CN100424204C - Precious metal recovery using thiocyanate lixiviant - Google Patents
Precious metal recovery using thiocyanate lixiviant Download PDFInfo
- Publication number
- CN100424204C CN100424204C CNB2004800155613A CN200480015561A CN100424204C CN 100424204 C CN100424204 C CN 100424204C CN B2004800155613 A CNB2004800155613 A CN B2004800155613A CN 200480015561 A CN200480015561 A CN 200480015561A CN 100424204 C CN100424204 C CN 100424204C
- Authority
- CN
- China
- Prior art keywords
- thiocyanate
- leaching
- leaching vat
- precious metal
- vat
- 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 - Fee Related
Links
- 239000010970 precious metal Substances 0.000 title claims abstract description 125
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000011084 recovery Methods 0.000 title claims description 31
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 title abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 790
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 191
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 176
- 239000011707 mineral Substances 0.000 claims abstract description 176
- 239000000463 material Substances 0.000 claims abstract description 158
- 230000002378 acidificating effect Effects 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 269
- 238000007254 oxidation reaction Methods 0.000 claims description 225
- 239000010931 gold Substances 0.000 claims description 218
- 229910052737 gold Inorganic materials 0.000 claims description 203
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 202
- 238000000034 method Methods 0.000 claims description 199
- 229910052742 iron Inorganic materials 0.000 claims description 171
- 230000003647 oxidation Effects 0.000 claims description 125
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 121
- 239000002253 acid Substances 0.000 claims description 120
- 239000010949 copper Substances 0.000 claims description 119
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 117
- 229910052802 copper Inorganic materials 0.000 claims description 117
- -1 iron ion Chemical class 0.000 claims description 116
- 238000002203 pretreatment Methods 0.000 claims description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 88
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 72
- 238000000605 extraction Methods 0.000 claims description 69
- 239000002994 raw material Substances 0.000 claims description 59
- 239000007787 solid Substances 0.000 claims description 59
- 229910052717 sulfur Inorganic materials 0.000 claims description 59
- 239000011593 sulfur Substances 0.000 claims description 59
- 229910052569 sulfide mineral Inorganic materials 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 53
- 238000002360 preparation method Methods 0.000 claims description 47
- 239000012141 concentrate Substances 0.000 claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 239000010953 base metal Substances 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 28
- 238000000638 solvent extraction Methods 0.000 claims description 27
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 24
- WQJONRMBVKFKOB-UHFFFAOYSA-N cyanatosulfanyl cyanate Chemical compound N#COSOC#N WQJONRMBVKFKOB-UHFFFAOYSA-N 0.000 claims description 23
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 23
- 230000008859 change Effects 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000000284 extract Substances 0.000 claims description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003456 ion exchange resin Substances 0.000 claims description 13
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 8
- 244000005700 microbiome Species 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012633 leachable Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052592 oxide mineral Inorganic materials 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 3
- 150000002500 ions Chemical group 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 150000004968 peroxymonosulfuric acids Chemical group 0.000 claims description 3
- 235000012976 tarts Nutrition 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 14
- 230000003197 catalytic effect Effects 0.000 claims 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims 1
- 229910052951 chalcopyrite Inorganic materials 0.000 claims 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052955 covellite Inorganic materials 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 117
- 238000012360 testing method Methods 0.000 description 107
- 229910052751 metal Inorganic materials 0.000 description 86
- 239000002184 metal Substances 0.000 description 86
- 239000000243 solution Substances 0.000 description 58
- 239000012266 salt solution Substances 0.000 description 42
- 150000003567 thiocyanates Chemical class 0.000 description 42
- 150000001875 compounds Chemical class 0.000 description 38
- 235000001508 sulfur Nutrition 0.000 description 35
- 239000003153 chemical reaction reagent Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 28
- 238000012545 processing Methods 0.000 description 25
- 238000010586 diagram Methods 0.000 description 24
- PDMYFWLNGXIKEP-UHFFFAOYSA-K gold(3+);trithiocyanate Chemical compound [Au+3].[S-]C#N.[S-]C#N.[S-]C#N PDMYFWLNGXIKEP-UHFFFAOYSA-K 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 21
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 13
- 239000005864 Sulphur Substances 0.000 description 13
- 235000011941 Tilia x europaea Nutrition 0.000 description 13
- 239000004571 lime Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 241000294743 Gamochaeta Species 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011365 complex material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- 229910052952 pyrrhotite Inorganic materials 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 210000000707 wrist Anatomy 0.000 description 3
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241001124569 Lycaenidae Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 241000605118 Thiobacillus Species 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 235000014987 copper Nutrition 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000027555 hydrotropism Effects 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000726121 Acidianus Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000589921 Leptospirillum ferrooxidans Species 0.000 description 1
- SZZRMCOLWUGEGL-UHFFFAOYSA-M N#C[O-].N#CO.N#CO.S.[K+] Chemical compound N#C[O-].N#CO.N#CO.S.[K+] SZZRMCOLWUGEGL-UHFFFAOYSA-M 0.000 description 1
- WMGJULKRDUBDII-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[S+2]=O Chemical compound S(=S)(=O)([O-])[O-].[S+2]=O WMGJULKRDUBDII-UHFFFAOYSA-L 0.000 description 1
- 241001134779 Sulfobacillus thermosulfidooxidans Species 0.000 description 1
- NMKZCXMNWUEAHB-UHFFFAOYSA-N [Au].[Au]=S Chemical compound [Au].[Au]=S NMKZCXMNWUEAHB-UHFFFAOYSA-N 0.000 description 1
- SXKZZFLSYPUIAN-UHFFFAOYSA-N [Cu].[Zn].[Au] Chemical compound [Cu].[Zn].[Au] SXKZZFLSYPUIAN-UHFFFAOYSA-N 0.000 description 1
- CQHGAGSNWPSHHU-UHFFFAOYSA-N [O-]C#N.[NH4+].[S] Chemical compound [O-]C#N.[NH4+].[S] CQHGAGSNWPSHHU-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004973 alkali metal peroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- BWZOPYPOZJBVLQ-UHFFFAOYSA-K aluminium glycinate Chemical compound O[Al+]O.NCC([O-])=O BWZOPYPOZJBVLQ-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000010424 alunite Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- ADPOBOOHCUVXGO-UHFFFAOYSA-H dioxido-oxo-sulfanylidene-$l^{6}-sulfane;gold(3+) Chemical compound [Au+3].[Au+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S ADPOBOOHCUVXGO-UHFFFAOYSA-H 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- SAOPTAQUONRHEV-UHFFFAOYSA-N gold zinc Chemical compound [Zn].[Au] SAOPTAQUONRHEV-UHFFFAOYSA-N 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- DXTCFKRAUYBHRC-UHFFFAOYSA-L iron(2+);dithiocyanate Chemical compound [Fe+2].[S-]C#N.[S-]C#N DXTCFKRAUYBHRC-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- CIXFHVGWRUTUPZ-UHFFFAOYSA-N thiocyanic acid hydrate Chemical compound O.SC#N CIXFHVGWRUTUPZ-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Abstract
Precious metal-containing mineral material is subjected to an acidic thiocyanate leach to dissolve the precious metal as a precious metal-thiocyanate complex. A feed of the thiocyanate leach solution may include a large molar ratio of ferric iron to thiocyanate. Precious metal may be removed from pregnant thiocyanate leach solution, such as by transferring precious metal from precious metal-thiocyanate complex to precious metal-cyanide complex and then loading the precious metal-cyanide complex onto an adsorbent material. Remaining cyanide in the thiocyanate leach solution may be converted to thiocyanate for additional leaching of precious metal.
Description
Technical field
Described herein the present invention relates to a kind ofly is used for mineral processing to reclaim the method for precious metal, more specifically, relates to the purposes of thiocyanate lixiviant in reclaiming gold.
Background technology
A kind of common technology that from auriferous ore, reclaims gold be with golden leaching (leach) in prussiate water-based leaching vat, wherein gold is with the form dissolving of gold-cyanide complex.In some cases, directly leaching goes out gold the concentrate of making from ore or by mineral.Many oxide compound ores all are like this.In other cases, before the prussiate leaching, pre-treatment ore or ore concentrate with the generation chemical transformation, thereby improve prussiate leaching performance.For example, thus auriferous sulfide ore often is an infusible can't carry out direct prussiate leaching.Therefore, before the prussiate leaching, often this infusible sulfide ore or the sulfide concentrate made by this infusible sulfide ore are carried out oxidation pre-treatment, thereby decompose sulfide minerals, during follow-up prussiate leaching, discharge gold thus and be used for reclaiming.
The leaching vat that contains gold often is called " (pregant) that be rich in metal " leaching vat.After gold being dissolved in the prussiate leaching vat, from the prussiate leaching vat that is rich in metal, remove gold then.This realizes by the prussiate leaching vat that is rich in metal and activated carbon particle are contacted under the condition that helps gold-cyanide complex is adsorbed on the activated carbon particle usually.After carbon granule load gold, from lean ore prussiate leaching vat, separate carbon granule then, it can recirculation be used for the extra gold of leaching.By using suitable stripping solution (strip solution) (for example Re caustic solution) from carbon granule, instead to extract (strip) gold, thereby remove gold from the load carbon granule.Then, for example from stripping solution, remove gold, be called the crude metal product of ingot with preparation by electrowinning.Ingot is carried out further refining, obtain the high purity gold.
Can or in reactor, carry out the prussiate leaching at heap operation (heap operation).In heap operation, the charging of lean ore prussiate leaching vat is applied to the pending raw mineral materials surface of a pile.This heap raw material of prussiate leaching vat infiltrate and from raw mineral materials leaching go out gold.Collection makes it contact with activated carbon, thereby remove gold from the prussiate leaching vat that is rich in metal from the effusive prussiate leaching vat that is rich in metal of this heap raw material.
When in reactor, carrying out the prussiate leaching, with the raw mineral materials for the treatment of leaching with prussiate leaching vat enough time of pulp in reaction vessel (one or more), with leaching gold effectively.In carbon in so-called slurries (carbon-in-pulp) operation, after the prussiate leaching, activated carbon is contacted with slurries in a series of containers, wherein activated carbon is to advance by a series of containers with the form of the direction of motion adverse current of slurries.In carbon in so-called filtrate (carbon-in-leach) operation, in the presence of activated carbon, carry out leaching, thereby prussiate leaching and the absorption on activated carbon take place in identical container simultaneously.
The prussiate leaching process is the industrial standards that goes on well in many cases.But, exist the prussiate leaching to be difficult to carry out or unpractical situation.
A kind of in-problem situation relates to the processing of infusibility sulfide gold mine, and wherein gold is locked in one or more sulfide ores, is difficult for usually therefrom reclaiming gold by direct prussiate leaching.As noted, before the prussiate leaching of being everlasting, carry out oxidation pre-treatment to these ores or by the concentrate that these ores are made.During oxidation pre-treatment, at least a portion sulfide sulfur in the sulfide ore is oxidized, causes sulfide ore that gold takes place to decompose and discharge.After the oxidation pre-treatment, the gold that discharges from sulfide ore still is in the same place with solid, uses the described solid of prussiate leaching vat leaching with dissolve gold then.A kind of oxidation pre-treatment technology is a bio-oxidation, and it is oxidized that wherein biological activity causes the sulfide sulfur in ore or the concentrate.Another kind of oxidation pre-treatment technology is a pressure oxidation, wherein in autoclave, uses oxygen treatments applied ore or concentrate under high temperature and high pressure.Another oxidation pre-treatment technology is oxidizing roasting ore or concentrate.
The problem that exists in the prussiate leaching residual solid after the oxidation pre-treatment is, residual solid often is highly acid, and the prussiate leaching must be carried out under alkaline pH usually.As a result, in need be before the prussiate leaching and solid.This neutralization need add a large amount of lime or some other neutralizing agents usually in solid, and significantly increases the complicacy of expense and operation.For the bio-oxidation of in stockpile, having carried out, in and solid need after bio-oxidation, remove this heap raw material, by during other mixes with neutralizing agent with solid and lime or some and the solid of oxidation, deposit the neutralise mixt heap then, be used for the prussiate leaching.After bio-oxidation, remove a pile raw material, in and solid and deposition a pile new material so that the prussiate leaching, this can significantly increase the cost and the complicacy of golden reclaimer operation.And, even after adding neutralizing agent, solid still contains a large amount of sulfide sulfurs usually, its existence can make the reclaimer operation complexity of gold.For example, the sulfide sulfur of a tittle can continue oxidation in prussiate leaching operation, even the oxidation of low degree also can cause great material processing problem.The sulphur that a kind of material processing problem is oxidation can be with (for example, because the interpolation of lime) calcium reaction forms insoluble gypsum, and it can block the hole of stockpile, thereby causes the permeability part of stockpile during the prussiate leaching to reduce from neutralizing agent.As another example, the prussiate lixivium can be directly and remaining sulfide type reaction of Salmon-Saxl, causes the mass consumption prussiate.
Another in-problem situation relates to the processing of the sulfide gold mine of the sulfide mineral that only contains moderate content.Opposite with infusibility sulfide gold mine, lower sulfide sulfur composition is contained in the sulphur ore deposit of these moderate content usually and the gold of significant quantity can be by direct prussiate leaching recovery usually.But the prussiate leaching is difficult in operation, because these ore deposits are highly acid often, and when sulfide ore a large amount of sulfuric acid of frequent generation during oxidation in storage and prussiate leaching operation.In order to carry out prussiate leaching these ores that need neutralize, this has proposed important problem.
Another in-problem situation relates to processing and contains the sulfide or the oxide compound gold mine of significant quantity copper, and described copper has and is easy to be dissolved in form in the prussiate leaching vat with gold.There are a large amount of dissolved copper in the prussiate leaching vat, cause become complexity and tooling cost of the recovery of gold to increase.And, in order to dispose (disposal), needing to destroy cupric cyanide, this has further increased tooling cost.Though can for example use sulphuric acid soln pre-leaching copper from copper mine stone sometimes, still need before the prussiate leaching, neutralize to ore through pre-leaching.And, if after the pre-leaching of acidity, in heap operation, ore is processed, then need to remove stockpile, in and solid and deposit new stockpile and be used for the prussiate leaching, this has just proposed the similar problem of situation to aforesaid bio-oxidation infusible sulfide ore.
Another in-problem situation relates to sulfide or the oxide compound gold mine that processing contains significant quantity organic carbonaceous material, and described organic carbon material has the avidity of ADSORPTION OF GOLD-cyanide complex in the prussiate leaching.This infusible carbon containing ore so-called " pre-back production (preg-robbing) " ore is because can be by using organic carbonaceous material " back production (rob) " obtainable gold from the prussiate leaching vat that is rich in metal.Several preconditioning techniques have been proposed, to reduce or to remove the pre-back production ability of organic carbonaceous material.These preconditioning techniques stayed before the prussiate leaching usually and are in the ore that needs the neutral acid state.Scheme has been used thiosulphate lixivium leaching gold from infusible carbon containing ore as an alternative, and does not need pre-treatment ore at first to destroy the pre-back production ability of organic carbonaceous material.Compare with gold-cyanide complex, the gold that obtains-thiosulfuric acid salt complex is difficult for being attracted on the organic carbonaceous material.But, owing to use prussiate, must under alkaline pH, carry out the leaching operation of thiosulphate usually, this just need neutralize according to particular ore of being processed and the operation of employed particular process before the thiosulphate leaching in a large number.
Except foregoing, still there is the regularity restriction of the increase that the leaching of using prussiate to carry out gold is operated.Therefore, in the gold mining industry, the alternative method that establishment uses the lixivium except that prussiate to be used for the leaching gold has obtained concern.For example, the potential use of thiocarbamide and thiosulphate lixivium has been subjected to sizable attention.But, because thiocarbamide is very easy to oxidative degradation takes place, cause the consumption height of thiocarbamide, cause and use thiocarbamide normally unpractical.Use the thiosulphate lixivium to obtain bigger success, still, merit attention, thiosulphate leaching operation must be carried out under alkaline pH usually, cause in many cases with the front at the pointed constructed problem of prussiate leaching.And it is more more difficult than remove gold from the prussiate leaching vat that is rich in metal removing gold from the leaching vat of the thiosulphate that is rich in metal, because gold-thiosulfuric acid salt complex is difficult for being adsorbed on the activated carbon particle.Also the surrogate of other lixivium as prussiate used in suggestion, but it is not studied significantly, and the enforcement of its reality is uncertain.
Summary of the invention
About the present invention, have been found that, by controlling leaching requirement carefully, the dissolved thiocyanate-that only uses the extremely low concentration in the sour sulfur cyanate leaching vat is thiocyanate-leaching precious metal from the mineral raw material that contains precious metal effectively, particularly gold.And, have been found that and can reclaim some ore and the concentrate that precious metal uses to be used for handling advantageously with leaching of this sour sulfur cyanate and the combination of acid pretreatment operation in preparation.Described acid pretreatment operation can comprise, for example, and before reclaiming precious metal, oxidation pre-treatment to refractory mineral and concentrate, from sulfide mineral, to discharge precious metal, perhaps to the pre-leaching of the acidity of ore, thus optionally pre-leaching soluble copper or some other soluble components.
For the performance that improves the leaching of sour sulfur cyanate, control the character of thiocyanate-leaching vat (particularly being delivered to the thiocyanate-leaching vat in the thiocyanate-leaching vat charging of thiocyanate-leaching operation) carefully.The thiocyanate-leaching vat is acidic aqueous solution normally, in order to improve its performance, the pH of thiocyanate-leaching vat is controlled in the narrow pH scope, and with respect to the concentration of dissolved thiocyanate-, the thiocyanate-leaching vat contains the dissolved iron ion of high density.The dissolved thiocyanate-represents that leaching vat comprises the dissolved substance that comprises thiocyanate-chemistry group SCN.Main solubility thiocyanate-material is thiocyanate ion SCN normally
-, but also can there be other solubility thiocyanate-material, for example trithiocyanuric acid radical ion (SCN)
3 -And thiocyanogen (SCN)
2The dissolved thiocyanate-can comprise not complexing the thiocyanate-material and/or with the thiocyanate-material of one or more metal complexes (often and iron ion complexing).These Stability of Substance constants (Barbosa-Filho that table 1 illustrates some exemplary iron-thiocyanate complex materials and comes forth, O., and Monhemius, A.J., Leaching of goldin thiocyanate solutions-Part I:Chemistry and thermodynamics, Transactions ofthe Institute of MM and Metallurgy (Section C), 1994, Vol.103, C117-125).
Table 1
| Iron ion | Complex compound | Stability constant (25 ℃) |
| Fe 2+(ferrous ion) | FeSCN + | 2.04×10 1 |
| Fe 3+(iron ion) | FeSCN 2+Fe(SCN) 2 +Fe(SCN) 4 -Fe(SCN) 5 2-Fe(SCN) 6 3- | 1.05×10 3 2.00×10 5 3.31×10 5 1.58×10 6 1.26×10 6 |
Be dissolved in the leaching vat thiocyanate-can with the precious metal complexing, thereby with precious metal dissolving in leaching vat.These Stability of Substance constants (Barbosa-Filho that table 2 illustrates some exemplary gold-thiocyanate complex materials and comes forth, O., and Monhemius, A.J., Leaching of goldin thiocyanate solutions-Part I:Chemistry and thermodynamics, Transactions ofthe Institute of Mining and Metallurgy (Section C), 1994, Vol.103, C117-125).According to the present invention, under the thiocyanate-leaching requirement, dithiocyano gold (Au (SCN
2)
-) and four thiocyanogen gold (Au (SCN)
4 -) complex compound seemingly is used for the most important gold-thiocyanate complex material of dissolve gold during the thiocyanate-leaching.
Table 2
| Gold ion | Complex compound | Stability constant (25 ℃) |
| Au + | Au(SCN) aq Au(SCN) 2 - | 1.86×10 15 1.45×10 19 |
| Au 3+ | Au(SCN) 4 - Au(SCN) 5 2- Au(SCN) 6 3- | 4.57×10 43 4.17×10 43 4.68×10 43 |
In order to improve performance, the pH that is supplied to the thiocyanate-leaching vat charging of thiocyanate-leaching should be in the acid range, is limited to pH 0.75 under it, preferred pH 1, and more preferably pH 1.5, and are limited to pH 3.5 on it, preferred pH 3, more preferably pH 2.5.The preferable range of this thiocyanate-leaching vat charging is pH 1 to pH 3, and more preferably pH 1.5-pH 2.5.For the charging of thiocyanate-leaching vat, pH 2 is particularly preferred.In a feasible method enhanced scheme, can be in whole thiocyanate-leaching process, preferred also in follow-up metal recovery operation, the thiocyanate-leaching vat is remained in the above-mentioned pH scope.In another feasible method enhanced scheme, can prepare the charging of thiocyanate-leaching vat carefully, make it contain the iron ion of high density for the concentration of dissolved thiocyanate-.For this reason, the mol ratio of dissolved iron ion and dissolved thiocyanate-(is called [Fe with this ratio here sometimes in the charging of thiocyanate-leaching vat
3+]/[SCN]) preferably have and be at least 2, more preferably be at least 4, further preferably be at least 7, further preferably be at least 8, most preferably be at least 10 mol ratio.As another feasible enhanced scheme, the mol ratio of dissolved iron ion and dissolved thiocyanate-can remain on 20 the level that is not more than.Can be by the volumetric molar concentration of dissolved iron ion be determined the mol ratio of dissolved iron ion and dissolved thiocyanate-divided by the volumetric molar concentration of dissolved thiocyanate-.The gram mole number (abbreviating mole here as) of dissolved iron ion or dissolved thiocyanate-in volumetric molar concentration (here sometimes with symbol " M " expression of simplifying) every liter of solution of expression.As used herein, concentration is meant volumetric molar concentration, unless specifically note in addition.As used herein, the concentration that is expressed as " ppm " is meant the per 1,000,000 parts umber based on weight.Should be appreciated that the dissolved iron ion and the ratio of the volumetric molar concentration of dissolved thiocyanate-also equal the total mole number of dissolved iron ion in the leaching vat and the ratio of the total mole number of dissolved thiocyanate-.The ratio of the ratio of the volumetric molar concentration of component and the total mole number of component often abbreviates " mol ratio " of component here as.
The dissolved iron ion is remained the dissolution kinetics that high density can promote gold significantly with respect to the dissolved thiocyanate-.Be not bound by theory, but help to understand the present invention, think relevant with the process that is called " reduction automatically ", in this process, by the spontaneous reduction of iron ion to ferrous ion, thiocyanate ion SCN by promoted kinetics
-Oxidized.It is important being considered to for the oxidation of quickening gold during the thiocyanate-leaching and dissolving as the intermediate thiocyanate-material that the result produced of this automatic reduction process.
As another enhanced scheme, the concentration of dissolved thiocyanate-in the thiocyanate-leaching vat can be remained on low-down concentration.In order to carry out preferred operations, the concentration of dissolved thiocyanate-is not more than 0.03M in the charging of thiocyanate-leaching vat, more preferably no more than 0.02M, further preferably is not more than 0.01M.But the concentration of dissolved thiocyanate-is at least 0.0001M usually in the charging of thiocyanate-leaching vat, is preferably 0.001M at least, and 0.002M at least more preferably often is 0.005M at least.And, as another enhanced scheme, can be preferably during whole thiocyanate-leaching, also preferred during the reclaimer operation of precious metal, the concentration of dissolved thiocyanate-in the thiocyanate-leaching vat is remained on described lower concentration.As used herein, with respect to the SCN chemical group, determine the concentration of dissolved thiocyanate-.In fact, in order to determine the concentration of dissolved thiocyanate-, think that all thiocyanate-materials all have thiocyanate ion SCN
-Form.For example, SCN
-Be equivalent to 1 mole of dissolved thiocyanate-, and 1 mole (SCN)
2Be equivalent to 2 moles of dissolved thiocyanate-s, 1 mole (SCN)
3 -Be equivalent to 3 moles of dissolved thiocyanate-s.
As mentioned above, in the preferred thiocyanate-leaching vat concentration of dissolved iron ion obviously greater than the concentration of dissolved thiocyanate-.In a preferred embodiment, the concentration of dissolved iron ion is at least 0.05M in the charging of thiocyanate-leaching vat, preferably is at least 0.1M; But the concentration that needs in some cases, the dissolved iron ion is at least 0.2M or even higher.In a preferred embodiment, the concentration of dissolved iron ion is 0.05M-0.3M, more preferably 0.05M-0.2M in the charging of thiocyanate-leaching vat.
Can carry out the thiocyanate-leaching under temperature required any, prerequisite is that this temperature can be to the disadvantageous effect that is dissolved with of gold with gold-thiocyanate complex form.Usually, in 15-50 ℃ temperature range, carry out the thiocyanate-leaching.
The mineral raw material of processing according to the present invention that contains precious metal can comprise, for example one or more following materials: contain precious metal ore, contain the concentrate (for example obtaining) of precious metal and the solid residue that contains precious metal that obtained by former ore process operation (for example by former oxidation with handle solid that tungsten sulfide ore or concentrate obtain or the mine tailing that still contains precious metal that obtained by former exploitation) by flotation or other concentration technique processing ore.And the raw mineral materials that contains precious metal can comprise the combination of plurality of raw materials, for example, and the combination of two or more following materials: ore, concentrate and the solid residue that obtained by former exploitation process operation.
In one aspect, the present invention relates to a kind of method that is used to process the ore that contains precious metal, wherein ore is carried out the leaching of sour sulfur cyanate, performance, particularly pH, thiocyanate concn, iron concentration and the thiocyanate-of preferred careful control thiocyanate-leaching vat charging and the mol ratio of iron ion.Can prepare the charging of thiocyanate-leaching vat by adjusting the thiocyanate-leaching vat, described adjustment is included in the lean ore elutriant that reclaims recirculation thiocyanate-leaching vat behind the precious metal and increases iron concentration in the thiocyanate-leaching vat with respect to the iron concentration in the thiocyanate-leaching vat.Be in course of adjustment, the concentration that increases iron ion can comprise, for example in the thiocyanate-leaching vat, add the acid elutriant that is rich in iron ion from oxidation pre-treatment operation (biological example oxidation or pressure maintenance), in the thiocyanate-leaching vat, add iron content ionic reagent, and/or by the ferrous ion in the thiocyanate-leaching vat is oxidized to the iron ion form.
In one aspect, the present invention relates to a kind of being included in and acid pretreated method is carried out in the mineral charging before the thiocyanate-leaching.In one embodiment, the mineral charging comprises pre-back production organic carbon, reduces the pre-back production ability of ore with decomposition and/or passivation organic carbon thereby acid pre-treatment comprises oxide treatment.In another embodiment, the mineral charging comprises the precious metal that is locked in the sulfide ore, for example may be in the state that coexists with infusibility sulfide ore and concentrate, oxidation pre-treatment was to decompose sulfide ore to discharge precious metal before acid pre-treatment was included in the thiocyanate-leaching.In one embodiment, oxidation pre-treatment can comprise, biological example oxidation or the charging of pressure oxidation mineral.In another embodiment, the mineral charging can comprise non-iron base metal a large amount of for economic recovery (for example one or more copper, nickel, zinc and lead), acid pre-treatment can be included in the thiocyanate-leaching non-iron base metal of leaching from the mineral charging before, thereby extracts precious metal.The non-iron base metal of leaching also can comprise the decomposition sulfide ore, for example between bio-oxidation or pressure oxidation pre-treatment period, to decompose sulfide mineral.In one embodiment, acid pre-treatment can comprise acid leaching component from the mineral charging, and it can hinder and use the thiocyanate-leaching to reclaim precious metal or make it complicated.For example, when the mineral charging comprises the soluble copper of significant quantity, can for example use the property selected vitriol leaching vat in the pre-leaching of acidity, to remove soluble copper.For example can use this scheme before thiocyanate-leaching precious metal, from mineral raw material, to remove deleterious soluble copper, thereby from precious metal ore or concentrate, reclaim by product copper, or allow after from copper mine or concentrate, reclaiming copper, to reclaim the by product precious metal, for example in copper heap leaching operation.
When the solution of the present invention comprises acid pre-treatment before the leaching of sour sulfur cyanate, can be according to circumstances in reactor (jar, cylinder or pressurized vessel), carry out in two kinds of operations one or both.But in a preferred embodiment, order is carried out acid pre-treatment and thiocyanate-pre-treatment on the stockpile that comprises the mineral charging at first.This is possible for the present invention, because two kinds of operations are all carried out under acid pH, and do not need to remove stockpile and deposit new stockpile once more after acid pre-treatment, this is in must be in preparing the hydride leaching and the situation of the hydride leaching operation during solid.About Biological Pretreatment infusibility sulfide material, in one embodiment, the degree of oxidation of sulfide sulfur can be lower than hydride leaching required degree before between the bio-oxidation pre-treatment period.This is because the easy oxidized sulfide mineral of oxidation extraly can carry out under the acidic conditions of thiocyanate-leaching, and described extra oxidation meeting is unfavorable to the alkaline cyanide leaching.
On the other hand, the present invention relates to use sour sulfur cyanate leaching leaching precious metal from appropriate infusible sulfidic materials.The thiocyanate-leaching is very suitable for processing described natural acidic material.In one embodiment, can before the thiocyanate-leaching, carry out acid pre-treatment washing.
In one aspect, the present invention relates to reclaim precious metal from the thiocyanate-leaching vat that is rich in metal.In one embodiment, be rich in the acid leaching vat of thiocyanate-and (the organic extractant phase) contact mutually of organic extraction agent of metal, thereby the dissolved precious metal is transferred to organic extraction agent phase from aqueous sulfur cyanate leaching vat.In another embodiment, use different complexing agent (preferred prussiate) to change the precious metal in the acid leaching vat of thiocyanate-into another kind of complex compound from precious metal-thiocyanate complex, in the thiocyanate-leaching vat, to form different noble metal complexes, preferred precious metal-cyanide complex.Can from the thiocyanate-leaching vat, reclaim precious metal-cyanide complex then, for example pass through noble metal support on sorbing material (for example ion exchange resin or activated carbon).Change (transfer) in order to carry out complex compound, can in the acid leaching vat of the thiocyanate-that is rich in metal, introduce a spot of dissolving prussiate.In one embodiment, after removing precious metal, change the remaining prussiate in the thiocyanate-leaching vat into thiocyanate-.
In one aspect, the present invention relates to preparation and/or adjust the acid leaching vat of thiocyanate-, be included in and dissolve prussiate in the acidic aqueous liquid and change the dissolved thiocyanate-into.Can use this scheme for example initially to prepare thiocyanate salt solution or compensation thiocyanate-in the loss of thiocyanate-leaching operating period.
Description below partly provides the extra disclosure of relevant above and other aspect of the present invention.
Description of drawings
Fig. 1 is the universal method skeleton diagram of the embodiment of the scheme that comprises the thiocyanate-leaching of the present invention.
Fig. 2 of the present inventionly comprises the thiocyanate-leaching and the universal method skeleton diagram of the embodiment of the scheme of recirculation thiocyanate-leaching vat after reclaiming precious metal.
Fig. 3 is the universal method skeleton diagram that is included in the embodiment of the scheme of carrying out oxidation pre-treatment before the thiocyanate-leaching of the present invention.
Fig. 4 is the universal method skeleton diagram that the embodiment of the pretreated scheme of pressure oxidation is carried out in the thiocyanate-leaching before that is included in of the present invention.
Fig. 5 is the universal method skeleton diagram that the embodiment of the pretreated scheme of pressure oxidation is carried out in the thiocyanate-leaching before that is included in of the present invention, and wherein said pressure oxidation pre-treatment comprises general procedure autoclaving and solid adjustment.
Fig. 6 is the universal method skeleton diagram that the embodiment of the pretreated scheme of bio-oxidation is carried out in the thiocyanate-leaching before that is included in of the present invention.
Fig. 7 is the universal method skeleton diagram that aggregated particles shape mineral material of the present invention is used to pile the embodiment of spreading out the scheme of handling.
Fig. 8 is the universal method skeleton diagram that comprises the embodiment of the scheme that while bio-oxidation and thiocyanate-leaching different material are piled of the present invention.
Fig. 9 is the universal method skeleton diagram of embodiment that charge raw material is carried out the scheme of acidic cleaning that is included in before the thiocyanate-leaching of the present invention.
Figure 10 is the thiocyanate-leaching universal method skeleton diagram of the embodiment of the scheme of leaching copper from charge raw material before that is included in of the present invention.
Figure 11 is the universal method skeleton diagram of the embodiment of a scheme of the present invention, precious metal was reclaimed in solvent extraction (solventextraction) after described scheme was included in thiocyanate-leaching and recirculation thiocyanate-leaching vat, was used to prepare the thiocyanate-leaching vat charging that is supplied to the thiocyanate-leaching.
Figure 12 is the universal method skeleton diagram of the embodiment of a scheme of the present invention, described scheme is carried out the complex compound transformation during being included in precious metal reclaimer operation and recirculation thiocyanate-leaching vat, is used to prepare the thiocyanate-leaching vat charging that is supplied to the thiocyanate-leaching.
Figure 13 changes prussiate into universal method skeleton diagram that thiocyanate-is used in the embodiment of the scheme in the thiocyanate-leaching of the present invention comprising.
Figure 14 is the relation curve for the weight ratio of the golden extraction yield of the prussiate leaching test that provides among the embodiment 1 and thiocyanate-leaching vat and ore.
Figure 15 is for the golden extraction yield of the prussiate leaching test that provides among the embodiment 2 and the relation curve of the thiocyanate concn in the thiocyanate-leaching vat.
Figure 16 is for the golden extraction yield of the prussiate leaching test that provides among the embodiment 3 and the relation curve of the thiocyanate concn in the thiocyanate-leaching vat.
Figure 17 is for the golden extraction yield of the prussiate leaching test that provides among the embodiment 3 and the relation curve of the iron concentration in the thiocyanate-leaching vat.
Figure 18 is for the bar graph of the golden extraction yield of the thiocyanate-leaching test that provides among the embodiment 4 and the line graph of thiocyanate-consumption.
Figure 19 is golden extraction yield and the leaching time relation curve for thiocyanate-that provides among the embodiment 5 and prussiate leaching test.
Figure 20 is thiocyanate-or prussiate reagent consumption and the leaching time relation curve for thiocyanate-that provides among the embodiment 5 and prussiate leaching test.
Figure 21 is the relation curve for the gold concentration in the charge capacity of the gold on ion exchange resin of the ion-exchange recovery test that provides among the embodiment 9 and the thiocyanate salt solution that is rich in metal.
Figure 22 is for gold concentration and time relation curve in the thiocyanate salt solution of the ion-exchange precious metal recovery test that provides among the embodiment 9.
Figure 23 is the rate of recovery and the time relation curve for the gold from thiocyanate salt solution of the ion-exchange precious metal recovery test that provides among the embodiment 9.
Figure 24 is the universal method skeleton diagram of the embodiment of a scheme of the present invention, described scheme comprises by carrying out after the thiocyanate-leaching relevant with the precious metal recovery and the relevant pre-treatment leaching of non-iron base metal (base metal) recovery, processes the material that comprises non-iron base metal and precious metal.
Embodiment
As used herein, " precious metal " comprises gold and/or silver.Here main reference processing and reclaim gold and describe and example the present invention, but identical principle is applicable to processing and reclaims silver, also can simultaneously or not process and reclaim gold simultaneously.
Referring to Fig. 1, show universal method skeleton diagram according to the scheme of sour sulfur cyanate of the present invention leaching.As shown in Figure 1, under acidic conditions, auriferous mineral in granular form raw material 102 is carried out thiocyanate-leaching 104.During thiocyanate-leaching 104, the leaching gold makes it enter the thiocyanate-leaching vat from raw mineral materials 102.Thiocyanate-leaching vat charging 106 is delivered to thiocyanate-leaching 104 with contact mineral raw material 102.Remove the thiocyanate-leaching vat 108 that is rich in metal of the dissolve gold that contains gold-thiocyanate complex form from thiocyanate-leaching 104, can further process to remove the dissolved gold it.The residual solid 110 of extracting gold is carried out extra metal recovery operation, or further handle to jettison with suitable manner.Gold-thiocyanate complex is represented any and all may reside in solubility gold-thiocyanate-material in the thiocyanate-leaching vat 108 that is rich in metal, for example listed any material of table 2.
Before delivering to the thiocyanate-leaching, can carry out leaching vat to the thiocyanate-leaching vat and adjust 112.Adjust during 112 at leaching vat, the character of thiocyanate-leaching vat is adjusted to the required character of thiocyanate-leaching vat 106 that is supplied to thiocyanate-leaching 104.The character of the thiocyanate-leaching vat that can regulate when adjusting leaching vat includes but not limited to the concentration of dissolved thiocyanate-and dissolved iron and mol ratio, pH and temperature.Leaching vat adjustment 112 can comprise, Yi Xia one or more for example: regulate pH, attemperation, adjusting dissolved iron concentration, regulate the dissolved thiocyanate concn, precipitate unwanted component, expel liquid and interpolation liquid, thereby the character to the thiocyanate-leaching vat is carried out required adjusting, with preparation thiocyanate-leaching vat charging 106.
In a preferred embodiment of the invention, adjust during 112, regulate dissolved thiocyanate-and the concentration of dissolved iron ion and the mol ratio of dissolved iron ion and dissolved thiocyanate-at leaching vat.And, according to circumstances, can precipitate unwanted component, with prevent in the thiocyanate-leaching stream component excessively accumulation and with pH regulator to required scope.Because use thiocyanate-leaching gold to relate at least some iron ions are reduced into ferrous ion, so leaching vat adjustment 112 generally includes the iron concentration that increases in the thiocyanate-leaching vat.And, during adjusting 112, leaching vat adds at least some fresh thiocyanate-s usually, with the loss of compensation thiocyanate-.Can adjust the concentration that increases the iron ion in the thiocyanate-leaching vat during 112 at leaching vat by multiple technologies.For example, can in the thiocyanate-leaching vat, add the reagent that contains the iron ion that dissolves in the thiocyanate-leaching vat.
In a preferred variation, in the thiocyanate-leaching vat, introduce one or more oxygenant reagent, thereby the ferrous ion that causes being dissolved in the thiocyanate-leaching vat is oxidized into iron ion." oxygenant " or " oxygenant reagent " expression causes that the dissolved ferrous ion is oxidized into the dissolved iron ion in the thiocyanate-leaching vat separately or with another kind of combinations of substances.Can the how easily stage in office this oxygenant reagent be introduced in the thiocyanate-leaching vat.For example, in scheme shown in Figure 1, can oxygenant be introduced in the thiocyanate-leaching vat in thiocyanate-leaching 104 and/or during leaching vat adjustment 112.When introducing oxygenant in the thiocyanate-leaching vat in the process of leaching gold, for example during thiocyanate-leaching 104, preferred selective oxidation agent is so that its degraded that does not influence and preferably improve the leaching speed of gold and do not cause thiocyanate-.And, at this moment, should be by adding suitable reagent with oxidation potential in the thiocyanate-leaching vat and the suitable in this case degree of pH condition control.When introducing oxygenant behind the precious metal reclaimer operation in the thiocyanate-leaching vat of elutriant or recirculation, oxygenant should preferably provide required oxidation producing iron ion, but does not more preferably cause significantly destroying the thiocyanate-that is dissolved in the solution.The limiting examples of the potential oxygenant reagent that can use separately or use with other chemically compatible agent combination comprises Caro's acid (persulfuric acid), persulphate (for example ammonium persulphate and persulfuric acid an alkali metal salt, for example Potassium Persulphate and Sodium Persulfate), superoxide (inorganic peroxide for example, for example hydrogen peroxide and alkali metal peroxide, and organo-peroxide), Manganse Dioxide, ozone, halogen (for example chlorine, iodine and bromine) and hypochlorite (for example clorox).As mentioned above, one or more described oxygenant reagent can use separately or use with other chemically compatible agent combination.And the prerequisite that multiple oxygenant reagent can use together is that described multiple oxygenant reagent is chemically compatible in specific system.Preferably the example of the oxygenant reagent that uses with one or more other reagent is oxygen (for example providing in the oxygen composition of air or purification).In a preferred version, oxygen uses with another kind of at least agent combination, and the ferrous ion in the thiocyanate-leaching vat is oxidized into iron ion.For example can in the thiocyanate-leaching vat, introduce oxygen by the Oxygen Flow of injection air in the thiocyanate-leaching vat or purification.Another kind of reagent is sulfurous gas, hydrosulphite (for example alkali-metal hydrosulphite or ammonium bisulfite) or metabisulphite (for example sodium metabisulfite or Potassium hydrogen sulfite partially) preferably.Copper or other catalyzer for example copper sulfate can use to improve performance with oxygen and described another kind of reagent.When using sulfurous gas, can introduce sulfurous gas by sulfur dioxide gas is sprayed in the thiocyanate-leaching vat dividually with oxygen or with oxygen as described another kind of reagent.When using hydrosulphite or metabisulphite as described another kind of reagent, described another kind of reagent can be introduced in the thiocyanate-leaching vat as the solid that is dissolved in the thiocyanate-leaching vat, perhaps described another kind of reagent can be dissolved in the spissated reagent solution in advance.
In another version, leaching vat adjustment 112 is included under the acidic conditions, preferably in the pH scope that is suitable for, by microbial process the ferrous particle of dissolved is oxidized to the dissolved iron ion during thiocyanate-leaching 112.Oxidation can be carried out in all or part of thiocyanate-leaching vat in independent bio-reactor.Bio-reactor can be for example to contain the independent heap or a plurality of heap that are positioned at the microorganism on rock or some other carrier.As another example, bio-reactor can be one or more jar or cylinders that contain the microorganism that is positioned on rock or some other carrier.Preferably, it is highly porous and permeable being furnished with microorganism carrier on it.In this version, thiocyanate-is nontoxic to microorganism to be important, described microorganism for example name is called the U.S. Patent No. 6 of " Method of IsolatingThiocyanate Resistant Bacteria ", 379, disclosed in 919, its full content is incorporated this paper by reference into, as here all setting forth.
As another version, leaching vat adjustment 112 comprises in the following manner the ferrous ion in all or part of thiocyanate-leaching vat is oxidized to iron ion: by making all or part of thiocyanate-leaching vat electrochemical cell of flowing through, simultaneously on battery, apply enough electromotive forces, thereby cause the dissolved ferrous ion to be oxidized to the dissolved iron ion.
In a preferred version of the present invention, recirculation thiocyanate-leaching vat from the reclaimer operation of gold is used for reusing in extra thiocyanate-leaching.Referring now to Fig. 2,, show the universal method skeleton diagram of a scheme of the present invention, wherein recirculation thiocyanate-leaching vat after the recovery of gold is used for going out to reuse in thiocyanate-leaching operation.Except what point out in addition, used identical among Reference numeral and Fig. 1.As shown in Figure 2, the leaching vat 108 that is rich in metal is delivered to gold reclaim 118, produce the golden product 120 of purifying there, for example ingot.The lean ore elutriant that will comprise the thiocyanate-leaching vat 122 of all or part of thiocyanate-leaching vat is recycled to leaching vat adjustment 112, be used to prepare the thiocyanate-leaching vat charging 106 that is used for extra thiocyanate-leaching, described lean ore elutriant has been removed gold during gold reclaims 118.
Thiocyanate-leaching of the present invention can be used for processing the various raw mineral materialss that contain precious metal.For example, some other that make during the concentrate that raw mineral materials can comprise oxide compound ore, sulfide ore, made by oxide compound ore or sulfide ore, the former mineral process operation contains the solid product of precious metal, perhaps comprises the combination of the above-mentioned substance of any amount and ratio.But the present invention is particularly suitable for processing the advantageously raw mineral materials of leaching precious metal under acid pH, for example natural acid drift, acidic concentrate or the acid solid residue that was obtained by former oxidation pre-treatment.
In one embodiment, the present invention relates to from the mineral charging that contains precious metal that one or more sulfide ores, comprises precious metal, reclaim precious metal.Described mineral charging can comprise, for example sulfide gold mine and/or the auriferous sulfide concentrate for example made by flotation by the sulfide gold mine.Because gold sulfide gold mine so-called " infusible " sulfide by direct prussiate leaching recovery gold in bond and difficult enters the ore deposit in the sulfide mineralising.Described infusible sulfide gold mine has high sulfide type sulphur content usually, has the sulfide sulfur of at least 2 weight % usually, often has at least 3 weight % or more sulfide sulfur, but has the sulfide sulfur less than 10 weight % usually.Some ores contain more a spot of sulfide sulfur and because the mineralising of sulfide only is appropriate infusible, a large amount of gold can reclaim by direct cyanogenation.Except auriferous sulfide mineral component, these appropriate infusible ores can have a large amount of auriferous oxide mineral components, and in this case, described ore is called the transition ore sometimes.And, can obtain this appropriate infusible ore by the ore that long-time stock was contained the sulfide sulfur of high level originally because the oxidation of the sulfide sulfur of significant quantity can be during the stock who prolongs for example because spontaneous bacterium and spontaneous generation.Appropriateness infusible sulfide ore contains the sulfide sulfur less than 2 weight % usually, more generally contains the sulfide sulfur that is not more than 1.5 weight %, and contains the sulfide sulfur of at least 0.5 weight % usually.
The present invention can be used to handle infusible sulfide gold mine, appropriate infusible sulfide gold mine, and/or the sulfide concentrate of being made by one or more described ores.Should be appreciated that sulfide concentrate contains the sulfide type sulphur content higher than the ore of being made by concentrate.The sulfide type sulphur content of sulfide concentrate often is to make the twice at least of sulfide type sulphur content of the ore of concentrate, and more frequent is several times of described latter's content.The present invention can also be used to handle and contains a large amount of infusibility gold mine and concentrate that are difficult for the gold that reclaims by direct hydride leaching, except or be included in golden bound reason in the sulfide mineralising, for example because the existence of pre-back production organic carbon.
Referring now to Fig. 3,, show the universal method skeleton diagram of a scheme of the present invention, the concentrate that this scheme is used to process the infusibility gold mine, made by described infusibility gold mine and/or other contain the auriferous refractory mineral raw material that is difficult for by the gold of direct prussiate leaching recovery.Except what point out in addition, used identical among Reference numeral and Fig. 1 and 2.As shown in Figure 3, oxidation pre-treatment 130 is carried out in common refractory mineral charging 128 of a granular form.Because one or more characteristics of mineral charging, infusible mineral charging 128 may be an infusible.For example, infusible mineral charging 128 may be an infusible, because it contains a large amount of gold that is bound in the sulfide mineral and is difficult for reclaiming by direct prussiate leaching (infusible sulfide mineral raw material) and/or contains pre-back production organic carbon (infusible carbon containing mineral raw material) because of infusible sulfide mineral charging 128.Except infusible sulfide mineral material, infusible sulfide mineral raw material can contain pre-back production organic carbon.Equally, except pre-back production organic carbon, the charging of infusible carbon containing mineral can contain infusible sulfide mineral material.
During oxidation pre-treatment 130, the chemical property of infusible mineral charging .128 changes in well-oxygenated environment, has reduced the refractory properties of mineral material, thereby allows to reclaim the difficult gold that reclaims by direct prussiate leaching infusible mineral charging 128.Contain in refractory mineral charging 128 under the situation of infusibility sulfide mineral material, during oxidation pre-treatment 130, at least a portion sulfide sulfur of the sulfide mineral in the infusible sulfide mineral material is oxidized, thereby at least a portion sulfide mineral is decomposed, and discharges gold from sulfide mineral.Contain in refractory mineral charging 128 under the situation of infusible carbon containing mineral material, during oxidation pre-treatment 130, for example decomposition and/or the passivation by pre-back production organic carbon, the pre-back production ability drop of organic carbon.Contain in refractory mineral charging 128 under the situation of infusibility sulfide mineral material and infusible carbonaceous mineral material, during oxidation pre-treatment 130, at least a portion sulfide sulfur of the sulfide mineral in the infusible sulfide mineral material is oxidized, from sulfide mineral, discharge gold, perhaps the pre-back production ability drop of organic carbon perhaps takes place simultaneously.The mineral material 102 that stands thiocyanate-leaching 104 comprises the solid residue that is obtained by oxidation pre-treatment 130.Described solid residue is normally highly acid.
As shown in Figure 3, when oxidation pre-treatment produced a large amount of dissolved iron ion, the optional feature of this scheme was the acid elutriant 132 that contains high density dissolved iron ion of preparation during using oxidation pre-treatment 130 during the leaching vat adjustment 112.When using, acid elutriant 132 only contains the elutriant that some prepares usually during oxidation pre-treatment 130.Adjust during 112 at leaching vat, can in the thiocyanate-leaching vat, add acid elutriant 132, with the concentration of dissolved iron ion in the increase thiocyanate-leaching vat, thus preparation thiocyanate-leaching vat charging 106.In order to keep the suitable liquid volume of thiocyanate-leaching vat, can adjust at 112 o'clock at leaching vat and from the thiocyanate-leaching vat, discharge or remove part thiocyanate-liquid.For example, can be by adding before or after the acid elutriant 132, but preferably before adding acid elutriant 132, expel liquid or anhydrate by evaporating to remove.In order to implement the solution of the present invention, as shown in Figure 3, use acid elutriant 132, oxidation pre-treatment 130 is the methods that prepare the acid elutriant 132 of the dissolved iron ion with high density.
During use, acid elutriant 132 should contain the dissolved iron ion of dissolved iron concentration in the raw material that concentration is higher than thiocyanate-leaching vat 106.The example that is used for the preferred operations of oxidation pre-treatment 130 is pressure oxidation and bio-oxidation.
Preferably, the concentration of dissolved iron ion is the twice (more preferably at least four times) of dissolved iron concentration in the thiocyanate-leaching vat charging 106 at least in the acid elutriant 132.And in fact acid elutriant 132 can prepare during oxidation pre-treatment 132, perhaps can obtain by handling after oxidation pre-treatment 132.For example, can be as required with the pH of the acid elutriant of up-down adjustment before the thiocyanate-leaching vat mixes.And acid elutriant 132 can be to anhydrate by evaporating to remove the not too dense solution of for example making during oxidation pre-treatment 130, forms more spissated solution.When mixing with the thiocyanate-leaching vat during adjusting 112 at leaching vat, acid elutriant 132 preferably has the pH that is not more than pH3, and preferably is not more than pH 2.5.In a version, when mixing with the thiocyanate-leaching vat during adjusting 112 at leaching vat, acid elutriant 132 can have pH 2 or lower or even pH 1.5 or lower pH.In a version, when adding in the thiocyanate-leaching vat during leaching vat adjusts 112, acid elutriant 132 has the pH of pH 0.1-pH 3, is preferably the pH of pH 1 to pH 3.
For example, thereby when a large amount of thiocyanate-leaching vats of recirculation from golden reclaimer operation to utilize the preparation thiocyanate-leaching vat charging 106 (elutriant of recirculation thiocyanate-leaching vat 122 from golden reclaimer operation 118 for example once more, in the time of as shown in Figure 2), using acid elutriant 132 is favourable as iron ion source.During thiocyanate-leaching 104, quite a large amount of iron ions is reduced to ferrous ion usually, makes the thiocyanate-leaching vat of recirculation contain usually with respect to dissolved iron concentration iron ion still less in the thiocyanate-leaching vat charging 106.Limiting examples in the method that may use during the oxidation pre-treatment 130 comprises bio-oxidation (for example by handling), pressure oxidation (adding or do not add sulfuric acid, nitric acid or chloro-containing reagent), nitric acid oxidation (for example by handling) and chlorization (by use hypochlorite reagent or another kind of chloride oxidising agent processing in heap, jar or cylinder) in heap, jar or cylinder in heap, jar or cylinder.When refractory mineral charging 128 contained infusibility sulfide mineral material, the preferred working method that is used in during the oxidation pre-treatment 130 comprised bio-oxidation, pressure oxidation and nitric acid oxidation.When refractory mineral charging 128 contained infusible carbon containing mineral material, the preferred working method that is used in during the oxidation pre-treatment 130 comprised pressure oxidation and chlorination.When refractory mineral raw material 130 contained infusibility sulfide mineral material and infusible carbon containing mineral material, an example that is used in the optional working method during the oxidation pre-treatment 130 comprised pressure oxidation.
In a version of scheme shown in Figure 3, oxidation pre-treatment 130 comprises pressure oxidation, especially for handling the charging of infusibility sulfide mineral.Referring to Fig. 4, the universal method skeleton diagram of a scheme of this version is shown.Used identical among Reference numeral among Fig. 4 and Fig. 1-3, except what point out in addition.As shown in Figure 4, pressure oxidation pre-treatment 136 is carried out in refractory mineral charging 128 (be the example purpose, be described as the charging of infusibility sulfide mineral).Then to comprising that the mineral material 102 from the residual solid of pressure oxidation 136 carries out thiocyanate-leaching 104, with dissolve gold on residual solid.In one embodiment, can choose wantonly will comprise that some acid elutriants 132 that produce are supplied to leaching vat and adjust 112 in pressure oxidation pre-treatment 136, thereby iron ion source is provided, and regulate pH as required.During use, preferably include greater than 0.05M, more preferably greater than the dissolved iron ion of the concentration of 0.1M from the described acid elutriant 132 of pressure oxidation pre-treatment 136.
During pressure oxidation pre-treatment 136, at least a portion sulfide sulfur in the infusibility charging 128 is oxidized to sulphate form, with the destruction sulfide mineral, thereby discharges gold during thiocyanate-leaching 104.Pressure oxidation pre-treatment 136 is carried out in the reactor of one or more so-called autoclaves, and acid elutriant 132 can be the acidic aqueous liquid that for example discharges from autoclave.
Referring to Fig. 5, the version more specifically of the scheme of Fig. 4 is shown.Used identical among Reference numeral among Fig. 5 and Fig. 1-4, except what point out in addition.As shown in Figure 5, pressure oxidation pre-treatment 136 comprises processing 138 of general procedure autoclave and solid adjustment 142.Handle during 138 at autoclave, the charging 128 of infusibility sulfide mineral is under High Temperature High Pressure, and pressure oxidation in one or more autoclaves is sent into the oxygen of purifying in the autoclave simultaneously.When delivering to autoclave and handle 138, refractory mineral raw material 128 preferably is the pulverizing particle form with the waterborne liquid pulping.
Condition during autoclave is handled in the autoclave can be any condition that can effectively carry out the required pressure oxidation of infusibility sulfide mineral charging.Autoclave is handled 138 and is at high temperature carried out usually, and the temperature in the autoclave often reaches at least 160 ℃, but the temperature in the autoclave is often higher.In some cases, the temperature in the autoclave can be 235 ℃, perhaps even higher.Total pressure during pressure oxidation is handled in the autoclave generally includes the incompressible gas (for example carbonic acid gas and sulfurous gas) in the autoclave vapor pressure that causes and the superpressure that is supplied to the oxygen of autoclave.The pressure that the superpressure of oxygen represents to deliver to the oxygen of autoclave surpasses the pressure that is caused by other component in the autoclave (for example water vapor and incompressible gas).Even under low processing temperature, for example about 160 ℃, total pressure can be 85psi (586kPa) or bigger, and under higher temperature, for example about 225 ℃, total pressure can be 485psi (3,344kPa) or bigger.Usually at 10psi (68.9kPa) at least with often under the superpressure of 25psi (172.4kPa) oxygen is delivered to autoclave at least.When at high temperature operating, the oxygen superpressure can be 100psi, (689kPa), or even 125psi (862kPa) or higher.The preferred operating restraint of pressure oxidation is 180-225 ℃ a temperature, and 155psi (1,069kPa)-460psi (3, total pressure 172kPa), and the oxygen superpressure of 25psi (172kPa)-100psi (689kPa).Handling the pressure oxidation that takes place during 138 at autoclave causes in the refractory mineral charging 128 at least 80% and preferred at least 90% sulfide sulfur to be oxidized to sulphate form usually.In order to handle the pressure oxidation of carrying out required degree during 138 at autoclave, can use single autoclave, it can comprise a plurality of chambers of a plurality of arranged in series.In another scheme, a plurality of autoclaves can arranged in series.When a plurality of chamber in use autoclave or the placed in-line a plurality of autoclave, can under different condition, operate each different chamber or different autoclaves independently.And autoclave is handled can comprise single pressure oxidation treatment unit or a plurality of parallel pressure oxidation treatment unit.
Still referring to Fig. 5, adjust the 142 oxidation slurry of handling from autoclave processing 138 140, will be supplied to the mineral material 102 of cyanate leaching 104 with preparation by solid.Oxidation slurry 140 is the strongly-acid slurry that contain residual solid and acidic aqueous liquid, and described liquid contains 10g/L or more free sulfuric acid usually, also contains the dissolved iron ion of high density usually.In some cases, free sulfuric acid can for 20g/L at least or even 50g/L at least, but free sulfuric acid often also is not more than 100g/L.The dissolved iron concentration often is at least 0.05M (about 2.8g/L), preferred 0.1M (about 5.58g/L) at least, but the concentration of dissolved iron ion the most often is not more than 0.2M.
Adjust during 142 at solid, can implement the combination of any operation or operation,, be used for preparing the mineral material of handling in thiocyanate-leaching 104 102 with the residual solid of preparation oxidation slurry 140.Described operation can comprise, in for example liquid-solid separation, dilution, the part and solid, adding reagent, washing solid and slurrying solid again.In a version, solid adjustment 142 comprises that liquid-solid separation is with separating most in the autoclave discharge thing or all acidic liquids and solid, remove extra acidic liquid by the washing solid then and increase solid pH (but remaining tart), be used for thiocyanate-leaching 104.Additionally carry out pH regulator if desired, can add neutralizing agent (for example lime, Wingdale or oxyhydroxide).In a preferred version, mineral material 102 comprises handles all or some residual solid of 138 from autoclave, and it is to have acid pH, preferably has the dense slurry of the pH of pH 1 to pH 3.
A feature shown in the Figure 4 and 5 is the optional acidic liquid that uses all or a part to produce during pressure oxidation pre-treatment 136, is used for optionally supplying acid elutriant 132 to leaching vat and adjusts 112, is used to prepare thiocyanate-leaching vat charging 106.Use the scheme of Figure 4 and 5, acid elutriant 132 is isolated liquid from the oxidation slurry normally, and described oxidation slurry discharges from the pressure oxidation reactor.Can carry out or not carry out under the situation of pH regulator or other intermediate treatment, acid elutriant 132 is being provided to leaching vat adjustment 112.Referring to Fig. 5, in a version, can carry out liquid-solid separation to oxidation slurry 140 during solid adjustment 142, to isolate acidic liquid from solid, the isolating acidic liquid of at least a portion optionally is supplied to the leaching vat adjustment as acid elutriant 132 simultaneously.Can also wash solid if desired.Washing water and isolating acidic liquid can be made up, to prepare acid elutriant 132, perhaps can individual curing.
A version that is used for the processing of Figure 4 and 5 is individually acid elutriant 132 directly not to be delivered to leaching vat to adjust 112, but will deliver to thiocyanate-leaching 104 with the mineral material 102 that acid autoclave discharge liquid is sized mixing, carry out simultaneously or do not dilute, pH regulator or other processing.For example, referring to Fig. 5, can during adjusting 142, from oxidation slurry 140, isolate solid a part of acidic liquid, and can stay a part and have the acid autoclave discharge liquid of solid, they will deliver to thiocyanate-leaching 104 with mineral material 102, for thiocyanate-leaching 104 provides iron ion source.At this moment, even do not deliver to thiocyanate-leaching 104 separately, acidic liquid with mineral material 102 also is considered to part leaching vat charging 106, and helps to realize in the thiocyanate-leaching the required condition about dissolved iron ion and dissolved thiocyanate-, as mentioned above.As another replacement scheme, can not to leaching vat adjustment 112 add acid elutriants 132 and the situation of acid autoclave discharge liquid and raw mineral materials 102 not being sized mixing under raw mineral materials 102 is delivered to thiocyanate-leaching 104.
Refer again to Fig. 3, when oxidation pre-treatment 130 was included in oxidized ore in the reactor (for example, normally follow the pressure oxidation pre-treatment and may be to follow the bio-oxidation pre-treatment), thiocyanate-leaching 104 was also carried out in reactor usually.Reactor is represented one or more fluid involucrums that material was housed in particular procedure operating period.For example, for pressure oxidation pre-treatment 136 as shown in Figure 5, autoclave is handled 138 and be included in pressure oxidation of carrying out in the reactor (containers of one or more so-called autoclaves) and the thiocyanate-leaching of carrying out 104 in another reactor (for example one or more stirring tanks, cylinder or other container).
In another version of scheme shown in Figure 3, oxidation pre-treatment 132 comprises bio-oxidation.This is preferred a selection that is used to handle the charging of infusibility sulfide mineral.2 referring to Fig. 6, illustrates to comprise the universal method skeleton diagram of bio-oxidation as a scheme of oxidation pre-treatment step.Used identical of Reference numeral among Fig. 6 and Fig. 3 is except what point out in addition.As shown in Figure 6, bio-oxidation pre-treatment 146 is carried out in refractory mineral charging 128 (for illustrative purpose it is described as the charging of infusibility sulfide mineral), with at least a portion sulfide sulfur in the oxidation refractory mineral charging 128, be used for reclaiming thereby during thiocyanate-leaching 104, decompose sulfide mineral and discharge gold.Bio-oxidation pre-treatment 146 can be carried out in reactor (for example one or more stirring tanks or other container), and thiocyanate-leaching this moment 104 is also preferably carried out in reactor (for example one or more stirring tanks or other container).In a preferred variation, handle owing to use the present invention to be particularly conducive in heap, so bio-oxidation pre-treatment 146 and thiocyanate-leaching 104 are carried out in heap.Therefore embodiment shown in Figure 6 is described in the processing of main reference in heap.
Continue referring to Fig. 6 at heap operation, bio-oxidation pre-treatment 146 generally includes via the heap that initially the contains refractory mineral charging 128 acid bioleaching liquid that circulates.The circulation of proceeding acid bioleaching liquid proceeds to required degree until the oxidation of sulfide mineral.Fully after the bio-oxidation, remaining solid provides mineral charging 102 to be used for thiocyanate-leaching 104 at heap.During thiocyanate-leaching 104, thiocyanate-leaching vat 106 is applied on the heap, for example by the dropping liquid irrigation system, thiocyanate-leaching vat infiltrate overall stack, the gold of dissolve gold-thiocyanate complex form.When dripping from piling, collects the thiocyanate-leaching vat 108 that is rich in metal.Remain in golden depleted in the residual solid 110 in the heap after the thiocyanate-leaching 104.
As shown in Figure 6, the acid elutriant 132 that produces during the bio-oxidation pre-treatment 146 is supplied to leaching vat and adjusts 112, is used to prepare the raw material of thiocyanate-leaching vat 106.The level that acid elutriant 132 is rich in the dissolved iron ion and helps to regulate dissolved iron ion in the leaching vat, and regulate pH in the above described manner.Because produce a large amount of iron ions during bio-oxidation pre-treatment 146, therefore acid elutriant 132 has very high iron concentration usually.Acid elutriant 132 in the bio-oxidation scheme shown in Figure 6 contains concentration usually and is the dissolved iron ion of 0.1M (about 5.6g/L) at least, be more typically 0.3M (about 16.7g/L) at least, preferably be at least 0.4M (about 22.3g/L), but the dissolved iron concentration often is not more than 0.8M.And the pH of acid elutriant 132 is preferably pH 1 to pH 3.
When handling in the heap environment, the enhanced scheme that is used to operate is when the placer deposits raw material is piled with initial formation or assembles the mineral charging at the same time.For example, referring to Fig. 6, between the accumulative phase, the refractory mineral charging 128 of particle form can be inoculated liquid mixing with acid bacteria.Described gathering can realize that described particle usefulness microbionation liquid is moistening by mineral material particles and microbionation liquid are mixed under the condition of the aggregate unit that promotes particle aggregation Cheng Gengda.For example, microbionation liquid can be sprayed on granular refractory mineral material 128, can spray to promote between the gathering or to handle described granulate material by rotary drum during this period.
Be used to implement scheme of this accumulative as shown in Figure 7.As shown in Figure 7, the refractory mineral charging 128 that will have particle form is delivered to carrier 152 from store holder 150.When on carrier 152, advancing, be used for spraying refractory mineral charging 128 from the hydrosulphate inoculation liquid flushing liquor 154 that sprays device 156.Shift refractory mineral charging 128 and deposit by extra carrier 158 and 160 then and pile 162, can carry out bio-oxidation to it then to form.Use a plurality of carriers shown in Figure 7 152,158 and 160 to help the mixing of the inoculation solution of thorough mixing refractory mineral charging 128 particles and sprinkling.And, mineral material promotes refractory mineral charging 128 to be gathered into bigger aggregate unit from the effect that a carrier leaks to another carrier, it can improve the character of the heap 162 that is used for follow-up bio-oxidation and thiocyanate-leaching operation, for example permeability.
The present invention program's as shown in Figure 6 a importance is need not remove heap and deposited a new heap again after bio-oxidation pre-treatment 146 before thiocyanate-leaching 104.Bio-oxidation pre-treatment 146 and thiocyanate-leaching 104 are all carried out under acid pH, the solid in the heap that need neutralize between bio-oxidation 146 and thiocyanate-leaching 104.Therefore, finish between bio-oxidation pre-treatment 146 and the beginning thiocyanate-leaching 104, heap remains and is not subjected to structural destruction basically, need not deposit a new heap before carrying out thiocyanate-leaching 104 again.
When carrying out bio-oxidation/thiocyanate-leaching operation (being described with reference to figure 6 usually), described operation can relate to a plurality of heaps that are in a plurality of the treatment stage in any given time.For example, one or more heaps can experience bio-oxidation pre-treatment 146, and simultaneously one or more other heaps experience thiocyanate-leaching 104 simultaneously.One or more hydrosulphate solution of operating and produce dissolved iron ion under the acid pH that pile up of experience bio-oxidation pre-treatment 146 with high density.The pH commonly used of bioleaching liquid is less than pH 2.5, and more commonly used is pH 1.3-pH 2.0.Any suitable ferric oxide ionic acidophilia microorganism may be used to bio-oxidation pre-treatment 146.The example of described microorganism comprises thiobacillus ferrooxidant (thiobacillusferrooxidans), ferricoxidans (leptospirillunaferrooxidans), sulfobacillus thermosulfidooxidans (sulfboeillus tlaermosulfidooxidans), diligent living gold goal bacterium (metallospheara sedula) and Bu Shi acid bacterium (Acidianus brierley).United States Patent(USP) Nos. 5,246,486; 5,332,559; 5,834,294; 5,127,942 and 5,244,493 provide the extraneous information about bio-oxidation, and its full content is incorporated this paper into by introducing, as here all setting forth.
The important change form that comprises bio-oxidation and thiocyanate-leaching subsequently of the present invention is can choose wantonly from the acid elutriant that the heap that carries out bio-oxidation is collected to be used to prepare the charging of thiocyanate-leaching vat, and described charging puts on another heap that carries out the thiocyanate-leaching.Referring to Fig. 8, this illustrates a scheme of the present invention, wherein carries out bio-oxidation and thiocyanate-leaching on different heaps simultaneously.Reference numeral and Fig. 2,3 and 6 used identical are except what point out in addition.In the embodiment depicted in fig. 8, first heap 170 experience bio-oxidation pre-treatment 146 are experienced thiocyanate-leaching 104 simultaneously and lived through pretreated second heap 172 of bio-oxidation.In the practice, the distance that these two heaps can apart from each other or adjacent for the latter, is placed impermeable dividing plate between preferred two heaps 170 and 172, to prevent fluid communication between two heaps 170 and 172.
As shown in Figure 8, for example irrigate or other technology is applied to the acid charging 174 of acid bioleaching liquid on first heap 170 by dropping liquid.The acid elutriant 175 of the bioleaching liquid that collection flows down from first heap 170 is delivered to major part wherein and is handled 176 and be used for utilizing once more, puts on the bioleaching liquid charging 174 of first heap 170 with preparation.Handling during 176, can regulate pH, upwards be adjusted to the required scope of bio-oxidation pre-treatment 146 usually, can deposited components for example iron and arsenic, can add or remove liquid as required, and can add other reagent as required.For example can handle this solution by using lime or some other neutralizing agent, this solution and precipitate unwanted component partly neutralizes.
Simultaneously,, for example irrigate or other technology, thiocyanate-leaching vat charging 106 is applied to second heap 172 by dropping liquid by on first heap 170, carrying out bio-oxidation pre-treatment 146 operations.Collection is from second heap 172 thiocyanate-leaching vat 108 that are rich in metal that flow down and deliver to gold recovery 118, there gold is removed and prepared the golden product 120 of purifying from the thiocyanate-leaching vat 108 that is rich in metal.The lean ore elutriant that reclaims 118 thiocyanate-leaching vat 122 from gold is delivered to leaching vat and is adjusted 112, is used to prepare thiocyanate-leaching vat raw material 106.The elutriant (being rich in the dissolved iron ion) of part bioleaching liquid 175 provides acid elutriant 132, and described elutriant is supplied to leaching vat and adjusts 112.
When combination bio-oxidation pre-treatment of the present invention and thiocyanate-leaching, can obtain significant enhanced scheme, described enhanced scheme is only to carry out the bio-oxidation pre-treatment of short period of time before the leaching of beginning thiocyanate-, with respect to the bio-oxidation operation of carrying out before the prussiate leaching.And, can in the short time length, obtain the combination time length that bio-oxidation pre-treatment and thiocyanate-leaching are operated, with respect to the combination of bio-oxidation and prussiate leaching.When carrying out the operation of extra bio-oxidation/prussiate leaching, the sulfide sulfur composition in the mineral charging need be oxidized to such degree: in follow-up prussiate leaching operation, the not outer and significant oxidation of amount of sulfide sulfur.The acid that the oxidation of any extra sulfide sulfur produces will disturb the prussiate leaching to operate, because the prussiate leaching must be carried out under alkaline pH.But, by the present invention, need be in the further oxidation of thiocyanate-leaching operating period prevention sulfide sulfur, because operating under the acid pH, the thiocyanate-leaching carries out, during the thiocyanate-leaching, can carry out significant extra sulfide sulfur oxidation, as long as the pH of thiocyanate-leaching vat and other character keep within the acceptable range.
In the bio-oxidation of routine/prussiate leaching operating period, the bio-oxidation pre-treatment often continues 180 days or longer.Any specific required bio-oxidation time of ore materials will be depended on a plurality of variablees, comprise the mineralogy of treated material and the anchor of particle size.A significant advantage of the present invention is often can reduce the bio-oxidation pretreatment time.As an example, for some mineral material, according to the present invention, before the thiocyanate-leaching the pretreated time length of bio-oxidation can be time length required before the prussiate leaching half or even shorter.In this example, the pretreated mineral material of bio-oxidation that before the prussiate leaching of routine, needs 180 days only needs 90 days or shorter bio-oxidation pre-treatment before the thiocyanate-leaching in some cases.The shorter time length is enough for the present invention, an one reason is during the sour sulfur cyanate leaching of gold, the for example pyritous continuation oxidation of mineral does not produce the pH control problem of same type, and described problem will be present in during the normal alkaline cyanide leaching.By the present invention, when the degree of oxidation of sulfide sulfur less than 30% the time, can stop the bio-oxidation pre-treatment, but the total amount of the sulfide sulfur of oxidation can be greater than 30% during bio-oxidation and thiocyanate-leaching,, for example may be 50% or more often significantly greater than 30%.When using the short time length to carry out the bio-oxidation pre-treatment, identical with situation of the present invention, during the thiocyanate-leaching between the amount of the sulfide sulfur of oxidation and bio-oxidation pre-treatment period the ratio of the amount of the sulfide sulfur of oxidation in a scheme, be at least 1: 10, in another scheme, be at least 1: 5, in another scheme, be at least 1: 4, be at least 1: 3 in another scheme.A preferable range of this ratio is 1: 5-1: 2.
Concentrate except processing infusibility sulfide ore and these ores, the present invention also can be used to process the ore of the sulfide sulfur that only contains medium level and the concentrate of being made by these ores, therefore, described ore is appropriate infusible for the direct prussiate leaching that is used to reclaim gold.These appropriate infusible ores have usually less than the sulfide type sulphur content of 2 weight %, often are not more than the sulfide type sulphur content of 1.5 weight %, sometimes not even greater than the sulfide type sulphur content of 1 weight %.But these ores have the sulfide type sulphur content of at least 0.5 weight % usually.As mentioned above, when a large amount of gold was relevant with oxide mineral and sulfide mineral, these ores were called the transition ore.Method of the present invention is specially adapted to handle appropriate infusible sulfide ore, because often can use the present invention to handle these ores, and need not carry out the oxidation pre-treatment step and need not carry out the required trouble of prussiate leaching operation and expensive pH adjustment.Comprise under the situation of handling appropriate infusible mineral material in the solution of the present invention, preferred at least 50% gold, often at least 70% gold is the leachable gold of prussiate, measures by following lab investigation.These appropriate infusible mineral materials often produce a large amount of acid, and this can cause reclaiming gold by direct prussiate leaching significantly and become complicated and increase its cost.
When handling appropriate infusible sulfide ore, in a scheme, before the thiocyanate-leaching, ore is carried out the pickling pre-treatment.Referring to Fig. 9, the universal method skeleton diagram of a scheme of the present invention is shown, this scheme is used to handle appropriate infusible material.Used identical among Reference numeral and Fig. 1, except what point out in addition.As shown in Figure 9, pickling 182 is carried out in the appropriate refractory mineral charging 180 (for example appropriate infusible ore and/or the concentrate of being made by appropriate infusible ore) of particle form, preferably used the hydrosulphate washing soln.During pickling 182, the oxidation of the easy oxidized portion of sulfide mineral is promoted, thereby is promoted further to discharge gold.The Acidwash solution that is applied to the appropriate infusible mineral material 180 of contact can carry out under any acid pH, but preferably under the pH that is not higher than pH 4, carry out, more preferably under the pH that is not higher than pH 3, carry out, in the scope of the pH 0.1-pH 3 that is everlasting, more in the scope of the pH 1 to pH 3 that is everlasting.Pickling 182 can comprise the bio-oxidation pre-treatment, but in a version, does not add in the hydrosulphate washing soln and be used to promote the pretreated bacterium of bio-oxidation.Can proceed pickling 182 random time sections, the sulfide sulfur of preferably proceeding the easy oxidation in mineral charging 180 is oxidizing to required degree.After pickling 182, the residual solid with mineral material 102 forms is carried out thiocyanate-leaching 104.
In another scheme of the present invention, a kind of mineral material that contains copper mineization that is used to handle is provided, described copper mineization contains the soluble copper of significant quantity.As used herein, " soluble copper " be meant according to the present invention, if during the leaching of sour sulfur cyanate, exist, and if before the leaching of sour sulfur cyanate, do not remove, be dissolved in the copper in the thiocyanate-leaching vat easily.When mineral material was carried out the prussiate leaching, described soluble copper was soluble in the prussiate leaching vat usually.For example, described mineral material can be auriferous oxide compound ore or the concentrate that comprises the soluble copper of unhelpful amount.The copper of described unhelpful amount often may reside in the ore, and its amount usually can be from hundreds of ppm soluble copper-several thousand ppm soluble copper, may be more.Described unhelpful copper often has very little value or is not worth, and makes the recovery of gold become complicated when using traditional prussiate leaching dissolve gold, because copper is dissolved by the prussiate leaching vat easily, and causes high cyanide consumption.And cupric cyanide needing to cause the problem that jettisons of special processing.Example to the helpful mineralising of soluble copper content in the mineral material comprises elemental copper, copper bearing oxide mineral, and secondary copper bearing sulphide minerals (secondarycopper-containing sulfide mineral), for example copper glance (Cu
2S) or covellite (CuS) as the situation of post cure thing mineral (secondary sulfide material).
Perhaps, soluble copper can exist with the sufficiently high amount of economically valuable.On behalf of chief value in the ore (gold be by product be worth) or gold, copper can represent chief value in the ore (copper is that by-product is worth).
In some cases, when soluble copper was represented the chief value of ore, during conventional processing, it was uneconomic reclaiming the by product gold after reclaiming copper, the economic worth of Jin Dynasty table forfeiture.This may be the situation when reclaiming copper from rudimentary copper mine in acid heap leaching operation.In heap leaching operation, use the thick rock of cupric of hydrosulphate solution leaching raft, to dissolve diffluent copper.It often is uneconomic using the prussiate leaching to reclaim gold after the leaching of acidity heap, because must carry out the prussiate leaching under alkaline condition.
Referring to Figure 10, the universal method skeleton diagram of a scheme of the present invention is shown, this scheme is used to handle ore, concentrate or other mineral material of the soluble copper that contains significant quantity.Used identical among Reference numeral and Fig. 1, except what point out in addition.As shown in figure 10, acid copper leaching 188 is carried out in the mineral charging 186 that contains soluble copper.During copper leaching 188, use acid leaching vat (normally hydrosulphate leaching vat) leaching to contain the mineral charging 186 of soluble copper, with the dissolving soluble copper.Preferably, during copper leaching 188, most of or basically all soluble coppers dissolvings enter acid leaching vat.The mineral charging 186 that contains soluble copper can comprise auriferous oxide compound ore, transition ore and/or the concentrate of the soluble copper that for example contains significant quantity.As another example, the mineral charging 186 that contains soluble copper can comprise copper mine or the concentrate that contains the by product gold.The acid leaching vat charging that is supplied to copper leaching 188 has acid pH, preferably has the pH4 of being not more than, and more preferably has the pH that is not more than pH3, has the pH in pH 0.1-pH 3 scopes usually, more generally has the pH in pH 1 to pH 3 scope.When definite soluble copper has sweetened off from the mineral charging 186 that contains soluble copper fully, stop copper leaching 186, and the residual solid with mineral material 102 forms is carried out thiocyanate-leaching 104, with dissolve gold.In a preferred variation, in heap operation, carry out copper leaching 188 and thiocyanate-leaching 104.A preferred version is to carry out copper leaching 188 and thiocyanate-leaching 104 in same heap, makes to destroy the structure of piling between copper leaching 188 and thiocyanate-leaching 104, and needn't deposit new heap again and be used for the thiocyanate-leaching.In same heap, carry out copper leaching 188 and the thiocyanate-leaching is feasible, because two operations can advantageously be carried out under acidic conditions.
The solubility of copper-bearing mineral charging 186 can according to circumstances change with copper content.When copper bearing mineral charging 186 is when only containing the ore of the soluble copper of unhelpful amount, soluble copper content is 200ppm (0.02 weight %) at least normally, but often be 500ppm (0.05 weight %) at least, or even 1000ppm (0.1 weight %) or more at least.When copper-bearing mineral charging 186 was the concentrate of being made by described ore, the soluble copper content of concentrate can be quite little, and is quite big or identical with soluble copper content in the ore approximately, depends on the characteristic of particular ore.When copper-bearing mineral charging 186 is the ore (wherein soluble copper is the valuable constituent of ore) that contains enough soluble coppers, the soluble copper content of ore often is at least 0.1 weight %, can be at least 0.5 weight %, perhaps can be at least 1 weight %.When on behalf of the major metal of ore, soluble copper be worth, soluble copper content can be at least 2 weight %, perhaps even at least 5 weight % or more.When copper-bearing mineral charging 186 was the concentrate of described ore, soluble copper content was preferred significantly greater than the soluble copper content of the ore of making concentrate.But even for concentrate, soluble copper content often is to be not more than 20 weight %.
When soluble copper only exists with unhelpful amount, can carry out water treatment to the acid leaching vat elutriant that is loaded with dissolved copper that obtains by copper leaching 188, be used to jettison to remove dissolved copper and to prepare copper.When soluble copper is represented valuable product, can further handle the leaching vat elutriant that is loaded with dissolved copper that copper leaching 188 obtains, to reclaim copper.The recovery of described copper for example can comprise, iron gluing or solvent extraction.A preferred version that is used for the recovery of copper comprises from acid leaching vat solvent extraction dissolved copper.
In another scheme, the present invention can comprise that processing contains the mineral material of valuable precious metal values and valuable non-iron base metal value, the major part of one or both that contain in the sulfide mineral wherein that precious metal is worth and non-iron base metal is worth, described sulfide mineral must be decomposed and can be discharged metal values and be used for recovery.Non-iron base metal is represented the base metal beyond the deironing.The example of non-iron base metal comprises copper, zinc, nickel, cobalt, indium and chromium.For this scheme, particularly preferably be and contain copper and/or the golden mineral material that is worth as non-iron base metal.
In this scheme, after acid pretreatment operation, carry out the leaching of sour sulfur cyanate with the dissolving precious metal, between described pre-treatment period sulfide mineral be decomposed and non-iron base metal by leaching.Acid pre-treatment is in conjunction with decomposing sulfide mineral with the oxidation pre-treatment that discharges precious metal and/or non-iron base metal and be used to reclaim and the leaching of non-iron base metal.Figure 24 illustrates a concrete scheme.Used identical among Reference numeral among Figure 24 and Fig. 2, except what point out in addition.
As shown in figure 24, pre-treatment leaching 222 is carried out in mineral charging 220.During pre-treatment 222, the sulfide mineral in the raw mineral materials 222 be decomposed and non-iron base metal dissolved, form the acid leaching vat 224 that is rich in metal contain the non-iron base metal of dissolved.In thiocyanate-leaching 104, handle the mineral material 102 that comprises from the residual solid of pre-treatment 222 then, with dissolve gold.Then the leaching vat 224 that is rich in metal is carried out base metal and reclaim 226.Reclaim during 226 at base metal, remove non-iron base metal from the leaching vat 224 that is rich in metal, preparation contains the purified product of non-iron base metal.For example, when handling copper-gold mine stone or concentrate, reclaim during 226 at base metal, can remove copper in the leaching vat 224 that is rich in metal by solvent extraction, make it enter organic extraction agent phase, then from the opposite copper that is extracted that extracts of organic extraction agent, make it enter anti-extraction waterborne liquid and instead extract the cupric product that waterborne liquid is made by this by the strike or the precipitator method.As another example, when handling zinc-Gold Ore or concentrate, reclaim during 226 at base metal, can become oxyhydroxide by solvent extraction zinc or by depositing zinc optionally, from the leaching vat 224 that is rich in metal, remove dezincify.As another example, when handling copper-zinc-Gold Ore or concentrate, base metal reclaims 226 can comprise that for example solvent extraction is optionally to remove copper from the leaching vat 224 that is rich in metal, and optionally depositing zinc becomes oxyhydroxide then.
In yet another aspect, the present invention relates to remove precious metal from the thiocyanate-leaching vat that is rich in metal, particularly gold for example can contain the mineral material of precious metal by the thiocyanate-leaching.Referring to Fig. 2, reclaim during 118 at gold, can by to from the prussiate leaching vat, remove the similar mode of gold-cyanide complex, by being adsorbed on the activated carbon, from the thiocyanate-leaching vat 108 that is rich in metal, remove gold-thiocyanate complex.But the adsorption rate of gold-thiocyanate complex on activated carbon is very low.And activated carbon promotes that the dissolved iron ion is reduced to ferrous ion in the thiocyanate-leaching vat, and the latter is normally undesirable.Scheme can be removed gold-thiocyanate complex by ion exchange resin from the thiocyanate-leaching vat that is rich in metal as an alternative.But ion exchange resin is expensive, and makes spent ion exchange resin need handle complex compound with wash-out gold-thiocyanate complex optionally.By the present invention, gold-thiocyanate complex is adsorbed on the activated carbon and reclaims gold-thiocyanate complex on exchange resin is not the optimization technique that is used for removing from the thiocyanate-leaching vat that is rich in metal gold, but can use if desired.
Be used for removing precious metal from the thiocyanate-leaching vat that is rich in metal, particularly Jin a optimization technique of the present invention is solvent extraction.Solvent extraction can be removed gold effectively from sour sulfur cyanate leaching vat, and can realize being separated of good organic and water.And as the situation of using activated carbon, solvent extraction often can not promote the reduction of the iron ion of thiocyanate-leaching vat.During solvent extraction, the sour sulfur cyanate leaching vat that is rich in metal contacts with organic phase, and described organic phase comprises the extraction agent that is used for removing from the thiocyanate-leaching vat that is rich in metal gold-thiocyanate complex.Some examples of the extraction agent that uses in organic phase comprise phosphorous extraction agent, for example phosphoric acid salt, phosphonate, phosphinate and phosphine oxide extraction agent.As the phosphorous extraction agent that the present invention uses, phosphoric acid salt is particularly preferred.Other example of extraction agent comprises the amine extraction agent, and it can comprise primary, the second month in a season or tertiary amine.The present invention especially preferably uses the amine extraction agent to remove gold-thiocyanate complex by solvent extraction from the sour sulfur cyanate leaching vat that is rich in metal.After gold-thiocyanate complex extraction is entered organic phase, by anti-extraction it is entered in the anti-extraction aqueous solution (for example anti-aqueous solution that extracts of alkalescence) and from the organic phase of load, be removed.Do not fettered, but, think that using the amine extraction agent to extract gold-thiocyanate complex carries out according to following mechanism in order to help to understand the present invention by specific mechanisms:
1) form amino acid salt,
SCN
-+RNH
2+H
+＝(RNH
3+SCN
-)
2) amino acid and gold-thiocyanate complex forms ion pair,
(RNH
3+ SCN
-) ten Au (SCN)
2 -=(RNH
3Au (SCN)
2 -)+SCN
-
The scheme of solvent extraction recovery gold that comprises of the present invention is shown in the universal method skeleton diagram of Figure 11.Used identical of Reference numeral and Fig. 2 is except what point out in addition.As shown in figure 11, the thiocyanate-leaching vat 108 that is rich in metal is carried out gold reclaim 118, it comprises general procedure---solvent extraction 192, instead extract 194 and electrolytic deposition 196.
During solvent extraction 192, the thiocyanate-leaching vat 108 that is rich in metal contacts with the organic liquid phase that contains the extraction agent that is useful on gold-thiocyanate complex.Gold-thiocyanate complex enters organic liquid phase from the thiocyanate-leaching vat 108 that is rich in metal.Separate organic liquid phase and the thiocyanate-leaching vat being loaded with gold, the lean ore elutriant of thiocyanate-leaching vat 122 is supplied to leaching vat adjustment 112, be used to prepare thiocyanate-leaching vat charging 106.
Extract during 194 anti-, the organic liquid phase of load contacts with the anti-aqueous solution that extracts, and gold is transferred to anti-extraction solution from organic liquid phase.Anti-extraction solution for example can be alkaline aqueous solution.Then the anti-extraction solution that is loaded with gold is carried out electrolytic deposition 196, with the golden product 120 of preparation purifying.
In another preferred embodiment of the present invention, by using second kind of complexing agent that the precious metal in the solution is transformed into new complex compound from precious metal-thiocyanate complex, from the sour sulfur cyanate leaching vat that contains Valuable Minerals, remove precious metal, particularly golden, described new complex compound is easier to be removed from the thiocyanate-leaching vat that is rich in metal.In a preferred variation, second kind of complexing agent is prussiate, and new complex compound is precious metal-cyanide complex, particularly gold-cyanide complex.When adding a small amount of prussiate in the thiocyanate-leaching vat that is rich in metal that contains gold-thiocyanate complex, the gold in the solution promptly is transformed into gold-cyanide complex from gold-thiocyanate complex.Handle the thiocyanate-leaching vat that is rich in metal then, to remove gold-cyanide complex.For example, can from the thiocyanate-leaching vat that is rich in metal, remove gold-cyanide complex by the technology that in the prussiate leaching of routine operation, is used for removing gold-cyanide complex from the prussiate leaching vat.
In a preferred variation of this scheme, after gold is transformed into gold-cyanide complex,, from the leaching vat that is rich in metal, remove gold-cyanide complex by using sorptive material ADSORPTION OF GOLD-cyanide complex.Described sorptive material for example can be carbon (preferred gac) or ion exchange resin.Preferably, described sorptive material comprises and contains absorbent carbon, for example activated carbon granule.In case load gold-cyanide complex is just handled sorptive material and is reclaimed gold in the mode identical with conventional leaching operation.For example, load on gold-cyanide complex on the activated carbon granule and can extract instead from this particle that the causticity that enters heat is counter extracts solution or some other anti-extraction the solution, can for example reclaim gold by electrolytic deposition then become purified product.
Such preferred variation of the present invention is shown in the universal method skeleton diagram of Figure 12.Used identical of Reference numeral and Fig. 2 is except what point out in addition.As shown in figure 12, after thiocyanate-leaching 104, the thiocyanate-leaching vat 108 that is rich in metal is delivered to gold reclaim 118, it comprises treatment step commonly used in this scheme---complex compound changes 200, complex compound absorption 202, complex compound are counter extracts 204 and electrolytic deposition 206.Change during 200 at complex compound, the dissolving prussiate is introduced be rich in the thiocyanate-leaching vat 108 of metal, the Jin Congjin-thiocyanate complex that is dissolved in the thiocyanate-leaching vat 108 that is rich in metal is transformed into gold-cyanide complex.During complex compound absorption 202, gold-cyanide complex loads on the sorptive material (for example gac or ion exchange resin).The lean ore thiocyanate-leaching vat 122 of having removed gold-cyanide complex is supplied to leaching vat adjusts 112, be used to prepare thiocyanate-leaching vat charging 106.
Because gold-cyanide complex is more preferred than gold-thiocyanate complex on thermokinetics, therefore, change during 200 at complex compound, gold dissociates from the thiocyanate-complexing agent, forms complex compound with the prussiate complexing agent.Change during 200 at complex compound, preferably at least 80%, more preferably at least 90%, further preferably at least 95%, most preferably at least 98% the Jin Congjin-thiocyanate complex that is dissolved in the thiocyanate-leaching vat 108 that is rich in metal is transformed into gold-cyanide complex.
Complex compound transformation 200 and complex compound absorption 202 can be carried out separately or carry out together.For example, can be before adding sorptive material, the dissolving prussiate introduced is rich in the thiocyanate-leaching vat 108 of metal, with allow most of gold the thiocyanate-leaching vat 108 that is rich in metal be transformed into gold-cyanide complex before sorptive material contacts.But, in a preferred alternative hereto, before introducing the dissolving prussiate or add sorptive material approximately simultaneously, make complex compound change 200 and complex compound absorption 202 carry out simultaneously.During the anti-extraction 204 of complex compound, by anti-extraction gold-cyanide complex it is entered in the anti-extraction aqueous solution, from the sorptive material of load, remove gold-cyanide complex.During complex compound absorption 202, the anti-sorptive material that extracts can recycle, with the extra gold-cyanide complex of load.During electrolytic deposition 206, from the anti-extraction solution of load, remove gold by deposition, with the golden product 120 of preparation purifying.During complex compound transformation 200 and complex compound absorption 202, the thiocyanate-leaching vat preferably is in acid pH, more preferably has the pH of pH 1 to pH 3.Preferably, during whole thiocyanate-leaching 104, complex compound transformation 200 and complex compound absorption 202, the thiocyanate-leaching vat is remained on described acid pH.
By of the present invention comprising precious metal being transformed into the scheme of precious metal-cyanide complex from precious metal-thiocyanate complex, as shown in figure 12, to remove precious metal-cyanide complex on the sorptive material be preferred by loading on.But, although be not preferred, also can use other technology, after being transformed into precious metal-cyanide complex, precious metal from the thiocyanate-leaching vat 108 that is rich in metal, removes precious metal.For example, can remove gold-cyanide complex or can remove gold from the leaching vat that is rich in metal from the leaching vat that is rich in metal by solvent extraction by gluing.
In a preferred version of the present invention, can advantageously during complex compound changes 200, Jin Congjin-thiocyanate complex be transformed into gold-cyanide complex by adding the thiocyanate-leaching vat 108 that is rich in metal that only contains the minimal amounts of dissolved prussiate.The stoichiometry that complete and golden complexing forms the required prussiate of gold-cyanide complex is two moles of cyanide group CN/ mole gold, supposes that all gold are all with gold tricyanide ion A u (CN)
2 -Form dissolving.Can any suitable form for example sodium cyanide or potassium cyanide, disclosed prussiate introduced is rich in the thiocyanate-leaching vat 108 of metal.And, can any form easily, for example (for example pass through prussiate reagent, sodium cyanide or potassium cyanide) be dissolved in the thiocyanate-leaching vat 108 that is rich in metal, perhaps (preferably) prussiate is introduced is rich in the thiocyanate-leaching vat 108 of metal by in the thiocyanate-leaching vat 108 that is rich in metal, adding a small amount of previously prepared prussiate strong solution.And, the amount of the prussiate that adds in the thiocyanate-leaching vat 108 that is rich in metal makes that usually the prussiate of adding and the mol ratio of precious metal are not more than 20: 1 (stoichiometric 10 times), preferably be not more than 10: 1 (stoichiometric 5 times), more preferably no more than 5: 1 (stoichiometric 2.5 times), further preferably be not more than 4: 1 (stoichiometric 2 times).The add-on of prussiate makes that usually the mol ratio of prussiate and precious metal (preferably, the prussiate of adding and gold) is 2: 1 (stoichiometry) at least.And the amount of the prussiate that adds in the thiocyanate-leaching vat 108 that is rich in metal is usually less than the amount of dissolved thiocyanate-in the thiocyanate-leaching vat 108 that is rich in metal.The add-on of prussiate makes the mol ratio of prussiate and dissolved thiocyanate-be not more than 1: 2 usually, preferably is not more than 1: 4, more preferably no more than 1: 5, further preferably is not more than 1: 7, further preferably is not more than 1: 10.
To dissolve after prussiate introduces in the thiocyanate-leaching vat 108 be rich in metal, the dissolving prussiate of some or all of remnants can change the thiocyanate-in the thiocyanate-leaching vat into, preferably remove precious metal-cyanide complex from the thiocyanate-leaching vat after.Remaining prussiate in the thiocyanate-leaching vat changes the source that thiocyanate-provides new thiocyanate lixiviant into, compensates the thiocyanate-loss that produces during golden leaching and/or golden reclaimer operation partially or completely.And although use gac to tend to promote that as sorptive material the iron ion in the thiocyanate-leaching vat is reduced into ferrous ion, gold-cyanide complex is adsorbed on kinetics on the gac much larger than gold-thiocyanate-
The kinetics of complex compound absorption causes using the shorter duration of contact of activated carbon granule and/or lower concentration activated carbon granule, thereby has significantly reduced and the relevant potential problems of iron ion reduction.
In another scheme of the present invention, change the dissolved thiocyanate-into by dissolving prussiate, the part or all of thiocyanate-that is dissolved in the charging of thiocyanate-leaching vat is provided.For example, can by in hydrosulphate solution the dissolving prussiate then with solution in the dissolved prussiate change the dissolved thiocyanate-into, initial preparation thiocyanate-leaching vat.Described transformation can be before thiocyanate-leaching mineral material or is carried out during this period.For example, can use and initially contain the leaching vat that dissolves prussiate and begin from piling the leaching gold, when carrying out acid leaching, described prussiate is changed into the dissolved thiocyanate-.And, the thiocyanate-of making can be supplied in the thiocyanate-leaching vat of existence, to lose by adding a small amount of prussiate compensation several times thiocyanate-, described prussiate is changed into thiocyanate-then.This process can be carried out as mentioned above with golden reclaimer operation, perhaps carries out separately.This technology can be used for using prussiate reagent (for example sodium cyanide or potassium cyanide) rather than provides the dissolved thiocyanate-by the thiocyanate-reagent (for example Sodium Thiocyanate 99, potassium sulfocyanate or ammonium thiocyanate) that dissolving may be more expensive in the thiocyanate-leaching vat.
Referring now to Figure 13,, the universal method skeleton diagram of a version of this scheme is shown.As shown in figure 13, during adding prussiate 212, add prussiate in hydrotropisms's liquid, make that waterborne liquid contains the dissolving prussiate after adding prussiate 212.Described prussiate can for example previously prepared prussiate strong solution form add in the waterborne liquid or be dissolved in the waterborne liquid with the form of solid salt.Can any required form (for example sodium cyanide or potassium cyanide) add prussiate.After in being dissolved in waterborne liquid, be partly dissolved prussiate at least, preferably all dissolving prussiates are changed into the dissolved thiocyanate-during changing 214 basically, with preparation thiocyanate-leaching vat charging 106.Changing during 214, at least 80 moles of % usually, preferred at least 90 moles of %, more preferably all dissolving prussiates change the dissolved thiocyanate-into basically.Preferably, add prussiate 212 and change 214 and all under acid pH, carry out, more preferably carry out for 1 to pH 3 time at pH.Waterborne liquid can contain or not contain the dissolving prussiate before adding prussiate 212.As an example, the interpolation prussiate 212 of Figure 13 and transformation 214 parts that can be used as the leaching vat adjustment 112 of any scheme shown in any in Fig. 1-6,8-12 and 24 are carried out.As another example, the interpolation prussiate 212 of Figure 13 and transformation 214 can be included in beginning thiocyanate-leaching operation initial preparation thiocyanate salt solution before.
In a preferred variation of the scheme of Figure 13, by introducing suitable reagent during 214 in hydrotropisms's liquid and can promote during changing 214 that the dissolving prussiate change the dissolved thiocyanate-rapidly into changing.The preferred reagent that is used for prussiate is changed into thiocyanate-comprises sulfide and sulfhydrate material.The example of possible reagent comprises sodium sulphite, sodium sulfhydrate, potassium sulphide, potassium hydrosulfide, ammonium sulfide, hydrosulfide of ammonia and hydrogen sulfide.Other example of possible reagent comprises sulfide mineral, for example pyrrhotite.
As another example, for example owing to contact with being present in by the sulfide mineral in the mineral material of leaching (pyrrhotite), can be during the thiocyanate-leaching the some or all of prussiate of generation to the transformation of thiocyanate-.For example, refer again to Figure 12, by the sulfide mineral in the contact mineral material 102 (pyrrhotite), change the 200 some or all of prussiates of introducing in the thiocyanate-leaching vat and during the thiocyanate-leaching, change thiocyanate-in proper order into for carrying out complex compound.
Embodiment
Provide following examples to understand the present invention with further help rather than limit the scope of the invention.
Embodiment 1-post leaching appropriateness infusible ore
Appropriate infusible sulfide ore from the Lone Tree ore deposit of U.S. Nevada is tested.The XRD/XRF semi-quantitative analysis shows, this ore is made up of about 86% quartz, 6% kaolin, 3% pyrite, 2% alunite, 1% gypsum, 1% jarosite and 1% barite.The representative analytical information of this ore sample is as shown in table 3.This ore does not show pre-back production trend.
The representative ore sample analysis of table 3
| Au g/t (1) | The S-total amount (2)Weight % | S-sulfide (3)Weight % | Fe weight % | As ppm |
| 2.26 | 1.643 | 0.951 | 1.551 | 655.9 |
(1) gram/ton
(2) total content of sulphur
(3) content of sulfide sulfur
Carry out two groups of tests, one group is used the prussiate leaching vat, and another group is used the thiocyanate-leaching vat.All tests are all carried out the ore sample of minimum 10 orders (1.68mm), and described sample is placed in the post that diameter is 2 inches (50.8mm) and is used for leaching.
In order to carry out prussiate leaching test, with independent or be used for neutral lime blended 200g ore sample and be loaded in post, with sodium cyanide (NaCN) water-based leaching vat leaching to the weight ratio of final solution and ore is 2.68 (that is, every 200g sample is handled with the 536g leaching vat).Leaching vat contains 125ppm NaCN at first and pH is 9.8-10.The result of prussiate leaching test is summarised in the table 4.As shown in table 4, use in test the lime of maximum to obtain the maximum golden extraction yield of prussiate, so under the strongest pH of alkalescence, operate.When not using lime, gold recovery is very low.Figure 14 illustrates the relation curve of the golden extraction yield of each test to accumulation solution-ore weight ratio, has further shown the beneficial effect that carries out prussiate leaching operation under alkaline pH.
Table 4 prussiate leaching test-results
| Test | CN-1 | CN-2 | CN-3 | CN-4 |
| Lime adding amount (lb/st) (1) | 15 | 10 | 5 | 0 |
| The ratio of final solution and ore (2) | 2.68 | 2.68 | 2.68 | 2.68 |
| Finally be rich in the pH of the leaching vat of metal | 9.1 | 7.0 | 5.2 | 4.0 |
| Gold extraction yield (%) (3) | 56.67 | 51.52 | 44.24 | 30.61 |
| Gold extraction yield (%) (4) | 58.55 | 53.62 | 46.67 | 32.65 |
(1) pound lime/short ton (short ton) ore
(2) weight ratio of whole prussiate leaching vats and ore sample
(3) based on the charging gold of measuring
(4) based on the charging gold that calculates
For carrying out thiocyanate-leaching test, use the ammonium thiocyanate (NH that is dissolved in the water
4SCN) or potassium sulfocyanate (KSCN) reagent preparation thiocyanate-water-based leaching vat.In leaching vat, add ferric sulfate (Fe
2(SO
4)
3), obtain the dissolved iron ion of aequum and required redox-potential.The thiocyanate-leaching vat is in about pH2 at first.In each test the 800g ore sample is loaded in the post, uses thiocyanate-leaching vat leaching sample.Use the dissolved thiocyanate-and the dissolved iron ion of different concns to carry out the leaching vat test, carry out leaching with various final solutions-ore weight ratio.The result of thiocyanate-leaching test is summarised in the table 5.As shown in table 5, the gold recovery that in thiocyanate-leaching test, obtains usually with comprise that the golden extraction yield that the prussiate leaching duration of test that adds large quantities of lime obtains is the same high or higher than it.This is noticeable especially, because each thiocyanate-leaching test is all carried out under acid pH.
Table 5 thiocyanate-leaching test-results
| Test | SCN-1 | SCN-2 | SCN-3 | SCN-4 | SCN-5 | SCN-6 |
| SCN concentration (M) (1) | 0.05 | 0.05 | 0.02 | 0.02 | 0.01 | 0.01 |
| Fe 3+Concentration (M) (2) | 0.2 | 0.1 | 0.2 | 0.1 | 0.2 | 0.1 |
| Fe
3+/ |
4 | 2 | 10 | 5 | 20 | 10 |
| The weight ratio of final solution and ore | 4.125 | 4.112 | 3.066 | 2.546 | 4.300 | 4.505 |
| Gold extraction yield (%) (4) | 61.13 | 59.78 | 57.26 | 59.38 | 59.59 | 53.48 |
| Gold extraction yield (%) (5) | 61.31 | 60.14 | 56.61 | 59.90 | 54.42 | 51.83 |
(1) mole dissolved thiocyanate-/rise leaching vat (1 mole of dissolved thiocyanate-/molar sulphur ammonium cyanate or potassium sulfocyanate reagent that provides)
(2) every liter of leaching vat mole dissolved ferric sulfate
(3) the used thiocyanate-reagent of every liter of leaching vat and the mol ratio of ferric sulfate
(4) based on the charging gold of measuring
(5) based on the charging gold that calculates
Rolling bottle leaching (bottle roll leach) after the embodiment 2-bio-oxidation pre-treatment infusible sulfide ore
Infusible sulfide gold mine from Lone Tree ore deposit is tested.At internal diameter is in the post of 11 inches (279.4mm), can carry out the bio-oxidation pre-treatment, the bio-oxidation in the simulation heap by 100% 65.8 gram samples by 2 inches (50.8mm) to being crushed to.Before ore was put into post, the mixed culture medium (containing iron protoxide acid thiobacillus (Acidithiobacillus ferrooxidans) and ferricoxidans (Leptospirillum ferroxidans)) of acidophilic bacteria that can ferric oxide with 1920mL mixed with ore.During bio-oxidation, contain 0.4g/L (NH
4)
2SO
4, 0.4g/L MgSO
47H
2O and 0.04g/L K
2HPO
4Nutritive medium via the flow velocity continuously recirculation of post with about 6.5mL/min.Air velocity with 28.3L/h charges into air to post continuously from the bottom.The bio-oxidation pre-treatment was carried out 258 days under room temperature (about 20-22 ℃) continuously.When the bio-oxidation pre-treatment finishes, from post, remove ore.Between the bio-oxidation pre-treatment period, about 35% sulfide sulfur is oxidized.The representative analytical information of bio-oxidation is as shown in table 6.
The representative bio-oxidation ore sample of table 6 is analyzed
| Au g/t (1) | Sulphur total amount weight % | Sulfide sulfur weight % | Fe weight % | Cu ppm | As ppm |
| 2.81 | 3.14 | 2.72 | 2.63 | 30.46 | 1853 |
(1) gram/ton
After bio-oxidation finishes, the ore of washing bio-oxidation, removing soluble iron, dry and crush and be milled to P
80The particle that is of a size of about 200 orders (74 microns) is used for gold and extracts test.P
80The sieve in the hole of the sample of size Expressing 80 weight % by having described size.Extract test in order to carry out gold, with crushing and the biological compression functions that grinds and ore sample with the thiocyanate-leaching vat (pulp density is the solid of 20 weight %) of prepared fresh put into 1 gallon (3.78L) bottle.Use pH to be about 2 thiocyanate-leaching vat and carry out several times leaching test, described thiocyanate-leaching vat is to be dissolved in potassium sulfocyanate (KSCN) and ferric sulfate (Fe in the deionized water by change
2(SO4)
3) concentration prepare.
At thiocyanate-leaching duration of test, open the bottle ventilation, and take out solution example in the timed interval.Leaching amounts to and continues about 6 hours.Measure solution potential, pH value and thiocyanate concn.Analyze gold by atomic absorption spectrometry (AAS).In order to overcome matrix effect, all AAS calibration standard things of dilution in the used thiocyanate-leaching vat in the specific leaching test of representative.For some tests, by the solvent extraction of use diisobutyl ketone (containing 1% Aliquat 336) and the concentration of AAS analysis to measure gold.By the concentration of Volhard titration determination thiocyanate-, that this method is measured is total SCN
-Concentration.Measure total concentration of iron by AAS,, in the presence of sulfuric acid, use potassium permanganate (KMnO by at the complete post precipitation of thiocyanate ion
4) or potassium bichromate (K
2Cr
2O
7) carry out the titration determination ferrous ion concentration.Digest and AAS after using fire assay analysis representative sample, water thoroughly washs solid residue and the drying from each thiocyanate-leaching test then.
Table 7 has been summed up the volumetric molar concentration of thiocyanate-, iron ion and prussiate in the leaching vat of preparation.The result is summarised in the table 8.Table 8 provides the redox-potential (being expressed as E) of solution.As used herein, E is meant that use measures with respect to the platinum working electrode of silver/silver chloride (Ag/AgCl) reference electrode, with millivolt redox-potential of the solution of representing.Can determine Eh (with respect to the redox-potential of standard hydrogen electrode) from the E value that obtains by correction with respect to standard hydrogen electrode.
The leaching vat of table 7 preparation
| Test | [CN] M | [SCN] M | [Fe 3+] M | [Fe 3+]: the ratio of [SCN] |
| SCN-7 | -- | 0.01 | 0.1 | 10 |
| SCN-8 | -- | 0.02 | 0.1 | 5 |
| SCN-9 | -- | 0.05 | 0.1 | 2 |
| SCN-10 | -- | 0.01 | 0.2 | 20 |
| SCN-11 | -- | 0.02 | 0.2 | 10 |
| SCN-12 | -- | 0.05 | 0.2 | 4 |
| SCN-13 | -- | 0.01 | 0.3 | 30 |
| SCN-14 | -- | 0.02 | 0.3 | 15 |
| SCN-15 | -- | 0.05 | 0.3 | 6 |
Table 8 leaching result
| Test | Be rich in the pH of the leaching vat of metal | Be rich in the E mV of the leaching vat of metal | Gold extraction yield % |
| SCN-7 | 1.98 | 481 | 39.81 |
| SCN-8 | 1.95 | 476 | 41.10 |
| SCN-9 | 1.91 | 462 | 50.05 |
| SCN-10 | 1.88 | 498 | 47.49 |
| SCN-11 | 1.87 | 493 | 50.14 |
| SCN-12 | 1.85 | 480 | 56.55 |
| SCN-13 | 1.75 | 509 | 45.10 |
| SCN-14 | 1.74 | 504 | 48.60 |
| SCN-15 | 1.74 | 492 | 55.00 |
Figure 15 is illustrated under the situation that contains 0.1M iron ion, 0.2M iron ion and 0.3M iron ion in the thiocyanate-leaching vat respectively, the relation curve of the initial thiocyanate concn in golden extraction yield and the thiocyanate-leaching vat.As shown in figure 15, for the thiocyanate-of same concentrations, iron concentration is that the test of 0.2M and 0.3M is as one man expressed than iron concentration and only is the higher gold recovery of corresponding test of 0.1M.
Rolling bottle leaching after the embodiment 3-bio-oxidation pre-treatment infusibility sulfide ore
Use the bio-oxidation ore of embodiment 2, as described in embodiment 2, carry out rolling bottle leaching test.The thiocyanate-leaching vat that use contains the prepared fresh of dissolved thiocyanate-as shown in table 9 and iron ion is tested.In each test, leaching amounts to and continues 24 hours.For each test, obtain the leaching vat sample and located to analyze at 2 hours, 4 hours, 6 hours, 12 hours and 24 hours.In order to compare, the leachable gold of prussiate (cyanide leachable gold) of measuring this ore is 69%." the leachable gold of prussiate " is meant the gold that extracts by following stdn testing sequence from mineral material (for example ore or concentrate): will be crushed in the 5g mineral material sample of minimum 200 purpose sizes and the ionized water and put into developmental tube at the solution of sodium cyanide that contains 0.3 weight % and 0.3 weight % sodium hydroxide.Developmental tube at room temperature rotated 1 hour.Then by centrifugation solution and residual solid, by the gold content in the atomic absorption analysis mensuration solution.Then based on solution gold content (measuring), the leachable gold of prussiate is defined as entering golden extraction yield in the solution by atomic absorption analysis with respect to the original gold content in the mineral material (measuring) by fire assay.
The leaching vat of table 9 preparation
| Test | [SCN] M(g/L) | [Fe 3+] M(g/L) | [Fe 3+]: the mol ratio of [SCN] |
| SCN-16 | 0.01(0.58) | 0.2(11.1) | 20 |
| SCN-17 | 0.02(1.16) | 0.2(11.1) | 10 |
| SCN-18 | 0.05(2.9) | 0.2(11.1) | 4 |
| SCN-19 | 0.1(5.8) | 0.2(11.1) | 2 |
| SCN-20 | 0.05(2.9) | 0.1(5.58) | 2 |
| SCN-21 | 0.05(2.9) | 0.3(16.7) | 6 |
Determine that by prussiate leaching test about 69% gold is available prussiate leaching in the ore of bio-oxidation.The highest golden extraction yield of thiocyanate-leaching is about 65%.Table 10 has been summed up the total golden extraction yield during leaching in 24 hours in each test.
Table 10 gold extraction yield
| Test | Gold extraction yield (%) |
| SCN-16 | 50.0 |
| SCN-17 | 60.49 |
| SCN-18 | 64.15 |
| SCN-19 | 63.05 |
| SCN-20 | 62.93 |
| SCN-21 | 65.49 |
Table 11 has been summed up some test for data of the character of relevant thiocyanate-leaching vat, and described data are to be measured by the solution example that regularly obtains at duration of test.Be summarised in variation that data in the table 11 comprise thiocyanate-leaching vat pH and E, the iron ion in the thiocyanate-leaching vat to the reduction of ferrous ion and the degraded of thiocyanate-.Figure 16 illustrates for test SCN-16,17,18 and 19, the total golden extraction yield and the relation curve of thiocyanate concn in 6 hours leaching, and each is tested and all uses identical dissolved iron concentration and different dissolved thiocyanate concns.Golden extraction yield that it should be noted that test SCN-18 is higher than test SCN-19, although SCN-19 uses the dissolved thiocyanate-of low initial concentration in the thiocyanate-leaching vat.Figure 17 illustrates test SCN-18,20 and 21 the golden extraction yield and the relation curve of iron ion, and each is tested and all uses the dissolved thiocyanate-(0.05M) of same concentrations and the dissolved iron ion of different concns.As shown in figure 17, the golden extraction yield in these tests increases with the increase of iron concentration.
The analysis of table 11 thiocyanate salt solution
| Test/performance | 2 hours | 4 hours | 6 hours | 12 hours | 24 hours |
| Test SCN-17 | |||||
| pH | 1.69 | 1.69 | 1.71 | 1.64 | 1.58 |
| E，mV | 509 | 508 | 505 | 499 | 492 |
| Fe 2+Analyze M | 0.038 | 0.039 | 0.045 | 0.05 | 0.059 |
| Fe 3+To Fe 2+Reduction ratio, % | 19 | 19.5 | 22.5 | 25 | 29.5 |
| SCN analyzes, g/L | 0.99 | 1.05 | -- | 1.04 | 1.05 |
| Test SCN-18 | |||||
| pH | 1.73 | 1.73 | 1.71 | 1.66 | 1.60 |
| E，mV | 494 | 490 | 488 | 482 | 476 |
| Fe 2+Analyze M | 0.046 | 0.051 | 0.058 | 0.063 | 0.070 |
| Fe 3+To Fe 2+Reduction ratio, % | 23 | 26 | 29 | 31.5 | 35 |
| SCN analyzes, g/L | 2.70 | 1.75 | 2.16 | 2.22 | 2.66 |
| Test SCN-19 | |||||
| pH | 1.72 | 1.72 | 1.74 | 1.67 | 1.65 |
| E，mV | 479 | 478 | 475 | 471 | 465 |
| Fe 2+Analyze M | 0.056 | 0.062 | 0.066 | 0.071 | 0.080 |
| Fe 3+To Fe 2+Reduction ratio, % | 28 | 31 | 33 | 35.5 | 40 |
| SCN analyzes, g/L | 2.85 | 2.41 | 1.64 | 1.70 | 1.43 |
| Test SCN-20 | |||||
| pH | 1.94 | 1.94 | 1.88 | 1.83 | 1.74 |
| E，mV | 476 | 490 | 488 | 482 | 476 |
| Fe 2+Analyze M | 0.040 | 0.043 | 0.043 | 0.052 | 0.056 |
| Fe 3+To Fe 2+Reduction ratio, % | 40 | 43 | 43 | 52 | 56 |
| SCN analyzes, g/L | 2.74 | 2.75 | 2.08 | 1.15 | 2.08 |
| Test SCN-21 | |||||
| pH | 1.58 | 1.59 | 1.61 | 1.56 | 1.52 |
| E，mV | 506 | 502 | 500 | 494 | 489 |
| Fe 2+Analyze M | 0.049 | 0.058 | 0.061 | 0.067 | 0.078 |
| Fe 3+To Fe 2+Reduction ratio, % | 16.3 | 19.3 | 20.3 | 22.3 | 26 |
| SCN analyzes, g/L | 2.64 | 1.79 | 2.66 | 2.67 | 2.39 |
Post leaching after the embodiment 4-bio-oxidation pre-treatment infusible sulfide ore
Usually the infusibility sulfide gold mine from Lone Tree ore deposit that has type described in the embodiment 2 is carried out bio-oxidation.The representative analytical information of bio-oxidation ore is as shown in table 12.The ore of dry air part bio-oxidation also is ground into the size of minimum 10 orders (1.68mm), is used for gold and extracts test.
The representative bio-oxidation ore sample of table 12 is analyzed
| Au g/t (1) | Sulphur total amount weight % | Sulfide sulfur weight % | Fe weight % |
| 2.13 | 1.67 | 1.43 | 1.82 |
(1) gram/ton
Be loaded in by ore sample and carry out gold in the post that internal diameter is 2 inches (50.8mm) and extract test bio-oxidation.The sour sulfur cyanate leaching vat of about pH 2 of prepared fresh by the bio-oxidation ore in the post, is piled leaching simultaneously.Periodically analyze golden extraction yield and other character of the thiocyanate-leaching vat sample that is rich in metal.Table 13 has been summed up the iron ion of the thiocyanate-leaching vat that is used for testing of the concentration of thiocyanate-and iron ion and prepared fresh and the mol ratio of thiocyanate-.
The thiocyanate salt solution of table 13 preparation
| Test | [SCN] M | [Fe 3+] M | [Fe 3+]: the mol ratio of [SCN] |
| SCN-22 | 0.05 | 0.2 | 4 |
| SCN-23 | 0.05 | 0.1 | 2 |
| SCN-24 | 0.02 | 0.2 | 10 |
| SCN-25 | 0.02 | 0.1 | 5 |
| SCN-26 | 0.02 | 0.04 | 2 |
| SCN-27 | 0.01 | 0.1 | 10 |
| SCN-28 | 0.01 | 0.2 | 20 |
Figure 18 illustrates and enters the bar graph of the golden extraction yield in the thiocyanate-leaching vat and the thiocyanate-consumption of each test (the SCN poundage that the ore of every short ton of tested bio-oxidation consumes) linear graph in each test.
Post leaching after the embodiment 5 bio-oxidation pre-treatment infusibility sulfide ore A
The ore of the bio-oxidation of dry air part embodiment 4 also is ground into the size of minimum 32.8 orders (1.68mm), is used for gold and extracts test.After the pulverizing, 13.6kg bio-oxidation ore sample is loaded in three posts.The internal diameter of each post all is 4 inches (101.6mm).Use the bio-oxidation sample in prussiate leaching vat or each post of thiocyanate-leaching vat leaching, to extract gold.For carrying out prussiate leaching test, in being loaded in post before, use lime to assemble the ore sample of bio-oxidation with 6kg/ ton ore sample.Measure lime adding amount based on the neutralization test of carrying out for identical bio-oxidation ore.Ferric sulfate and potassium sulfocyanate that use is dissolved in the deionized water prepare the thiocyanate-leaching vat that pH is about pH2.Use the 0.25g/L sodium cyanide to prepare the prussiate leaching vat of pH as 10.5-11.The character of the leaching vat of preparation is summarised in the table 14.
The leaching vat of table 14 preparation
| Test | [NaCN] g/L | [SCN] M | [Fe 3+ +] M | [Fe 3+ +]: the ratio of [SCN] | PH value of solution | Solution E (1) |
| CN-5 | 0.25 | -- | -- | -- | -- | -- |
| SCN-29 | -- | 0.01 | 0.1 | 10 | 1.98 | 585 |
| SCN-30 | -- | 0.02 | 0.1 | 5 | 1.99 | 570 |
(1) millivolt
In each test, be the leaching vat deposit of 1900mL from original volume, with leaching vat with about 9.8L/hr-m
2Speed be applied to the top of the bio-oxidation ore sample in the post.Test duration 17 days.
For carrying out prussiate leaching test, contain the post of activated carbon particle by making rich pregnant solution contact, reclaim gold from the prussiate leaching vat that is rich in metal.After reclaiming gold, in lean ore prussiate leaching vat, add extra sodium cyanide, obtain the sodium cyanide concentration of 0.25g/L, and then circulation lean ore prussiate leaching vat is used for extra leaching to post.
For carrying out prussiate leaching test, remove the leaching vat that is rich in metal and analyze in every day of 1-10 and 13-16, the leaching vat of fresh 1900mL is provided.At the 17th day, remove the leaching vat that is rich in metal, and analyze.And,, analyze the gold content of cleaning solution with acid deionized water rinse solution (with sulfuric acid acidation to pH 2) washing column at the 17th day.
Figure 19 illustrates test CN-5, SCN-29 and SCN-30 and enters golden extraction yield and time relation curve in the leaching vat in the leaching of going through 13 days.Figure 20 illustrates potassium sulfocyanate or the sodium cyanide consumption (potassium sulfocyanate of every short ton of processed bio-oxidation ore sample consumption or the poundage of sodium cyanide) and time relation curve of test CN-5, SCN-29 and SCN-30.Table 15 and 16 has been summed up the result of test SCN-29 and SCN-30.
The result of table 15 test SCN-29
(1) millivolt
The result of table 16 test SCN-30
(1) millivolt
Gold is removed in embodiment 6-solvent extraction from thiocyanate salt solution
By dissolve sulfur potassium cyanate, ferric sulfate and gold in deionized water, the acid synthetic thiocyanate salt solution of preparation.The character of the thiocyanate salt solution of preparation is summarised in the table 17.Preparation comprises Armeen
TMTwo kinds of different organic liquid phase of 312 (Akzo Nobel) extraction agent.Arneen
TMThe 312nd, the tertiary amine extraction agent.First organic phase (O-1) is 0.05M ArMeen
TM312 kerosin.Second organic phase (O-2) is the O-1 of 0.9 parts by volume and decyl alcohol (the 0.045M Armeen of 0.1 parts by volume
TM312) mixture.
The thiocyanate salt solution of table 17 preparation
| Be rich in the thiocyanate salt solution of metal | [Au] (ppm) | [SCN] (ppm) | [Fe] (1) (ppm) | pH | E (2) (mV) |
| A-1 | 36.5 | 957 | 4488 | 1.72 | 530 |
| A-2 | 10.2 | 996 | 5074 | 1.74 | 549 |
| A-3 | 4.79 | 1121 | 5105 | 1.76 | 556 |
| A-4 | 1.95 | 1083 | 5058 | 1.75 | 556 |
(1) total dissolved iron
(2) millivolt
In each test, the thiocyanate-aqueous solution that about 250mL is rich in metal is put into separating funnel with organic phase, and wherein the volume ratio of organic phase and water is 1: 1 or 1: 2.The vibration separating funnel is about 10 minutes on the wrist vibrator.Make organic phase and aqueous phase separation, remove the organic phase of water-based residual solution and load then in the separating funnel.The result is summarised in the table 18.Shown in table 18, all tests to enter the gold recovery of organic phase from water all very high.And the water after solvent extraction of all tests and the separating effect of organic phase are all fine.
Table 18 solvent extraction test-results
(1) volume ratio of organic phase (organic extraction agent) and water (being rich in the thiocyanate salt solution of metal)
Embodiment 7-removes gold from the thiocyanate salt solution solvent extraction
Obtain the concentrated solution of different amine extraction agents, the concentrated solution that dilutes 0.2 parts by volume that obtains by the dimethylbenzene that uses 0.8 parts by volume prepares the organic liquid phase that contains different extraction agents.Prepare the thiocyanate-aqueous solution that is rich in metal through the pretreated infusibility sulfide of bio-oxidation gold ore sample by leaching.The dissolved iron (the dissolved iron of 290.4ppm is ferrous) that contains 2.06ppm dissolved gold, 899ppm dissolved thiocyanate-and amount to 6450ppm from the thiocyanate-leaching vat that is rich in metal of post leaching, and the pH of this leaching vat be 1.5 and E be 489mV.The extraction agent that test is used is Alamine
TM336 (tertiary amines, three-C8-C10-alkylamine is from Cognis), Amberlite
TMLA-2 (secondary amine, lauryl-alkyl amine is from Cognis), Armeen
TM(primary amine, lauryl amine is from Akzo Nobel) and Armen
TM312 (tertiary amines, three lauryl amines are from Akzo Nobel).
For each test, the thiocyanate-leaching vat that about 250mL is rich in metal is with isopyknic approximately organic phase (O: A=1: 1) put into separating funnel.The vibration separating funnel is about 10 minutes on the wrist vibrator.Separate organic phase and water-based, from separating funnel, remove the organic phase of water-based residual solution and load.The result is shown in table 19.Test SX-21 obtains best being separated, but being separated of all tests is all fine.
Table 19 solvent extraction test-results
(1) iron total amount
Gold is removed in embodiment 8-solvent extraction from the thiocyanate salt solution that is rich in metal
Preparation contains the dissolved thiocyanate-of dissolve gold, 905ppm (0.15M) of 2.21ppm and the synthetic thiocyanate-aqueous solution that amounts to the dissolved iron of 6470ppm (0.11M) in deionized water, the pH of this solution be 1.84 and E be 493.3mV.Tributyl phosphate (" TBP ") is used as organic extraction agent phase, and uses various TBP and the volume ratio that is rich in the thiocyanate salt solution of metal.For each test, combination TBP and the thiocyanate salt solution that is rich in metal of the about 500mL of cumulative volume are put into separating funnel, and on the wrist vibrator, vibrate 10 minutes, separate organic phase and water then.From separating funnel, remove the organic phase of water-based residual solution and load.The result is shown in table 20, comprises the golden yield that enters organic phase from water.Being separated of all tests is all fine.
Table 20 solvent extraction test-results
(1) volume ratio of organic phase (TBP) and water (being rich in the thiocyanate salt solution of metal)
Embodiment 9-removes gold from the exchange of thiocyanate salt solution intermediate ion
Obtain gel-type reinforcing yin essence ion exchange resin Purolite
TMThe sample of 600 (Purolite Company) also is divided into two parts.Remove from a copy of it by vacuum filtration and to anhydrate, and the dry weight of definite resin, thereby information about the water-content of wet resin is provided.Wet resin contains the resin of the 65.72 weight % that have an appointment and the water of about 34.28 weight %.In each test, the thiocyanate salt solution that 480mL is rich in metal adds in the flask of 1L with 1gPurolite 600 resins (containing the 0.6572g ion exchange resin of having an appointment), uses the content in the magnetic stirring apparatus mixing flask.When finishing in 1 hour, 3 hours and 7 hours, from flask, take out and respectively analyze for the sample of 20mL.The gold of use load different levels in being rich in the thiocyanate salt solution of metal is tested, and described solution contains the thiocyanate-of the 0.02M that has an appointment or the thiocyanate-of about 0.05M.The gold of sensing lead on resin (based on dried resin weight) when finishing in 7 hours.
Test-results is summarised in the table 21.Figure 21 is illustrated in and uses the metallographic that loads on after the resin absorption gold on the resin (dried resin weight) relation curve for the gold concentration in the thiocyanate salt solution.Use the test of thiocyanate-of about 0.02M and the about 0.05M of use thiocyanate test separate curve as shown in figure 21.Figure 22 illustrates for test IX-2 (0.02M thiocyanate-) and test IX-5 (0.05M thiocyanate-), and the gold concentration in the solution is with respect to the time relation curve.Figure 23 illustrates for test IX-2 (0.02M thiocyanate-) and test IX-5 (0.05M thiocyanate-), from the gold and the time relation curve of thiocyanate salt solution recovery.Shown in table 20 and Figure 21-23, the performance of ion exchange resin is better when using the thiocyanate-of lower concentration in being rich in the thiocyanate salt solution of metal.
Table 21 ion-exchange test-results
(1) iron total amount
(2) milligram gold/kilogram resin (dry basis)
Embodiment 10-removes gold with prussiate/carbon from thiocyanate salt solution
Four kinds of different thiocyanate-aqueous solution of preparation in deionized water.In each test, be that about 20 thiocyanate salt solutions that restrain activated carbon particles/liter be rich in metal are put into the flask of 500mL with concentration with the thiocyanate salt solution of about 250mL preparation.Is that 10 amount adds in the flask with sodium cyanide with the mol ratio that is enough to provide sodium cyanide and gold.Content on mechanical vibrator in the shaking flask 2 hours takes out the content in the flask then and analyzes.
The character of the thiocyanate salt solution of preparation and the result of each test are summarised in the table 22 in each test.In all tests, reclaim from the gold of thiocyanate salt solution all fine, but reclaim better from gold with the thiocyanate salt solution of lower concentration thiocyanate-preparation.
Table 22 prussiate/carbon adsorption test
Embodiment 11-removes gold with prussiate/activated carbon from thiocyanate salt solution A
In deionized water the preparation contain 5.25ppm gold, 0.02M thiocyanate-, 0.1M iron ion and 0.0016M ferrous ion, and pH be 1.67 and E be the thiocyanate salt solution of 560mV.For each test, the thiocyanate salt solution of about 250mL preparation is put into the big mouth of 500mL beaker with activated carbon particle, the concentration of described activated carbon particle is 20g activated carbon particle/liter the be rich in thiocyanate salt solution of metal.Sodium cyanide (NaCN) is added in the flask with enough amounts, is 10 so that the sodium cyanide and the mol ratio of gold to be provided.Content different time for each test shaking flask on mechanical vibrator.After vibration, analyze thiocyanate salt solution, to assess the reduction of gold recovery kinetics and iron ion to ferrous ion.
The result is summarised in the table 23.Shown in table 23, it is very fast that gold reclaims kinetics, and iron ion is not too much to the reduction of ferrous ion.
Table 23 prussiate/carbon adsorption test
Embodiment 12-removes gold with prussiate/activated carbon from thiocyanate salt solution
Test as described in embodiment 11, difference is to use the mol ratio of different sodium cyanides and gold, and each test duration 2 hours, analyzes the content in the flask afterwards.The result is summarised in the table 24.Even the gold recovery that also can obtain when using the mol ratio of low prussiate and gold.
Table 24 prussiate/carbon adsorption test
Embodiment 13-removes gold with prussiate/activated carbon from thiocyanate salt solution
Test as described in embodiment 11, difference is to use the activated carbon particle of different concns, and each test duration 2 hours, analyzes the content in the flask afterwards.The result is summarised in the table 25.
Table 25 prussiate/carbon adsorption test
(1) gram activated carbon particle/the rise thiocyanate salt solution of preparation
Embodiment 14-is oxidized to iron ion with ferrous ion in thiocyanate salt solution
By in deionized water, dissolving ferrous sulfate (FeSO
4) and potassium sulfocyanate prepare thiocyanate salt solution, add sulfuric acid with the pH bar to about pH 2.This thiocyanate salt solution contains 0.67 grams per liter (0.0120M) dissolving ferrous ion and 1.96 grams per liters (0.0337M) dissolved thiocyanate-.In each test, the 200mL thiocyanate salt solution is put into the 500mL flask, add Potassium Persulphate (K then
2S
2O
8).Mixture on vibrator in the shaking flask reaches 10 minutes, collects 20 molar solution samples then and analyze from flask.Make surplus solution in flask, leave standstill about 47 hours and 50 minutes (, amount to 48 hours, the involving vibrations time) and analyze.The result is summarised in the table 26.
Ferrous ion in the table 26 sulfur oxide thiosulfate
(1) MR=K
2S
2O
8With Fe
2+Mol ratio
Provide above-mentioned discussion of the present invention for setting forth and describe purpose.Foregoing is not to limit the invention to concrete disclosed form here.Therefore, relevant with the technology of above-mentioned instruction and this area or knowledge changes and improvements belong to scope of the present invention.Above-described embodiment is used for further explaining puts into practice best mode of the present invention, is that those of ordinary skill in the art can utilize the present invention and make application-specific of the present invention or various improvement that purposes is required with described embodiment or other embodiment.Claims should be interpreted as the replacement scheme that comprises that prior art allows.Though description of the invention comprised one or more can scheme and specific change and improvement, other changes and improvements also belong in the scope of the present invention, for example belong to the skills and knowledge of understanding those skilled in the art after the disclosure.Expectation can obtain to comprise the right of alternate embodiment with the degree that allows, described alternate embodiment comprises the surrogate of desired right, structure, function, scope or step interchangeable and/or of equal value, no matter whether described surrogate, structure, function, scope or step interchangeable and/or of equal value be open here, and do not attempt to refer in particular to publicly any patentable subject name.And any feature of describing or advocate at any open scheme can make up with one or more any further features of any other scheme, reach described feature and need not to be technical compatible degree, and these combinations belongs in the scope of the present invention.
Term " comprises ", the variation of " comprising ", " having " and " containing " and these terms can be used for the existence of representation feature, only is used for indication and has special characteristic, and do not attempt to limit the existence of further feature.Phrase method " at least a portion " represents some or all of materials, preferred most of material.
Claims (129)
1. a mineral material that uses round-robin thiocyanate-leaching vat to handle to contain precious metal is to reclaim the method for precious metal from mineral material, and described method comprises:
Use the thiocyanate-leaching vat that mineral material is carried out the thiocyanate-leaching, described thiocyanate-leaching vat contains dissolved thiocyanate-and dissolved iron ion, and during the thiocyanate-leaching, at least a portion enters the thiocyanate-leaching vat from the precious metal of mineral material with the form dissolving of precious metal-thiocyanate complex;
The charging of thiocyanate-leaching vat is supplied to the thiocyanate-leaching, the charging of thiocyanate-leaching vat is in acid pH, and the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 2 in the charging of thiocyanate-leaching vat, and during the thiocyanate-leaching, at least a portion dissolved iron ion in the charging of thiocyanate-leaching vat is reduced to the dissolved ferrous ion;
Reclaim at least a portion precious metal from the thiocyanate-leaching vat, after reclaiming, the dissolved iron concentration is less than dissolved iron ion in the charging of thiocyanate-leaching vat in the lean ore elutriant of thiocyanate-leaching vat;
Adjust the thiocyanate-leaching vat, with the charging of preparation thiocyanate-leaching vat, at least a portion lean ore elutriant of thiocyanate-leaching vat is supplied to adjustment, be used to prepare the charging of thiocyanate-leaching vat, described adjustment comprises the concentration that increases dissolved iron ion in the thiocyanate-leaching vat with respect to the concentration of dissolved iron ion in the lean ore elutriant of the thiocyanate-leaching vat that is supplied to adjustment.
2. the process of claim 1 wherein that precious metal comprises gold, and during the thiocyanate-leaching, the most of at least gold in the mineral material is entered in the thiocyanate-leaching vat by leaching.
3. the method for claim 1, wherein reclaim and be included in thiocyanate-leaching solvent extraction precious metal from the thiocyanate-leaching vat afterwards, described solvent extraction comprises makes the thiocyanate-leaching vat contact organic extraction agent phase, and at least a portion dissolved precious metal is transferred to organic extraction agent phase from the thiocyanate-leaching vat.
4. the method for claim 3, wherein organic extraction agent comprises the phosphorated extraction agent mutually.
5. the method for claim 3, wherein organic extraction agent comprises the amine extraction agent mutually.
6. the process of claim 1 wherein:
Recovery makes thiocyanate-leaching vat contact ions exchange resin after being included in the thiocyanate-leaching; And
At described period of contact, at least a portion precious metal is removed and is loaded on the ion exchange resin from the thiocyanate-leaching vat.
7. the process of claim 1 wherein to reclaim to comprise, and change at least a portion precious metal in the thiocyanate-leaching vat into precious metal-cyanide complex from precious metal-thiocyanate complex in the dissolved prussiate introducing thiocyanate-leaching vat.
8. the method for claim 7 wherein reclaims and comprises remove at least a portion precious metal-cyanide complex from the thiocyanate-leaching vat.
9. the method for claim 8 is wherein removed and is comprised at least a portion precious metal-cyanide complex is loaded on the sorptive material.
10. the method for claim 9, wherein sorptive material comprises activated carbon.
11. the method for claim 9, wherein sorptive material comprises ion exchange resin.
12. each method in the claim 7 is wherein introduced and is comprised prussiate is added in the thiocyanate-leaching vat that wherein the prussiate in the thiocyanate-leaching vat and the mol ratio of precious metal are not more than 20.
13. the method for claim 7, wherein:
Precious metal in the thiocyanate-leaching vat comprises gold; And
Introducing comprises prussiate is added in the thiocyanate-leaching vat that wherein the mol ratio of prussiate in the thiocyanate-leaching vat and the gold in the thiocyanate-leaching vat is not more than 20.
14. the method for claim 13, wherein the prussiate in the thiocyanate-leaching vat is 2-20 with the mol ratio of gold.
15. the process of claim 1 wherein thiocyanate-leaching, recovery and the adjustment period between, the thiocyanate-leaching vat is remained on acid pH.
16. the process of claim 1 wherein thiocyanate-leaching, recovery and the adjustment period between, the pH of thiocyanate-leaching vat is remained on pH1 to pH3.
17. the process of claim 1 wherein to adjust to comprise, and to the thiocyanate-leaching, at least a portion dissolved prussiate changed thiocyanate-leaching vat raw material supplying into thiocyanate-with in the dissolved prussiate introducing thiocyanate-leaching vat.
18. the process of claim 1 wherein to adjust to comprise, and to the thiocyanate-leaching, all dissolved prussiates changed thiocyanate-leaching vat raw material supplying into thiocyanate-with in the dissolved prussiate introducing thiocyanate-leaching vat.
19. the process of claim 1 wherein that the thiocyanate-leaching comprises:
The charging of thiocyanate-leaching vat is supplied to the heap that comprises mineral material; And
Make the described heap of thiocyanate-leaching vat infiltrate.
20. the method for claim 19 is included in before the thiocyanate-leaching, the preparation mineral material, and described preparation comprises:
Form the heap that comprises granular feedstock at first, described granular feedstock comprises sulfide mineral; And
Raw material in the bio-oxidation heap is to decompose at least a portion sulfide mineral.
21. the method for claim 1, wherein said adjustment comprises adding tart bio-oxidation elutriant in the thiocyanate-leaching vat, and described tart bio-oxidation elutriant contains the iron ion of concentration greater than dissolved iron concentration in the thiocyanate-leaching vat raw material.
22. the method for claim 1 is included in before the thiocyanate-leaching, the preparation mineral material, and described preparation is included in acidic conditions overdraft oxidation raw material, and described granular feedstock is included in the sulfide mineral that decomposes during the pressure oxidation.
23. the method for claim 22, wherein raw material comprises the sulfide sulfur of at least 2 weight %.
24. the method for claim 23, wherein raw material comprises one of at least following: (i) contain the ore of the sulfide sulfur of at least 2 weight %, and the sulfide concentrate of (ii) making by described ore.
25. the method for claim 1, be included in before the thiocyanate-leaching, the preparation mineral material, described preparation comprises uses acid leaching vat that raw material is carried out acid leach, described raw material packet cupric, and during acid leaching, at least a portion copper dissolution enters in the acid leaching vat, thereby removes soluble copper before the thiocyanate-leaching from raw material.
26. the method for claim 25, wherein copper-containing raw material contains the copper of at least 200 ppm by weight, and described copper dissolution enters acid leaching vat during acid leach.
27. it is one of at least following to the process of claim 1 wherein that mineral material contains: (i) contain at least 0.5 weight % and less than the ore of the sulfide sulfur of 2 weight %, and the concentrate of (ii) making by described ore.
28. the method for claim 27, wherein said ore comprises the sulfide sulfur that is not more than 1.5 weight %.
29. the process of claim 1 wherein that increasing in the thiocyanate-leaching vat dissolved iron concentration comprises add the dissolved iron ion in the thiocyanate-leaching vat.
30. the method for claim 29 wherein adds the dissolved iron ion and comprises the acid bio-oxidation elutriant of adding in the thiocyanate-leaching vat.
31. the process of claim 1 wherein that increasing in the thiocyanate-leaching vat dissolved iron concentration comprises at least a portion dissolved ferrous ion in the thiocyanate-leaching vat is oxidized to the iron ion form.
32. the method for claim 31, wherein oxidation comprises in the thiocyanate-leaching vat and introduces oxygenant.
33. the method for claim 32, wherein oxygenant comprises persulphate.
34. the method for claim 32, wherein oxygenant comprises the component that is selected from persulfuric acid, superoxide, Manganse Dioxide, ozone, halogen and hypochlorite.
35. the method for claim 31, wherein oxidation comprises and makes thiocyanate-leaching vat catalytic oxidation gas.
36. the method for claim 35, wherein oxidation comprises the component that makes thiocyanate-leaching vat catalytic oxidation gas and be selected from sulfur dioxide gas, hydrosulphite and metabisulphite.
37. the method for a separate precious metal from the heap of the raw mineral materials that contains precious metal that comprises particle form at first, described method comprises:
Pre-treatment heap, described pre-treatment comprise acid preprocessing solution raw material are applied on the heap, and make this heap of preprocessing solution infiltrate;
After pre-treatment, the described heap of thiocyanate-leaching, described thiocyanate-leaching comprises sour sulfur cyanate leaching vat raw material is applied on the heap, and make this heap of preprocessing solution infiltrate, thereby at least a portion precious metal from described heap is entered in the thiocyanate-leaching vat with precious metal-thiocyanate complex form dissolving, wherein thiocyanate-leaching vat raw material contains dissolved iron ion and dissolved thiocyanate-, and the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 2.
38. the method for claim 37, wherein:
During permeating, at least a portion dissolved iron ion in the thiocyanate-leaching vat is reduced, with the dissolving ferrous ion, and the thiocyanate-leaching comprises elutriant and a part of at least thiocyanate-leaching vat of the recirculation elutriant of extracting the thiocyanate-leaching vat from described heap out, with preparation thiocyanate-leaching vat raw material;
Recirculation comprises increases dissolved iron concentration in a part of thiocyanate-leaching vat elutriant.
39. first heap that the method for claim 38, wherein said heap are a plurality of heaps carries out independently pre-treatment and thiocyanate-leaching to each heap; And
During first heap of thiocyanate-leaching, be applied to the elutriant that thiocyanate-leaching vat raw material on first heap comprises at least a portion preprocessing solution, described elutriant is extracted out from second heap during second heap of pre-treatment.
40. the method for claim 39, wherein the elutriant of the preprocessing solution of extracting out from second heap the dissolved iron concentration greater than the concentration of dissolved iron ion from the elutriant of the thiocyanate-leaching vat of first heap extraction.
41. the method for claim 37, wherein mineral material contains the soluble copper of at least 0.1 weight %, and described copper dissolves during pre-processing and enters preprocessing solution.
42. the method for claim 37, wherein precious metal contains gold, and the gold of at least 50 weight % in the mineral material raw material is the leachable gold of prussiate.
43. the method for claim 37, wherein the pH of preprocessing solution raw material is pH0.1-pH3.
44. the method for claim 43, wherein the raw material of preprocessing solution comprises hydrosulphate solution.
45. the method for claim 44, wherein at least a portion precious metal in the mineral material is locked in and contains in the iron sulfide mineral, and preprocessing solution contains at least a acidophilia microorganism strains that can ferric oxide; And
During pre-processing, the ferruginous sulfide mineral of at least a portion decomposes through bio-oxidation, thereby discharges at least a portion precious metal, to be dissolved in during the thiocyanate-leaching in the acid leaching vat of thiocyanate-.
46. the method for claim 45, wherein:
Mineral material comprises sulfide sulfur; And
Pre-treatment comprises oxidation first part sulfide sulfur, and the thiocyanate-leaching comprises oxidation second section sulfide sulfur;
Wherein the ratio of second section sulfide sulfur and first part's sulfide sulfur was at least 1: 4.
47. the method for claim 46, wherein during pre-processing, the sulfide sulfur that is not more than 30 weight % is oxidized.
48. the method for claim 45, wherein the pre-treatment time length is no more than 90 days.
49. the method for claim 37, wherein during pre-processing, with respect to precious metal, at least a component except that precious metal of mineral material is optionally dissolved and is entered preprocessing solution.
50. the method for claim 37, wherein precious metal contains gold.
51. the method for separate precious metal from the raw mineral materials that contains precious metal, wherein at least a portion precious metal is locked in one or more sulfide minerals, and described method comprises:
Bio-oxidation contains the heap of the raw mineral materials of particle form at first, and during bio-oxidation, first part's sulfide sulfur is oxidized; With
After bio-oxidation, the described heap of thiocyanate-leaching, described thiocyanate-leaching comprises sour sulfur cyanate leaching vat raw material is applied to described heap, and make the described heap of thiocyanate-leaching vat infiltrate, described thiocyanate-leaching vat raw material contains the dissolved thiocyanate-, and during leaching, precious metal enters the thiocyanate-leaching vat from the form dissolving of described heap with precious metal-thiocyanate complex;
Wherein during the thiocyanate-leaching, the second section sulfide sulfur is oxidized, and the ratio of second section sulfide sulfur and first part's sulfide sulfur was at least 1: 10.
52. the method for claim 51, wherein the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 4 in the thiocyanate-leaching vat raw material.
53. the method for claim 51, wherein in raw mineral materials, first part's sulfide sulfur and second section sulfide sulfur contain the sulfide sulfur greater than 30% altogether.
54. the method in the claim 51, wherein the ratio of second section sulfide sulfur and first part's sulfide sulfur was at least 1: 4.
55. the method for claim 51, wherein the ratio of second section sulfide sulfur and first part's sulfide sulfur was at least 1: 3.
56. a method of removing precious metal from raw mineral materials, described raw mineral materials contains the precious metal that is locked in one or more sulfide minerals, and described method comprises:
Pressure oxidation is with the raw mineral materials of particle form pulp in waterborne liquid, to decompose at least a portion sulfide mineral;
Reclaim from the solid residue of pressure oxidation and acidic liquid elutriant, described solid residue contains at least a portion precious metal from raw mineral materials; And
Use sour sulfur cyanate leaching vat thiocyanate-leaching at least a portion solid residue, thereby the form of at least a portion precious metal with precious metal-thiocyanate complex entered the thiocyanate-leaching vat from the solid residue dissolving.
57. the method for claim 56 wherein is supplied to the thiocyanate-leaching with at least a portion from the acid elutriant of pressure oxidation, so that the dissolved iron ion is conducted to the thiocyanate-leaching.
58. the method for claim 56 is supplied to wherein that the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 2 in the thiocyanate-leaching vat raw material of thiocyanate-leaching.
59. the method for claim 56, wherein elutriant contains the free sulfuric acid of at least 10 grams per liters.
60. the method for claim 56, wherein the mineral charging contains the sulfide sulfur of at least 2 weight %.
61. the method for claim 56, wherein pressure oxidation is at least 160 ℃ temperature with carry out under the oxygen superpressure of 68.9kPa at least.
62. the method for claim 56, wherein pressure oxidation is carried out under the oxygen superpressure of 180-235 ℃ temperature and 68.9kPa-861.8kPa.
63. the method for claim 56, wherein:
The mineral charging contains non-iron base metal;
Pressure oxidation comprises the dissolving of the non-iron base metal of at least a portion is entered waterborne liquid that elutriant contains the non-iron base metal that some exists in solution thus; And
From elutriant, separate the non-iron base metal of at least a portion.
64. the method for claim 63, wherein non-iron base metal is selected from copper, nickel, lead and zinc.
65. the method for claim 64, wherein the mineral charging contains the non-iron base metal of at least 1 weight %, and described non-iron base metal dissolves during pressure oxidation and enters in the waterborne liquid, separates from elutriant between separation period then.
66. the method for claim 63, wherein non-iron base metal is a copper, and separation comprises that solvent extraction at least a portion copper enters organic extraction agent liquid phase.
67. the method for a separate precious metal from the mineral material that contains precious metal and at least a copper-bearing mineral, described method comprises:
Use the charging of acid first leaching vat, the first leaching mineral material, thus with respect to precious metal optionally with copper leaching to the first leaching vat;
After first leaching, use contains the second leaching mineral material of the sour sulfur cyanate leaching vat of dissolved thiocyanate-and dissolved iron ion, and during second leaching, at least a portion enters second leaching vat from the precious metal of mineral material with precious metal-thiocyanate complex form dissolving;
Be supplied to wherein that the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 2 in the thiocyanate-leaching vat charging of second leaching.
68. the method for claim 67, wherein the charging of the mineral material dissolving during first leaching that contains at least 0.01 weight % enters the copper of first leaching vat.
69. the method for claim 67, wherein:
The pH that is supplied to the first leaching vat charging of first leaching is pH0.1-pH3.
70. the method for claim 67, wherein the charging of mineral material comprises the secondary copper-bearing mineral.
71. the method for claim 70, wherein the secondary copper-bearing mineral is selected from copper glance, covellite and combination thereof.
72. the method for claim 67, wherein the charging of the mineral material dissolving during first leaching that contains at least 0.02 weight % enters the copper of first leaching vat.
73. the method for claim 67, wherein the charging of the mineral material dissolving during first leaching that contains at least 1 weight % enters the copper of first leaching vat.
74. the method for claim 67, wherein copper-bearing mineral comprises THE RECOGNITION OF MAIN COPPER.
75. the method for claim 74, wherein THE RECOGNITION OF MAIN COPPER is a chalcopyrite.
76. the method for claim 67, wherein copper-bearing mineral is copper bearing sulfide mineral; And first leaching comprises the copper bearing sulfide mineral of bio-oxidation at least a portion.
77. the method for claim 67, wherein first leaching is included in the charging that there is overdraft oxide mineral material in oxygen.
78. the method for claim 67, wherein first leaching comprises the charging of dumping the leaching mineral material.
79. the method for claim 67 wherein before first leaching, make up the heap of the mineral material charging that contains particle form, and wherein first leaching comprises that the described heap of the first leaching vat infiltrate, second leaching are comprised makes the described heap of thiocyanate-leaching vat infiltrate.
80. the method for a direct leaching precious metal from the appropriate infusible sulfide mineral material that contains precious metal, this method comprises:
Use sour sulfur cyanate leaching vat leaching mineral material, thereby the form dissolving with precious metal-thiocyanate complex enters in the thiocyanate-leaching vat from the precious metal of mineral material to make at least a portion, described mineral material is selected from: (i) contain the sulfide sulfur of at least 0.5 weight % and less than the ore of the sulfide sulfur of 2 weight %, the (ii) sulfide concentrate of making by described ore, and (iii) their combination.
81. the method for claim 80 is supplied to wherein that the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 2 in the thiocyanate-leaching vat charging of described leaching.
82. the method for claim 80 is included in before the leaching, uses hydrosulphate solution pre-treatment mineral material.
83. the method for claim 82, wherein during leaching, mineral material is the form of heap, and
Pre-treatment be included in form heap during, the mineral material of particle form is mixed with at least a portion hydrosulphate solution.
84. the method for claim 80, wherein the pH of thiocyanate-leaching vat is pH1 to pH3.
85. the method for claim 80, wherein ore contains the sulfide sulfur of 0.5-1.5 weight %.
86. the method for a separate precious metal from the mineral material that contains precious metal, this method comprises:
Use contains the acid leaching mineral material of thiocyanate-leaching vat of dissolved thiocyanate-and dissolved iron ion, wherein during leaching, at least a portion enters the thiocyanate-leaching vat from the precious metal of mineral material with the form dissolving of precious metal-thiocyanate complex;
The thiocyanate-leaching vat raw material that wherein is supplied to leaching is in acid pH, and contains the dissolved iron ion that concentration is at least 0.1 mol, and the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 2.
87. the method for a separate precious metal from the mineral material that contains precious metal, this method comprises:
Use contains the acid leaching mineral material of thiocyanate-leaching vat of dissolved thiocyanate-and dissolved iron ion, wherein during leaching, at least a portion enters the thiocyanate-leaching vat from the precious metal of mineral material with the form dissolving of precious metal-thiocyanate complex;
Wherein the charging of thiocyanate-leaching vat is in acid pH, and the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 7.
88. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein the pH of thiocyanate-leaching vat raw material is pH1 to pH3.
89. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein the concentration of dissolved thiocyanate-is not more than 0.03 mol in the charging of thiocyanate-leaching vat.
90. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein the concentration of dissolved thiocyanate-is 0.0001 mol-0.02 mol in the charging of thiocyanate-leaching vat.
91. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein the concentration of dissolved iron ion is at least 0.05 mol in the charging of thiocyanate-leaching vat.
92. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein the concentration of dissolved iron ion is at least 0.1 mol in the charging of thiocyanate-leaching vat.
93. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 4 in the charging of thiocyanate-leaching vat.
94. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein the concentration of dissolved thiocyanate-is 0.0001 mol-0.03 mol in the charging of thiocyanate-leaching vat, the concentration of dissolved iron ion is at least 0.05 mol in the charging of thiocyanate-leaching vat, and the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 7 in the charging of thiocyanate-leaching vat.
95. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 7.
96. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein thiocyanate-leaching vat raw material comprises following all character: (i) concentration of dissolved thiocyanate-is not more than 0.02 mol, (ii) the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 7, and (iii) pH is pH1 to pH3.
97. claim 1-55,58,67-79,81,86 and 87 method in each, the pH of wherein said thiocyanate-leaching vat raw material is pH1 to pH3, the concentration of dissolved thiocyanate-is 0.0001 mol-0.03 mol, and the concentration of dissolved iron ion is at least 0.05 mol.
98. each method among claim 1-55,58, the 67-79,81,86 and 87, wherein said mol ratio is at least 10.
99. a method that reclaims precious metal from the mineral material that contains precious metal, this method comprises:
Use thiocyanate-leaching vat thiocyanate-leaching mineral material, make at least a portion enter the thiocyanate-leaching vat with the form dissolving of precious metal-thiocyanate complex from the precious metal of mineral material;
The dissolved prussiate is introduced in the thiocyanate-leaching vat, changed at least a portion precious metal into precious metal-cyanide complex from precious metal-thiocyanate complex;
From the thiocyanate-leaching vat, remove the precious metal that at least a portion changes precious metal-cyanide complex into.
100. the method for claim 99 comprises:
After removing, a part of at least thiocyanate-leaching vat of recirculation, with preparation thiocyanate-leaching vat raw material, and
With thiocyanate-leaching vat raw material supplying to the thiocyanate-leaching.
101. the method for claim 100, wherein recirculation comprises dissolved at least a portion prussiate in the thiocyanate-leaching vat is converted into the dissolved thiocyanate-.
102. the method for claim 99, wherein between introducing and tour, the mol ratio of dissolved prussiate and dissolved thiocyanate-is no more than 1: 2 in the thiocyanate-leaching vat.
103. the method for claim 102, wherein said mol ratio is no more than 1: 4.
104. the method for claim 99 is wherein removed at least a portion precious metal that comprises that separation has precious metal-cyanide complex form from the thiocyanate-leaching vat.
105. the method for claim 99 is wherein removed the precious metal with precious metal-cyanide complex form that comprises separation at least 90 weight % from the thiocyanate-leaching vat, described precious metal was dissolved in before the next-door neighbour removes in the thiocyanate-leaching vat.
106. the method for claim 99 is wherein removed and is comprised and make thiocyanate-leaching vat contact sorptive material, and precious metal loads on the sorptive material with the form of precious metal-cyanide complex.
107. the method for claim 106, wherein sorptive material comprises ion exchange resin.
108. the method for claim 106, wherein sorptive material comprises carbon.
109. the method for claim 106 comprises, after removing, is extracted into the anti-extraction solution at least a portion precious metal is counter from sorptive material.
110. the method for claim 109, wherein:
During leaching, introducing, changing and remove, the thiocyanate-leaching vat is in acid pH; And
The anti-solution that extracts is in alkaline pH.
111. the method for claim 99, wherein the thiocyanate-leaching vat is in acid pH during the thiocyanate-leaching.
112. the method for claim 99, wherein, during the thiocyanate-leaching, the thiocyanate-leaching vat is in the acid pH of pH1-pH3.
113. the method for claim 99, wherein during thiocyanate-leaching, introducing, changing and remove, the thiocyanate-leaching vat is in acid pH.
114. the method for claim 99, wherein during thiocyanate-leaching, introducing, changing and remove, the thiocyanate-leaching vat is in the acid pH of pH1-pH3.
115. the method for claim 99 wherein, between the introductory phase, adds prussiate in the thiocyanate-leaching vat, the prussiate of adding is not more than 20 with the mol ratio that is dissolved in the precious metal in the described thiocyanate-leaching vat.
116. the method for claim 115, wherein said mol ratio is not more than 10.
117. the method for claim 115, wherein said mol ratio is not more than 5.
118. the method for claim 99 comprises that with thiocyanate-leaching vat raw material supplying to the thiocyanate-leaching, the concentration of dissolved thiocyanate-is the 0.0001-0.03 mol in the thiocyanate-leaching vat raw material.
119. the method for claim 118, wherein the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 2 in the thiocyanate-leaching vat raw material.
120. each method among the claim 99-120, wherein the pH of thiocyanate-leaching vat raw material is pH1-pH3.
121. the method for claim 98, wherein precious metal comprises gold.
122. a method that reclaims precious metal from the thiocyanate-leaching vat, wherein precious metal is dissolved in the thiocyanate-leaching vat with the form of precious metal-thiocyanate complex, and this method comprises:
Change the precious metal-thiocyanate complex of at least a portion precious metal from the thiocyanate-leaching vat in the thiocyanate-leaching vat precious metal-cyanide complex; And
From the thiocyanate-leaching vat, remove the precious metal that at least a portion changes precious metal-cyanide complex form into.
123. the method for claim 122, wherein between tour, the thiocyanate-leaching vat is in acid pH.
124. the method for a separate precious metal from the mineral material that contains precious metal, this method comprises:
Use sour sulfur cyanate leaching vat leaching mineral material, thereby at least a portion precious metal is entered in the thiocyanate-leaching vat with the form dissolving of precious metal-thiocyanate complex, and
The acid charging of preparation thiocyanate-leaching vat, and the charging of thiocyanate-leaching vat is supplied to leaching, described preparation comprise and are dissolved in prussiate in the waterborne liquid and prussiate are changed into the dissolved thiocyanate-after dissolving.
125. the method for claim 124, wherein thiocyanate-leaching vat raw material contains the dissolved thiocyanate-that concentration is the 0.001-0.03 mol.
126. the method for claim 124, wherein preparation comprises the concentration that increases dissolved iron ion in the waterborne liquid.
127. the method for claim 124, wherein the mol ratio of dissolved iron ion and dissolved thiocyanate-is at least 2 in the thiocyanate-leaching vat raw material.
128. the method for claim 124-127 in each, wherein the pH of thiocyanate-leaching vat raw material is pH1 to pH3.
129. the method for claim 128, wherein the concentration of dissolved iron ion is at least 0.05 mol in the thiocyanate-leaching vat raw material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46079503P | 2003-04-04 | 2003-04-04 | |
| US60/460,795 | 2003-04-04 | ||
| US60/470,045 | 2003-05-12 |
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| CN100424204C true CN100424204C (en) | 2008-10-08 |
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| CN102534204B (en) * | 2012-03-06 | 2014-11-05 | 昆明理工大学 | Thiosulfate gold extraction method taking Fe (III) cyanide salts as oxidants |
| CN102976360B (en) * | 2012-11-22 | 2014-12-10 | 长沙铂鲨环保设备有限公司 | Thiocyanate-containing gold complex as well as preparation method and application thereof |
| GB2551980A (en) * | 2016-06-30 | 2018-01-10 | Commw Scient Ind Res Org | Method and system for low level metal analysis of mineral samples |
| CN108441648A (en) * | 2018-04-13 | 2018-08-24 | 韩志永 | A kind of environmental protection proposes golden agent and preparation method thereof |
| CN109499625B (en) * | 2018-11-06 | 2021-09-28 | 长春黄金研究院有限公司 | High-efficiency elution method for gold-loaded resin |
| CN112881380A (en) * | 2021-01-22 | 2021-06-01 | 中新苏州工业园区清城环境发展有限公司 | Method and device for detecting different concentrations of sodium persulfate in acidic water environment and using method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054268A (en) * | 1990-02-23 | 1991-09-04 | 克拉服务有限公司 | The method of extraction and recovery gold |
| US5061459A (en) * | 1989-10-27 | 1991-10-29 | The British Petroleum Company P.L.C. | Prevention of copper dissolution during cyanidation of gold ores |
| US5885327A (en) * | 1995-09-12 | 1999-03-23 | Henkel Corporation | Process for the recovery of gold |
| US6355175B1 (en) * | 1997-06-09 | 2002-03-12 | Hw Process Technologies, Inc. | Method for separating and isolating precious metals from non precious metals dissolved in solutions |
-
2004
- 2004-03-25 CN CNB2004800155613A patent/CN100424204C/en not_active Expired - Fee Related
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2005
- 2005-11-03 ZA ZA200508919A patent/ZA200508919B/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061459A (en) * | 1989-10-27 | 1991-10-29 | The British Petroleum Company P.L.C. | Prevention of copper dissolution during cyanidation of gold ores |
| CN1054268A (en) * | 1990-02-23 | 1991-09-04 | 克拉服务有限公司 | The method of extraction and recovery gold |
| US5885327A (en) * | 1995-09-12 | 1999-03-23 | Henkel Corporation | Process for the recovery of gold |
| US6355175B1 (en) * | 1997-06-09 | 2002-03-12 | Hw Process Technologies, Inc. | Method for separating and isolating precious metals from non precious metals dissolved in solutions |
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| CN1826420A (en) | 2006-08-30 |
| ZA200508919B (en) | 2007-04-25 |
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