JPH01141816A - Method for recovering heavy metal - Google Patents
Method for recovering heavy metalInfo
- Publication number
- JPH01141816A JPH01141816A JP62300559A JP30055987A JPH01141816A JP H01141816 A JPH01141816 A JP H01141816A JP 62300559 A JP62300559 A JP 62300559A JP 30055987 A JP30055987 A JP 30055987A JP H01141816 A JPH01141816 A JP H01141816A
- Authority
- JP
- Japan
- Prior art keywords
- heavy metals
- chelating agent
- group
- acid
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002738 chelating agent Substances 0.000 claims abstract description 55
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000524 functional group Chemical group 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052770 Uranium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000004131 Bayer process Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 11
- -1 polyethylene Polymers 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002443 hydroxylamines Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 229960001755 resorcinol Drugs 0.000 description 4
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 3
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 3
- 229960004979 fampridine Drugs 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MXOQNVMDKHLYCZ-UHFFFAOYSA-N benzamidoxime Chemical compound ON=C(N)C1=CC=CC=C1 MXOQNVMDKHLYCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical class C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- RJRFWWMJLFAKEK-UHFFFAOYSA-N 2-(1h-benzimidazol-2-ylsulfanyl)-n'-hydroxyethanimidamide Chemical compound C1=CC=C2NC(SCC(/N)=N/O)=NC2=C1 RJRFWWMJLFAKEK-UHFFFAOYSA-N 0.000 description 1
- KMFIBMMXVGITIG-UHFFFAOYSA-N 2-(3-chlorophenyl)sulfinyl-n'-hydroxyethanimidamide Chemical compound O\N=C(/N)CS(=O)C1=CC=CC(Cl)=C1 KMFIBMMXVGITIG-UHFFFAOYSA-N 0.000 description 1
- MFLHJEVZMKQLKF-UHFFFAOYSA-N 2-(cyanomethyl)-5-hydroxybenzonitrile Chemical compound Oc1ccc(CC#N)c(c1)C#N MFLHJEVZMKQLKF-UHFFFAOYSA-N 0.000 description 1
- DNTWMFCMRPNQIZ-UHFFFAOYSA-N 2-amino-2-hydroxybutanedinitrile Chemical compound N#CC(O)(N)CC#N DNTWMFCMRPNQIZ-UHFFFAOYSA-N 0.000 description 1
- RRCAJFYQXKPXOJ-UHFFFAOYSA-N 4-aminobenzene-1,2-dicarbonitrile Chemical compound NC1=CC=C(C#N)C(C#N)=C1 RRCAJFYQXKPXOJ-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- XGYKKVTZDQDYJQ-UHFFFAOYSA-N 4-aminobutanenitrile Chemical compound NCCCC#N XGYKKVTZDQDYJQ-UHFFFAOYSA-N 0.000 description 1
- FTVOPKROFUTOKY-UHFFFAOYSA-N 4-hydroxybenzene-1,2-dicarbonitrile Chemical compound OC1=CC=C(C#N)C(C#N)=C1 FTVOPKROFUTOKY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical group ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- AGSPXMVUFBBBMO-UHFFFAOYSA-N beta-aminopropionitrile Chemical compound NCCC#N AGSPXMVUFBBBMO-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- WREDNSAXDZCLCP-UHFFFAOYSA-N dithiocarboxylic acid group Chemical group C(=S)S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 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
- 235000010755 mineral Nutrition 0.000 description 1
- AEXITZJSLGALNH-UHFFFAOYSA-N n'-hydroxyethanimidamide Chemical compound CC(N)=NO AEXITZJSLGALNH-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method 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
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〉
本発明は重金属を含有する溶液からの重金属の回収方法
に関する。さらに詳細には官能基としてアミドキシム基
および／またはイミドジオキシム基を有するキレート化
剤の官能基を分解処理して得られるキレート化剤を使用
する重金属を含有する溶液からの重金属の回収方法に関
する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for recovering heavy metals from a solution containing heavy metals.More specifically, the present invention relates to a method for recovering heavy metals from a solution containing heavy metals. The present invention relates to a method for recovering heavy metals from a solution containing heavy metals using a chelating agent obtained by decomposing the functional groups of the agent.
〈従来の技術〉
近年、キレート化剤を工場廃液からの重金属の除去剤と
して、また有価金属を含有する溶液から有価金属の捕集
剤等として利用することが広く行われている。例えば、
排水等の数ＩＩＷ／ｌまたはそれ以下の濃度の重金属を
含有する溶液から有価金属を除去するに当り、スチレン
−ジビニルベンゼン共重合体をクロルメチル化し、次い
でイミノジ酢酸を反応せしめて得られるキレート樹脂（
日化協月報２５ （１）、２４頁（１９７２））、お
よびイミノジ酢酸、フェノール類、アルデヒド類共存下
でマンニッヒ反応を行った後、アルデヒド類、フェノー
ル類をさらに加え重縮合せしめて得られるキレート樹脂
（特開昭５０−１０７０９２号公報、特開昭５０４０１
４９０号公報、特開昭５０−１０３５９０号公報）を使
用する方法等が提案されている。<Prior Art> In recent years, chelating agents have been widely used as agents for removing heavy metals from industrial waste fluids, and as agents for collecting valuable metals from solutions containing valuable metals. for example,
When removing valuable metals from solutions containing heavy metals at a concentration of several IIW/l or lower, such as wastewater, a chelate resin obtained by chloromethylating a styrene-divinylbenzene copolymer and then reacting it with iminodiacetic acid is used.
JCIA Monthly Report 25 (1), p. 24 (1972)), and a chelate obtained by performing a Mannich reaction in the coexistence of iminodiacetic acid, phenols, and aldehydes, and then adding aldehydes and phenols for polycondensation. Resin (JP-A-50-107092, JP-A-50401)
490, Japanese Unexamined Patent Publication No. 50-103590), etc. have been proposed.
〈発明が解決しようとする問題点〉
しかし、公知のキレート樹脂はいずれも溶液中に存在す
る他の共存イオンの影響を受は易いため、共存イオンが
混在する工場排水等の場合には著しく吸着能力が低下す
るとか、また塩濃度が高い水溶液下での重金属の吸着平
衡濃度が高いという不都合を存している。<Problems to be solved by the invention> However, all known chelate resins are susceptible to the effects of other coexisting ions present in the solution, so in the case of industrial wastewater etc. where coexisting ions are mixed, they are significantly adsorbed. There are disadvantages such as a decrease in capacity and a high equilibrium adsorption concentration of heavy metals in an aqueous solution with a high salt concentration.
かかる事情に鑑み、本発明者らは共存イオンの影響を受
けにくく、また塩濃度の高い水溶液下でも重金属の吸着
平衡濃度を低くすることができる重金属の回収方法を見
い出すべく鋭意研究した結果、本発明方法を完成するに
至った。In view of these circumstances, the present inventors conducted extensive research to find a method for recovering heavy metals that is less susceptible to the effects of coexisting ions and can lower the equilibrium adsorption concentration of heavy metals even in aqueous solutions with high salt concentrations. The invented method has been completed.
く問題を解決するための手段〉
すなわち本発明は、官能基としてアミドキシム基および
／またはイミドジオキシム基を有するキレート化剤を酸
またはアルカリ水溶液と加熱することにより官能基を分
解処理して得られるキレート化剤と重金属を含有する溶
液とを接触させることを特徴とする重金属の回収方法で
ある。In other words, the present invention provides a chelating agent having an amidoxime group and/or imidodioxime group as a functional group, which is obtained by heating the chelating agent with an acid or alkaline aqueous solution to decompose the functional group. This is a method for recovering heavy metals, which is characterized by bringing a chelating agent into contact with a solution containing heavy metals.
本発明の官能基の分解処理に付されるキレート化剤とし
ては、例えば以下のものが挙げられる。Examples of the chelating agent to be subjected to the functional group decomposition treatment of the present invention include the following.
■アクリロニトリル、α−クロルアクリロニトリル、シ
アン化ビニリデン、メタアクリロニトリル等のシアン化
ビニル系単量体の重合体またはシアン化ビニル系単量体
と共重合が可能な他のエチレン系不飽和単量体との共重
合体に、ヒドロキシルアミンまたはヒドロキシルアミン
の誘導体を反応させて得られるアミドキシム基および／
またはイミドジオキシム基を有する樹脂、■アクリロニ
トリル、α−クロルアクリロニトリル、シアン化ビニリ
デン、メタアクリロニトリル等のシアン化ビニル系単量
体にヒドロキシルアミンまたはヒドロキシルアミン誘導
体を反応させて得られるシアン化ビニル系誘導体を単独
重合または共重合可能な他のエチレン系不飽和単量体と
重合させて得られる樹脂、
■クロルメチル基、スルホニルクロリド基、カルボニル
クロリド基、イソシアナート基、エポキシ基、アルデヒ
ド基等のアミンとの反応性がある官能基を有したスチレ
ン−ジビニルベンゼン共重合体、フェノール樹脂、ポリ
エチレン、ポリプロピレン、ポリ塩化ビニル等の重合体
く以下、アミン反応性基を有した樹脂と称す。）にアミ
ノアセトニトリル、アミノマロンニトリル、ジアミノマ
レオニトリル、ジシアンジアミド、イミノジアセトニト
リル、１−アミノ−２−シアノエタン、４−アミノベン
ゾニトリル、１−アミノ−３−シアノプロパン等のアミ
ノ基、イミノ基を有するニトリル化合物を反応させ、次
いでヒドロキシルアミンまたはヒドロキシルアミン誘導
体を反応させて得られる樹脂、■前記アミノ基、イミノ
基を有するニトリル化合物とヒドロキシルアミンまたは
ヒドロキシルアミン誘導体との反応により得られる生成
物を前記のアミンとの反応性がある官能基を有する樹脂
に反応させて得られる樹脂、
■スルホン酸基、カルボン酸基、燐酸基、ジチオカルボ
ン酸基、アルキルアミノ基等を有するスチレン−ジビニ
ルベンゼン共重合体、フェノール樹脂等の樹脂をハロゲ
ン化処理して得られる樹脂に前記アミノ基、イミノ基を
有するニトリル化合物とヒドロキシルアミンまたはヒド
ロキシルアミン誘導体との反応により得られる生成物を
反応させて得られる樹脂、
■ベンズアミドキシム、ベンジルアミノ−Ｎ−メタンジ
アミドジオキシム、ヘンシルアミノ−Ｎ−エタンジアミ
ドジオキシム、（２−ベンゾイミダゾリルチオ）アセト
アミドキシム、（２−ベンゾイミダゾリルチオ）エチル
アミドキシム、（２−ベンゾイミダゾリルチオ）プロピ
ルアミドキシム、１．２−ベンズイソキサゾール−３−
アセトアミドキシム、５−フルオロ−１゜２−ベンズイ
ソキサゾール−３−アセトアミドキシム、フェニルスル
フィニルアセトアミドキシム、（３−クロルフェニルス
ルフィニル）−アセトアミドキシム等の少くとも分子中
に１個のアミドキシム基を有する化合物、前記化合物の
混合物または前記化合物とアニリン、レゾルシン、３−
アミノピリジン、４−アミノピリジン、４−アミノベン
ゼンスルホン酸、４−アミノカルボン酸との混合物とホ
ルマリン、エピクロルヒドリン、エピブロムヒドリン等
とを縮合反応させて得られる樹脂、
■３，４−ジシアノフェノール、３−シアノ−４−シア
ノメチルフェノール、３．４−ジシアノアニリン等のジ
シアノ化合物、前記化合物の混合物または前記化合物と
アニリン、レゾルシン、３−アミノピリジン、４−アミ
ノピリジン、４−アミノベンゼンスルホン酸、４−アミ
ノカルボン酸との混合物とホルマリン、エピクロルヒド
リン、エピブロムヒドリン等との縮合反応生成物にヒド
ロキシルアミンまたはヒドロキシルアミン誘導体を反応
させて得られる樹脂、■前記ジシアノ化合物とヒドロキ
シルアミンまたはヒドロキシルアミン誘導体との反応に
より得られる生成物とアニリン、レゾルシン、３−アミ
ノピリジン、４−アミノピリジン、４−アミノベンゼン
スルホン酸、４−アミノカルボン酸との混合物とホルマ
リン、エピクロルヒドリン、エピブロムヒドリン等とを
縮合反応させて得られる樹脂、
■ラウリルベンズアミドキシム、ラウリルアミドキシム
、オクチルベンズアミドキシム、オクチルアミドキシム
等低分子アミドキシム化合物または３−オクチルピロリ
ジン−２，５−ジオキシム、３−オクチルピペリジン−
２，６−ジオキシム、４−ラウリルピペラジン−２，６
−ジオキシム等の低分子イミドジオキシム化合物、［相
］上記アミドキシム基および／またはイミドジオキシム
基を有する樹脂または低分子化合物を活性炭、アルミナ
、ゼオライト等に吸着担持した複合吸着剤。■ Polymers of vinyl cyanide monomers such as acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, methacrylonitrile, etc., or other ethylenically unsaturated monomers that can be copolymerized with vinyl cyanide monomers. Amidoxime groups and/or
or a resin having an imidodioxime group; ■ a vinyl cyanide derivative obtained by reacting a vinyl cyanide monomer such as acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, methacrylonitrile, etc. with hydroxylamine or a hydroxylamine derivative; with other ethylenically unsaturated monomers that can be homopolymerized or copolymerized with amines such as chloromethyl groups, sulfonyl chloride groups, carbonyl chloride groups, isocyanate groups, epoxy groups, and aldehyde groups. Polymers such as styrene-divinylbenzene copolymers, phenol resins, polyethylene, polypropylene, and polyvinyl chloride that have reactive functional groups are hereinafter referred to as resins that have amine-reactive groups. ) has an amino group or an imino group such as aminoacetonitrile, aminomalonitrile, diaminomaleonitrile, dicyandiamide, iminodiacetonitrile, 1-amino-2-cyanoethane, 4-aminobenzonitrile, 1-amino-3-cyanopropane, etc. A resin obtained by reacting a nitrile compound and then reacting with hydroxylamine or a hydroxylamine derivative; Resin obtained by reacting with a resin having a functional group that is reactive with amines; ■ Styrene-divinylbenzene copolymer having sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, dithiocarboxylic acid groups, alkylamino groups, etc. , a resin obtained by reacting a resin obtained by halogenating a resin such as a phenol resin with a product obtained by reacting the nitrile compound having an amino group or imino group with hydroxylamine or a hydroxylamine derivative; Benzamidoxime, benzylamino-N-methanediamide dioxime, hensylamino-N-ethanediamide dioxime, (2-benzimidazolylthio)acetamidoxime, (2-benzimidazolylthio)ethylamidoxime, (2-benzimidazolylthio)propylamidoxime, 1 .2-Benzisoxazole-3-
Having at least one amidoxime group in the molecule, such as acetamidoxime, 5-fluoro-1゜2-benzisoxazole-3-acetamidoxime, phenylsulfinyl acetamidoxime, (3-chlorophenylsulfinyl)-acetamidoxime, etc. a compound, a mixture of said compounds, or said compound and aniline, resorcinol, 3-
Resin obtained by condensation reaction of a mixture of aminopyridine, 4-aminopyridine, 4-aminobenzenesulfonic acid, and 4-aminocarboxylic acid with formalin, epichlorohydrin, epibromohydrin, etc., ■3,4-dicyanophenol , 3-cyano-4-cyanomethylphenol, dicyano compounds such as 3,4-dicyanoaniline, mixtures of the above compounds or the above compounds and aniline, resorcinol, 3-aminopyridine, 4-aminopyridine, 4-aminobenzenesulfonic acid , a resin obtained by reacting hydroxylamine or a hydroxylamine derivative with a condensation reaction product of a mixture of 4-aminocarboxylic acid and formalin, epichlorohydrin, epibromohydrin, etc., (2) the dicyano compound and hydroxylamine or hydroxylamine; A mixture of a product obtained by reaction with a derivative, aniline, resorcinol, 3-aminopyridine, 4-aminopyridine, 4-aminobenzenesulfonic acid, 4-aminocarboxylic acid, and formalin, epichlorohydrin, epibromohydrin, etc. resin obtained by condensation reaction, ■Low-molecular amidoxime compounds such as laurylbenzamidoxime, laurylamidoxime, octylbenzamidoxime, octylamidoxime, or 3-octylpyrrolidine-2,5-dioxime, 3-octylpiperidine-
2,6-dioxime, 4-laurylpiperazine-2,6
- A low-molecular-weight imidodioxime compound such as dioxime, [Phase] A composite adsorbent in which a resin or a low-molecular compound having the above amidoxime group and/or imidodioxime group is adsorbed and supported on activated carbon, alumina, zeolite, or the like.
官能基の分解処理は前記アミドキシム基および／または
イミドジオシム基を有するキレート化剤を酸またはアル
カリ水溶液と加熱処理することにより行われる。The decomposition treatment of the functional group is carried out by heating the chelating agent having the amidoxime group and/or imidodiosim group with an acid or alkaline aqueous solution.
酸水溶液としては例えば塩酸、硫酸等の鉱酸水溶液が、
アルカリ水溶液としては例えば水酸化ナトリウム、水酸
化カリウム等の水溶液が用いられる。酸またはアルカリ
水溶液の濃度は特に限定されるものではなく、酸とアル
カリでは多少異なるが、通常０．５〜１０規定程規定水
溶液が用いられる。Examples of acid aqueous solutions include mineral acid aqueous solutions such as hydrochloric acid and sulfuric acid.
As the alkaline aqueous solution, for example, an aqueous solution of sodium hydroxide, potassium hydroxide, etc. is used. The concentration of the acid or alkali aqueous solution is not particularly limited, and although it differs somewhat between acid and alkali, normally a normal aqueous solution of about 0.5 to 10 N is used.
通常、アルカリ水溶液を用いる場合には約７０〜１１０
℃で約１〜１２時間、酸水溶液を用いる場合には約４０
〜８０℃で約１０分〜６時間加熱する。Usually, when using an alkaline aqueous solution, about 70 to 110
℃ for about 1 to 12 hours, or about 40℃ when using an acid aqueous solution.
Heat at ~80°C for about 10 minutes to 6 hours.
これらの条件は、酸またはアルカリ水溶液の量、種類、
濃度等によって変わるので、これは適宜予備実験を行う
ことによって設定することができる。These conditions include the amount and type of acid or alkaline aqueous solution,
Since it varies depending on the concentration, etc., this can be determined by conducting preliminary experiments as appropriate.
官能基としてアミドキシム基および／またはイミドジオ
キシム基を有するキレート化剤を酸またはアルカリ水溶
液と加熱することにより官能基を分解処理して得られる
キレート化剤が如何なる官能基を有するかは定かではな
いが、分解処理中にアンモニアおよび／またはヒドロキ
シルアミンが発生することから脱アンモニア、脱ヒドロ
キシアミン、加水分解等により、分子内に酸アミド、イ
ミドモノオキシム等の官能基が生成しているものと考え
られる。It is not certain what kind of functional group a chelating agent has, which is obtained by decomposing the functional group by heating a chelating agent having an amidoxime group and/or imidodioxime group as a functional group with an acid or alkaline aqueous solution. However, since ammonia and/or hydroxylamine are generated during the decomposition process, it is thought that functional groups such as acid amide and imidomonoxime are generated within the molecule due to deammonia, dehydroxyamine, hydrolysis, etc. It will be done.
上記のような方法で製造したアミドキシム基および／ま
たはイミドジオキシム基を分解処理して得られるキレー
ト化剤と重金属を含有する溶液との接触方法は、特に制
限されるものではなく、例えば、アミドキシム基および
／またはイミドジオキシム基を分解処理して得られるキ
レート化剤が固体状である場合には、キレート化剤を充
填した塔内へ重金属を含有する溶液を通液する方法、重
金属を含有する溶液の中へキレート化剤を浸漬し、次い
で濾過分離する方法等が、またキレート化剤が溶液状の
場合には、そのままあるいは溶媒の存在下に重金属含有
溶液と接触させた後、分液分離する方法等が採用される
。The method of contacting the chelating agent obtained by decomposing the amidoxime group and/or imidodioxime group produced by the method described above with the solution containing heavy metals is not particularly limited, and for example, amidoxime When the chelating agent obtained by decomposing a group and/or an imidodioxime group is in a solid state, a method containing a heavy metal may be passed through a column filled with the chelating agent, or a method containing a heavy metal. If the chelating agent is in solution, it may be brought into contact with a heavy metal-containing solution either directly or in the presence of a solvent, and then separated by filtration. A method of separating is adopted.
キレート化剤と重金属を含有する溶液との接触温度は特
に制限されるものではないが、通常１０〜１００℃の温
度で実施される。The temperature at which the chelating agent and the heavy metal-containing solution are brought into contact is not particularly limited, but it is usually carried out at a temperature of 10 to 100°C.
また接触時間も特に制限されるものではない。Further, the contact time is not particularly limited either.
本発明のキレート化剤により吸着された重金属は適当な
溶離剤、例えば塩酸、硫酸、硝酸、燐酸、硫化ソーダ、
イミノジ酢酸、エチレンジアミン四酢酸等を用いて溶離
回収するとか、加熱して溶離剤と接触することにより、
重金属をキレート化剤から分離する。The heavy metals adsorbed by the chelating agents of the present invention can be removed using suitable eluents such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium sulfide,
By elution and recovery using iminodiacetic acid, ethylenediaminetetraacetic acid, etc., or by heating and contacting with an eluent,
Separate heavy metals from chelating agents.
このようにして分離回収された重金属は、そのまま、あ
るいは金属の種類、用途、分離方法によっても異なるが
、中和、濾過等の処理を行って金属水酸化物として回収
したり、あるいはそのまま還元剤による処理または電解
を実施することにより、金属として回収し、使用するこ
とができる。The heavy metals separated and recovered in this way can be recovered as they are, or they can be recovered as metal hydroxides through neutralization, filtration, etc., depending on the type of metal, purpose, and separation method, or they can be recovered as metal hydroxides as they are, or they can be recovered as metal hydroxides as they are, or they can be recovered as metal hydroxides after undergoing treatments such as neutralization and filtration. It can be recovered and used as a metal by treatment or electrolysis.
このようにして重金属を脱着した後のキレート化剤は、
そのまま、あるいは必要に応じて水洗及びまたは水酸化
ナトリウム、水酸化カリウム、水酸化カルシウム、水酸
化マグネシウム、アンモニア等の塩基性水溶液、塩酸、
硫酸、硝酸、燐酸等の酸性水溶液と接触処理を行った後
、再び重金属の吸着捕集剤として繰り返し用いることが
できる。The chelating agent after desorbing heavy metals in this way is
Leave as is, or wash with water as necessary and/or wash with basic aqueous solutions such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, hydrochloric acid,
After contact treatment with an acidic aqueous solution such as sulfuric acid, nitric acid, or phosphoric acid, it can be repeatedly used as a heavy metal adsorption/collection agent.
〈発明の効果〉
本発明方法によれば、共存イオンの影響を受けにくく、
また塩濃度の高い水溶液下での重金属の吸着平衡濃度を
低くすることが可４能であり、その工業的価値は大きい
。<Effects of the Invention> According to the method of the present invention, it is less susceptible to the influence of coexisting ions;
Furthermore, it is possible to lower the adsorption equilibrium concentration of heavy metals in an aqueous solution with a high salt concentration, which has great industrial value.
〈実施例〉
以下、本発明を実施例によってさらに詳細に説明するが
、本発明はこれらの実施例によって限定されない。<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples.
実施例１
アクリロニトリル−ジビニルベンゼン共重合体とヒドロ
キシルアミン水溶液との反応により得られたアミドキシ
ム基を有するキレート化剤（窒素含量２１．５重量％）
１３０重量部を２０重量％濃度の苛性ソーダ水溶液２０
０重量部と８０〜９０℃で６時間加熱し、アミドオキシ
ム基の分解処理を行った。加熱処理中アンモニアとヒド
ロキシルアミンの発生が見られた。加熱処理後、濾過、
水洗、乾燥したところ、窒素含ｉｔ １７．１重量％の
アミドキシム基を分解処理したキレート他剤１１９重量
部を得た。（以下、本キレート化剤をキレート化剤Ａと
称す。）キレート化剤Ａ１０＋ｄを内径１２１１φのカ
ラムに充填し、塔頂よりウラン１００■／１、コバルト
１００■／β、マンガンｌｏｏｍｇ／ｌ、パラジウムｌ
ｏｏｍｇ／Ｉ！、塩化ナトリウム３ｇ／ｌ濃度の溶液Ｉ
Ｉ２を５時間で流し、流出液中の各金属元素濃度の分析
を行ったところ、ウラン０．８■／１１コバルト０．２
■／ｆ、マンガン０．３■／１、パラジウム０．９■／
ｌであった。Example 1 A chelating agent having an amidoxime group obtained by the reaction of an acrylonitrile-divinylbenzene copolymer with an aqueous hydroxylamine solution (nitrogen content: 21.5% by weight)
130 parts by weight of a 20% by weight aqueous solution of caustic soda 20
The mixture was heated at 80 to 90° C. for 6 hours to decompose the amidoxime groups. Ammonia and hydroxylamine were observed to be generated during the heat treatment. After heat treatment, filtration,
After washing with water and drying, 119 parts by weight of the chelate and other agents obtained by decomposing the amidoxime group and having a nitrogen content of 17.1% by weight were obtained. (Hereinafter, this chelating agent will be referred to as chelating agent A.) Chelating agent A10+d was packed into a column with an inner diameter of 1211φ, and from the top of the column, uranium 100 μ/1, cobalt 100 μ/β, manganese loomg/L, palladium l
oomg/I! , solution I with a concentration of 3 g/l sodium chloride
When I2 was run for 5 hours and the concentration of each metal element in the effluent was analyzed, it was found that uranium was 0.8/11 and cobalt was 0.2.
■/f, manganese 0.3■/1, palladium 0.9■/
It was l.
比較例１
実施例１のキレート化剤Ａの代わりに実施例１で分解処
理に用いたアミドキシムを有するキレート化剤（以下、
本キレート化剤を分解未処理キレート化剤へと称す。）
を用いた以外は、実施例１と同様にして同一組成、濃度
の溶液を流した。流出液中の各金属元素濃度はウラン７
３■／Ｉｔ、コバルト８７■／ｆ、マンガン９３■／１
、パラジウム６７ｍｇ／ｌであった。Comparative Example 1 In place of the chelating agent A of Example 1, a chelating agent containing amidoxime (hereinafter referred to as
The present chelating agent is referred to as a degraded untreated chelating agent. )
A solution having the same composition and concentration was flowed in the same manner as in Example 1, except that a solution of the same composition and concentration was used. The concentration of each metal element in the effluent is uranium 7
3■/It, cobalt 87■/f, manganese 93■/1
, palladium 67 mg/l.
実施例２〜４．比較例２〜４
実施例１で用いたアミドキシム基を有するキレート化剤
の代わりに、以下のキレート化剤を用いた以外は実施例
１と同様の方法でアミドキシム基および／またはイミド
ジオキシム基の分解処理を行った。Examples 2-4. Comparative Examples 2 to 4 An amidoxime group and/or imidodioxime group was prepared in the same manner as in Example 1 except that the following chelating agent was used instead of the chelating agent having an amidoxime group used in Example 1. Decomposition treatment was performed.
キレート他剤Ｂ；クロルメチル化スチレンジビニルベン
ゼン樹脂にジアミノマレオニトリルを反応させ、さらに
ヒドロキシルアミンを反応させて得られるイミドジオキ
シム基を有するキレート化剤（以下、本キレート化剤を
分解未処理キレート化剤Ｂと称す、）を実施例１と同様
な方法で分解処理を行って得たキレート化剤。Other chelating agent B: A chelating agent having an imidodioxime group obtained by reacting a chloromethylated styrene divinylbenzene resin with diaminomaleonitrile and further reacting with hydroxylamine (hereinafter, this chelating agent is referred to as a decomposed untreated chelating agent). A chelating agent (referred to as agent B) obtained by decomposing the agent (referred to as agent B) in the same manner as in Example 1.
キレート他剤Ｃ；シアン化ビニリデンとジビニルベンゼ
ンとアクリル酸メチルとの共重合体をヒドロキシルアミ
ンと反応させて得られたビニルジアミドジオキシム−ジ
ビニルベンゼン−アクリル酸系キレート化剤（以下、本
キレート化剤を分解未処理キレート化剤Ｃと称す、）を
実施例１と同様な方法で分解処理を行って得たキレート
化剤。Other chelating agent C; vinyl diamide dioxime-divinylbenzene-acrylic acid-based chelating agent obtained by reacting a copolymer of vinylidene cyanide, divinylbenzene, and methyl acrylate with hydroxylamine (hereinafter referred to as the present chelating agent) A chelating agent obtained by decomposing chelating agent (referred to as undecomposed chelating agent C) in the same manner as in Example 1.
キレート他剤Ｄ；ベンズアミドキシムとレゾルシンとホ
ルマリンを反応させて得たキレート化剤（以下、本キレ
ート化剤を分解未処理キレート化剤りと称す、）を実施
例１と同様な方法で分解処理を行って得たキレート化剤
。Other chelating agent D: A chelating agent obtained by reacting benzamidoxime, resorcin, and formalin (hereinafter, this chelating agent is referred to as undecomposed chelating agent) was decomposed in the same manner as in Example 1. A chelating agent obtained by
以上のキレート化剤を、各々１０−を内径１２ｆｉφの
カラムに充填し、塔頂よりウランが１００■／１、ガリ
ウムが１５０■／１、濃度のバイヤー法アルミナ製造工
程のアルミン酸ナトリウム水溶液１１を２０時間で流し
、流出液中のウラン、ガリウム濃度の分析を行った。結
果を第１表に示す。A column with an inner diameter of 12 fiφ was filled with 10 μm of each of the above chelating agents, and from the top of the column, a sodium aluminate aqueous solution 11 from the Bayer process alumina manufacturing process was poured into the column with a concentration of 100 μ/1 for uranium and 150 μ/1 for gallium. It was drained for 20 hours and the uranium and gallium concentrations in the effluent were analyzed. The results are shown in Table 1.
実施例５〜８、比較例５〜８
実施例１〜４および比較例１〜４で用いたキレート化剤
Ａ、Ｂ、Ｃ，Ｄおよび未分解キレート化剤Ａ、Ｂ、Ｃ，
Ｄの各々ｌＯ−を内径が１２鶴φのカラムに充填し、イ
ツトリウム（Ｙ）、ランタン（Ｌａ）、ネオジム（Ｎｄ
）、サマリウム（Ｓｍ） 、ユーロピウム（Ｅｕ）、ガ
ドリニウム（Ｇｄ）、テルビウム（Ｔｂ）、ホロミウム
（Ｐ ｏ）およびインテルビウム（Ｙｂ）をそれぞれ１
００呵／ｌ含み、ｐＨ−１，５の溶液１１を１０時間で
塔頂より流したところ、塔用口の流出液中の金属濃度は
第２表の通りであった。Examples 5-8, Comparative Examples 5-8 Chelating agents A, B, C, D and undecomposed chelating agents A, B, C, used in Examples 1-4 and Comparative Examples 1-4,
A column with an inner diameter of 12 mm was filled with 1O− of D, and yttrium (Y), lanthanum (La), neodymium (Nd)
), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), holmium (Po) and interbium (Yb) at 1 each
When solution 11 containing 0.00 m/l and having a pH of -1.5 was flowed from the top of the column for 10 hours, the metal concentration in the effluent from the column outlet was as shown in Table 2.
実施例９〜１２、比較例９〜１２
実施例１〜４で用いたものと同じアミドキシム基および
／またはイミドジオキシム基を有する重合体の各々１０
０重量部を９．８重量パーセント濃度の硫酸水溶液２０
０重量部と５０℃で４時間加熱処理し、アミドキシム基
および／またはイミドジオキシム基の分解処理を行った
後、濾過水洗して得たキレート化剤（以下、これらのキ
レート化剤をそれぞれキレート化剤Ｅ、Ｆ、Ｇ、Ｈと称
す、）の各々１０−を内径１２鶴φのカラムに充填し、
ウラン１０■／１、金１０■／Ｉｌ、銅１０■／ｍｌ、
パラジウムｌＯ噌／ｌ、ゲルマニウム１０■／１、塩化
ナトリウム３ｇ／Ｉｔ、ＰＨ２，３の溶液１ｊ！を５時
間で塔頂より流したところ塔出口の流出液中の金属濃度
は第３表に示すような結果であった。Examples 9 to 12, Comparative Examples 9 to 12 10 each of the same amidoxime group and/or imidodioxime group-containing polymers as used in Examples 1 to 4
0 parts by weight to 9.8% by weight aqueous sulfuric acid solution 20
0 parts by weight at 50°C for 4 hours to decompose the amidoxime group and/or imidodioxime group, and then filtered and washed with water to obtain a chelating agent (hereinafter, these chelating agents were respectively referred to as chelating agents). 10 of each of the oxidizing agents E, F, G, and H) were packed into a column with an inner diameter of 12 φ,
Uranium 10■/1, gold 10■/Il, copper 10■/ml,
1 j of a solution of palladium 10/l, germanium 10/1, sodium chloride 3 g/It, PH2.3! was allowed to flow from the top of the column for 5 hours, and the metal concentration in the effluent at the column outlet was as shown in Table 3.
第 １ 表 第 ２ 表 第 ３ 表Table 1 Table 2 Table 3
Claims (1)
ジオキシム基を有するキレート化剤を酸またはアルカリ
水溶液と加熱することにより官能基を分解処理して得ら
れるキレート化剤と重金属を含有する溶液とを接触させ
ることを特徴とする重金属の回収方法。 ２ 官能基の分解処理が脱アンモニア加水分解または脱
ヒドロキシルアミン加水分解反応である特許請求の範囲
第１項記載の重金属の回収方法。 ３ 重金属がゲルマニウム、セシウム、コバルト、マン
ガン、ウラン、パラジウム、鉄、銅、ニッケルおよび白
金からなる群より選ばれた少なくとも一種の金属である
特許請求の範囲第１項記載の重金属の回収方法。 ４ 重金属が希土類金属である特許請求の範囲第１項記
載の重金属の回収方法。 ５ 重金属を含有する溶液がバイヤー法アルミナ製造工
程のアルミン酸ナトリウム水溶液または原子力発電プラ
ント工程水である特許請求の範囲第１項記載の重金属の
回収方法。 ６ 重金属を含有する溶液が鉱石溶出液である特許請求
の範囲第１項記載の重金属の回収方法。 ７ 酸水溶液が塩酸または硫酸の水溶液である特許請求
の範囲第１項記載の重金属の回収方法。 ８ アルカリ水溶液が水酸化ナトリウムまたは水酸化カ
リウムの水溶液である特許請求の範囲第１項記載の重金
属の回収方法。[Scope of Claims] 1 Contains a chelating agent having an amidoxime group and/or imidodioxime group as a functional group and a heavy metal obtained by heating the chelating agent with an acid or aqueous alkali solution to decompose the functional group. A method for recovering heavy metals, the method comprising bringing the metals into contact with a solution in which the heavy metals are recovered. 2. The method for recovering heavy metals according to claim 1, wherein the decomposition treatment of the functional group is deammonia hydrolysis or dehydroxylamine hydrolysis reaction. 3. The method for recovering heavy metals according to claim 1, wherein the heavy metal is at least one metal selected from the group consisting of germanium, cesium, cobalt, manganese, uranium, palladium, iron, copper, nickel, and platinum. 4. The method for recovering heavy metals according to claim 1, wherein the heavy metals are rare earth metals. 5. The method for recovering heavy metals according to claim 1, wherein the solution containing heavy metals is a sodium aluminate aqueous solution in the Bayer process alumina production process or nuclear power plant process water. 6. The method for recovering heavy metals according to claim 1, wherein the heavy metal-containing solution is an ore eluate. 7. The method for recovering heavy metals according to claim 1, wherein the acid aqueous solution is an aqueous solution of hydrochloric acid or sulfuric acid. 8. The method for recovering heavy metals according to claim 1, wherein the alkaline aqueous solution is an aqueous solution of sodium hydroxide or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62300559A JP2508162B2 (en) | 1987-11-28 | 1987-11-28 | Heavy metal recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62300559A JP2508162B2 (en) | 1987-11-28 | 1987-11-28 | Heavy metal recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01141816A true JPH01141816A (en) | 1989-06-02 |
| JP2508162B2 JP2508162B2 (en) | 1996-06-19 |
Family
ID=17886290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62300559A Expired - Lifetime JP2508162B2 (en) | 1987-11-28 | 1987-11-28 | Heavy metal recovery method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2508162B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000065107A1 (en) * | 1999-04-27 | 2000-11-02 | Ebara Corporation | Metal-collecting apparatus and method for elution and recovery of metal from metal-collecting material |
| JP2009167036A (en) * | 2008-01-11 | 2009-07-30 | Toagosei Co Ltd | Method for producing high purity alkali metal carbonate aqueous solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5916812A (en) * | 1982-07-21 | 1984-01-28 | Hokko Chem Ind Co Ltd | Agricultural and horticultural germicide |
| JPS5933416A (en) * | 1982-08-20 | 1984-02-23 | Olympus Optical Co Ltd | Adapter lens for photographing |
| JPS5933417A (en) * | 1982-08-18 | 1984-02-23 | Minolta Camera Co Ltd | Two-component wire angle zoom lens system |
| JPS5954626A (en) * | 1982-09-21 | 1984-03-29 | Sumitomo Chem Co Ltd | Separation and recovery of rare earth element and gallium |
-
1987
- 1987-11-28 JP JP62300559A patent/JP2508162B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5916812A (en) * | 1982-07-21 | 1984-01-28 | Hokko Chem Ind Co Ltd | Agricultural and horticultural germicide |
| JPS5933417A (en) * | 1982-08-18 | 1984-02-23 | Minolta Camera Co Ltd | Two-component wire angle zoom lens system |
| JPS5933416A (en) * | 1982-08-20 | 1984-02-23 | Olympus Optical Co Ltd | Adapter lens for photographing |
| JPS5954626A (en) * | 1982-09-21 | 1984-03-29 | Sumitomo Chem Co Ltd | Separation and recovery of rare earth element and gallium |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000065107A1 (en) * | 1999-04-27 | 2000-11-02 | Ebara Corporation | Metal-collecting apparatus and method for elution and recovery of metal from metal-collecting material |
| US6852233B1 (en) | 1999-04-27 | 2005-02-08 | Ebara Corporation | Metal-collecting apparatus and method for elution and recovery of metal from metal-collecting material |
| JP2009167036A (en) * | 2008-01-11 | 2009-07-30 | Toagosei Co Ltd | Method for producing high purity alkali metal carbonate aqueous solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2508162B2 (en) | 1996-06-19 |
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