JP4182217B2 - Selective recovery agent and selective recovery method for platinum group metal ions - Google Patents
Selective recovery agent and selective recovery method for platinum group metal ions Download PDFInfo
- Publication number
- JP4182217B2 JP4182217B2 JP2003435923A JP2003435923A JP4182217B2 JP 4182217 B2 JP4182217 B2 JP 4182217B2 JP 2003435923 A JP2003435923 A JP 2003435923A JP 2003435923 A JP2003435923 A JP 2003435923A JP 4182217 B2 JP4182217 B2 JP 4182217B2
- Authority
- JP
- Japan
- Prior art keywords
- pgms
- selective
- acid
- platinum group
- group metal
- 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.)
- Expired - Lifetime
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 60
- 238000011084 recovery Methods 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 43
- 229910021645 metal ion Inorganic materials 0.000 title claims description 37
- 239000003795 chemical substances by application Substances 0.000 title claims description 26
- 239000000243 solution Substances 0.000 claims description 56
- -1 amino compound Chemical class 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 35
- 238000000926 separation method Methods 0.000 claims description 29
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- 239000003929 acidic solution Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 230000001376 precipitating effect Effects 0.000 claims description 20
- 239000011964 heteropoly acid Substances 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 12
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010808 liquid waste Substances 0.000 claims description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 5
- 230000002285 radioactive effect Effects 0.000 claims description 5
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 5
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000010842 industrial wastewater Substances 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 30
- 229910052763 palladium Inorganic materials 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 15
- 229910052703 rhodium Inorganic materials 0.000 description 14
- 239000010948 rhodium Substances 0.000 description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 13
- 229910052707 ruthenium Inorganic materials 0.000 description 13
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000004993 emission spectroscopy Methods 0.000 description 3
- 239000002927 high level radioactive waste Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002915 spent fuel radioactive waste Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000581652 Hagenia abyssinica Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- OVSARSKQWCLSJT-UHFFFAOYSA-N n,n-di(propan-2-yl)aniline Chemical compound CC(C)N(C(C)C)C1=CC=CC=C1 OVSARSKQWCLSJT-UHFFFAOYSA-N 0.000 description 1
- MMFBQHXDINNBMW-UHFFFAOYSA-N n,n-dipropylaniline Chemical compound CCCN(CCC)C1=CC=CC=C1 MMFBQHXDINNBMW-UHFFFAOYSA-N 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- FRCFWPVMFJMNDP-UHFFFAOYSA-N n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC=C1 FRCFWPVMFJMNDP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、白金族金属イオン類（ルテニウム、ロジウム、パラジウム等、以下に、PGMsと略記する。）の、選択沈殿剤及び選択的分離・回収方法に関するものであり、更に詳しくは、各種酸性溶液中に溶存するPGMsを選択的に分離・回収する、アミノ化合物又はアミノ化合物とヘテロポリ酸とを組み合わせた選択沈殿剤及びこの選択沈殿剤を使用したPGMsの選択的分離・回収方法に関するものである。
本発明は、原子力産業及び各種鉱・工業の技術分野において、従来、白金族元素は、いずれも工業的に重要な金属であるうえ、資源的に極めて希少な貴金属であるため、資源確保の観点から、白金族金属を溶存する各種溶液中からの分離・回収が種々検討されていること、しかし、それらの多くは、実用上解決されるべき種々の問題点を有していること、を踏まえ、低コストで選択性に優れた新しい分離・回収プロセスを開発したものであり、例えば、有害な廃物、廃液等を処理し、貴重な金属である白金族金属を回収し、資源として再利用するとともに、環境問題を解消することを可能とする白金族金属元素の新しい実用可能な分離・回収技術を提供するものとして有用である。
また、本発明は、例えば、高レベル放射性廃液中からのPGMsの分離・回収法として極めて有用であり、種々の廃触媒の浸出液、装飾品等の各種金属の酸洗浄液（ピクリング浴液）や各種鉱・工業排水中に微量に含まれるPGMsの分離・回収技術として有用である。更に、本発明は、地質学試料等の分析の際のPGMsの前処理濃縮法として、分析化学の技術分野にも応用することができる。
本発明は、装飾品のみならず、電子材料、電気材料として、電気産業の技術分野、また、触媒として、合成化学、石油化学、自動車産業等の技術分野、において利用されている重要な金属である白金族金属の再資源化技術を供給することを可能とするものであって、新規な白金族金属の選択沈殿剤、及びそれを用いた新規で簡便な白金族金属の回収方法を提供するものである。
The present invention relates to a selective precipitant and a selective separation / recovery method for platinum group metal ions (ruthenium, rhodium, palladium, etc., hereinafter abbreviated as PGMs), and more specifically, various acidic solutions. The present invention relates to a selective precipitating agent that selectively separates and recovers PGMs dissolved therein and a combination of an amino compound or an amino compound and a heteropolyacid, and a method for selectively separating and recovering PGMs using the selective precipitating agent.
In the technical field of the nuclear power industry and various minerals and industries, the present invention has hitherto been considered that platinum group elements are all industrially important metals and are extremely rare noble metals. Based on the fact that various separation and recovery from various solutions in which platinum group metals are dissolved have been studied, but many of them have various problems to be solved in practice. Developed a new separation / recovery process with low cost and excellent selectivity, for example, processing hazardous wastes and waste liquids, recovering precious metals such as platinum group metals, and reusing them as resources At the same time, it is useful for providing a new practical separation / recovery technology for platinum group metal elements that can solve environmental problems.
In addition, the present invention is extremely useful as a method for separating and recovering PGMs from high-level radioactive liquid waste, for example, various kinds of waste catalyst leachate, various metal acid cleaning liquids (picking bath liquid) such as ornaments, and various It is useful as a technology for separating and recovering PGMs contained in trace amounts in mineral and industrial wastewater. Furthermore, the present invention can be applied to the technical field of analytical chemistry as a pretreatment concentration method for PGMs in the analysis of geological samples and the like.
The present invention is an important metal used not only as a decorative product, but also as an electronic material, an electrical material, a technical field of the electrical industry, and as a catalyst in a technical field of synthetic chemistry, petrochemistry, the automobile industry, etc. The present invention provides a platinum group metal recycling technique, and provides a novel platinum group metal selective precipitant and a novel and simple method for recovering a platinum group metal using the same. Is.
従来、ルテニウム、ロジウム、パラジウム等の白金族金属元素は、各種触媒、合金、坩堝、試薬、電気接点、電極、ピボット、熱電対等として広範に用いられている、工業的に非常に重要かつ平均価格の極めて高い貴金属元素である。更に、白金やパラジウムは装飾品としても重要な貴金属元素である（非特許文献１）。それらの金属の、地殻中の平均濃度（クラーク数：g/トン = ppm）は、最も含有量の高いパラジウムでも0.015ppm、最も含有量の低いロジウムやイリジウムでは0.0001ppmと、いずれも全元素中71〜80位を占める稀少金属元素類である（非特許文献２）。
資源的には、単体、銅及びニッケルの硫化物、白金族鉱石及びヒ化物等として産出するが、ロシア、カナダ、南アフリカ、コロンビア等の極一部の国々に遍在する。産出量は白金以外の元素で数トン／年、白金で白金族元素全体の約半量と見積もられている（非特許文献１）。白金族金属は、いずれも上記の鉱石資源を化学処理して得られた白金族元素の濃縮液より、(NH4)2[PtCl6]等の塩化白金族金属酸アンモニウム塩として沈澱分離した後、それらを水素で還元処理して製造されている（非特許文献３）。また、白金族元素は、種々の廃液、廃物、例えば、使用済み核燃料の再処理廃液、廃触媒中にも相当量含まれているので、それらの中から白金族元素を回収する技術が提案されている（特許文献１、２）。
Conventionally, platinum group metal elements such as ruthenium, rhodium and palladium have been widely used as various catalysts, alloys, crucibles, reagents, electrical contacts, electrodes, pivots, thermocouples, etc. Is an extremely high noble metal element. Furthermore, platinum and palladium are precious metal elements that are important as decorations (Non-Patent Document 1). The average concentration of these metals in the earth's crust (Clark number: g / ton = ppm) is 0.015 ppm even for the highest palladium content, and 0.0001 ppm for the lowest rhodium and iridium content. These are rare metal elements occupying positions 71 to 80 (Non-patent Document 2).
In terms of resources, it is produced as a simple substance, copper and nickel sulfide, platinum group ore and arsenide, etc., but it is ubiquitous in very few countries such as Russia, Canada, South Africa and Colombia. The output is estimated to be several tons / year for elements other than platinum, and about half of the total platinum group elements for platinum (Non-patent Document 1). All platinum group metals are precipitated and separated as ammonium chloride salts of platinum group metals such as (NH 4 ) 2 [PtCl 6 ] from the concentrated solution of platinum group elements obtained by chemical treatment of the above ore resources. These are produced by reduction treatment with hydrogen (Non-patent Document 3). In addition, platinum group elements are also contained in a variety of waste liquids and wastes, such as spent nuclear fuel reprocessing waste liquids and waste catalysts, so a technique for recovering platinum group elements from them is proposed. (Patent Documents 1 and 2).
このように、白金族元素はいずれも工業的に重要な金属元素であるうえ、資源的に極めて希少な貴金属であるため、資源確保の観点から廃触媒等の白金族元素を含む各種使用済製品からの回収、あるいは微量ではあるが、白金族元素を溶存する各種溶液中からの分離・回収法が種々検討されている。水溶液中に、微量に溶存する白金族金属イオン類の分離・回収法として、従来、沈澱法、イオン交換・吸着及び抽出法等種々の湿式精錬プロセスが開発されている（非特許文献４）。これらの湿式精錬プロセスのうち、特に、沈澱法は操作が簡単なことから開発例が多く、種々の還元剤や沈澱剤を用いた、各種鉱酸溶液中からの白金族元素の分離・回収プロセスが数多く公表されている（非特許文献４，５）。しかし、それらの多くは１）還元剤や沈澱剤を添加する前の白金族金属イオンを含む酸性溶液の濃度や温度等の調整が必要である、２）特殊な還元剤や沈澱剤を用いている、３）回収率が低い、４）沈澱の生成に長時間を要する、４）生成沈澱のろ過性が悪い等、実用上解決されるべき種々の問題点を有していた。このため、簡便、低コスト且つ選択性に優れた白金族元素の分離・回収プロセスの開発が切望されている（非特許文献６）。 In this way, all platinum group elements are industrially important metal elements, and are extremely rare noble metals in terms of resources, so various used products containing platinum group elements such as waste catalysts from the viewpoint of securing resources. Various methods for separation and recovery from various solutions in which platinum group elements are dissolved, although they are collected in small amounts, have been studied. Conventionally, various wet refining processes such as precipitation, ion exchange / adsorption and extraction have been developed as separation / recovery methods for platinum group metal ions dissolved in trace amounts in an aqueous solution (Non-patent Document 4). Of these hydrometallurgical processes, the precipitation method is particularly easy to operate and has many examples of development. Processes for separating and recovering platinum group elements from various mineral acid solutions using various reducing agents and precipitants Have been published (Non-Patent Documents 4 and 5). However, most of them require 1) adjustment of the concentration and temperature of the acidic solution containing platinum group metal ions before adding the reducing agent or precipitating agent. 2) Using special reducing agents or precipitating agents. 3) The recovery rate is low, 4) it takes a long time to form a precipitate, 4) the filterability of the formed precipitate is poor, and there are various problems to be solved in practice. For this reason, development of a separation / recovery process for platinum group elements that is simple, low-cost, and excellent in selectivity is eagerly desired (Non-Patent Document 6).
このような状況の中で、本発明者らは、上記従来技術に鑑みて、簡単な工程によって、白金族金属イオン類（PGMs）の分離沈殿・回収が、高度の選択性を持って実施できる、沈殿剤及び分離・回収方法を開発することを目標に鋭意研究を積み重ねた結果、アミノ化合物又はアミノ化合物とヘテロポリ酸を組み合わせた選択沈澱剤を使用することにより、PGMsの選択的分離・回収が、簡便に、高選択性で実現できることを見出し、本発明を完成するに至った。
即ち、本発明の目的は、各種酸性被処理溶液中から、PGMsが、高い選択性及び回収率で分離回収できる、アミノ化合物又はアミノ化合物とヘテロポリ酸の組み合わせからなる、新しい選択沈澱剤及びそれを用いた選択的分離・回収プロセスを提供することである。
また、本発明の目的は、各種酸性溶液中に溶存するPGMsを、高い選択性及び回収率でもって、回収するにあたり、アミノ化合物とヘテロポリ酸との組み合わせを選択することにより、PGMs間の分別回収を可能とするプロセスを提供することである。
また、本発明の目的は、特殊な還元剤や沈澱剤を用いなくても、回収率及び選択性が高い、PGMsの分離・回収プロセスを提供することである。
また、本発明の目的は、還元剤や沈澱剤を添加する前に、PGMsを含む酸性溶液の濃度や温度等を調整する等の前処理が必要でないPGMsの分離・回収プロセスを提供することである。
また、本発明の目的は、沈澱の生成が短時間で終了し、生成した沈澱のろ過性が良い、PGMsの分離・回収プロセスを提供することである。
Under such circumstances, the present inventors can carry out separation precipitation and recovery of platinum group metal ions (PGMs) with a high degree of selectivity by a simple process in view of the above-described conventional technology. As a result of intensive research aimed at developing precipitants and separation / recovery methods, selective separation / recovery of PGMs can be achieved by using selective precipitation agents that combine amino compounds or amino compounds and heteropoly acids. The inventors have found that it can be realized easily and with high selectivity, and have completed the present invention.
That is, an object of the present invention is to provide a new selective precipitating agent composed of an amino compound or a combination of an amino compound and a heteropolyacid, which can separate and recover PGMs from various acidic treated solutions with high selectivity and recovery rate. It is to provide a selective separation and recovery process used.
The object of the present invention is to separate and recover PGMs by selecting a combination of an amino compound and a heteropolyacid when recovering PGMs dissolved in various acidic solutions with high selectivity and recovery rate. Is to provide a process that enables
Another object of the present invention is to provide a process for separating and recovering PGMs that has a high recovery rate and selectivity without using a special reducing agent or precipitating agent.
Another object of the present invention is to provide a PGMs separation / recovery process that does not require pretreatment such as adjusting the concentration or temperature of an acidic solution containing PGMs before adding a reducing agent or a precipitating agent. is there.
Another object of the present invention is to provide a process for separating and recovering PGMs in which the production of precipitates is completed in a short time and the produced precipitates have good filterability.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）酸性溶液中に溶存する白金族金属イオン類（ＰＧＭｓ）を、選択的に沈殿させる作用を有する選択沈澱剤であって、少なくともアミノ化合物からなること、該アミノ化合物が、ピリジン、トリエチルアミン、ジエチルアミン、ジエタノールアミン、トリエタノールアミン、エチルアミン及びテトラエチルアミンのうち何れか１種であること、を特徴とするＰＧＭｓの選択沈澱剤。
（２）選択沈澱剤が、上記アミノ化合物、及びヘテロポリ酸からなることを特徴とする前記（１）に記載の選択沈澱剤。
（３）ヘテロポリ酸が、リンモリブデン酸、ケイモリブデン酸、リンタングステン酸、又はケイタングステン酸であることを特徴とする前記（２）に記載の選択沈殿剤。
（４）前記（１）に記載のＰＧＭｓの選択沈澱剤を用いた、酸性溶液中に溶存するＰＧＭｓの選択的分離・回収方法であって、上記酸性溶液を、少なくともアミノ化合物からなる選択沈殿剤で処理して、ＰＧＭｓを選択的に沈殿させた後、これを分離・回収することを特徴とするＰＧＭｓの選択的分離・回収方法。
（５）選択沈殿剤が、アミノ化合物、及びヘテロポリ酸からなることを特徴とする前記（４）に記載の選択的分離・回収方法。
（６）ヘテロポリ酸が、リンモリブデン酸、ケイモリブデン酸、リンタングステン酸、又はケイタングステン酸であることを特徴とする前記（５）に記載のＰＧＭｓの選択的分離・回収方法。
（７）酸性溶液が、高レベル放射性廃液、廃触媒の浸出液、金属の酸洗浄液（ピクリング浴液）、又は、鉱・工業排水であることを特徴とする前記（４）から（６）のいずれか１項に記載のＰＧＭｓの選択的分離・回収方法。
（８）前記（４）から（７）のいずれかに記載の方法で分離回収したＰＧＭｓ濃縮物を、更に、精製工程に供して高純度化し、再資源化することを特徴とする白金族金属元素の再資源化方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) A selective precipitant having an action of selectively precipitating platinum group metal ions (PGMs) dissolved in an acidic solution, comprising at least an amino compound, the amino compound comprising pyridine, triethylamine, A selective precipitation agent for PGMs, which is any one of diethylamine, diethanolamine, triethanolamine, ethylamine and tetraethylamine.
(2) The selective precipitation agent according to (1), wherein the selective precipitation agent comprises the amino compound and a heteropolyacid.
(3) The selective precipitant according to (2), wherein the heteropolyacid is phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, or silicotungstic acid.
(4) said with selective precipitating agent PGMs as described in (1), a selective separation and recovery method of PGMs dissolved in the acidic solution, the acidic solution comprises at least an amino compound selected precipitant A method for selectively separating and recovering PGMs, characterized in that PGMs are selectively precipitated by treatment with the method, and then separated and recovered.
(5) The selective separation / recovery method as described in (4) above, wherein the selective precipitant comprises an amino compound and a heteropolyacid.
(6) The method for selectively separating and recovering PGMs according to ( 5 ) above, wherein the heteropolyacid is phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, or silicotungstic acid.
(7) Any of (4) to (6) above, wherein the acidic solution is a high-level radioactive liquid waste, a waste catalyst leachate, a metal acid cleaning liquid (picking bath liquid), or a mineral / industrial wastewater The method for selectively separating and recovering PGMs according to claim 1.
(8) The platinum group metal, wherein the PGMs concentrate separated and recovered by the method according to any one of (4) to (7) above is further subjected to a purification step to be highly purified and recycled. Element recycling method.
次に、本発明について更に詳細に説明する。
本発明は、白金族金属イオン類を溶存する各種酸性溶液に、選択沈殿剤として、アミノ化合物又はアミノ化合物とヘテロポリ酸を組み合わせて用いることにより、当該白金族金属イオン類を被処理酸性溶液中から選択的に沈澱として分離・回収することを特徴とするものである。また、本発明は、各種酸性溶液中に溶存する、白金族金属イオンを、高選択的に、高回収率で、分離・沈殿回収することを可能とするものであり、本発明により、多くの共存金属が存在する酸性溶液から、白金族金属イオンを、高選択的に、高回収率で分離・回収することができる。更に、本発明は、用いる沈殿剤の組成に応じて、沈殿として分離・回収される白金族金属の種類が相違し、また、回収率も相違するので、選択沈殿剤の組み合わせを変えることによって、白金族金属の中の所望の金属のみを効率良く選択的に分離・回収することができる。
Next, the present invention will be described in more detail.
The present invention uses an amino compound or a combination of an amino compound and a heteropolyacid as a selective precipitating agent in various acidic solutions in which platinum group metal ions are dissolved. It is characterized by being selectively separated and recovered as a precipitate. In addition, the present invention makes it possible to separate and precipitate and recover platinum group metal ions dissolved in various acidic solutions with high selectivity and high recovery rate. Platinum group metal ions can be separated and recovered with high selectivity and high selectivity from an acidic solution containing coexisting metals. Furthermore, according to the present invention, depending on the composition of the precipitating agent to be used, the type of platinum group metal separated and recovered as a precipitate is different, and the recovery rate is also different. Only the desired metal in the platinum group metal can be efficiently and selectively separated and recovered.
本発明の、適用対象である白金族金属イオンが溶存する各種酸性溶液としては、特に限定されないが、各種工業の過程において得られる白金族金属を含んだ液、例えば、使用済み核燃料の再処理工場で発生する高レベル放射性廃液、使用済み触媒の浸出液、ピクリング浴液等の廃液、廃水等が例示される。また、地質学試料等の分析の際の、白金族金属の前処理段階での一括濃縮、分別濃縮等に適用することができる。こうした、本発明が対象とする、白金族金属イオンを含有する各種酸性溶液の化学的性状については、特に限定されない。また、共存する金属イオンの種類及び存在量についても特に限定されるものではない。被処理溶液の一例として、高レベル放射性廃液が例示される。
また、本発明において、白金族金属イオンとは、周期律表第ＶIII族元素に含まれる金属であり、例えば、パラジウム、ロジウム、ルテニウム、白金、イリジウム、オスミウムが例示され、これらの金属イオンは、いずれの金属イオンも、本発明により選択的に分離・回収される。
Various acidic solutions in which platinum group metal ions to be applied of the present invention are dissolved are not particularly limited, but include liquids containing platinum group metals obtained in various industrial processes, for example, reprocessing plants for spent nuclear fuel. Examples include high-level radioactive waste liquid generated in the above, waste liquid of spent catalyst, waste liquid such as pickling bath liquid, waste water and the like. In addition, the present invention can be applied to collective concentration, fractional concentration, etc. at the pretreatment stage of platinum group metals when analyzing geological samples. Such chemical properties of various acidic solutions containing platinum group metal ions targeted by the present invention are not particularly limited. Further, the type and abundance of the coexisting metal ions are not particularly limited. A high level radioactive waste liquid is illustrated as an example of the solution to be treated.
In the present invention, the platinum group metal ion is a metal contained in Group VIII elements of the Periodic Table, and examples thereof include palladium, rhodium, ruthenium, platinum, iridium, and osmium. Any metal ions are selectively separated and recovered by the present invention.
本発明の選択沈殿剤としてのアミノ化合物については、好ましくは、１）脂肪族第一級アミン：エチルアミン、n-プロピルアミン、iso-プロピルアミン、n-ブチルアミン、iso-ブチルアミン、sec-ブチルアミン、t-ブチルアミン、エタノールアミン、n-プロパノールアミン、iso-プロパノールアミン、4-アミノ-1-ブタノール、２−アミノ-1-ブタノール、1-アミノ-2-ブタノール、エチレンジアミン、1,3-プロパンジアミン、1,4-ブタンジアミン、1,6-ヘキサメチレンジアミン等、２）脂肪族第二級アミン：ジエチルアミン、ジ-n-プロピルアミン、ジ-iso-プロピルアミン、ジ-n-ブチルアミン、ジ-iso-ブチルアミン、ジ-sec-ブチルアミン、ジエタノールアミン、ジ-n-プロパノールアミン、ジ-iso-プロパノールアミン等、３）脂肪族第三級アミン：トリエチルアミン、トリ-n-プロピルアミン、トリ-iso-プロピルアミン、トリ-n-ブチルアミン、トリ-iso-ブチルアミン、トリエタノールアミン、トリ-n-プロパノールアミン、トリ-iso-プロパノールアミン等、４）脂肪族第四級アミン：テトラエチルアンモニウム塩、テトラブチルアンモニウム塩、セチルトリメチルアンモニウム塩等、５）芳香族第一級アミン：アニリン等、６）芳香族第二級アミン：N-メチルアニリン、N-エチルアニリン、N-n-プロピルアニリン、N-iso-プロピルアニリン等、７）芳香族第三級アミン：N,N-ジメチルアニリン、N,N-ジエチルアニリン、N,N-ジ-n-プロピルアニリン、N,N-ジ-iso-プロピルアニリン等及び８）環状第三級アミン：ピリジン、ビピリジン、ピペリジン、ピペラジン等が例示される。また、選択沈殿剤としての、ヘテロポリ酸についても特に限定されるものではないが、好ましくは、リンモリブデン酸、ケイモリブデン酸、ケイタングステン酸、リンタングステン酸等が例示される。本発明の選択沈殿剤を用いて、白金族金属イオンを回収するに当たって、金属イオンと選択沈殿剤との比率、選択沈殿剤の種類、その組み合わせ、及び添加順序については、被処理溶液の種類、回収する白金族金属の種類、濃度等を考慮して適宜設計することができる。 The amino compound as the selective precipitant of the present invention is preferably 1) aliphatic primary amine: ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, t -Butylamine, ethanolamine, n-propanolamine, iso-propanolamine, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, ethylenediamine, 1,3-propanediamine, 1 , 4-butanediamine, 1,6-hexamethylenediamine, etc. 2) Aliphatic secondary amines: diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso- Butylamine, di-sec-butylamine, diethanolamine, di-n-propanolamine, di-iso-propanolamine, etc. 3) Aliphatic tertiary amine: triethylamine, Ri-n-propylamine, tri-iso-propylamine, tri-n-butylamine, tri-iso-butylamine, triethanolamine, tri-n-propanolamine, tri-iso-propanolamine, etc. 4) Aliphatic secondary Quaternary amine: tetraethylammonium salt, tetrabutylammonium salt, cetyltrimethylammonium salt, etc. 5) Aromatic primary amine: aniline, etc. 6) Aromatic secondary amine: N-methylaniline, N-ethylaniline, Nn-propylaniline, N-iso-propylaniline, etc. 7) Aromatic tertiary amine: N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-propylaniline, N, N -Di-iso-propylaniline and the like and 8) cyclic tertiary amines: pyridine, bipyridine, piperidine, piperazine and the like. Moreover, although it does not specifically limit about heteropoly acid as a selective precipitant, Preferably, phosphomolybdic acid, silicomolybdic acid, silicotungstic acid, phosphotungstic acid, etc. are illustrated. In recovering platinum group metal ions using the selective precipitating agent of the present invention, the ratio of metal ions to the selective precipitating agent, the type of selective precipitating agent, the combination thereof, and the order of addition, the type of solution to be treated, It can be appropriately designed in consideration of the type and concentration of the platinum group metal to be recovered.
本発明は、上述のごとき、高濃度から低濃度に至るまで広範囲の白金族金属イオンを含んだ各種酸性溶液に適用でき、溶液の酸性度についても適用範囲が広いため、対象とされる被処理酸性溶液は、白金族金属を含んでいるものであれば何れの溶液であっても良い。したがって、本発明を適用し、白金族金属イオンを選択的に分離・回収するにあたっては、対象とする溶液に、前処理、例えば、酸性度、金属イオン濃度等の調整、を施す必要はない。
本発明の、白金族金属イオンと選択沈殿剤とが反応する沈殿形成反応は、常温常圧下で迅速に進行するため、特別な反応装置を用意する必要はなく、白金族金属イオンの溶液に、選択沈殿剤を混入し、十分撹拌することで反応は進行し、沈殿を形成する。
白金族金属の溶液と選択沈殿剤との接触時間は、通常は、５分〜３０分で十分であり、この時間内に沈殿反応は完結する。生成した白金族金属の沈殿物は、固液分離が容易なため、分離ろ過操作により、効率良く、溶液中の固体−液体を分離することができ、吸引ろ過、遠心分離等の慣用のろ過操作を用いることができる。生成した、白金族金属の沈殿物は、通常の方法で加工することにより、種々の利用分野で再利用される。
The present invention can be applied to various acidic solutions containing a wide range of platinum group metal ions from a high concentration to a low concentration as described above, and the applicable range of the acidity of the solution is wide. The acidic solution may be any solution as long as it contains a platinum group metal. Therefore, when the present invention is applied and the platinum group metal ions are selectively separated and recovered, it is not necessary to subject the target solution to pretreatment, for example, adjustment of acidity, metal ion concentration, or the like.
In the present invention, the precipitation formation reaction in which the platinum group metal ion and the selective precipitant react rapidly proceeds at room temperature and normal pressure, so there is no need to prepare a special reaction apparatus. The reaction proceeds and a precipitate is formed by mixing the selective precipitant and stirring sufficiently.
The contact time between the platinum group metal solution and the selective precipitant is usually 5 to 30 minutes, and the precipitation reaction is completed within this time. Since the generated platinum group metal precipitates are easily separated into solid and liquid, the solid-liquid in the solution can be efficiently separated by the separation and filtration operation, and the conventional filtration operations such as suction filtration and centrifugal separation can be performed. Can be used. The produced platinum group metal precipitates can be reused in various fields by being processed in the usual manner.
本発明では、用いる選択沈殿剤の組成に応じて、選択的に沈殿回収される白金族金属の種類が相違し、また、その回収率も相違するので、沈殿剤の組み合わせを変えることによって、白金族金属イオンのうち、所望の金属のみを効率良く選択的に分離・回収することができる。 In the present invention, depending on the composition of the selective precipitant used, the type of platinum group metal selectively precipitated and recovered is different, and the recovery rate is also different. Of the group metal ions, only the desired metal can be selectively separated and recovered efficiently.
本発明により、１）各種酸性被処理溶液中に溶存する白金族金属イオン類（PGMs）を選択的に分離・回収することが可能な、新しい選択沈殿剤及びそのプロセスを提供することができる、２）各種酸性溶液中に溶存するPGMsを、高い回収率及び選択性で、回収することができる、３）アミノ化合物とヘテロポリ酸との組み合わせを変えることにより、PGMsのうち所望の金属のみの分別沈殿回収を可能とする、４）本発明の方法は、高レベル放射性廃液、廃触媒の浸出液等、広範囲にわたる各種鉱工業の廃物、廃液等に適用できる、５）特殊な還元剤や沈澱剤を用いなくても、回収率及び選択性が高い、６）還元剤や沈澱剤を添加する前に、PGMsを含む酸性溶液の濃度や温度を調整する等の前処理を必要としない、７）沈澱の生成が、常温常圧下で、短時間に終了し、生成した沈澱のろ過性が良く、固液分離が容易な、PGMsの分離回収技術を提供することができる、という効果が奏される。 According to the present invention, 1) a new selective precipitant capable of selectively separating and recovering platinum group metal ions (PGMs) dissolved in various acidic treatment solutions and a process thereof can be provided. 2) PGMs dissolved in various acidic solutions can be recovered with a high recovery rate and selectivity. 3) By changing the combination of amino compounds and heteropolyacids, fractionation of only desired metals among PGMs is possible. 4) The method of the present invention can be applied to a wide variety of industrial wastes, waste liquids, etc., such as high-level radioactive liquid waste, waste catalyst leachate, etc. 5) Using special reducing agents and precipitants Even if not, recovery and selectivity are high. 6) Pretreatment such as adjusting the concentration and temperature of acidic solution containing PGMs is not required before adding reducing agents and precipitants. 7) Precipitation Generation at normal temperature and pressure, There is an effect that it is possible to provide a technique for separating and recovering PGMs, which is completed in a short time, has good filterability of the generated precipitate, and is easy to separate into solid and liquid.
次に、本発明を実施例に基づいて具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。
以下の実施例については、白金族金属イオンの選択的分離・回収試験を実施するにあたり、一例として、以下の、沈殿剤溶液及び被処理溶液の調製を行ったが、本発明は、以下の被処理溶液に限らず、各種酸性溶液中に溶存する白金族金属イオン類に同様に適用し得るものであることが実証された。
EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by these Examples.
In the following examples, the following precipitant solution and the solution to be treated were prepared as an example in carrying out the selective separation / recovery test of platinum group metal ions. It has been proved that the present invention can be applied not only to the treatment solution but also to platinum group metal ions dissolved in various acidic solutions.
１．選択沈澱剤溶液の調製
１）アミノ化合物溶液
アミノ化合物として、市販試薬の、ピリジン（小宗化学製：一級品）、トリエチルアミン（ナカライテクス製：特級品）、ジエチルアミン（東京化成：特級品）、ジエタノールアミン（ナカライテクス製：特級品）、トリエタノールアミン（ナカライテクス製：特級品）及びエチルアミン（和光純薬製：純度70%品）をそのまま用いて、アミノ化合物溶液を調製した。また、臭化テトラエチルアンモニウム（関東化学製：特級品）の10.5ｇを50ｃｍ3の蒸留水に溶解させて、1Ｍ（Ｍ＝mole/dm3）のテトラエチルアミン溶液を調製した。
1. Preparation of selective precipitant solution 1) Amino compound solution As amino compounds, commercially available reagents such as pyridine (manufactured by Kosou Kagaku: first grade), triethylamine (manufactured by Nacalai Tex: special grade), diethylamine (Tokyo Kasei: special grade), diethanolamine An amino compound solution was prepared using as is (Nacalai Tex: special grade), triethanolamine (Nacalai Tex: special grade) and ethylamine (Wako Pure Chemicals: purity 70%). Further, 10.5 g of tetraethylammonium bromide (manufactured by Kanto Chemical Co., Ltd .: special grade) was dissolved in 50 cm 3 of distilled water to prepare a 1M (M = mole / dm 3 ) tetraethylamine solution.
２） ヘテロポリ酸溶液
２種類のヘテロポリ酸水溶液を、市販試薬から次のようにして調製した。
a) 0.2 Mリンモリブデン酸溶液：
市販試薬のリンモリブデン酸（Fluka製: H3Mo12O40P.aq）の18.3gを50cm3の蒸留水に溶解させて、0.2 M の リンモリブデン酸水溶液を調製した。ICP 発光分光分析法により測定した当該溶液中のモリブデン濃度から求めたこの溶液の力価は0.870であった。
2) Heteropoly acid solution Two types of heteropoly acid aqueous solutions were prepared from commercially available reagents as follows.
a) 0.2 M phosphomolybdic acid solution:
A 0.2 M aqueous phosphomolybdic acid solution was prepared by dissolving 18.3 g of commercially available reagent phosphomolybdic acid (Fluka: H 3 Mo 12 O 40 P.aq) in 50 cm 3 of distilled water. The titer of this solution, determined from the molybdenum concentration in the solution measured by ICP emission spectroscopy, was 0.870.
b) 0.14 Mケイモリブデン酸溶液：
50cm3の蒸留水に市販試薬の三号水ガラス（小宗化学製: SiO2 28-30%）0.5g及びモリブデン酸アンモニウム（キシダ化学製:(NH4)6Mo7O244H2O）2.12gをそれぞれ加え、撹拌・溶解させた後、6M 塩酸にてpH1.5に調整した。pH調整後、50℃で３時間撹拌した後、白色不溶物を濾別したものをケイモリブデン酸溶液として用いた。ICP発光分光分析法により測定した当該溶液中のモリブデン濃度から求めたこの溶液の力価は1.01であった。
b) 0.14 M silicomolybdic acid solution:
Commercially available reagent No.3 water glass (manufactured by Koso Chemical: SiO2 28-30%) 0.5 g and ammonium molybdate (manufactured by Kishida Chemical: (NH 4 ) 6 Mo 7 O 24 4H 2 O) 2.12 in 50 cm 3 of distilled water Each g was added, stirred and dissolved, and then adjusted to pH 1.5 with 6M hydrochloric acid. After adjusting the pH, the mixture was stirred at 50 ° C. for 3 hours, and a white insoluble material was filtered off and used as a silicomolybdic acid solution. The titer of this solution determined from the molybdenum concentration in the solution measured by ICP emission spectroscopy was 1.01.
２．被処理溶液の調製
被処理溶液としては、酸濃度が高く、かつ共存成分数が多いため現在の技術では溶存する白金族金属イオン類の選択的分離・回収が最も困難な対象溶液の一つとされている高レベル放射性廃液組成の模擬溶液（Sep.Sci.Technol.,34,2347-2354(1999)：以下、モデル被処理溶液と略記する。）を用いた。モデル被処理溶液の化学組成を表１に示す。
2. Preparation of treated solution The treated solution is considered to be one of the most difficult target solutions for selective separation and recovery of dissolved platinum group metal ions with the current technology due to its high acid concentration and the large number of coexisting components. A high-level radioactive waste liquid composition (Sep. Sci. Technol., 34, 2347-2354 (1999): hereinafter abbreviated as model solution) was used. Table 1 shows the chemical composition of the model treated solution.
３．分離・回収試験方法
当該白金族金属イオンの分離・回収試験は、それぞれ、所定量のモデル被処理溶液に、上記アミノ化合物溶液を単独で、あるいは上記ヘテロポリ酸溶液とともに添加後、所定時間撹拌して両者を接触反応させた。生成した沈澱を直ちに濾過（ADVANTEC TOYO製：定量濾紙No.5Bを使用）して母液より分離後、濾紙上の沈澱を蒸留水で洗浄した。濾液及び洗液に、酸濃度が0.1Mとなるように濃硝酸の一定量を加え、蒸留水で定容とした後、当該溶液中の各白金族金属イオン濃度をICP 発光分光分析法により測定し、処理前後のモデル被処理溶液中の各白金族金属イオン濃度(ppm）から、次式により回収率を算出した。
3. Separation / Recovery Test Method The platinum group metal ion separation / recovery test was conducted by adding the amino compound solution alone or together with the heteropoly acid solution to a predetermined amount of the model treatment solution and stirring for a predetermined time. Both were contact-reacted. The formed precipitate was immediately filtered (manufactured by ADVANTEC TOYO: using quantitative filter paper No. 5B) and separated from the mother liquor, and the precipitate on the filter paper was washed with distilled water. After adding a certain amount of concentrated nitric acid to the filtrate and washing solution so that the acid concentration becomes 0.1M and making constant volume with distilled water, the concentration of each platinum group metal ion in the solution is measured by ICP emission spectroscopy. The recovery rate was calculated from the platinum group metal ion concentration (ppm) in the model treated solution before and after treatment by the following formula.
回収率(%) =｛（処理前の被処理溶液中の濃度 − 処理後の被処理溶液中の濃度）／（処理前の被処理溶液中の濃度）｝×100%
なお、上記の分離・回収試験の条件は、室温（20±3℃）、常圧下、撹拌時間10分間一定として行った。
Recovery rate (%) = {(concentration in the solution to be treated before treatment−concentration in the solution to be treated after treatment) / (concentration in the solution to be treated before treatment)} × 100%
The separation / recovery test was conducted under the conditions of room temperature (20 ± 3 ° C.), normal pressure, and stirring time of 10 minutes.
４．試験及び結果
モデル被処理溶液１cm3に、各種アミノ化合物0.5 cm3を添加し、室温（20±3℃）、常圧下、撹拌時間10分間一定としてPGMsの回収試験を行った。その結果を表２に示す。
表２の結果から、以下のことが明らかとなった。
１）本実施例で用いた７種のアミノ化合物の単独添加により、各金属イオンの回収率に差はあるものの、モデル被処理溶液中のPGMsを沈澱として分離・回収することが可能である。
２）上記アミノ化合物の中でも、トリエチルアミン及びジエチルアミンは、３種の金属イオンの回収率が78%以上と高く、PGMsの一括沈澱分離・回収に適している。
4). Tests and Results PGMs recovery test was performed by adding 0.5 cm 3 of various amino compounds to 1 cm 3 of the model solution to be treated, and keeping the stirring time constant at room temperature (20 ± 3 ° C.) and normal pressure for 10 minutes. The results are shown in Table 2.
From the results in Table 2, the following became clear.
1) By adding the seven amino compounds used in this example alone, although there is a difference in the recovery rate of each metal ion, PGMs in the model solution can be separated and recovered as a precipitate.
2) Among the above amino compounds, triethylamine and diethylamine have a high recovery rate of three kinds of metal ions of 78% or more, and are suitable for collective precipitation separation and recovery of PGMs.
３）ピリジン、トリエチルアミン、ジエチルアミン、エチルアミン及びジエタノールアミン添加試験系のロジウム／ルテニウム回収率は、いずれも90%以上であり、これらのアミノ化合物のロジウム／ルテニウム選択性は非常に高い。これらのアミノ化合物のうち、特にトリエチルアミン及びジエチルアミンのパラジウム選択性は極めて高い。
４）ロジウム／ルテニウム選択性の高いピリジン及びジエタノールアミンと、パラジウム選択性の高いトリエチルアミン及びジエチルアミンを用いた多段沈澱処理を行うことにより、ロジウム／ルテニウムとパラジウムの分別沈澱分離・回収が可能である。
3) The rhodium / ruthenium recovery rate of the pyridine, triethylamine, diethylamine, ethylamine and diethanolamine addition test systems is 90% or more, and the rhodium / ruthenium selectivity of these amino compounds is very high. Of these amino compounds, triethylamine and diethylamine have particularly high palladium selectivity.
4) Separation and separation of rhodium / ruthenium and palladium can be achieved by multi-stage precipitation using pyridine and diethanolamine with high rhodium / ruthenium selectivity and triethylamine and diethylamine with high palladium selectivity.
本実施例では、モデル被処理溶液１cm3に、上記0.2 M リンモリブデン酸溶液0.5 cm3及び上記各種アミノ化合物0.5cm3を添加し、室温（20±3℃）、常圧下、撹拌時間10分間一定としてPGMsの回収試験を行った。その結果を表３に示す。
表３の結果から、以下のことが明らかとなった。
１）0.2 M リンモリブデン酸溶液単独及びトリエタノールアミン添加系のPGMsの回収率は、いずれも20%以下と低く、選択性は、パラジウム＞ルテニウム＞ロジウムの順に低下する傾向がみられる。
In this embodiment, the model solution to be treated 1 cm 3, was added the 0.2 M phosphomolybdic acid solution 0.5 cm 3 and the various amino compounds 0.5 cm 3, room temperature (20 ± 3 ℃), atmospheric pressure, stirring time 10 minutes A recovery test of PGMs was conducted as a constant. The results are shown in Table 3.
From the results in Table 3, the following became clear.
1) The recoveries of 0.2 M phosphomolybdic acid solution alone and triethanolamine-added PGMs are both as low as 20% or less, and the selectivity tends to decrease in the order of palladium>ruthenium> rhodium.
２）エチルアミン、ジエチルアミン、トリエチルアミン及びピリジン添加系のPGMsの回収率は、いずれも77〜99%と高く、成分間の選択性の差は小さいが、選択性は、ルテニウム、ロジウム＞パラジウムの順に低下する傾向がみられる。
３）ジエタノールアミン添加系では、３成分間の回収率に大きな差がみられ、選択性は、ルテニウム＞＞パラジウム＞ロジウムの順に大である。
2) The recovery rate of PGMs with ethylamine, diethylamine, triethylamine and pyridine added is as high as 77 to 99%, and the selectivity difference between the components is small, but the selectivity decreases in the order of ruthenium, rhodium> palladium. There is a tendency to
3) In the diethanolamine addition system, a large difference is observed in the recovery rate among the three components, and the selectivity is in the order of ruthenium >>palladium> rhodium.
４）表３において、a) リンモリブデン酸単独添加系では、３成分の回収率が、いずれも20%以下と低く、ピリジン、トリエチルアミン、ジエチルアミン、エチルアミン、ジエタノールアミン添加系の高いPGMsの回収率は、表２に示したアミノ化合物の添加によるものと考えられる。しかし、b)ピリジン、エチルアミン及びジエタノールアミン添加系では、アミノ化合物単独添加系に比べてパラジウム回収率が著しく上昇した。また、表３のジエタノールアミン添加系では、３種の金属イオン間の回収率に大きな差が生じている。これらの結果は、いずれも、表２のアミノ化合物単独添加系の回収結果からは説明できない、リンモリブデン酸の共存効果と考えることができ、これらの沈殿剤の組み合わせを変えることで、所定の金属イオンの選択的分離・回収が可能となる。 4) In Table 3, a) In the phosphomolybdic acid single addition system, the recovery rate of the three components is as low as 20% or less, and the high PGMs recovery rate in the pyridine, triethylamine, diethylamine, ethylamine, diethanolamine addition system is This is considered to be due to the addition of the amino compound shown in Table 2. However, in the b) pyridine, ethylamine and diethanolamine addition systems, the palladium recovery rate was significantly increased compared to the amino compound addition system. Moreover, in the diethanolamine addition system of Table 3, a big difference has arisen in the recovery rate between three types of metal ions. These results can be considered as coexistence effects of phosphomolybdic acid, which cannot be explained from the recovery results of the amino compound single addition system shown in Table 2, and by changing the combination of these precipitants, a predetermined metal It is possible to selectively separate and collect ions.
本実施例では、モデル被処理溶液１cm3に、上記0.14 Mケイモリブデン酸溶液0.5 cm3及び上記各種アミノ化合物0.5cm3を添加し、室温（20±3℃）、常圧下、撹拌時間10分間一定としてPGMsの回収試験を行った。その結果を表４に示す。表４の結果から、以下のことが明らかとなった。
１）0.14Mイモリブデン酸溶液単独添加系では、PGMsは殆ど回収されない。テトラエチルアミン、トリエタノーアミン及びジエタノールアミンの添加によりPGMsの回収率は向上するものの、いずれの金属イオンも20%以下と低い。
２）エチルアミン、ジエチルアミン、トリエチルアミン及びピリジン添加系では、回収率は、いずれの金属イオンについても86〜99%と高く、金属イオン間の選択性に大きな差はみられないが、選択性は、ルテニウム＞ロジウム＞パラジウムの順に低下する傾向がみられる。
３）表４において、a) 0.14 Mケイモリブデン酸溶液単独添加系のPGMsの回収率が極めて低いことから、エチルアミン、ジエチルアミン、トリエチルアミン及びピリジン添加系にみられる高い回収率は、これらのアミノ化合物の添加（表２）による効果と考えることができる。しかし、b)エチルアミン及びピリジン添加系では、これらのアミノ化合物の単独添加系の場合（表２）に比べ、パラジウムの回収率が著しく向上する一方、ジエタノールアミン添加系では、単独系に比べ、ロジウム／ルテニウムの回収率が著しく低下している。このようなPGMs成分間にみられる選択性の変化は、いずれも、アミノ化合物単独添加系の結果からは説明できない、 ケイモリブデン酸溶液の共存効果と考えることができ、これらの沈殿剤の組み合わせを変えることで所定の金属イオンの選択的分離・回収が可能となる。
In this embodiment, the model solution to be treated 1 cm 3, was added the 0.14 M silicomolybdic acid solution 0.5 cm 3 and the various amino compounds 0.5 cm 3, room temperature (20 ± 3 ℃), atmospheric pressure, stirring time 10 minutes A recovery test of PGMs was conducted as a constant. The results are shown in Table 4. From the results in Table 4, the following became clear.
1) PGMs are hardly recovered in the system with 0.14M imolybdic acid solution added alone. Although the recovery of PGMs is improved by the addition of tetraethylamine, triethanolamine and diethanolamine, all metal ions are as low as 20% or less.
2) In the ethylamine, diethylamine, triethylamine and pyridine addition systems, the recovery rate is as high as 86 to 99% for any metal ion, and there is no significant difference in selectivity between metal ions, but the selectivity is ruthenium. There is a tendency to decrease in the order of>rhodium> palladium.
3) In Table 4, a) 0.14 M silicomolybdic acid solution added system has a very low recovery rate of PGMs, so the high recovery rate seen in ethylamine, diethylamine, triethylamine and pyridine added systems is This can be considered as an effect of addition (Table 2). However, in the case of b) ethylamine and pyridine addition system, the recovery rate of palladium is remarkably improved as compared with the case where these amino compounds are added alone (Table 2), while in the case of diethanolamine addition system, rhodium / The ruthenium recovery rate is significantly reduced. These changes in selectivity between the PGMs components can be considered as coexistence effects of silicomolybdic acid solution, which cannot be explained from the results of the amino compound alone addition system. By changing it, it becomes possible to selectively separate and recover predetermined metal ions.
以上詳述したように、本発明は、白金族金属（ルテニウム、ロジウム、パラジウム等）イオン類（PGMs）の、選択沈殿剤及び選択回収方法に係るものであり、各種酸性溶液中に溶存するPGMsを選択回収することが可能な、アミノ化合物又はアミノ化合物とヘテロポリ酸とを組み合わせた選択沈殿剤、及びこの選択沈殿剤を使用したPGMsの選択的分離・回収方法を提供することができる。本発明の方法の各種沈殿剤の添加による、種々の酸性溶液からのPGMsの沈殿生成反応は、常温、常圧下での簡単な操作により迅速、かつ選択的に進行する。本発明の方法は、高酸濃度の処理対象液に対しても直接的適用が可能であり、一切の前処理が不要である。また、生成沈殿物のろ過性がよく、固液分離が容易なため、本発明の方法による、PGMsの分離・回収操作はきわめて簡単な装置により再現良く行うことができる。本発明では、アミノ化合物とヘテロポリ酸の組み合わせを変えることにより、白金族金属イオンの分別沈殿回収が可能である。
更に、本発明は、例えば、原子力産業及び各種鉱・工業の技術分野において問題となっている、有害な廃物、廃液等を処理し、鉱・工業において貴重な金属である白金族金属を回収し、資源として再利用するとともに、環境問題を解消することを可能とするものである。本発明は、例えば、高レベル放射性廃液中からのPGMsの分離・回収法として極めて有用である。また、本発明は、種々の廃触媒の浸出液、装飾品等の各種金属の酸洗浄液（ピクリング浴液）や各種鉱・工業排水中に微量含まれるPGMsの分離・回収法として有用である。更に、本発明は、例えば、地質学試料等の分析の際のPGMsの前処理濃縮等として分析化学の技術分野にも応用することができる。
As described above in detail, the present invention relates to a selective precipitation agent and a selective recovery method for platinum group metal (ruthenium, rhodium, palladium, etc.) ions (PGMs), and PGMs dissolved in various acidic solutions. It is possible to provide a selective precipitating agent capable of selectively recovering an amino compound or a combination of an amino compound and a heteropolyacid, and a method for selectively separating and recovering PGMs using the selective precipitating agent. Precipitation reaction of PGMs from various acidic solutions by addition of various precipitants in the method of the present invention proceeds rapidly and selectively by a simple operation at normal temperature and normal pressure. The method of the present invention can be directly applied to a treatment target liquid having a high acid concentration, and does not require any pretreatment. In addition, since the produced precipitate has good filterability and solid-liquid separation is easy, the separation and recovery operation of PGMs by the method of the present invention can be performed with a very simple apparatus with good reproducibility. In the present invention, the platinum group metal ions can be separated and recovered by changing the combination of the amino compound and the heteropolyacid.
Furthermore, the present invention treats harmful wastes, waste liquids, etc., which are problematic in the technical field of the nuclear industry and various minerals and industries, and recovers platinum group metals that are valuable metals in the minerals and industries. In addition to being reused as a resource, environmental problems can be solved. The present invention is extremely useful, for example, as a method for separating and recovering PGMs from high-level radioactive liquid waste. In addition, the present invention is useful as a method for separating and recovering PGMs contained in trace amounts in various metal pickling solutions (picking bath liquid) and various minerals and industrial effluents such as leaching solutions of various waste catalysts and ornaments. Furthermore, the present invention can be applied to the technical field of analytical chemistry as, for example, pretreatment concentration of PGMs in the analysis of geological samples and the like.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003435923A JP4182217B2 (en) | 2003-12-26 | 2003-12-26 | Selective recovery agent and selective recovery method for platinum group metal ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003435923A JP4182217B2 (en) | 2003-12-26 | 2003-12-26 | Selective recovery agent and selective recovery method for platinum group metal ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005194546A JP2005194546A (en) | 2005-07-21 |
| JP4182217B2 true JP4182217B2 (en) | 2008-11-19 |
Family
ID=34815831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003435923A Expired - Lifetime JP4182217B2 (en) | 2003-12-26 | 2003-12-26 | Selective recovery agent and selective recovery method for platinum group metal ions |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4182217B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5128238B2 (en) * | 2007-10-30 | 2013-01-23 | 国立大学法人佐賀大学 | Method for producing noble metal fine particles, photocatalyst used in the method, and method for recovering noble metal from waste |
| JP2010144240A (en) * | 2008-12-22 | 2010-07-01 | Sumitomo Chemical Co Ltd | Method for recovering platinum group metal ion |
| US7935173B1 (en) * | 2010-07-23 | 2011-05-03 | Metals Recovery Technology Inc. | Process for recovery of precious metals |
| WO2012111542A1 (en) | 2011-02-18 | 2012-08-23 | 三菱瓦斯化学株式会社 | Method for collection of ruthenium or ruthenium compound |
| JP6532051B2 (en) * | 2014-12-03 | 2019-06-19 | 国立研究開発法人日本原子力研究開発機構 | Separation and recovery method of platinum group material and separation and recovery apparatus therefor |
| JP6762064B2 (en) * | 2016-03-28 | 2020-09-30 | 国立大学法人秋田大学 | Rhodium recovery agent and rhodium recovery method |
| WO2017170444A1 (en) * | 2016-03-28 | 2017-10-05 | 国立大学法人秋田大学 | Method for recovering noble metal and noble metal recovering agent |
| JP6923195B2 (en) * | 2017-09-21 | 2021-08-18 | 国立研究開発法人産業技術総合研究所 | Platinum group metal precipitation separation method |
| JP7017780B2 (en) * | 2018-03-19 | 2022-02-09 | 国立大学法人秋田大学 | Rhodium recovery method |
| JP7307460B2 (en) * | 2019-05-23 | 2023-07-12 | 国立研究開発法人量子科学技術研究開発機構 | Recovery device, recovery system, and recovery method |
| JP2022134611A (en) * | 2021-03-03 | 2022-09-15 | 国立大学法人秋田大学 | Platinum-group metal recovery agent and platinum-group metal recovery method |
| WO2024053621A1 (en) * | 2022-09-05 | 2024-03-14 | 田中貴金属工業株式会社 | Noble metal separation method |
-
2003
- 2003-12-26 JP JP2003435923A patent/JP4182217B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005194546A (en) | 2005-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4182217B2 (en) | Selective recovery agent and selective recovery method for platinum group metal ions | |
| US10221467B2 (en) | Tungsten and vanadium separation | |
| US4440734A (en) | Process for the recovery of sulfuric acid | |
| KR20050035976A (en) | Recovery of precious metals from waste catalysts | |
| US5256187A (en) | Separation of precious metals by an ion exchange process | |
| CN113337723A (en) | Method for separating and extracting silver, palladium, copper and germanium from silver separating slag | |
| CN109338120B (en) | Method for separating gold by flotation in ammonium thiocyanate-cetylpyridinium bromide-water system | |
| JPH06508179A (en) | Metal recovery method | |
| JP7198079B2 (en) | Method for treating acidic liquids containing precious metals, selenium and tellurium | |
| US6890496B2 (en) | Extraction of metals with diquaternary amines | |
| AU2010274628B2 (en) | Aqueous leaching process for recovery of precious metals with addition of dithiooxamide ligand | |
| KR100354980B1 (en) | Purification of the Platinum group | |
| JP6756235B2 (en) | How to collect bismuth | |
| RU2425363C1 (en) | Procedure for determination of quantitative contents of valuable metals in rock and piles of metal mining production | |
| EP1964936B1 (en) | Process for recovering noble metals from electric and electronic wastes | |
| CA1070504A (en) | Method for removing arsenic from copper electrolytic solutions or the like | |
| RU2221060C2 (en) | Method of extraction of platinum and palladium from materials having porous base | |
| KR100378050B1 (en) | High purity separating method of palladium | |
| KR100286392B1 (en) | High purity separation and purification method of platinum and palladium | |
| US7189380B2 (en) | Extraction of metals with diquaternary amines | |
| JP2011195935A (en) | Method for separating and recovering platinum group element | |
| JP5799340B2 (en) | Method for recovering precious metals from liquid containing precious metals | |
| RU2188247C1 (en) | Method of recovering platinum metals from refining production solutions | |
| JP3253123B2 (en) | Palladium separation method | |
| KR20240060749A (en) | Precious metal extraction methods and devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050616 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070201 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080121 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080321 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080513 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080710 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080804 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4182217 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |