceous earth supported by 1-cyano-1-octylpyrrole bromide having a load of 43%.
Step 4: 400g of 1-cyano-1-octylpyrrole bromide loaded diatomaceous earth obtained in step 3, loaded at 43%, were added to 30L of solution [ PdCl 4]2- ] containing 8 mg/ml.
Step 5: the solution in the step 4 was stirred and reacted for 20 minutes, and the concentration of [ PdCl 4]2- ] in the solution after the reaction was 0.24mg/ml, and the extraction rate of palladium ions was 97%.
Step 6: the diatomite loaded with the 1-cyano-1-octyl pyrrole bromine salt extracted with palladium ions in the step 5 is added into 20L of 0.1mol/L thiourea hydrochloric acid solution to react for 10min, the concentration of palladium in the solution after back extraction is 7.53mg/ml, and the back extraction rate is 97%.
Step 7: adding the diatomite extractant loaded with the 1-cyano-1-octyl pyrrole bromine salt and subjected to back extraction in the step 6 into 10L of 1M HBr solution, drying the mixture in a vacuum drying oven at room temperature for 24 hours, and removing water to complete the reactivation of the diatomite loaded with the 1-cyano-1-octyl pyrrole bromine salt. Can be used again for the extraction of palladium ions in steps 4-6.
Example 17
Step 1: the selected inorganic porous material is column chromatography silica gel, the specific surface area is 400m 2/g, the pore diameter is 100A, the pore volume is 0.75cm 3/ g, and 1000g of column chromatography silica gel is calcined for 2 hours under the condition of 300 ℃ air to remove residual moisture and impurities. This was then added to 10L of toluene solution to give a silica gel fully saturated with toluene.
Step 2: 570g of trioctyl methyl ammonium nitrate was dissolved in 10L of xylene to give a xylene solution of trioctyl methyl ammonium nitrate.
Step 3: adding the toluene solution containing the silica gel treated in the step 1 into the xylene solution of the trioctyl methyl ammonium nitrate treated in the step 2, stirring for half an hour, and drying in a fume hood for 24 hours to obtain the column chromatography silica gel loaded with the trioctyl methyl ammonium nitrate with the loading of 57 percent
Step 4, adding 600g of trioctyl methyl ammonium nitrate loaded column chromatography silica gel with 57% loading into 50L of Sm, cobalt Co magnet and nitrate acid leaching solution of related waste copper, wherein the compositions are 93 g.L -1Co2+,92g·L-1Sm3+ and 8 g.L -1Cu 2+,
Step 5: stirring and reacting for 20min, wherein the extraction rates of the element composition in the solution after the reaction are respectively 99.3%,1.9% and 97.8% of the element composition in the solution after the reaction is 0.651 g.L -1Co(II),90.252g·L-1Sm3+ and 0.176 g.L -1Cu 2+,Co2+、Sm3+、Cu 2+.
Step 6: adding the trioctyl methyl ammonium nitrate loaded column chromatography silica gel extracted with Cu 2+ and Co 2+ obtained in the step 5 into 50L of deionized water, reacting for 10min, wherein the concentration of Cu 2+,Co2+ in the solution after back extraction is 91.61 g.L -1、6.439g·L-1, and the back extraction efficiency is 99.2% and 82.3%.
Step 7: and (3) adding the column chromatography silica gel extractant loaded by the trioctyl methyl ammonium nitrate subjected to back extraction in the step (6) into 10L of 1M HNO 3 solution, drying for 24 hours at room temperature in a vacuum drying oven, and removing water to complete the reactivation of the column chromatography silica gel loaded by the trioctyl methyl ammonium nitrate. Can be used for extracting Cu 2+,Co2+ ions in the fourth step again.
Example 18
Step 1: the inorganic porous material is spherical hollow mesoporous silica with the specific surface area of 970m 2/g, the aperture of 5nm and the pore volume of 0.26cm 3/g, 1000g of spherical hollow mesoporous silica is calcined for 2 hours under the condition of 300 ℃ air to remove residual moisture and impurities, and then the spherical hollow mesoporous silica is added into 10L cyclohexane solution to obtain the hollow mesoporous silica immersed by cyclohexane.
Step 2: 200g of 1-butyl-3-methylimidazole hexafluorophosphate and 200g of 1-octyl-3-methylimidazole hexafluorophosphate were dissolved in 50L of n-octane to obtain n-octane solutions of 1-butyl-3-methylimidazole hexafluorophosphate and 1-octyl-3-methylimidazole hexafluorophosphate.
Step 3: 1000g of cyclohexane solution of spherical hollow mesoporous silica infiltrated by cyclohexane and n-octane solution of 1-butyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium hexafluorophosphate obtained in the step 2 are stirred for half an hour, and then dried in a fume hood for 24 hours to obtain spherical hollow mesoporous silica loaded by 1-butyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium hexafluorophosphate with 40 percent of loading.
Step 4: 300g of 1-butyl-3-methylimidazolium hexafluorophosphate with 40 percent of load and spherical hollow mesoporous silica with 1-octyl-3-methylimidazolium hexafluorophosphate load are added into 60L mercury-containing waste liquid, wherein the mercury ion concentration is 60 mg.L -1, 6 percent of dithizone is contained, the mixture is stirred and reacted for 20 minutes, the mercury concentration in the reacted solution is 0.78 mg.L -1, and the extraction rate is 98.7 percent
Step 5: and (3) adding the spherical hollow mesoporous silica loaded by the 1-butyl-3-methylimidazolium hexafluorophosphate and the 1-octyl-3-methylimidazolium hexafluorophosphate which are obtained in the step (4) and extracted with mercury into 30L 1M HNO 3, reacting for 10min, wherein the concentration of mercury in the solution after back extraction is 115.36 mg.L -1, and the back extraction efficiency is 97.4%.
Step 6: adding the spherical hollow mesoporous silica extractant loaded by the back-extracted 1-butyl-3-methylimidazole hexafluorophosphate and 1-octyl-3-methylimidazole hexafluorophosphate in the step 5 into 10L of 1M KPF 6 solution, drying at room temperature for 24 hours in a vacuum drying oven, and removing water to complete the reactivation of the spherical hollow mesoporous silica loaded by the 1-butyl-3-methylimidazole hexafluorophosphate and 1-octyl-3-methylimidazole hexafluorophosphate. Can be used again for the extraction of mercury ions in the fourth step.
Example 19
Step 1: the selected inorganic porous material is a hierarchical porous silica microsphere, the specific surface area is 470m 2/g, and the aperture is 4nm; and spherical porous alumina as carrier, with particle size of 500 mesh, specific surface area of 200m 2/g and pore volume of 0.3cm 3/g, calcining 500g of porous silica microsphere and 500g of spherical porous alumina at 300 deg.C for 2 hr to remove residual water and impurities, adding into 50L toluene solution, and obtaining toluene solution containing porous silica microsphere and alumina after toluene completely infiltrates into pore canal.
Step 2: 350g of 1-hexyl-3- (3-methylthioureidopropyl) imidazole hexafluorophosphate were dissolved in 50L of acetone to give an acetone solution of 1-hexyl-3- (3-methylthioureidopropyl) imidazole hexafluorophosphate.
Step 3, adding 500g of the multistage porous silica microspheres obtained in the step 1 and 500g of spherical porous aluminum oxide into the acetone solution of the 1-hexyl-3- (3-methyl thiourea propyl) imidazole hexafluorophosphate obtained in the step 2, stirring for half an hour, and drying in a fume hood for 24 hours to obtain a mixed sample of the multistage porous silica microspheres loaded with the 1-hexyl-3- (3-methyl thiourea propyl) imidazole hexafluorophosphate with the loading amount of 35 percent and the spherical porous aluminum oxide.
Step 4, adding 300g of mixed sample of 1-hexyl-3- (3-methyl thiourea propyl) imidazole hexafluorophosphate loaded hierarchical porous silica microsphere and spherical porous aluminum oxide with 35% loading into 60L industrial zinc-containing waste liquid, wherein the zinc concentration is 200 mg.L -1.
Step 5, stirring and reacting for 20min, and separating the mixed sample of the 1-hexyl-3- (3-methyl thiourea propyl) imidazole hexafluorophosphate loaded hierarchical porous silica microsphere and spherical porous aluminum oxide with zinc ions extracted by a 1000-mesh filter screen from an aqueous solution, wherein the concentration of zinc in the separated solution is 18 mg.L -1, namely the extraction efficiency of the zinc ions is 91 percent
Step 6, adding the mixed sample of the multistage porous silica microsphere loaded by the zinc extracted 1-hexyl-3- (3-methyl thiourea propyl) imidazole hexafluorophosphate and spherical porous aluminum oxide obtained in the step 5 into 30L of 0.1% HNO 3, reacting for 10min, wherein the concentration of zinc in the solution after back extraction is 357.81 mg.L -1, and the back extraction efficiency is 98.3%.
Step 7: adding the multi-stage porous silica microsphere and spherical porous aluminum oxide mixed sample extractant loaded by the back-extracted 1-hexyl-3- (3-methyl thiourea propyl) imidazole hexafluorophosphate in the step 6 into 10L1M KPF 6 solution, drying at room temperature for 24 hours in a vacuum drying box, removing water, and then completing the reactivation of the multi-stage porous silica microsphere and spherical porous aluminum oxide mixed sample loaded by the 1-hexyl-3- (3-methyl thiourea propyl) imidazole hexafluorophosphate, and re-using the multi-stage porous silica microsphere and spherical porous aluminum oxide mixed sample in the step 4 for extracting zinc ions.
From the results of the above examples, it can be seen that, in the present invention, the disadvantage of the conventional method that oil-water separation is required is avoided, the pollution to the environment is reduced, the disadvantage of the ionic liquid having a relatively high viscosity can be avoided, and the ionic liquid can be directly used for the extraction reaction in the liquid phase; because the adopted porous material has larger specific surface area, the extraction time can be reduced to a few minutes, and the extraction efficiency is greatly improved.
Claims (9)
1. A method for extracting mineral ions by using an inorganic porous material supported ionic liquid technology, comprising the following steps:
step 1: adding the inorganic porous material into an organic solvent, so that the organic solvent can completely infiltrate the pore channels of the inorganic porous material;
The inorganic porous material is porous silica, porous alumina, porous titanium dioxide, KIT-6 molecular sieve, SBA-15 molecular sieve, MCM-22 molecular sieve, TS-1 molecular sieve, SAPO-11 molecular sieve, ZSM-5 molecular sieve, beta molecular sieve, ZSM-23 molecular sieve, 13X molecular sieve, MCM-48 molecular sieve or titanium silicon inorganic porous material;
step 2: adding the ionic liquid into an organic solvent to enable the ionic liquid to be completely dispersed;
Step 3: mixing and stirring the organic solvent containing the inorganic porous material and the organic solvent containing the ionic liquid obtained in the step 1 and the step 2 respectively, and removing the organic solvent to obtain an extracted inorganic porous material containing the ionic liquid;
Step 4: adding the extracted inorganic porous material containing the ionic liquid into an aqueous solution containing extracted mineral ions for extraction;
Step 5: separating the extracted inorganic porous material containing the extracted mineral ions from the aqueous solution to obtain an extracted inorganic porous material containing the extracted mineral ions;
Step 6: and separating the extracted mineral ions from the extracted inorganic porous material containing the extracted mineral ions.
2. The method of claim 1, wherein the inorganic porous material is a hierarchical porous silica microsphere or diatomaceous earth.
3. The method of claim 1, wherein the organic solvent comprises: one or more of fatty alcohol, acetonitrile, toluene, acetone, cyclohexane, DMF, NMP, tetrahydrofuran, thiourea, propanethiol, methyl chloride, dichloromethane or carbon disulfide.
4. A method according to claim 3, wherein the organic solvent in step 1 and the organic solvent in step2 are miscible.
5. The method of claim 1, wherein the ionic liquid comprises: one or more of imidazole, pyridine, quaternary phosphorus, pyrrolidine, morpholine, piperidine and quaternary ammonium ionic liquid.
6. The method of claim 5, wherein the cations of the ionic liquid comprise: one or more of N-hexylpyridine ion, trihexyl (tetradecyl) phosphine ion, (tributyl) N-tetradecylphosphine ion, tri-N-octylmethylammonium ion, 1-hexyl-3-methylimidazole ion, 1-butyl-3-methylimidazole ion, tetraoctylphosphonium ion, 1-octyl-3-methylimidazole, 1-methyl-3- [ tris- (trimethylsiloxy) ] silylimidazolium ion, trioctylmethylammonium ion, 1-hexyl-3- (3-methylthioureidopropyl) imidazole ion, and 1-cyano-1-octylpyrrole ion.
7. The method of claim 5, wherein the anions of the ionic liquid are: one or more of chloride, bromide, trifluoromethanesulfonyl, hexafluorophosphate, thiosalicylate, di (2-ethylhexyl) phosphate, oleate, nitrate, or tetrafluoroborate.
8. The method of claim 1, wherein the mineral ions comprise: au, pd, pt, cu, fe, mn, al, Y, eu, ce, co, V, pb, mo, U, th, hg, zn or Cd ions one or more of them.
9. The method according to claim 1, wherein the extracted mineral ions are separated in step 6, and the corresponding mineral material is obtained by post-treatment, and the solid phase is an extracted inorganic porous material containing ionic liquid, and can be reused for the treatment in steps 4-6 after the conventional treatment method is adopted.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211627574.2A CN115786703B (en) | 2022-12-16 | 2022-12-16 | Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid |
| PCT/CN2023/132481 WO2024125210A1 (en) | 2022-12-16 | 2023-11-18 | Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211627574.2A CN115786703B (en) | 2022-12-16 | 2022-12-16 | Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115786703A CN115786703A (en) | 2023-03-14 |
| CN115786703B true CN115786703B (en) | 2024-08-13 |
Family
ID=85425525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211627574.2A Active CN115786703B (en) | 2022-12-16 | 2022-12-16 | Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115786703B (en) |
| WO (1) | WO2024125210A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115786703B (en) * | 2022-12-16 | 2024-08-13 | 吉林大学 | Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736157A (en) * | 2009-12-14 | 2010-06-16 | 北京有色金属研究总院 | Process for absorbing and extracting valuable metal ions in leachate of laterite nickel ore by applying immobilized room temperature ionic liquid |
| CN104131164A (en) * | 2014-08-19 | 2014-11-05 | 中国科学院长春应用化学研究所 | Application and method of neutral phosphamide extraction agent for extracting and separating thorium |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578217A (en) * | 1994-11-30 | 1996-11-26 | Alliedsignal Inc. | Use a solvent impregnated crosslinked matrix for metal recovery |
| US5840271A (en) * | 1996-02-09 | 1998-11-24 | Intevep, S.A. | Synthetic material with high void volume associated with mesoporous tortuous channels having a narrow size distribution |
| JP4660793B2 (en) * | 2004-04-21 | 2011-03-30 | 国立大学法人 千葉大学 | Adsorbing material carrying extraction reagent and method for producing the same |
| WO2012115273A1 (en) * | 2011-02-22 | 2012-08-30 | National Institute For Materials Science | Method for extraction and separation of lanthanoid elements and actinoid elements, and means for extraction and separation of lanthanoid elements and actinoid elements |
| CN102417981B (en) * | 2011-11-22 | 2013-05-01 | 中国科学院过程工程研究所 | Method for extracting and separating platinum, palladium and rhodium by using ionic liquid-based three-liquid phase system |
| CN102671628B (en) * | 2012-05-11 | 2014-10-15 | 华南理工大学 | Microporous molecular sieve-functionalized ionic liquid composite material and preparation method thereof |
| FR3001961B1 (en) * | 2013-02-13 | 2015-03-06 | Commissariat Energie Atomique | SOL-GEL PROCESS FOR SEPARATING METAL IONS FROM AQUEOUS SOLUTION |
| WO2015106324A1 (en) * | 2014-01-17 | 2015-07-23 | Katholieke Universiteit Leuven Ku Leuven Research & Development | Process for extraction and separation of rare earths by split-anion extraction with ionic liquids |
| CN109589949B (en) * | 2018-12-21 | 2021-11-02 | 齐鲁工业大学 | Synthesis method and application of ionic liquid loaded porous material |
| CN115433832B (en) * | 2021-06-02 | 2024-03-19 | 中国科学院过程工程研究所 | Nickel and cobalt synergistic extractant and application thereof |
| CN115786703B (en) * | 2022-12-16 | 2024-08-13 | 吉林大学 | Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid |
-
2022
- 2022-12-16 CN CN202211627574.2A patent/CN115786703B/en active Active
-
2023
- 2023-11-18 WO PCT/CN2023/132481 patent/WO2024125210A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736157A (en) * | 2009-12-14 | 2010-06-16 | 北京有色金属研究总院 | Process for absorbing and extracting valuable metal ions in leachate of laterite nickel ore by applying immobilized room temperature ionic liquid |
| CN104131164A (en) * | 2014-08-19 | 2014-11-05 | 中国科学院长春应用化学研究所 | Application and method of neutral phosphamide extraction agent for extracting and separating thorium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115786703A (en) | 2023-03-14 |
| WO2024125210A1 (en) | 2024-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115786703B (en) | Method for extracting mineral ions by using inorganic porous material loaded with ionic liquid | |
| CN102002589B (en) | Method for three-phase extraction and one-step separation of platinum, palladium and rhodium from leaching solution of precious metal catalyst | |
| CN105238933B (en) | It is a kind of from the method containing removing and reclaiming element mercury in sulfur dioxide flue gas | |
| CN109012565A (en) | A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating | |
| CN105152433A (en) | Method for removing COD (chemical oxygen demand) from copper/molybdenum extraction raffinate mixed wastewater | |
| CN114436997A (en) | Amide ionic liquid, synthesis method thereof and application thereof in gold extraction and separation | |
| Alam et al. | Adsorptive separation of rhodium (lll) using Fe (Ill)-templated oxine type of chemically modified chitosan | |
| CN1113890A (en) | Process for the removal of species containing metallicions from effluents | |
| CN110624517B (en) | Nano hollow polyaniline and preparation method and application thereof | |
| US5009868A (en) | Process for the extended use of strip acid employed in the reclamation of battery acid fluid from expanded lead-acid batteries | |
| EP1743044B1 (en) | Method for recovery of palladium | |
| JP4654406B2 (en) | Sequential separation of plutonium and uranium from aqueous solution by microorganisms | |
| CN116637636A (en) | Method for preparing manganese-based low-temperature SCR catalyst by using waste FCC catalyst | |
| CN107081153B (en) | Method for reducing Cr (VI) based on catalyst photocatalysis | |
| CN109811130B (en) | Method for recovering thallium and mercury from smelting acid wastewater | |
| CN104785204A (en) | Liquid-modified composite mercury remover for molecular sieves and preparation method of liquid-modified composite mercury remover | |
| CN1037127A (en) | The extractive technique scheme of the diffusing precious metal of rock decay earth absorbent type rare | |
| TWI623623B (en) | Treating method for recycling noble metal | |
| CN111672487A (en) | Selective heavy metal ion adsorption material and preparation method and application thereof | |
| EP0090551A1 (en) | Metal ion extraction process | |
| JP3493752B2 (en) | Method for producing a carrier in which a compound having a hydroquinone skeleton is supported on a porous carrier | |
| EP4372111A1 (en) | Metal recovering method | |
| CN116272872A (en) | Nonmetallic doped bulk carbon material for adsorbing thallium, preparation method and method for removing thallium in water | |
| CN115055187B (en) | Copper doped beta-Bi 2 O 3 Preparation method of crystal catalyst and benzene series wastewater purification method | |
| CN106903147A (en) | A kind of drip washing material and preparation method with absorption, organochlorine pollutant of degrading |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |