KR20170055021A - Method for recovering multivalent metal ion from leaching solution containing sulfuric acid in which metal ions are leached, and composite membrane therefor - Google Patents
Method for recovering multivalent metal ion from leaching solution containing sulfuric acid in which metal ions are leached, and composite membrane therefor Download PDFInfo
- Publication number
- KR20170055021A KR20170055021A KR1020170056883A KR20170056883A KR20170055021A KR 20170055021 A KR20170055021 A KR 20170055021A KR 1020170056883 A KR1020170056883 A KR 1020170056883A KR 20170056883 A KR20170056883 A KR 20170056883A KR 20170055021 A KR20170055021 A KR 20170055021A
- Authority
- KR
- South Korea
- Prior art keywords
- sulfuric acid
- metal ions
- composite membrane
- leached
- metal ion
- Prior art date
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000002386 leaching Methods 0.000 title claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 41
- 150000001412 amines Chemical class 0.000 claims abstract description 38
- 239000004952 Polyamide Substances 0.000 claims abstract description 35
- 229920002647 polyamide Polymers 0.000 claims abstract description 35
- 125000003118 aryl group Chemical group 0.000 claims abstract description 34
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 rare earth metal ions Chemical class 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000003723 Smelting Methods 0.000 claims abstract description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 13
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000768 polyamine Polymers 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 32
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001266 acyl halides Chemical class 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012466 permeate Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 claims description 2
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 claims description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 2
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000307 polymer substrate Polymers 0.000 claims description 2
- 150000003461 sulfonyl halides Chemical class 0.000 claims description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 2
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 150000004986 phenylenediamines Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000035699 permeability Effects 0.000 abstract description 6
- 230000004907 flux Effects 0.000 abstract description 4
- 150000002366 halogen compounds Chemical class 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000000178 monomer Substances 0.000 description 14
- 150000002739 metals Chemical class 0.000 description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- 150000002433 hydrophilic molecules Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229960002684 aminocaproic acid Drugs 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LZXHHNKULPHARO-UHFFFAOYSA-M (3,4-dichlorophenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].C1=C(Cl)C(Cl)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LZXHHNKULPHARO-UHFFFAOYSA-M 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- HJORCZCMNWLHMB-UHFFFAOYSA-N 1-(3-aminopropyl)pyrrolidin-2-one Chemical compound NCCCN1CCCC1=O HJORCZCMNWLHMB-UHFFFAOYSA-N 0.000 description 1
- QKWWDTYDYOFRJL-UHFFFAOYSA-N 2,2-dimethoxyethanamine Chemical compound COC(CN)OC QKWWDTYDYOFRJL-UHFFFAOYSA-N 0.000 description 1
- VPMMJSPGZSFEAH-UHFFFAOYSA-N 2,4-diaminophenol;hydrochloride Chemical compound [Cl-].NC1=CC=C(O)C([NH3+])=C1 VPMMJSPGZSFEAH-UHFFFAOYSA-N 0.000 description 1
- PAOXFRSJRCGJLV-UHFFFAOYSA-N 2-[4-(2-aminoethyl)piperazin-1-yl]ethanamine Chemical compound NCCN1CCN(CCN)CC1 PAOXFRSJRCGJLV-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- SNKZJIOFVMKAOJ-UHFFFAOYSA-N 3-Amino-1-propanesulfonic acid Natural products NCCCS(O)(=O)=O SNKZJIOFVMKAOJ-UHFFFAOYSA-N 0.000 description 1
- ULUIMLJNTCECJU-UHFFFAOYSA-N 3-amino-4-hydroxybenzenesulfonate;hydron Chemical compound NC1=CC(S(O)(=O)=O)=CC=C1O ULUIMLJNTCECJU-UHFFFAOYSA-N 0.000 description 1
- GSCPDZHWVNUUFI-UHFFFAOYSA-N 3-aminobenzamide Chemical compound NC(=O)C1=CC=CC(N)=C1 GSCPDZHWVNUUFI-UHFFFAOYSA-N 0.000 description 1
- KDHWOCLBMVSZPG-UHFFFAOYSA-N 3-imidazol-1-ylpropan-1-amine Chemical compound NCCCN1C=CN=C1 KDHWOCLBMVSZPG-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- IVUOMFWNDGNLBJ-UHFFFAOYSA-N 4-azaniumyl-2-hydroxybutanoate Chemical compound NCCC(O)C(O)=O IVUOMFWNDGNLBJ-UHFFFAOYSA-N 0.000 description 1
- KNILZINKISHVIQ-UHFFFAOYSA-N 4-azaniumylbutane-1-sulfonate Chemical compound NCCCCS(O)(=O)=O KNILZINKISHVIQ-UHFFFAOYSA-N 0.000 description 1
- FQTXRLQVJKDWIM-UHFFFAOYSA-N 5-amino-5-hydroxycyclohexa-1,3-diene-1-carboxylic acid Chemical compound NC1(O)CC(C(O)=O)=CC=C1 FQTXRLQVJKDWIM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- WSYUEVRAMDSJKL-UHFFFAOYSA-N ethanolamine-o-sulfate Chemical compound NCCOS(O)(=O)=O WSYUEVRAMDSJKL-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C22B3/0005—
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C22B3/001—
-
- C22B3/0012—
-
- C22B3/0013—
-
- C22B3/0031—
-
- C22B3/0098—
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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Abstract
Description
본 발명은 금속 이온이 침출된 황산 함유 침출액으로부터 다가 금속 이온을 회수하는 방법 및 이를 위한 복합 멤브레인에 관한 것이다.The present invention relates to a method for recovering polyvalent metal ions from a leaching solution containing sulfuric acid in which metal ions are leached, and a composite membrane therefor.
제련산업은 희소금속 및 유가금속이 포함된 원석을 다양한 공법으로 고순도의 소재로 정제하여 생산하는 산업이다. 동제련, 아연제련 등의 비철제련 업종에서는 대부분 황화광석을 원료로 하므로, 제련 과정 중에 황산농도 2 내지 15%의 불순물을 함유한 폐황산이 발생한다. 제련 과정 중 발생하는 폐황산에는 다양한 희소금속들이 포함되어 있으나, 공정수에서 희소금속 회수가 처리기술 부족으로 중화되어 폐기되고 있는 실정이다.The smelting industry is an industry that produces raw materials containing rare metals and valuable metals by refining them with high purity materials using various methods. In the nonferrous smelting industries such as copper smelting and zinc smelting, since most of the raw materials are sulphide ores, waste sulfuric acid containing impurities with a sulfuric acid concentration of 2 to 15% is generated during the smelting process. The waste sulfuric acid generated during the smelting process contains various rare metals, but in the process water, the recovery of rare metals is neutralized due to the lack of processing technology.
일반적으로 습식제련공정에서의 모액(침출액)은 황산(10~15%) 용액 상태이며, 모액 중의 유가금속 (Cu, Zn 등) 및 희소금속(In, Se, Re 등)은 보통 수 ppm에서 수 % 단위로 용해되어 있다. 모액 중 용해되어 있는 유가/희소금속을 회수하기 위하여 종래에는 주로 중화법이나, 치환법, 흡착법, 이온교환법 등을 사용하고 있다. 그러나, 이들 방법은 대부분 비용이 많이 발생하거나, 폐기물을 다량 발생하여 친환경적이지 못한 단점이 있다. 특히, 분리막을 회수공정에 적용하는데 있어서, 희소금속이 포함된 모액은 다량의 1가이온(Na, Cl, F)과 다가이온(Ca, Mg, Pb, As) 등을 함께 포함하고 있기 때문에 우선적으로 이온별 분리성능이 우수해야 하며, 지속적인 분리/농축을 위해서는 산에 대한 화학적 안정성이 무엇보다도 중요시된다.In general, the mother liquor (leach solution) in the wet smelting process is in the form of sulfuric acid (10 to 15%) solution and the valuable metals (Cu, Zn etc.) and rare metals (In, Se, Re etc.) %. Conventionally, a neutralization method, a substitution method, an adsorption method, and an ion exchange method are mainly used for recovering the oil / rare metal dissolved in the mother liquor. However, these methods are disadvantageous in that they are costly in most cases or are not environmentally friendly due to a large amount of waste. Particularly, in applying the separation membrane to the recovery process, since the mother liquor containing the rare metal contains a large amount of monovalent ions (Na, Cl, F) and polyvalent ions (Ca, Mg, Pb, As) , And the chemical stability of the acid is most important for continuous separation / concentration.
한편, 전형적인 폴리아미드막은 다관능성 아민과 다관능성 아실 할라이드의 계면 중합에 의해 얻을 수 있다. 이미 언급한 역삼투 복합막의 한 예는 캐도트 (Cadotte)에서 출원한 미국특허 제4,277,344호(1981.07.07 등록)이다. 이 특허는 두개의 1급 아민 치환체를 함유하는 방향족 다관능성 아민과 세 개 이상의 아실할라이드 관능기를 갖는 방향족의 아실할라이드를 계면 중합시켜 얻은 방향족의 폴리아미드 박막에 관한 특허이다. 구체적으로 살펴보면 아래의 공정을 따른다. 미세 다공성 폴리술폰 지지체 상에서 메타페닐렌디아민(m-phenylenediamine)을 코팅한다. 잉여의 메타페닐 디아민 용액을 지지층 상에서 제거한 후, 이 코팅된 지지층상에 프레온(trichlorotrifluoro ethane, Freon TF, DuPont사)에 녹인 트리메조일클로라이드(TMC)와 반응시킨다. 접촉 시간은 10초 정도이며 실제 반응시간은 1초 이내에 다 일어난다. 이때 그 성능이 아주 우수하다고 발표하였다. 폴리아미드 층을 형성시키는 모노머나 첨가제의 농도나 성분 등을 조절하는 상기의 특허 이외에 멤브레인의 후처리를 통해 물성을 조절하기 위한 방법들도 연구되어 왔다. 미국특허 제5,755,964호는 폴리아미드 분리층을 가지는 역삼투막 또는 나노막을 암모니아나 알킬 아민류로 후처리하여 플럭스를 증가시키는 방법을 개시한 바 있다. 상기의 방법으로 제조된 역삼투막이나 나노막의 Flux와 Rejection을 조절할 수 있고, 역삼투막을 나노막으로 바꾸는 것도 가능하였다. 한편, 미국특허 제6,280,853호는 폴리아미드막에 폴리알킬렌 옥사이드를 그라프팅하여 rejection을 NF 수준으로 감소시키고 내오염성을 향상시킨 막을 개시한 바 있다.On the other hand, a typical polyamide membrane can be obtained by interfacial polymerization of a polyfunctional amine and a polyfunctional acyl halide. One example of the aforementioned reverse osmosis composite membrane is US Pat. No. 4,277,344 (Registered on July 1, 1987), filed by Cadotte. This patent relates to an aromatic polyamide thin film obtained by interfacial polymerization of an aromatic polyfunctional amine containing two primary amine substituents and an aromatic acyl halide having three or more acyl halide functional groups. Specifically, the following steps are followed. M-phenylenediamine is coated on the microporous polysulfone support. The excess of the metaphenyldiamine solution is removed on the supporting layer, and then reacted with trimethoyl chloride (TMC) dissolved in Freon (trichlorotrifluoro ethane, Freon TF, DuPont) on the coated support layer. The contact time is about 10 seconds, and the actual reaction time is within 1 second. At that time, the performance was excellent. In addition to the above-mentioned patents for controlling the concentration and the components of the monomers and additives forming the polyamide layer, methods for controlling physical properties through post-treatment of membranes have also been studied. U.S. Patent No. 5,755,964 discloses a method of post-treating a reverse osmosis membrane or nanofiber having a polyamide separation layer with ammonia or alkyl amines to increase the flux. Flux and rejection of the reverse osmosis membrane or nanofiltration membrane prepared by the above method can be controlled and it is also possible to convert the reverse osmosis membrane into nanofilm. On the other hand, U.S. Patent No. 6,280,853 discloses a membrane obtained by grafting a polyalkylene oxide onto a polyamide membrane to reduce rejection to NF levels and to improve resistance to contamination.
산 공급액 처리용으로 이용가능한 통상의 기술은 유용한 추출된 성분의 손실 뿐만 아니라 환경적 폐기물 처리 및 오염된 산의 처분과 관련된 비용 때문에 비효율적이다. 추가로, 그 중에서도 산 공급액 스트림으로부터 유용한 성분의 회수 및/또는 재생용 산의 회수를 효율적이게 하는 분리 매질 및/또는 기술이 지속적으로 필요하다.Conventional techniques available for treatment of acid feeds are inefficient due to costs associated with environmental waste treatment and the disposal of contaminated acid as well as loss of useful extracted components. In addition, there is a continuing need for a separation medium and / or technique which, amongst others, makes it possible to recover useful components from the acid feed stream and / or to recover the acid for regeneration.
그러나, 아직까지 산에 대한 이례적인 안정성 및 투과성을 가지면서 액체 기재 공급액 스트림으로부터 용존 금속 양이온 및 유기 화합물을 제거할 수 있는 반투과성 막이 부족하다.However, there is still a lack of semipermeable membranes that can remove dissolved metal cations and organic compounds from the liquid base feed stream with exceptional stability and permeability to acids.
본 발명의 목적은 제련공정에 적용하여 발생되는 유가금속 및 희소금속을 효율적이고 경제적으로 회수하는 방법 및 상기 방법에 적용할 수 있는 내산성이 우수한 고투과성 복합 멤브레인을 제공하는 것이다.An object of the present invention is to provide a method for efficiently and economically recovering valuable metals and rare metals generated in a smelting process, and a highly permeable composite membrane excellent in acid resistance that can be applied to the method.
본 발명의 제1양태는 금속 이온이 침출된 황산 함유 침출액으로부터 다가 금속 이온을 회수하는 방법에 있어서, A first aspect of the present invention is a method for recovering polyvalent metal ions from a sulfuric acid-containing leach solution containing leached metal ions,
다공성 고분자 지지체; 및 상기 다공성 고분자 지지체 표면상에서 방향족 다가 아민 및 지방족 다가 아민의 혼합물과 다관능성 산할로겐 화합물의 계면중합에 의해 형성된 폴리아미드 코팅층을 포함하는 복합 멤브레인에 금속 이온이 침출된 황산 함유 침출액을 공급하여 다가 금속 이온을 회수하는 제1단계를 포함하고, A porous polymeric support; And a polyamide coating layer formed by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound on the surface of the porous polymer scaffold and supplying a leaching solution containing a sulfuric acid into which a metal ion is leached, A first step of recovering ions,
여기에서, 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 상기 복합 멤브레인의 수투과유량이 40 gallon/ft2·day 이상인 것이 특징인 방법을 제공한다.Here, when the leach solution containing 2,000 ppm sulfuric acid in which metal ions are leached is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the permeation flow rate of the composite membrane is 40 gallon / ft 2 · day or more ≪ / RTI >
본 발명의 제2양태는 다공성 고분자 지지체; 및 상기 다공성 고분자 지지체 표면상에서 방향족 다가 아민 및 지방족 다가 아민의 혼합물과 다관능성 산할로겐 화합물의 계면중합에 의해 형성된 폴리아미드 코팅층을 포함하고,A second aspect of the present invention provides a porous polymer scaffold comprising: a porous polymer scaffold; And a polyamide coating layer formed on the surface of the porous polymer substrate by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound,
금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 상기 복합 멤브레인의 수투과유량이 40 gallon/ft2·day 이상인 것이 특징인, 금속 이온이 침출된 황산 함유 침출액으로부터 다가 금속 이온을 회수하기 위한 복합 멤브레인을 제공한다.Characterized in that the permeate flow rate of the composite membrane is at least 40 gallon / ft 2 · day when fed at a pressure of 15 kgf / cm 2 and at a temperature of 25 ° C, wherein the leachate containing 2,000 ppm sulfuric acid, And a composite membrane for recovering polyvalent metal ions from the leached sulfuric acid-containing leaching solution.
본 발명의 제3양태는 상기 제2양태에 따른 복합 멤브레인을 포함하는 수처리용 장치를 제공한다.A third aspect of the present invention provides a water treatment apparatus comprising a composite membrane according to the second aspect.
이하 본 발명의 구성을 상세히 설명한다.Hereinafter, the configuration of the present invention will be described in detail.
황화광석을 원료로 하는 습식 비철 제련시 발생하는 공정수에는 다양한 희소금속들이 포함되어 있어 이로부터 희소금속들의 분리 회수 기술이 필요하다. 이를 위해서는 우선적으로 주로 희소금속들에 해당하는 다가 금속 이온의 배제율이 일가 금속 이온의 배제율보다 높고 수투과유량이 우수해야 한다. 또한, 상기 공정수가 2 내지 15%의 수준의 황산을 함유하고 있어 지속적인 분리/농축을 위해서는 황산에 대한 화학적 안정성이 요구된다.The process water generated from the non-ferrous smelting process using sulphide ore as raw material contains various rare metals. Therefore, the separation and recovery technology of rare metals is needed. For this purpose, the rejection rate of the polyvalent metal ions, which are mainly rare metals, should be higher than the rejection rate of the monovalent metal ions and be excellent in the water permeation flow rate. In addition, since the above process contains sulfuric acid at a level of 2 to 15%, chemical stability to sulfuric acid is required for continuous separation / concentration.
본 발명은 황화광석을 원료로 하는 습식 비철 제련시 발생하는, 금속 이온이 침출된 황산 함유 침출액으로부터 다가 금속 이온을 회수함에 있어, 다가 아민과 다관능성 산할로겐 화합물의 계면중합에 의해 형성된 폴리아미드 코팅층을 포함하는 복합 멤브레인을 사용하고, 이때 특히 다가 아민으로서 방향족 다가 아민을 사용함으로써 황산에 대한 화학적 안정성을 향상시킬 수 있음을 발견하였다. 더 나아가, 이때 방향족 다가 아민과 함께 지방족 다가 아민을 조합하여 사용함으로써 황산에 대한 화학적 안정성을 향상시킬 수 있는 동시에 수투과유량도 향상시킬 수 있음을 발견하였다. 또한, 상기 복합 멤브레인을 사용함으로써 다가 금속 이온의 배제율이 일가 금속 이온의 배제율보다 높아 희소금속들의 회수율을 높일 수 있음을 발견하였다. 본 발명은 이에 기초한다.The present invention relates to a polyamide coating layer formed by interfacial polymerization of a polyhydric amine and a polyfunctional acid halide in the recovery of polyvalent metal ions from a sulfuric acid-containing leach solution containing metal ions leached during wet nonferrous smelting using a sulfide ore as a raw material, And that the chemical stability to sulfuric acid can be improved by using an aromatic polyamine as a polyhydric amine. Furthermore, it has been found that by using aliphatic polyvalent amines in combination with aromatic polyvalent amines at this time, the chemical stability against sulfuric acid can be improved and the water permeation flow rate can be improved. Further, by using the composite membrane, it has been found that the rejection rate of polyvalent metal ions is higher than the rejection rate of monovalent metal ions, so that the recovery rate of rare metals can be increased. The present invention is based on this.
전술한 바와 같이, 본 발명에 따른 금속 이온이 침출된 황산 함유 침출액으로부터 다가 금속 이온을 회수하는 방법은, As described above, the method for recovering polyvalent metal ions from the leaching solution containing sulfuric acid from which the metal ions are leached according to the present invention,
다공성 고분자 지지체; 및 상기 다공성 고분자 지지체 표면상에서 방향족 다가 아민 및 지방족 다가 아민의 혼합물과 다관능성 산할로겐 화합물의 계면중합에 의해 형성된 폴리아미드 코팅층을 포함하는 복합 멤브레인에 금속 이온이 침출된 황산 함유 침출액을 공급하여 다가 금속 이온을 회수하는 제1단계를 포함하고, A porous polymeric support; And a polyamide coating layer formed by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound on the surface of the porous polymer scaffold and supplying a leaching solution containing a sulfuric acid into which a metal ion is leached, A first step of recovering ions,
여기에서, 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 상기 복합 멤브레인의 수투과유량이 40 gallon/ft2·day 이상일 수 있다.Here, when the leached solution containing 2,000 ppm sulfuric acid in which metal ions are leached is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the water permeation flow rate of the composite membrane may be 40 gallon / ft 2 · day or more.
금속 이온이 침출된 황산 함유 침출액은 예를 들어 황화광석을 원료로 하는 습식 비철 제련시 발생하는 것일 수 있다. 제련시 발생하는 공정수 또는 폐수는 금속 이온이 침출된 황산 함유 침출액일 수 있으며, 이는 주로 1가 이온 (H+ 및 HSO4 -)을 포함하고, 2가 이상의 다가 금속 이온을 함께 포함하고 있다. 본 발명에서, 상기 복합 멤브레인은 다가 금속 이온은 더욱 잘 체류시키는 반면 본질적으로 1가인 황산은 더욱 잘 투과시키는 능력을 갖는다. 구체적으로, 본 발명에서 사용하는 복합 멤브레인은 다가 금속 이온의 배제율이 일가 금속 이온의 배제율보다 높아 희소금속들의 회수율을 높음을 확인하였다(표 1).The leachate containing sulfuric acid in which the metal ions are leached may be generated, for example, during non-ferrous smelting using a sulphide ore as a raw material. The process water or wastewater generated during the smelting process may be a sulfuric acid-containing leaching solution in which the metal ions are leached, which mainly include monovalent ions (H + and HSO 4 - ), and include multivalent metal ions having two or more valences. In the present invention, the composite membrane has the ability to more easily retain the polyvalent metal ions while allowing the inherently monovalent sulfuric acid to permeate better. Specifically, in the composite membrane used in the present invention, the rejection rate of the polyvalent metal ion was higher than the rejection rate of the univalent metal ion (Table 1).
전술한 바와 같이, 본 발명에 따른 금속 이온이 침출된 황산 함유 침출액으로부터 다가 금속 이온을 회수하기 위한 복합 멤브레인은, 다공성 고분자 지지체; 및 상기 다공성 고분자 지지체 표면상에서 방향족 다가 아민 및 지방족 다가 아민의 혼합물과 다관능성 산할로겐 화합물의 계면중합에 의해 형성된 폴리아미드 코팅층을 포함하고, 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 상기 복합 멤브레인의 수투과유량이 40 gallon/ft2·day 이상일 수 있다.As described above, the composite membrane for recovering polyvalent metal ions from the leaching solution containing sulfuric acid from which the metal ions are leached according to the present invention comprises a porous polymer scaffold; And a polyamide coating layer formed by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound on the surface of the porous polymer scaffold, wherein the leached solution containing 2,000 ppm sulfuric acid in which the metal ions are leached is treated with 15 kgf / Cm < 2 > and a temperature of 25 DEG C, the water permeation flow rate of the composite membrane may be 40 gallon / ft < 2 > day or more.
본 발명에 따른 복합 멤브레인은 하기 단계를 포함하는 제조방법으로 제조할 수 있다.The composite membrane according to the present invention can be produced by a manufacturing method comprising the following steps.
a) 다공성 고분자 지지체를 준비하는 단계;a) preparing a porous polymer scaffold;
b) 상기 다공성 고분자 지지체를 방향족 다가 아민 및 지방족 다가 아민의 혼합물을 함유하는 수용액에 침지하는 단계; 및b) immersing the porous polymeric support in an aqueous solution containing a mixture of an aromatic polyamine and an aliphatic polyamine; And
c) 상기 다공성 고분자 지지체를 다관능성 산할로겐 화합물을 함유하는 유기용액에 침지하여 계면중합을 통해 폴리아미드 코팅층을 형성시키는 단계.c) immersing the porous polymer scaffold in an organic solution containing a polyfunctional acid halide compound to form a polyamide coating layer by interfacial polymerization;
바람직하기로, 상기 단계 b) 및 단계 c) 사이에 하기 단계를 추가로 포함할 수 있다.Preferably, between step b) and step c) further comprises the following step.
b-1) 상기 단계 b)에서 침지시킨 다공성 고분자 지지체에 잔류하는 과잉의 방향족 다가 아민 및 지방족 다가 아민의 혼합물을 함유하는 수용액을 제거하는 단계.b-1) removing an aqueous solution containing a mixture of an excess of an aromatic polyamine and an aliphatic polyamine remaining in the porous polymer scaffold immersed in the step b).
바람직하기로, 상기 단계 c) 이후에 하기 단계를 추가로 포함할 수 있다.Preferably, after step c), the method may further comprise the steps of:
c-1) 상기 단계 c)에서 침지시킨 다공성 고분자 지지체를 건조시키는 단계.c-1) drying the porous polymer scaffold immersed in step c).
본 발명에서, 다공성 고분자 지지체는 평균 기공 크기가 10 ㎚ 내지 1 ㎛일 수 있다.In the present invention, the porous polymer scaffold may have an average pore size of 10 nm to 1 m.
상기 단계 a)에서, 다공성 고분자 지지체의 준비는 당업계에 공지된 상업화된 다공성 고분자 지지체를 구입하거나, 당업계에 공지된 다공성 고분자 지지체 제조방법을 제한없이 이용하여 제조함으로써 달성될 수 있다. 바람직하게, 상기 제1단계는 증기유도 상분리법(vapor-induced phase separation, VIPS), 비용매유도상분리법(Non-solvent Induced Phase Separation: NIPS), 열유도상분리법(Thermally Induced Phase Separation: TIPS) 또는 이들의 병용하여 수행될 수 있다.In step a) above, the preparation of the porous polymer scaffold can be accomplished by purchasing a commercialized porous polymer scaffold known in the art, or by using the method of manufacturing porous polymer scaffolds known in the art without limitation. Preferably, the first step is a vapor-induced phase separation (VIPS), a non-solvent induced phase separation (NIPS), a thermally induced phase separation (TIPS) Or a combination thereof.
증기유도 상분리법에 의하면, 고분자 수지를 양용매(good solvent)에 용해시킨 고분자 용액을 성형하고, 상기 성형된 고분자 용액을 수증기에 노출시켜 상전이 시킴으로써 막을 제조한다. 비용매유도 상분리법에 의하면, 고분자 수지를 양용매(good solvent)에 용해시킨 고분자 용액을 성형하고, 상기 성형된 고분자 용액을 비용매(non-solvent)를 포함하는 액에 접촉시킴으로써 상기 고분자 용액의 고화를 유도하여 막을 제조한다. 반면, 열 유도 상 분리법에 의하면, 고분자 수지를 상 분리 온도 이상에서 빈용매(poor solvent)에 강제로 용해시킴으로써 고분자 용액을 제조한다. 이 고분자 용액을 성형하고, 성형된 고분자 용액을 상 분리 온도 이하의 냉각액에 접촉시킴으로써 고분자 용액을 응고시켜 막을 제조한다.According to the steam-induced phase separation method, a polymer solution in which a polymer resin is dissolved in a good solvent is formed, and the formed polymer solution is exposed to water vapor to form a phase transition. According to the non-solvent-derived phase separation method, a polymer solution in which a polymer resin is dissolved in a good solvent is formed, and the formed polymer solution is brought into contact with a solution containing a non-solvent, And solidification is induced to produce a film. On the other hand, according to the heat-induced phase separation method, the polymer solution is prepared by forcibly dissolving the polymer resin in a poor solvent at a temperature higher than the phase separation temperature. The polymer solution is molded, and the polymer solution is contacted with a cooling liquid at a phase separation temperature or lower to coagulate the polymer solution to produce a film.
상기 다공성 고분자 지지체의 소재는 다공성 고분자 지지체 형태로 성형가능하고 표면을 폴리아미드 계면중합할 수 있는 한, 당업계에 공지된 다공성 고분자 지지체 제조에 사용되는 고분자를 제한없이 사용할 수 있다. 본 발명에서는, 상기 다공성 고분자 지지체로서 폴리술폰, 폴리에테르술폰, 셀룰로스아세테이트, 폴리아미드 또는 이의 조합으로 이루어진 것을 사용할 수 있다.The material of the porous polymer scaffold can be formed into a porous polymer scaffold, and as long as the surface of the porous scaffold can be polyamide-interfacial polymerized, the polymer used in the production of the porous polymer scaffold known in the art can be used without limitation. In the present invention, as the porous polymer scaffold, polysulfone, polyethersulfone, cellulose acetate, polyamide or a combination thereof may be used.
본 발명에서, 다공성 고분자 지지체는 필름 형태일 수 있다. 상기 다공성 고분자 지지체의 두께는 20 내지 150 ㎛, 바람직하기로는 30 내지 100 ㎛일 수 있다. 또한, 상기 다공성 고분자 지지체는 부직포로 보강될 수 있다.In the present invention, the porous polymer scaffold may be in the form of a film. The thickness of the porous polymer scaffold may be 20 to 150 μm, preferably 30 to 100 μm. In addition, the porous polymer scaffold may be reinforced with a nonwoven fabric.
상기 단계 b)에서, 다가 아민과 다관능성 산할로겐 화합물의 계면중합에 의해 폴리아미드 코팅층을 형성함에 있어, 다가 아민으로서 방향족 다가 아민과 지방족 다가 아민의 혼합물을 사용함으로써 산에 대한 화학적 안정성을 높이면서 우수한 수투과유량을 확보할 수 있다.In the step b), when a polyamide coating layer is formed by interfacial polymerization of a polyfunctional amine and a polyfunctional acid halide compound, the use of a mixture of an aromatic polyamine and an aliphatic polyamine as a polyamine increases the chemical stability of the acid A good water permeation flow rate can be secured.
본 발명에서, 방향족 다가 아민 및 지방족 다가 아민의 혼합물 중 방향족 다가 아민:지방족 다가 아민의 중량비는 1:1 내지 1.9:0.1, 바람직하기로는 1.5:0.5 내지 1.8:0.2일 수 있다. 즉, 방향족 다가 아민 1 내지 1.9 중량부:지방족 다가 아민 0.1 내지 1 중량부의 비율로 사용될 수 있다. 본 발명에서는 다가 아민으로서 방향족 다가 아민을 주성분으로 하고 여기에 투과유량 증진을 위해 지방족 다가 아민을 조합하여 사용한다. 만일 방향족 다가 아민:지방족 다가 아민의 중량비에서 방향족 다가 아민의 중량비가 1 중량부보다 적으면 산에 대한 화학적 안정성이 떨어질 수 있고 1.9 중량부보다 많으면 수투과유량이 떨어질 수 있다.In the present invention, the weight ratio of the aromatic polyamine to the aliphatic polyamine in the mixture of the aromatic polyamine and the aliphatic polyamine may be from 1: 1 to 1.9: 0.1, preferably from 1.5: 0.5 to 1.8: 0.2. That is, the aromatic polyhydric amine may be used at a ratio of 1 to 1.9 parts by weight: 0.1 to 1 part by weight of an aliphatic polyvalent amine. In the present invention, as the polyvalent amine, an aromatic polyvalent amine is used as a main component and an aliphatic polyvalent amine is used in combination to increase the permeation flow rate. If the weight ratio of the aromatic polyvalent amine to the aliphatic polyvalent amine is less than 1 part by weight, the chemical stability to the acid may be deteriorated. If the weight ratio of the aromatic polyvalent amine is more than 1.9 parts by weight, the water permeation flow rate may be decreased.
구체적으로, 본 발명의 실시예에서는 다가 아민 모노머로서 방향족 다가 아민 및 지방족 다가 아민의 혼합물을 사용한 경우 산에 대한 화학적 안정성이 우수하면서 수투과유량도 향상시킬 수 있음을 확인하였다(표 1 및 표 2). 그러나, 이에 반해 비교예 1에서 다가 아민 모노머로서 지방족 다가 아민을 사용한 경우에는 내산성이 떨어지고(표 2), 비교예 2에서 다가 아민 모노머로서 방향족 다가 아민을 사용한 경우 내산성은 향상되나(표 2) 수투과량이 급격히 떨어지는 것을 확인하였다(표 1 및 표 2).Specifically, in the examples of the present invention, it was confirmed that when a mixture of an aromatic polyamine and an aliphatic polyamine as a polyamine amine monomer was used, the chemical stability to the acid was excellent and the water permeation flow rate could be improved (see Tables 1 and 2 ). On the contrary, in Comparative Example 1, when the aliphatic polyamine was used as an aliphatic polyamine, the acid resistance was poor (Table 2), and when the aromatic polyamine was used as the polyamine monomer in Comparative Example 2, the acid resistance was improved (Table 2) It was confirmed that the permeation amount dropped sharply (Table 1 and Table 2).
본 발명에서, 상기 방향족 다가 아민 및 지방족 다가 아민의 혼합물은 계면 중합시 전체 수용액 중 0.1 내지 10 중량%, 예를 들어 1 내지 5 중량%, 구체적으로 2 중량%의 농도로 함유하는 수용액 형태로 사용할 수 있다.In the present invention, the mixture of the aromatic polyamine and the aliphatic polyamine is used in the form of an aqueous solution containing 0.1 to 10% by weight, for example, 1 to 5% by weight, specifically 2% by weight, .
본 발명에서 사용하는 용어, "방향족 다가 아민"은 2개 이상의 아민기를 함유하는 방향족 화합물을 의미할 수 있다. 본 발명에서, 방향족 다가 아민은 메타페닐렌디아민, 파라페닐렌디아민, 1,3,6-벤젠트리아민, 4-클로로-1,3-페닐렌디아민, 6-클로로-1,3-페닐렌디아민, 3-클로로-1,4-페닐렌 디아민, 3,5-디아미노 벤조산, 2,4-디아미노톨루엔, 2,4-디아미노아니솔, 아미돌, 크실렌디아민 또는 이의 조합일 수 있으며, 이에 제한되는 것은 아니다.As used herein, the term "aromatic polyvalent amine" may refer to an aromatic compound containing two or more amine groups. In the present invention, the aromatic polyvalent amine is at least one selected from the group consisting of metaphenylenediamine, paraphenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylene Diamino, 3-chloro-1,4-phenylenediamine, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, amidol, xylenediamine or combinations thereof , But is not limited thereto.
본 발명에서 사용하는 용어, "지방족 다가 아민"은 2개 이상의 아민기를 함유하는 지방족 화합물을 의미할 수 있다. 본 발명에서, 지방족 다가 아민은 에틸렌디아민, 1,3-다이아미노프로판, 트리스(2-아미노에틸)아민 또는 이의 조합일 수 있으며, 이에 제한되는 것은 아니다.The term "aliphatic polyvalent amine " used in the present invention may mean an aliphatic compound containing two or more amine groups. In the present invention, the aliphatic polyvalent amine may be ethylenediamine, 1,3-diaminopropane, tris (2-aminoethyl) amine or a combination thereof, but is not limited thereto.
상기 단계 b)에서, 내오염성이 향상된 폴리아미드 코팅층을 제공하기 위하여 상기 방향족 다가 아민 및 지방족 다가 아민의 혼합물을 포함하는 수용액은 친수성 화합물, 즉 친수성기를 함유하는 화합물을 더 포함할 수 있다. 이때, 상기 친수성기를 함유하는 화합물은 수용액 상에 0.001 내지 8중량%로 존재하고, 더욱 바람직하게는 0.01 내지 4중량%로 존재할 수 있다.In the step b), the aqueous solution containing a mixture of the aromatic polyamine and the aliphatic polyamine may further comprise a hydrophilic compound, i.e., a compound containing a hydrophilic group, in order to provide a polyamide coating layer having improved stain resistance. At this time, the compound containing the hydrophilic group may be present in an amount of 0.001 to 8% by weight, more preferably 0.01 to 4% by weight, in the aqueous solution.
상기 방향족 다가 아민 및 지방족 다가 아민의 혼합물을 포함하는 수용액에 첨가되는 친수성 화합물은 하이드록시기, 술폰화기, 카르보닐기, 트리알콕시실란기, 음이온기 및 3급 아미노기로 이루어진 군에서 선택되는 적어도 어느 하나의 친수성 기능기를 가지는 친수성 화합물이다. 더욱 바람직하게는 친수성 아미노 화합물이다.The hydrophilic compound added to the aqueous solution containing the mixture of the aromatic polyvalent amine and the aliphatic polyvalent amine is at least one selected from the group consisting of a hydroxyl group, a sulfonated group, a carbonyl group, a trialkoxysilane group, an anion group and a tertiary amino group Is a hydrophilic compound having a hydrophilic functional group. More preferably a hydrophilic amino compound.
더욱 구체적으로, 하이드록시기를 가지는 친수성 화합물의 비제한적인 예로는 2-에틸-1,3-헥산디올, 1,3-디아미노-2-프로판올, 에탄올아민, 디에탄올아민, 3-아미노-1-프로판올, 4-아미노-1-부탄올, 2-아미노-1-부탄올 또는 이들의 혼합물 등이 있다.More specifically, non-limiting examples of the hydrophilic compound having a hydroxy group include 2-ethyl-1,3-hexanediol, 1,3-diamino-2-propanol, ethanolamine, diethanolamine, -Propanol, 4-amino-1-butanol, 2-amino-1-butanol or mixtures thereof.
카르보닐기를 가지는 친수성 화합물의 비제한적인 예로는 아미노아세트알데히드 디메틸 아세탈, ａ-아미노부틸로락톤, 3-아미노벤즈아미드, 4-아미노벤즈아미드, N-(3-아미노프로필)-2-피롤리디논 또는 이들의 혼합물 등이 있다.Non-limiting examples of hydrophilic compounds having a carbonyl group include aminoacetaldehyde dimethylacetal, a-aminobutylolactone, 3-aminobenzamide, 4-aminobenzamide, N- (3-aminopropyl) -2-pyrrolidinone Or mixtures thereof.
또한, 트리알콕시실란기를 함유한 친수성 화합물의 비제한적인 예로는 (3-아미노프로필)트리에톡시실란, (3-아미노프로필)트리메톡시실란 또는 이들의 혼합물 등이 있다.In addition, non-limiting examples of hydrophilic compounds containing a trialkoxysilane group include (3-aminopropyl) triethoxysilane, (3-aminopropyl) trimethoxysilane, and mixtures thereof.
상기 음이온기를 가지는 친수성 화합물의 비제한적인 예로는 캄포술폰산, 3-아미노-1-프로펜술폰산, 4-아미노-1-부텐술폰산, 2-아미노에틸 하이드로젠 설페이트, 3-아미노벤젠술폰산, 3-아미노-4-하이드록시벤젠술폰산, 4-아미노벤젠술폰산, 3-아미노프로필포술폰산, 3-아미노-4-하이드록시벤조산, 4-아미노-3-하이드록시벤조산, 6-아미노헥산산, 3-아미노부탄산, 4-아미노-2-하이드록시부탄산, 4-아미노부탄산, 글리신, 타우린, 글루탐산 또는 이들의 혼합물 등이 있다.Non-limiting examples of the hydrophilic compound having an anionic group include camphorsulfonic acid, 3-amino-1-propanesulfonic acid, 4-amino-1-butanesulfonic acid, 2-aminoethylhydrogensulfate, 3- Amino-3-hydroxybenzoic acid, 6-aminohexanoic acid, 6-aminohexanoic acid, 3- amino-4-hydroxybenzenesulfonic acid, Aminobutanoic acid, 4-amino-2-hydroxybutanoic acid, 4-aminobutanoic acid, glycine, taurine, glutamic acid, or a mixture thereof.
또한, 하나 또는 그 이상의 3급 아미노기를 가지는 친수성 화합물로는 트리에틸아민, 3-(디메틸아미노)프로필아민, 3-(디에틸아미노)프로필아민, 4-(2-아미노에틸)모폴린, 1-(2-아미노에틸)피페라진, 3,3'-디아미노-N-메틸디프로필아민, 1-(3-아미노프로필)이미다졸 또는 이들의 혼합물 등이 있다.Examples of the hydrophilic compound having one or more tertiary amino groups include triethylamine, 3- (dimethylamino) propylamine, 3- (diethylamino) propylamine, 4- (2-aminoethyl) - (2-aminoethyl) piperazine, 3,3'-diamino-N-methyldipropylamine, 1- (3-aminopropyl) imidazole or mixtures thereof.
상기 단계 b-1)에서, 과잉의 방향족 다가 아민 및 지방족 다가 아민의 혼합물을 함유하는 수용액의 제거는 롤러를 이용하거나 상온에서 방치하거나 이들 둘 모두를 수행하여 달성할 수 있다.In the above step b-1), the removal of the aqueous solution containing the mixture of the excess aromatic polybasic amine and the aliphatic polybasic amine can be achieved by using a roller or by leaving at room temperature or both.
본 발명에서, 상기 다관능성 산할로겐 화합물은 다관능성 아실할라이드, 다관능성 술포닐할라이드, 다관능성 이소시아네이트 또는 이의 혼합물일 수 있으나, 이에 제한되지 않는다. 바람직하게, 상기 다관능성 산할로겐 화합물은 트리메조일 할라이드, 벤조페논테트라카르복실산 할라이드, 트리멜리트산 할라이드(trimellitic acid halide), 피로메리트산 할라이드(pyromellitic acid halide), 이소프탈산 할라이드, 테레프탈산 할라이드, 나프탈렌디카르복실산 할라이드, 다이카르복실산 할라이드, 1,3,5-사이클로헥산 트리카르복실산 할라이드, 1,3-사이클로헥산 디카르복실산 할라이드, 1,4-사이클로헥산 디카르복실산 할라이드 또는 이의 혼합물일 수 있으나, 이에 제한되지 않는다.In the present invention, the polyfunctional acid halide compound may be a polyfunctional acyl halide, a polyfunctional sulfonyl halide, a polyfunctional isocyanate, or a mixture thereof, but is not limited thereto. Preferably, the polyfunctional acid halide is selected from the group consisting of trimesoyl halide, benzophenone tetracarboxylic acid halide, trimellitic acid halide, pyromellitic acid halide, isophthalic acid halide, terephthalic acid halide, Naphthalene dicarboxylic acid halide, dicarboxylic acid halide, 1,3,5-cyclohexanetricarboxylic acid halide, 1,3-cyclohexanedicarboxylic acid halide, 1,4-cyclohexanedicarboxylic acid halide Or a mixture thereof.
본 발명에서, 상기 다관능성 산할로겐 화합물은 계면 중합시 전체 유기용액 중 0.01 내지 2 중량%, 예를 들어 0.05 내지 0.5 중량%, 구체적으로 0.1 중량%의 농도로 함유하는 유기용액 형태로 사용할 수 있다.In the present invention, the polyfunctional acid halide compound can be used in the form of an organic solution containing 0.01 to 2% by weight, for example, 0.05 to 0.5% by weight, specifically 0.1% by weight, of the total organic solution in interfacial polymerization .
본 발명에서, 다관능성 산할로겐 화합물을 함유하는 유기용액은 유기용매로서 C8-12 이소파라핀(isoparaffin)계 용매, 구체적으로 ISOL-c(SK 에너지, 대한민국, CAS번호 64741-66-8)를 사용할 수 있다.In the present invention, the organic solution containing the polyfunctional acid halide compound is preferably a C 8-12 isoparaffin-based solvent, specifically, ISOL-c (SK Energy, Korea, CAS No. 64741-66-8) Can be used.
상기 단계 c-1)에서, 다공성 고분자 지지체의 건조는 40 내지 80℃의 온도, 예를 들어 50 내지 70℃의 온도에서 1분 내지 30분, 예를 들어 5분 내지 15분 동안 수행할 수 있다.In the above step c-1), drying of the porous polymer scaffold can be performed at a temperature of 40 to 80 ° C, for example, at a temperature of 50 to 70 ° C for 1 minute to 30 minutes, for example, 5 minutes to 15 minutes .
전술한 바와 같이, 본 발명에 따른 복합 멤브레인은 다가 금속 이온의 배제율이 일가 금속 이온의 배제율보다 높다. 구체적으로, 본 발명에 따른 복합 멤브레인은 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 다가 금속 이온의 배제율이 일가 금속 이온의 배제율보다 높다. 바람직하기로, 본 발명에 따른 복합 멤브레인은 다가 금속 이온의 배제율이 50% 이상일 수 있다. 본 발명에 따른 복합 멤브레인은 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 상기 복합 멤브레인의 수투과유량이 40 gallon/ft2·day 이상, 구체적으로 40 내지 120 gallon/ft2·day일 수 있다. 따라서, 본 발명에 따른 복합 멤브레인을 사용함에 따라 상기 제1단계에서 다가 금속 이온의 배제율이 일가 금속 이온의 배제율보다 높으면서도 우수한 수투과유량, 예를 들어 40 gallon/ft2·day 이상의 수투과유량을 나타낼 수 있다. 예를 들어, 상기 제1단계에서 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 다가 금속 이온의 배제율이 일가 금속 이온의 배제율보다 높으면서도 우수한 수투과유량, 예를 들어 40 gallon/ft2·day 이상의 수투과유량을 나타낼 수 있다.As described above, in the composite membrane according to the present invention, the rejection rate of the polyvalent metal ion is higher than the rejection rate of the monovalent metal ion. Specifically, when the leaching solution containing 2,000 ppm sulfuric acid in which the metal ions are leached is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the rejection rate of the polyvalent metal ion Rate. Preferably, the composite membrane according to the present invention may have a rejection rate of polyvalent metal ions of 50% or more. When feeding a composite membrane leachate containing 2,000 ppm sulfuric acid, the metal ion is leached according to the invention to a pressure and a temperature of 25 ℃ of 15 kgf / ㎠, the permeate flux of the composite membrane 40 gallon / ft 2 · day Specifically, 40 to 120 gallon / ft < 2 > day. Therefore, by using the composite membrane according to the present invention, the rejection rate of the polyvalent metal ion in the first step is higher than the rejection rate of the monovalent metal ion, and also excellent water permeation flow rate, for example, 40 gallon / ft 2 · day The permeate flow rate can be shown. For example, when the leaching solution containing 2,000 ppm sulfuric acid in which the metal ions are leached in the first step is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the rejection rate of the polyvalent metal ion Higher water permeation flow rate, for example, a water permeation flow rate of 40 gallon / ft < 2 > day or more.
또한, 본 발명에 따른 복합 멤브레인은 전술한 바와 같이 산에 대한 화학적 안정성이 우수하다. 바람직하기로, 본 발명에 따른 복합 멤브레인은 10일 이상, 예를 들어 3주 이상, 10일 내지 100일 동안 15 중량% 황산 수용액에 침지한 후에도 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 80% 이상의 다가 금속 이온의 배제율을 나타낼 수 있다. 구체적으로, 본 발명에서는 복합 멤브레인을 15 중량% 황산 수용액에 침지하고 28일 뒤, 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급하여 다가 금속 이온의 배제율을 조사한 결과, 80% 이상의 다가 금속 이온의 배제율을 나타내는 것을 확인하였다. 따라서, 이를 통해 본 발명의 복합 멤브레인이 장시간 동안 산성 조건 하에 노출되어도 손상 없이 우수한 다가 금속 이온 회수율을 나타낼 수 있음을 알 수 있다.In addition, the composite membrane according to the present invention has excellent chemical stability to an acid as described above. Preferably, the composite membrane according to the present invention has a leach solution containing 2,000 ppm sulfuric acid in which metal ions have been leached even after immersing in a 15 wt% sulfuric acid aqueous solution for 10 days or more, for example, 3 weeks or more and 10 days to 100 days When it is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the rejection rate of polyvalent metal ions of 80% or more can be shown. Specifically, in the present invention, the composite membrane is immersed in a 15 wt% sulfuric acid aqueous solution, and after 28 days, the leached solution containing 2,000 ppm sulfuric acid in which metal ions are leached is supplied at a pressure of 15 kgf / As a result of examining the rejection rate of the ions, it was confirmed that the rejection rate of the polyvalent metal ions was 80% or more. Thus, it can be seen that the composite membrane of the present invention can exhibit excellent polyvalent metal ion recovery without damaging even when exposed under acidic conditions for a long time.
본 발명에 따른 복합 멤브레인은 수처리용 장치, 구체적으로 산성 환경을 제공하는 장치, 예를 들어 제련 공정수 처리 장치 등에 사용될 수 있다.The composite membrane according to the present invention can be used for a water treatment apparatus, specifically an apparatus for providing an acidic environment, for example, a smelting water treatment apparatus.
본 발명은 황화광석을 원료로 하는 습식 비철 제련시 발생하는, 금속 이온이 침출된 황산 함유 침출액으로부터 다가 금속 이온을 회수함에 있어, 방향족 다가 아민과 지방족 다가 아민의 혼합물과 다관능성 산할로겐 화합물의 계면중합에 의해 형성된 폴리아미드 코팅층을 포함하는 복합 멤브레인을 사용함으로써 황산에 대한 화학적 안정성을 향상시킬 수 있을 뿐만 아니라 이와 동시에 수투과유량도 향상시킬 수 있고, 특히 다가 금속 이온의 배제율이 일가 금속 이온의 배제율보다 높아 희소금속들의 회수율을 높일 수 있다.The present invention relates to a method for recovering polyvalent metal ions from a sulfuric acid-containing leach solution containing leached metal ions, which occurs during non-ferrous smelting using a sulfide ore as a raw material, in which an interface between a mixture of aromatic polyvalent amine and aliphatic polyvalent amine and a polyfunctional acid halide By using a composite membrane comprising a polyamide coating layer formed by polymerization, it is possible not only to improve the chemical stability to sulfuric acid but also to improve the water permeation flow rate. In particular, the rejection rate of the polyvalent metal ion The recovery rate of rare metals can be increased.
이하, 실시예를 통해 본 발명의 구성 및 효과를 보다 더 구체적으로 설명하고자 하나, 이들 실시예는 본 발명의 예시적인 기재일 뿐 본 발명의 범위가 이들 실시예에만 한정되는 것은 아니다.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 invention, as claimed.
실시예 1: 내산성 폴리아미드 복합막의 제조 1Example 1: Preparation of acid-resistant polyamide composite membrane 1
먼저, 다가 아민 모노머로서 1.5 중량%의 메타페닐렌디아민(MPD, Sigma-Aldrich)과 0.5 중량%의 에틸렌디아민(ED, Sigma-Aldrich)을 사용하고 아울러 친수성 화합물로서 1 중량%의 트리에틸아민(TEA, Sigma-Aldrich), 1.1 중량%의 캄파술폰산(Camphorsulfonic acid; CSA, Sigma-Aldrich) 및 0.2 중량%의 2-에틸-1,3-헥산디올(2-ethyl-1,3-hexanediol; EHD, Sigma-Aldrich)을 추가로 사용하여 이들을 함께 수 중에 용해시켜 다관능성 아민 수용액 500 ㎖를 준비하였다. 부직포 상에, 캐스팅된 30 nm 크기의 기공을 가지는 다공성 폴리술폰 지지체를 상기에서 준비한 다관능성 아민 수용액 500 ㎖에 2분간 침지하였다.First, 1.5 wt% of metaphenylenediamine (MPD, Sigma-Aldrich) and 0.5 wt% of ethylenediamine (ED, Sigma-Aldrich) were used as the polyamine amine monomer and 1 wt% of triethylamine TEA, Sigma-Aldrich), 1.1 wt% camphorsulfonic acid (CSA, Sigma-Aldrich) and 0.2 wt% 2-ethyl-1,3-hexanediol (EHD , Sigma-Aldrich) were further dissolved in water to prepare 500 ml of a polyfunctional amine aqueous solution. On the nonwoven fabric, a porous polysulfone support having pores having a pore size of 30 nm, which had been cast, was immersed in 500 ml of the above-prepared polyfunctional amine aqueous solution for 2 minutes.
그 다음, 상기 다관능성 아민 수용액에 침지시킨 다공성 폴리술폰 지지체에 잔류하는 과잉의 다관능성 아민 수용액을 고무 롤러를 이용하여 제거한 후, 상온에 방치하여 완전히 제거하였다.Then, excess polyfunctional amine aqueous solution remaining in the porous polysulfone support immersed in the polyfunctional amine aqueous solution was removed using a rubber roller, and then left at room temperature to be completely removed.
그 다음, 0.1 중량%의 트리메조일클로라이드(TMC, Sigma-Aldrich)를 유기용매로서 ISOL-c(SK 에너지, 대한민국, CAS번호 64741-66-8)를 사용하여 용해시켜 다관능성 아실 할라이드 유기용액 500 ㎖를 준비하였다. 이후, 상기 과잉의 수용액을 제거한 다공성 폴리술폰 지지체를 상기 다관능성 아실 할라이드 유기용액에 1 분간 침지하였다.Then, 0.1% by weight of trimesoyl chloride (TMC, Sigma-Aldrich) was dissolved by using ISOL-c (SK Energy, Korea, CAS No. 64741-66-8) as an organic solvent to prepare a polyfunctional acyl halide organic solution 500 ml were prepared. Thereafter, the porous polysulfone support from which the excess aqueous solution was removed was immersed in the polyfunctional acyl halide organic solution for 1 minute.
그 다음, 상기 다관능성 아실 할라이드 유기용액에 침지시킨 다공성 폴리술폰 지지체를 오븐에서 60℃의 온도로 10분간 건조시켜 폴리아미드 복합막을 얻었다.Then, the porous polysulfone support immersed in the polyfunctional acyl halide organic solution was dried in an oven at a temperature of 60 DEG C for 10 minutes to obtain a polyamide composite membrane.
실시예Example 2: 2: 내산성Acid resistance 폴리아미드 Polyamide 복합막의Composite membrane 제조 2 Manufacturing 2
상기 실시예 1의 단계 1에서 다가 아민 모노머로서 1.3 중량%의 메타페닐렌디아민(MPD, Sigma-Aldrich), 0.5 중량%의 파라페닐렌디아민(PPD, Sigma-Aldrich) 및 0.2 중량%의 에틸렌디아민(ED, Sigma-Aldrich)을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하여 폴리아미드 복합막을 제조하였다.(MPD, Sigma-Aldrich), 0.5% by weight of paraphenylenediamine (PPD, Sigma-Aldrich) and 0.2% by weight of ethylenediamine as a polyamine monomer in Step 1 of Example 1 (ED, Sigma-Aldrich) was used instead of the polyimide composite membrane.
실시예Example 3: 3: 내산성Acid resistance 폴리아미드 Polyamide 복합막의Composite membrane 제조 3 Manufacturing 3
상기 실시예 1의 단계 1에서 다가 아민 모노머로서 1.1 중량%의 메타페닐렌디아민(MPD, Sigma-Aldrich), 0.7 중량%의 파라페닐렌디아민(PPD, Sigma-Aldrich) 및 0.2 중량%의 에틸렌디아민(ED, Sigma-Aldrich)을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하여 폴리아미드 복합막을 제조하였다.(MPD, Sigma-Aldrich), 0.7% by weight of paraphenylenediamine (PPD, Sigma-Aldrich) and 0.2% by weight of ethylenediamine as a polyamine monomer in Step 1 of Example 1 (ED, Sigma-Aldrich) was used instead of the polyimide composite membrane.
실시예Example 4: 4: 내산성Acid resistance 폴리아미드 Polyamide 복합막의Composite membrane 제조 4 Manufacturing 4
상기 실시예 1의 단계 1에서 다가 아민 모노머로서 1.7 중량%의 파라페닐렌디아민(PPD, Sigma-Aldrich), 0.2 중량%의 에틸렌디아민(ED, Sigma-Aldrich) 및 0.1 중량%의 1,3-다이아미노프로판(DAP, Sigma-Aldrich)을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하여 폴리아미드 복합막을 제조하였다.(PPD, Sigma-Aldrich), 0.2% by weight of ethylenediamine (ED, Sigma-Aldrich) and 0.1% by weight of 1,3-propanediol as monohydric amine monomers in Step 1 of Example 1, Dianaminopropane (DAP, Sigma-Aldrich) was used in place of di-aminopropane (DAP, Sigma-Aldrich) to prepare a polyamide composite membrane.
실시예Example 5: 5: 내산성Acid resistance 폴리아미드 Polyamide 복합막의Composite membrane 제조 5 Manufacturing 5
상기 실시예 1의 단계 1에서 다가 아민 모노머로서 1.6 중량%의 파라페닐렌디아민(PPD, Sigma-Aldrich), 0.2 중량%의 에틸렌디아민(ED, Sigma-Aldrich) 및 0.2 중량%의 1,3-다이아미노프로판(DAP, Sigma-Aldrich)을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하여 폴리아미드 복합막을 제조하였다.(PPD, Sigma-Aldrich), 0.2% by weight of ethylenediamine (ED, Sigma-Aldrich) and 0.2% by weight of 1,3-propanediol dianhydride as a polyamine monomer in Example 1, Dianaminopropane (DAP, Sigma-Aldrich) was used in place of di-aminopropane (DAP, Sigma-Aldrich) to prepare a polyamide composite membrane.
실시예Example 6: 6: 내산성Acid resistance 폴리아미드 Polyamide 복합막의Composite membrane 제조 6 Manufacturing 6
상기 실시예 1의 단계 1에서 다가 아민 모노머로서 1.5 중량%의 파라페닐렌디아민(PPD, Sigma-Aldrich), 0.2 중량%의 에틸렌디아민(ED, Sigma-Aldrich) 및 0.3 중량%의 1,3-다이아미노프로판(DAP, Sigma-Aldrich)을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하여 폴리아미드 복합막을 제조하였다.(PPD, Sigma-Aldrich), 0.2% by weight of ethylenediamine (ED, Sigma-Aldrich) and 0.3% by weight of 1,3-propanediol dianhydride as a polyamine monomer in Example 1, Dianaminopropane (DAP, Sigma-Aldrich) was used in place of di-aminopropane (DAP, Sigma-Aldrich) to prepare a polyamide composite membrane.
비교예Comparative Example 1 One
상기 실시예 1의 단계 1에서 다가 아민 모노머로서 2 중량%의 피페라진 (PIP, Sigma-Aldrich)을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 폴리아미드 복합막을 제조하였다.A polyamide composite membrane was prepared in the same manner as in Example 1, except that 2 wt% piperazine (PIP, Sigma-Aldrich) was used as the polyamine amine in Step 1 of Example 1 above.
비교예Comparative Example 2 2
상기 실시예 1의 단계 1에서 모노머로서 2 중량%의 메타페닐렌디아민 (MPD, Sigma-Aldrich)을 단독으로 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 폴리아미드 복합막을 제조하였다.A polyamide composite membrane was prepared in the same manner as in Example 1 except that 2 wt% of metaphenylenediamine (MPD, Sigma-Aldrich) was used alone as a monomer in Step 1 of Example 1 above.
실험예 1: 폴리아미드 복합막의 투과특성 측정Experimental Example 1: Measurement of permeation property of polyamide composite membrane
본 발명에 따른 분리막의 투과특성을 확인하기 위하여 실시예 1 내지 6 및 비교예 1 내지 2를 통해 제조된 폴리아미드 복합막을 25℃의 온도 및 15 kgf/cm2의 압력 조건 하에서 2,000 ppm 농도의 염화나트륨(NaCl) 수용액과 2,000 ppm 농도의 황산마그네슘(MgSO4) 수용액을 이용하여 막의 물성을 측정하였다. 그 결과를 하기 표 1에 나타내었다.In order to confirm the permeation characteristics of the separator according to the present invention, the polyamide composite membranes prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were impregnated with sodium chloride at a concentration of 2,000 ppm at a temperature of 25 ° C. and a pressure of 15 kgf / cm 2 (NaCl) and an aqueous solution of magnesium sulfate (MgSO 4 ) at a concentration of 2,000 ppm were measured. The results are shown in Table 1 below.
(gallon/ft2·day)Water permeability
(gallon / ft 2 .day)
(gallon/ft2·day)Water permeability
(gallon / ft 2 .day)
실험예 2: 폴리아미드 복합막의 내산성 유지 능력 측정Experimental Example 2: Measurement of acid resistance of polyamide composite membrane
본 발명에 따른 폴리아미드 복합막의 내산성 유지기간을 확인하기 위해서, 실시예 1 내지 6 및 비교예 1 내지 2를 통해 제조된 폴리아미드 복합막을 15 중량% 황산(H2SO4, Sigma-Aldrich) 수용액에 침지하여 28일 뒤의 배제율을 측정하였다. 이때 25℃의 온도 및 15 kgf/cm2의 압력 조건 하에서 2,000 ppm 농도의 황산마그네슘(MgSO4) 수용액을 이용하여 막의 물성을 측정하였다. 그 결과를 하기 표 2에 나타내었다.The polyamide composite membranes prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were immersed in a 15 wt% aqueous solution of sulfuric acid (H 2 SO 4 , Sigma-Aldrich) in order to confirm the acid- And the rejection rate after 28 days was measured. At this time, physical properties of the membrane were measured using an aqueous solution of magnesium sulfate (MgSO 4 ) at a concentration of 2,000 ppm at a temperature of 25 ° C and a pressure of 15 kgf / cm 2 . The results are shown in Table 2 below.
비교예 1에서 다가 아민 모노머로서 피페라진을 사용한 경우 수투과량은 높고 NaCl의 배제율은 낮으며, MgSO4의 배제율은 높은 투과 특성을 나타내었다. 비교예 2에서 아민 모노머로서 메타페닐렌디아민을 사용한 경우 수투과량은 낮고 NaCl의 배제율은 높으며, MgSO4의 배제율도 높은 투과 특성을 나타내었다. 그러나, 비교예 1의 경우 내산성 실험 결과 산에 약하여 쉽게 망가지는 것을 확인하였고(표 2), 비교예 2의 경우 내산성은 매우 뛰어났지만(표 2) 기본적으로 수투과량이 매우 낮고, 1가 이온의 염 배제율이 매우 높아 황산 모액에 적용하기는 어려운 점이 있었다. In the case of using piperazine as a polyamine monomer in Comparative Example 1, the water permeation rate was high, the rejection rate of NaCl was low, and the rejection rate of MgSO 4 was high. In the case of using metaphenylenediamine as the amine monomer in Comparative Example 2, the water permeation amount was low, the rejection rate of NaCl was high, and the rejection ratio of MgSO 4 was also high. However, in the case of Comparative Example 1, the acid resistance test showed that it was easily broken by acid, and that it was easily broken (Table 2). Comparative Example 2 showed excellent acid resistance (Table 2) The salt rejection rate was so high that it was difficult to apply it to the mother liquor.
또한, 비교예 2와 실시예 1을 비교할 때, 에틸렌디아민을 첨가한 경우 수투과량이 증가하면서 배제율은 감소한 것을 알 수 있었다. 실시예 1 내지 3은 에틸렌디아민은 0.2 중량%로 고정하고, 메타페닐렌디아민과 파라페닐렌디아민의 비율을 조절한 경우이다. 그 결과 배제율은 유지시키면서 수투과량을 증가시킨 결과를 나타내었다. 실시예 4 내지 6은 에틸렌디아민은 0.2 중량%로 고정하고, 파라페닐렌디아민과 1.3-다이아미노프로판의 비율을 조절한 경우이다. 1.3-다이아미노프로판의 첨가량이 증가하면서 수투과량이 증가하면서 배제율은 매우 감소한 수치를 나타내었다.In addition, when Comparative Example 2 and Example 1 were compared, it was found that the addition of ethylenediamine decreased the rejection rate as the water permeation amount increased. In Examples 1 to 3, ethylenediamine was fixed at 0.2% by weight and the ratio of m-phenylenediamine and p-phenylenediamine was adjusted. As a result, the water permeation amount was increased while maintaining the rejection rate. In Examples 4 to 6, ethylenediamine was fixed at 0.2% by weight and the ratio of paraphenylenediamine to 1.3-diaminopropane was adjusted. As the amount of 1,3-diaminopropane was increased, the water removal rate was increased and the rejection rate was decreased.
상기 결과를 통해, 기본적인 막 투과 성능이 정해지면 방향족아로마틱 폴리아미드 모노머를 사용한 경우 내산성에는 매우 뛰어난 결과를 나타내는 것을 알 수 있었다. 최소 성능 유지기간은 3주 이상이었으며, 피페라진 모노머(비교예 1)로 제조된 막과 비교하여 높은 수투과도와 내산성을 동시에 가짐을 확인하였다.From the above results, it has been found that when the basic membrane permeability is determined, the aromatic acid polyamide monomer shows excellent acid resistance. The minimum performance maintenance period was more than 3 weeks, and it was confirmed that the membrane had high water permeability and acid resistance as compared with the membrane made with the piperazine monomer (Comparative Example 1).
Claims (14)
다공성 고분자 지지체; 및 상기 다공성 고분자 지지체 표면상에서 방향족 다가 아민 및 지방족 다가 아민의 혼합물과 다관능성 산할로겐 화합물의 계면중합에 의해 형성된 폴리아미드 코팅층을 포함하는 복합 멤브레인에 금속 이온이 침출된 황산 함유 침출액을 공급하여 다가 금속 이온을 회수하는 제1단계를 포함하고,
여기에서, 금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 상기 복합 멤브레인의 수투과유량이 40 gallon/ft2·day 이상인 것이 특징인 방법.
A method for recovering polyvalent metal ions from a sulfuric acid-containing leach solution containing leached metal ions,
A porous polymeric support; And a polyamide coating layer formed by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound on the surface of the porous polymer scaffold and supplying a leaching solution containing a sulfuric acid into which a metal ion is leached, A first step of recovering ions,
Here, when the leach solution containing 2,000 ppm sulfuric acid in which metal ions are leached is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the permeation flow rate of the composite membrane is 40 gallon / ft 2 · day or more Way.
The method according to claim 1, wherein the sulfuric acid-containing leach solution containing leached metal ions is generated during wet non-ferrous smelting using a sulfide ore as a raw material.
The method of claim 1, wherein the porous polymeric support comprises polysulfone, polyethersulfone, cellulose acetate, polyamide, or a combination thereof.
The method of claim 1, wherein the weight ratio of aromatic polyamine: aliphatic polyamine in the mixture of aromatic polyamine and aliphatic polyamine is from 1: 1 to 1.9: 0.1.
The method of claim 1 wherein the weight ratio of aromatic polyamine: aliphatic polyamine in the mixture of aromatic polyamine and aliphatic polyamine is from 1.5: 0.5 to 1.8: 0.2.
The aromatic polyamine according to claim 1, wherein the aromatic polyvalent amine is selected from the group consisting of metaphenylenediamine, paraphenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6- Diamino benzene, phenylene diamine, 3-chloro-1,4-phenylenediamine, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, amidol, xylenediamine, ≪ / RTI >
The process according to claim 1, wherein the aliphatic polyvalent amine is ethylenediamine, 1,3-diaminopropane, tris (2-aminoethyl) amine or a combination thereof.
The method of claim 1, wherein the polyfunctional acid halide compound is a polyfunctional acyl halide, a polyfunctional sulfonyl halide, a polyfunctional isocyanate, or a mixture thereof.
The method according to claim 1, wherein the rejection rate of the polyvalent metal ion is higher than the rejection rate of the monovalent metal ion.
The method according to claim 1, wherein the rejection rate of the polyvalent metal ion is 50% or more.
금속 이온이 침출된 2,000 ppm 황산을 함유하는 침출액을 15 kgf/㎠의 압력 및 25℃의 온도로 공급할 때, 상기 복합 멤브레인의 수투과유량이 40 gallon/ft2·day 이상인 것이 특징인, 금속 이온이 침출된 황산 함유 침출액으로부터 다가 금속 이온을 회수하기 위한 복합 멤브레인.
A porous polymeric support; And a polyamide coating layer formed on the surface of the porous polymer substrate by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound,
Characterized in that the permeate flow rate of the composite membrane is at least 40 gallon / ft 2 · day when fed at a pressure of 15 kgf / cm 2 and at a temperature of 25 ° C, wherein the leachate containing 2,000 ppm sulfuric acid, And recovering the polyvalent metal ion from the leached sulfuric acid-containing leach solution.
12. The composite membrane according to claim 11, wherein the rejection rate of the polyvalent metal ion is higher than the rejection rate of the monovalent metal ion.
12. A water treatment apparatus comprising the composite membrane of claim 11.
14. The water treatment apparatus according to claim 13, characterized by being a smelting process water treatment apparatus.
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| KR20230008292A (en) | 2021-07-06 | 2023-01-16 | 전북대학교산학협력단 | Method for selective recovery of copper and gold from waste printed circuit boards |
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| KR20190142019A (en) * | 2018-06-15 | 2019-12-26 | 경희대학교 산학협력단 | Nanofiltration Composition Membrane Having Improved Acid and Heat Resistance And Manufacturing Method Thereof |
| KR20230008292A (en) | 2021-07-06 | 2023-01-16 | 전북대학교산학협력단 | Method for selective recovery of copper and gold from waste printed circuit boards |
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