CN109621904B - Purifying agent for nickel-containing aqueous solution and method for purifying nickel-containing aqueous solution - Google Patents
Purifying agent for nickel-containing aqueous solution and method for purifying nickel-containing aqueous solution Download PDFInfo
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- CN109621904B CN109621904B CN201811167866.6A CN201811167866A CN109621904B CN 109621904 B CN109621904 B CN 109621904B CN 201811167866 A CN201811167866 A CN 201811167866A CN 109621904 B CN109621904 B CN 109621904B
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- Prior art keywords
- nickel
- aqueous solution
- purifying
- solution containing
- compound
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 287
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 143
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000012629 purifying agent Substances 0.000 title claims abstract description 11
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical class NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 17
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 14
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 20
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 15
- 239000001110 calcium chloride Substances 0.000 claims description 15
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 150000002506 iron compounds Chemical class 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 4
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 abstract description 17
- 230000000536 complexating effect Effects 0.000 abstract description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 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 9
- -1 iron ions Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 239000012990 dithiocarbamate Substances 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 229910001453 nickel ion Inorganic materials 0.000 description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
- 229920002873 Polyethylenimine Polymers 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- IMENJLNZKOMSMC-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCN IMENJLNZKOMSMC-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 2
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Chemical compound [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZYTUJDHYVZOBJE-UHFFFAOYSA-N Cl.[Ba] Chemical compound Cl.[Ba] ZYTUJDHYVZOBJE-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910001621 beryllium bromide Inorganic materials 0.000 description 1
- PBKYCFJFZMEFRS-UHFFFAOYSA-L beryllium bromide Chemical compound [Be+2].[Br-].[Br-] PBKYCFJFZMEFRS-UHFFFAOYSA-L 0.000 description 1
- ZBUQRSWEONVBES-UHFFFAOYSA-L beryllium carbonate Chemical compound [Be+2].[O-]C([O-])=O ZBUQRSWEONVBES-UHFFFAOYSA-L 0.000 description 1
- 229910000023 beryllium carbonate Inorganic materials 0.000 description 1
- 229910001627 beryllium chloride Inorganic materials 0.000 description 1
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 description 1
- 229910001633 beryllium fluoride Inorganic materials 0.000 description 1
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 1
- JUCWKFHIHJQTFR-UHFFFAOYSA-L beryllium iodide Chemical compound [Be+2].[I-].[I-] JUCWKFHIHJQTFR-UHFFFAOYSA-L 0.000 description 1
- 229910001639 beryllium iodide Inorganic materials 0.000 description 1
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- FQDSYGKTHDFFCM-UHFFFAOYSA-N beryllium sulfide Chemical compound S=[Be] FQDSYGKTHDFFCM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- LBVNUQQORDPZCR-UHFFFAOYSA-N calcium;sulfane Chemical compound S.[Ca] LBVNUQQORDPZCR-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- LXICEIPQWZZDRV-UHFFFAOYSA-N magnesium;sulfane Chemical compound [Mg].S LXICEIPQWZZDRV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- GIKWXTHTIQCTIH-UHFFFAOYSA-L radium bromide Chemical compound [Br-].[Br-].[Ra+2] GIKWXTHTIQCTIH-UHFFFAOYSA-L 0.000 description 1
- 229910001624 radium bromide Inorganic materials 0.000 description 1
- 229940075451 radium bromide Drugs 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 description 1
- 229910001643 strontium iodide Inorganic materials 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003560 thiocarbamic acids Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to a purifying agent for an aqueous solution containing nickel and a method for purifying an aqueous solution containing nickel. The present invention provides a method for purifying an aqueous solution containing nickel, which reduces the nickel concentration of an aqueous solution containing a compound having a capability of complexing nickel and nickel. A method for producing a nickel-containing aqueous solution comprising a nickel-complexing compound, wherein a dithiocarbamic acid salt, a polyamine having 3 to 8 nitrogen atoms, and an alkaline earth metal compound are added to the nickel-complexing compound and the nickel-containing aqueous solution, an inorganic flocculant is added in an amount equal to or greater than the nickel-complexing compound, and solids are removed.
Description
Technical Field
The present invention relates to a purification method capable of removing nickel from an aqueous solution containing a compound having a capability of complexing nickel and nickel.
Background
The following treatment methods are known for aqueous solutions containing nickel: this is sent to a wastewater treatment facility, for example, a treatment is performed in which iron ions are added to become alkaline to precipitate nickel ions and the like as hydroxides together with iron ions and other contained ions, and the like, and the resulting solution is separated from an aqueous solution and discharged.
Nickel is a harmful heavy metal, and is designated as a type 1 designated chemical substance in the chemical substance emission control and management promoting method, and is set as an important monitoring item in an environmental standard related to water quality pollution, and the importance of wastewater treatment is increased.
However, there are many cases where waste water from plating plants, electronic parts/machine parts manufacturing plants, automobile plants, thermal power plants, garbage incineration plants, and the like contains organic acids such as citric acid, gluconic acid, compounds having ability to complex with nickel such as ethylenediamine tetraacetic acid (hereinafter abbreviated as EDTA), cyano groups, amines, ammonia, polyphosphoric acid, and the like, and cannot be treated by the above hydroxide method.
On the other hand, a method is known in which a compound having a capability of complexing with nickel is chemically treated and then the nickel is insolubilized. However, in the present situation, even if chemical treatments such as oxidation methods using chlorine-based reagents, electrolytic oxidation methods, hydrogen peroxide-ferrite methods, ozone oxidation methods, wet oxidation methods, and the like are used, there are problems such as inhibition of oxidation reactions due to coexisting heavy metal elements, formation of oxidized scales, and the like, and thus, sufficient purification treatment cannot be performed.
As a technique for removing various heavy metal elements contained in wastewater, for example, an aggregation separation method by adding an inorganic flocculant or an organic flocculant, a removal method by electrolysis, an adsorption removal method by activated carbon, an inorganic adsorbent or an organic polymer material, a dry-solid method for evaporating wastewater by heating, a reverse osmosis method using a membrane, an electrodialysis method, an ultrafiltration method, or the like are proposed.
Even when the above-described various methods are used, there are problems as follows, and any method needs to be improved in accordance with the above-described method. For example:
(1) Aggregation separation division: the nickel may not be adequately treated,
(2) Adsorption removal method, etc.: for example, even if nickel can be adsorbed, a large amount of solid components are generated after the treatment,
(3) Reverse osmosis, electrodialysis, ultrafiltration, etc.: is difficult to remove when the wastewater contains organic matters, has high treatment cost,
(4) Dry solidification by heating evaporation: the treatment method is complicated and the treatment cost is high.
Thus, a method of using a salt of dithiocarbamic acid as a heavy metal treatment agent in wastewater has been proposed (for example, see patent documents 1 to 4). However, the methods described in these patent documents are insufficient in the effect of purifying a heavy metal from nickel-containing wastewater containing a compound having a capability of complexing with the heavy metal.
Further, a heavy metal treatment agent comprising a polyamine having three or more amino groups in the molecule and an amine dithiocarboxylate has been proposed (for example, refer to patent document 5). However, in the method disclosed in patent document 5, the purifying treatment effect of nickel is insufficient.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2009-249399
Patent document 2: japanese patent laid-open publication No. 2011-074350
Patent document 3: japanese patent laid-open publication No. 2014-088477
Patent document 4: japanese patent laid-open No. 2002-177902
Patent document 5: japanese patent No. 5272306
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above background, and an object thereof is to provide: a scavenger for reducing the concentration of nickel in an aqueous solution containing a compound capable of complexing with nickel and nickel; and a method for purifying a nickel-containing aqueous solution using the purifying agent.
Solution for solving the problem
The present inventors have repeatedly studied in order to solve the above problems, and as a result, found that: the present invention has been completed by using the novel method for purifying an aqueous solution containing nickel disclosed in the present invention, and by using the method, the nickel concentration of an aqueous solution containing a compound capable of complexing with nickel and nickel can be reduced in a simple manner.
That is, the present invention has the following gist.
[1] A cleaning agent for nickel-containing aqueous solutions, which is characterized by comprising 20 parts by weight or more of a polyamine having 3 to 8 nitrogen atoms and an alkaline earth metal compound per 100 parts by weight of a dithiocarbamic acid salt.
[2] A cleaning agent for nickel-containing aqueous solutions, which is characterized by comprising 20 parts by weight or more of a polyamine having 3 to 8 nitrogen atoms, an alkaline earth metal compound, and an inorganic sulfide, based on 100 parts by weight of a dithiocarbamic acid salt.
[3] The purifying agent for an aqueous solution containing nickel according to the above [2], wherein the inorganic sulfide is sodium hydrogen sulfide.
[4] The scavenger for nickel-containing aqueous solutions according to the above [1] or [2], characterized in that the salt of dithiocarbamic acid is a reaction product of an amine compound having at least one amino group selected from the group consisting of a primary amino group and a secondary amino group with carbon disulfide and an alkali metal hydroxide.
[5] The scavenger for nickel-containing aqueous solutions according to the above [1] or [2], characterized in that the salt of dithiocarbamic acid is a reaction product of an amine compound having 2 or more amino groups selected from the group consisting of primary amino groups and secondary amino groups with carbon disulfide and an alkali metal hydroxide.
[6] The scavenger for nickel-containing aqueous solutions according to the above [1] or [2], characterized in that the salt of dithiocarbamic acid is a reaction product of piperazine or tetraethylenepentamine with carbon disulfide and an alkali metal hydroxide.
[7] A method for purifying a nickel-containing aqueous solution, comprising adding the purifying agent for a nickel-containing aqueous solution according to any one of the above [1] to [6] to a nickel-containing aqueous solution, and removing the solid formed.
[8] The method for purifying a nickel-containing aqueous solution according to the above [7], characterized in that the nickel-containing aqueous solution further comprises a compound having an ability to complex with nickel.
[9] The method for purifying a nickel-containing aqueous solution according to the above [8], wherein the compound having an ability to complex with nickel is a compound having a functional group selected from the group consisting of a carboxyl group and an amino group in a molecule.
[10] The method for purifying a nickel-containing aqueous solution according to any one of the above [7] to [9], wherein an inorganic flocculant is added before removing solids.
[11] The method for purifying a nickel-containing aqueous solution according to any one of the above [7] to [9], wherein an inorganic flocculant and a polymeric flocculant are added before removing solids.
[12] The method for purifying a nickel-containing aqueous solution according to the above [10] or [11], wherein the inorganic flocculant is a substance selected from the group consisting of iron compounds and aluminum compounds.
ADVANTAGEOUS EFFECTS OF INVENTION
The purifying agent for nickel-containing aqueous solutions of the present invention is extremely useful in industry because it can reduce the concentration of nickel even in nickel-containing aqueous solutions (for example, aqueous solutions containing a compound having a capability of complexing nickel and nickel) where the purification treatment of nickel is difficult.
Detailed Description
The present invention will be described in detail below.
The purifying agent for nickel-containing aqueous solutions is characterized by comprising 20 parts by weight or more of a polyamine having 3 to 8 nitrogen atoms and an alkaline earth metal compound per 100 parts by weight of a dithiocarbamic acid salt.
The salt of dithiocarbamic acid is not particularly limited as long as it is a compound having a dithiocarbamoyl group in the molecule. Examples include: an amine compound having at least one amino group selected from the group consisting of a primary amino group and a secondary amino group, and carbon disulfide and an alkali metal hydroxide. More preferably, the amine compound having 2 or more amino groups selected from the group consisting of primary amino groups and secondary amino groups is reacted with carbon disulfide and an alkali metal hydroxide.
As the amine compound having at least one amino group selected from the group consisting of a primary amino group and a secondary amino group, specifically, there can be exemplified: diethylamine, piperazine, diethylenetriamine, N- (2-aminoethyl) piperazine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, heptaethyleneoctamine, and the like.
Among these, preferred are compounds obtained by reacting piperazine or tetraethylenepentamine with carbon disulfide and an alkali metal hydroxide in view of handling properties of nickel and stability as a compound. Among them, since only a composition containing a linear body [ see the following formula (1) ] as a main component and an analogue [ see the following formulas (2) to (4) ] is industrially produced as a salt of a dithiocarbamate of tetraethylenepentamine, the obtained salt of a dithiocarbamate is also a composition, and there is a disadvantage that quality control becomes complicated. In contrast, salts of piperazine's dithiocarbamate do not suffer from such drawbacks, and are particularly preferred.
The alkali metal hydroxide is particularly preferably sodium hydroxide or potassium hydroxide from the viewpoint of easy availability.
Examples of the polyamine having 3 to 8 nitrogen atoms include: diethylenetriamine, N- (2-aminoethyl) piperazine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, heptaethyleneoctamine, polyethyleneimines with a weight average molecular weight of 300.
The amount of the polyamine having 3 to 8 nitrogen atoms added is preferably 20 parts by weight or more based on 100 parts by weight of the dithiocarbamic acid salt. By adding 20 parts by weight or more, a sufficient nickel-treating ability can be obtained.
Examples of the alkaline earth metal compound include: beryllium fluoride, beryllium chloride, beryllium bromide, beryllium iodide, beryllium oxide, beryllium hydroxide, beryllium carbonate, beryllium nitrate, beryllium sulfate, beryllium sulfide, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium oxide, calcium hydroxide, calcium carbonate, calcium bicarbonate, calcium nitrate, calcium sulfate, calcium sulfide, calcium phosphate, calcium acetate, calcium oxalate, magnesium chloride, magnesium bromide, magnesium iodide, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, magnesium nitrate, magnesium sulfate, magnesium sulfide, magnesium phosphate, magnesium acetate, strontium fluoride, strontium chloride, strontium bromide, strontium iodide, strontium oxide, strontium hydroxide, strontium carbonate, strontium nitrate, strontium sulfate, strontium sulfide, strontium phosphate, strontium acetate, barium chloride, barium bromide, barium iodide, barium oxide, barium hydroxide, barium carbonate, barium nitrate, barium sulfide, barium sulfate, barium sulfide, barium phosphate, barium acetate, radium chloride, radium bromide, and the like. Among these, calcium chloride and calcium hydroxide are particularly preferred from the viewpoint of easy availability.
When the alkaline earth metal compound is added in an amount of 0.01g/L or more, the nickel-treating ability is obtained, and when the alkaline earth metal compound is added in an excessive amount, the nickel-containing wastewater treatment cost is increased, and it is uneconomical to add 5 parts by weight or more to 100 parts by weight of the thiocarbamic acid salt, even if it exceeds 250000 parts by weight.
Examples of the inorganic sulfide include: sodium sulfide, sodium hydrogen sulfide, potassium hydrogen sulfide, calcium hydrogen sulfide, magnesium hydrogen sulfide, ammonium sulfide, and the like. Among these, sodium hydrogen sulfide is preferable from the economical point of view.
The amount of the inorganic sulfide added is preferably 250 parts by weight or more per 100 parts by weight of the dithiocarbamic acid salt. By adding 250 parts by weight or more, sufficient nickel-treating ability can be obtained.
The purifying agent of the present invention is particularly useful for purifying an aqueous solution containing nickel.
The method for purifying a nickel-containing aqueous solution of the present invention is characterized by adding the above-described purifying agent of the present invention to a nickel-containing aqueous solution and then removing the solid formed. The solid formed here contains nickel immobilized with the scavenger of the present invention.
The purification method of the present invention is particularly effective for an aqueous solution containing nickel (for example, a compound having the ability to complex with nickel) and an aqueous solution of nickel, which are difficult to handle nickel.
The compound having the ability to complex with nickel is not particularly limited as long as it is a compound that forms a complex with nickel. Examples of the compound include compounds having a functional group selected from the group consisting of a carboxyl group and an amino group in a molecule. Specifically, there may be mentioned: EDTA, polyphosphoric acid, and the like, and in particular, EDTA is used as a compound forming a strong complex with nickel.
When a salt of dithiocarbamic acid, a polyamine having 3 to 8 nitrogen atoms, and an alkaline earth metal compound are added to each of the nickel-containing aqueous solutions, the order of addition is not particularly limited.
In order to rapidly remove solids, it is preferable to add a flocculant before removing solids. Examples of the flocculant include: inorganic flocculants and polymeric flocculants are more preferably used in combination.
As the inorganic flocculant, a commercially available inorganic flocculant can be used, and is not particularly limited. Examples include: iron compounds such as ferric trichloride, aluminum compounds such as aluminum sulfate and polyaluminum chloride, and the like.
When the nickel-containing aqueous solution contains a compound having a capability of complexing with nickel, the addition amount of the inorganic flocculant is preferably set to be equal to or greater than the content of the compound having a capability of complexing with nickel contained in the nickel-containing aqueous solution. By setting the addition amount of the inorganic flocculant to be equal to or more than the content of the compound having the ability to complex with nickel, the aggregation increases, and the nickel concentration of the treated aqueous solution is easily reduced to be equal to or less than the drainage standard.
The content of the compound having the ability to complex with nickel in the aqueous nickel-containing solution may be calculated by performing analysis such as HPLC, gas chromatography, titration, or the like.
The polymeric flocculant may be a commercially available polymeric flocculant, and is not particularly limited. Examples include: acrylic acid polymers, acrylamide polymers, dimethylaminoethyl methacrylate polymers, and the like. From the viewpoint of aggregation properties, a weakly anionic acrylic polymer is preferable. The polymer flocculant may be added before the removal of the solids, thereby facilitating the treatment of the removed solids.
When the inorganic flocculant and the polymeric flocculant are used in combination, the order of adding these flocculants is not particularly limited, and it is preferable to add the inorganic flocculant and then add the polymeric flocculant.
The method for removing the solid is not particularly limited, and examples thereof include: and a method of separating the supernatant after filtration, centrifugation and sedimentation of the solid.
Examples
The present invention will be specifically described below, but the present invention is not limited to these examples.
(analytical method)
The nickel ion concentration in the aqueous solution was measured by an ICPE-9800 (manufactured by Shimadzu corporation) emission spectrometry.
Preparation example 1
The salts of dithiocarbamic acid used in the examples and comparative examples were prepared according to the following methods.
(preparation of salt of dithiocarbamic acid A)
112g of piperazine (manufactured by Tosoh corporation) and 386g of pure water were mixed, and then, 306g of 48 wt% potassium hydroxide (manufactured by Kishida Chemical Co., ltd.) and 196g of carbon disulfide (manufactured by Kishida Chemical Co., ltd.) were each divided into 4 parts by weight and alternately added dropwise under stirring at 25 ℃. Stirring was carried out for 1 hour to obtain a 40% by weight aqueous solution containing the compound represented by the formula (5).
(preparation of salt of dithiocarbamic acid B)
159g of tetraethylenepentamine (Tosoh Co., ltd.) and 331g of pure water were mixed, and then, 48 wt% sodium hydroxide 281g (Kishida Chemical Co., ltd.) and 230g (Kishida Chemical Co., ltd.) were divided into 4 parts by weight and alternately added dropwise with stirring in a nitrogen stream at 25 ℃. Stirring was carried out for 1 hour to obtain a 40% by weight aqueous solution containing the compound represented by the formula (6).
(salt of dithiocarbamic acid C)
As the salt C of dithiocarbamate, a 40 wt% aqueous solution obtained by adding water to sodium N, N-diethyldithiocarbamate trihydrate (manufactured by FUJIFILM Wako Pure Chemical Corporation) represented by the chemical formula (7) was used.
(polyamine)
As polyamines, the following ethyleneamines manufactured by Tosoh Co., ltd, nippon Shokubai Co., ltd were used.
Ethylene diamine (hereinafter abbreviated as EA (2)).
Diethylenetriamine (hereinafter abbreviated as EA (3)).
Triethylenetetramine (hereinafter abbreviated as EA (4)).
Tetraethylenepentamine (hereinafter abbreviated as EA (5)).
Pentaethylenehexamine (hereinafter abbreviated as EA (6)).
Heptaethyleneoctamine (hereinafter abbreviated as EA (8)).
The product of polyethyleneimine having a weight average molecular weight of 300 (hereinafter abbreviated as PEI (300)).
A product of polyethyleneimine having a weight average molecular weight of 1800 (hereinafter abbreviated as PEI (1800)).
(alkaline earth metal compound)
As the alkaline earth metal compound, the following compound manufactured by Kishida Chemical co.
Magnesium chloride, calcium hydroxide, strontium chloride, barium nitrate and barium hydrochloride.
(inorganic flocculant)
As the inorganic flocculant, the following aqueous solutions were used.
To water was added Kishida Chemical co., ltd. 30g of polyaluminum chloride was produced to form a total of 100g of an aqueous solution (30 wt% polyaluminum chloride aqueous solution).
Kishida Chemical co., ltd. Make 38 wt% aqueous ferric trichloride solution.
(Polymer flocculant)
As the polymeric flocculant, organo Corporation OA-23 (weakly anionic polymer) was used.
Example 1
A coagulation test stirrer (Jar Tester) was placed in a 500mL beaker, and 500mL of an aqueous solution containing 10mg/L of nickel ions and 25mg/L of EDTA was added. Next, 500mg/L of the dithiocarbamic acid salt A, 400mg/L of diethylenetriamine [ EA (3) ] and 1g/L of calcium chloride were added while stirring at 150rpm, the pH was adjusted to 11, and stirring was performed at 150rpm for 1 hour. Then, 1000mg/L of a 30 wt% aqueous solution of polyaluminum chloride (hereinafter abbreviated as PAC) was added thereto, the pH was adjusted to 7, and the mixture was stirred at 150rpm for 5 minutes. The pH of the aqueous solution was adjusted to be always at a predetermined pH using a small amount of hydrochloric acid and sodium hydroxide. After completion of stirring, the mixture was allowed to stand for 10 minutes, and the aqueous solution was filtered through a filter paper manufactured by Advantech Co., ltd. 5A, and the nickel concentration of the treated aqueous solution was measured. The results are shown in Table 1.
Examples 2 to 11
The nickel concentration of the aqueous solution after the treatment was measured in the same manner as in example 1 except that the added reagent was changed to the reagent shown in tables 1 and 2. These results are shown together in tables 1 and 2.
TABLE 1
TABLE 2
As shown in examples 1 to 8, the nickel concentration of the aqueous solution after treatment of EDTA-containing wastewater was reduced to 0.8mg/L or less.
Comparative example 1
A coagulation test stirrer (Jar Tester) was placed in a 500mL beaker, and 500mL of an aqueous solution containing 10mg/L of nickel ions and 25mg/L of EDTA was added. Next, the pH was adjusted to 11 and stirred at 150rpm for 1 hour. Then, 1000mg/L of 30 wt% PAC aqueous solution was added thereto, the pH was adjusted to 7, and the mixture was stirred at 150rpm for 5 minutes. The pH of the aqueous solution was adjusted to be always at a predetermined pH using a small amount of hydrochloric acid and sodium hydroxide. After completion of stirring, the mixture was allowed to stand for 10 minutes, and the aqueous solution was filtered through a filter paper manufactured by Advantech Co., ltd. 5A, and the nickel concentration of the treated aqueous solution was measured. The results are shown in Table 3.
Comparative examples 2 to 13
The nickel concentration of the aqueous solution after the treatment was measured in the same manner as in example 1 except that the added reagent was changed to the reagent shown in tables 3 and 4. These results are shown together in tables 3 and 4.
Reference example 1
A coagulation test stirrer (Jar Tester) was placed in a 500mL beaker, and 500mL of an aqueous solution containing 10mg/L of nickel ions and 25mg/L of EDTA was added. Subsequently, 500mg/L of the dithiocarbamic acid salt A and 400mg/L of pentaethylenehexamine were added while stirring at 150rpm, the pH was adjusted to 11, and stirring was performed at 150rpm for 14 hours. Then, 1000mg/L of 30 wt% PAC aqueous solution was added thereto, the pH was adjusted to 7, and the mixture was stirred at 150rpm for 5 minutes. The pH of the aqueous solution was adjusted to be always at a predetermined pH using a small amount of hydrochloric acid and sodium hydroxide. After completion of stirring, the mixture was allowed to stand for 10 minutes, and the aqueous solution was filtered through a filter paper manufactured by Advantech Co., ltd. 5A, and the nickel concentration of the treated aqueous solution was measured. The results are shown in Table 4.
TABLE 3
TABLE 4
Comparative example 1 is an example of a treatment method in which aluminum ions are added to neutralize and nickel ions are precipitated together with aluminum ions in the form of hydroxide. The nickel concentration of the treated aqueous solution was 7.0mg/L, and the nickel could not be reduced.
Comparative examples 2 and 3 are examples of treatments with only calcium chloride. The nickel concentration of the treated aqueous solution is 4.7-5.3 mg/L, and nickel cannot be reduced.
Comparative examples 4 to 6 are examples in which only a salt of dithiocarbamic acid was added. The nickel concentration of the treated aqueous solution is 4.9-5.5 mg/L, and nickel cannot be reduced.
Comparative example 7 is an example in which only the salt a of dithiocarbamate and sodium hydrogen sulfide were added. The nickel concentration of the treated aqueous solution was 5.2mg/L, and the nickel could not be reduced.
Comparative example 8 is an example in which a salt a of dithiocarbamate and calcium chloride are added. The nickel concentration of the treated aqueous solution was 4.3mg/L, and the nickel could not be sufficiently reduced.
Comparative example 9 is an example in which only polyamine was added. The nickel concentration of the treated aqueous solution was 10mg/L, which was the same value as before the addition of the reagent, and it was impossible to reduce nickel.
Comparative example 10 is an example in which polyamine and calcium chloride were added. The nickel concentration of the treated aqueous solution was 10mg/L, which was the same value as before the addition of the reagent, and it was impossible to reduce nickel.
Comparative example 11 is an example in which a salt A of dithiocarbamate and polyamine were added. The nickel concentration of the treated aqueous solution was 3.0mg/L, and the nickel could not be sufficiently reduced.
Comparative example 12 is an example in which dithiocarbamic acid salt a, EA (2) outside the scope of the present invention, and calcium chloride were added, and the nickel concentration of the treated aqueous solution was not found to have an improvement effect on the nickel treatment as compared with comparative example 8 in which EA (2) was not added.
Comparative example 13 is an example in which dithiocarbamic acid salt A, PEI (1800) outside the scope of the present invention, and calcium chloride were added, and the nickel concentration of the treated aqueous solution was 3.5mg/L, and nickel could not be sufficiently reduced.
Reference example 1 shows an example in which the stirring time after reagent addition was changed from 1 hour to 14 hours as the same amount of reagent addition as in comparative example 11. The nickel concentration of the treated aqueous solution was almost the same as that of example 4 in which calcium chloride was added, but a long time was required to reduce the nickel concentration.
Examples 12 to 16 and comparative example 14
The nickel concentration of the aqueous solution after the treatment was measured in the same manner as in example 1 except that the reagent to be added was changed to the reagent shown in table 5. The results are shown in Table 5.
TABLE 5
Examples 12 to 16 are examples of treatments in which the weight parts of polyamines were changed within the scope of the present invention. The concentration of nickel can be reduced to 1.6mg/L or less independently of the weight parts of polyamine.
Comparative example 14 is an example in which a dithiocarbamic acid salt A and a polyamine in an amount lower than the range of the present invention were added, and the nickel concentration of the aqueous solution after treatment was 4.1mg/L, and the nickel could not be reduced.
Examples 17 to 21
The nickel concentration of the aqueous solution after the treatment was measured in the same manner as in example 1 except that the reagent to be added was changed to the reagent shown in table 6. The results are shown in Table 6.
TABLE 6
Examples 17 to 21 are examples of treatments in which the types of alkaline earth metals were changed within the scope of the present invention. The concentration of nickel can be reduced to 1.0mg/L or less independently of the kind of alkaline earth metal.
Examples 22 to 25 and comparative example 15
The nickel concentration of the aqueous solution after the treatment was measured in the same manner as in example 1 except that the reagent to be added was changed to the reagent shown in table 7. The results are shown in Table 7.
TABLE 7
Examples 22 to 25 were treated with varying amounts of calcium chloride as an alkaline earth metal. By adding calcium chloride in an amount of 0.01g/L or more, the concentration of nickel can be reduced to 0.2mg/L or less.
Comparative example 15 is an example in which the addition amount of calcium chloride as an alkaline earth metal was treated at 0.001 g/L. As shown in comparative example 15, it was found that the effect of lowering nickel was low when the amount of alkaline earth metal used in combination with the dithiocarbamic acid salt and polyamine was small.
Examples 26 to 27
The nickel concentration of the aqueous solution after the treatment was measured in the same manner as in example 1 except that the reagent to be added was changed to the reagent shown in table 8. The results are shown in Table 8.
TABLE 8
Examples 26 and 27 are examples of treatments in which the addition amount of the inorganic sulfide was changed. The concentration of nickel can be reduced to below 1.2 mg/L.
Example 28
A coagulation test stirrer (Jar Tester) was placed in a 500mL beaker, and 500mL of an aqueous solution containing 10mg/L of nickel ions and 25mg/L of EDTA was added. Next, 500mg/L of the dithiocarbamic acid salt A, 400mg/L of diethylenetriamine [ EA (3) ] and 1g/L of calcium chloride were added while stirring at 150rpm, the pH was adjusted to 11, and stirring was performed at 150rpm for 1 hour. Then, 1000mg/L of 30 wt% PAC aqueous solution was added thereto, the pH was adjusted to 7, and the mixture was stirred at 150rpm for 5 minutes. Next, 2000mg/L of a 0.1 wt% OA-23 aqueous solution was added as a polymeric flocculant, the pH was adjusted to 7, and the mixture was stirred at 50rpm for 5 minutes. The pH of the aqueous solution was adjusted to be always at a predetermined pH using a small amount of hydrochloric acid and sodium hydroxide. After completion of stirring, the mixture was allowed to stand for 10 minutes, and the aqueous solution was filtered through a filter paper manufactured by Advantech Co., ltd. 5A, and the nickel concentration of the treated aqueous solution was measured. The results are shown in Table 9.
Example 29
The nickel concentration of the treated aqueous solution was measured in the same manner as in example 28 except that the 30 wt% PAC aqueous solution was changed to 38 wt% aqueous solution of ferric chloride. The results are shown in Table 9.
TABLE 9
Example 28 is an example in which a polymeric flocculant was added to example 1. The nickel concentration of the treated aqueous solution was the same as that of the case where the polymeric flocculant was not added, and the nickel treatment was sufficient.
Example 29 is an example in which an aqueous ferric trichloride solution was used as the inorganic flocculant. The nickel concentration of the treated aqueous solution was 0.2mg/L, and the nickel treatment was sufficient regardless of the kind of the inorganic flocculant.
Industrial applicability
According to the method for purifying a nickel-containing aqueous solution of the present invention, even though it is difficult to treat nickel, the nickel concentration of the nickel-containing aqueous solution can be reduced, and therefore, as a novel method for purifying a nickel-containing aqueous solution, there is a possibility of using the nickel-containing aqueous solution for treating nickel-containing wastewater from plating factories, electronic/mechanical parts manufacturing factories, automobile factories, and the like.
Claims (9)
1. A cleaning agent for nickel-containing aqueous solutions, which comprises 20 parts by weight or more of diethylenetriamine, triethylenetetramine or tetraethylenepentamine and 5 parts by weight or more of an alkaline earth metal compound per 100 parts by weight of a dithiocarbamic acid salt,
the salt of dithiocarbamic acid is the reaction product of piperazine or tetraethylenepentamine with carbon disulphide and an alkali metal hydroxide,
the alkaline earth metal compound is magnesium chloride, calcium chloride, strontium chloride, barium chloride or barium sulfate.
2. A cleaning agent for nickel-containing aqueous solutions, which comprises, per 100 parts by weight of a dithiocarbamic acid salt, 20 parts by weight or more of diethylenetriamine, triethylenetetramine or tetraethylenepentamine, 5 parts by weight or more of an alkaline earth metal compound, and 250 parts by weight or more of sodium hydrogen sulfide,
the salt of dithiocarbamic acid is the reaction product of piperazine or tetraethylenepentamine with carbon disulphide and an alkali metal hydroxide,
the alkaline earth metal compound is magnesium chloride, calcium chloride, strontium chloride, barium chloride or barium sulfate.
3. A method for purifying an aqueous solution containing nickel, comprising adding the purifying agent for an aqueous solution containing nickel according to claim 1 or 2 to an aqueous solution containing nickel, and removing the solid formed.
4. A method for purifying an aqueous solution containing nickel according to claim 3, further comprising a compound having an ability to complex with nickel.
5. The method for purifying an aqueous solution containing nickel according to claim 4, wherein the compound having an ability to complex with nickel is a compound having a functional group selected from the group consisting of a carboxyl group and an amino group in a molecule.
6. The method for purifying an aqueous solution containing nickel according to any one of claims 3 to 5, wherein an inorganic flocculant is added before removing solids.
7. The method for purifying an aqueous solution containing nickel according to any one of claims 3 to 5, wherein an inorganic flocculant and a polymeric flocculant are added before removing solids.
8. The method for purifying an aqueous solution containing nickel according to claim 6, wherein the inorganic flocculant is a substance selected from the group consisting of iron compounds and aluminum compounds.
9. The method for purifying an aqueous solution containing nickel according to claim 7, wherein the inorganic flocculant is a substance selected from the group consisting of iron compounds and aluminum compounds.
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