EP0119685B1 - Procédé hydrométallurgique pour traiter des arsénopyrites - Google Patents
Procédé hydrométallurgique pour traiter des arsénopyrites Download PDFInfo
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- EP0119685B1 EP0119685B1 EP84300292A EP84300292A EP0119685B1 EP 0119685 B1 EP0119685 B1 EP 0119685B1 EP 84300292 A EP84300292 A EP 84300292A EP 84300292 A EP84300292 A EP 84300292A EP 0119685 B1 EP0119685 B1 EP 0119685B1
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- Prior art keywords
- concentrate
- species
- solution
- oxidized
- arsenic
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 47
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 title claims description 34
- 229910052964 arsenopyrite Inorganic materials 0.000 title description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 61
- 239000012141 concentrate Substances 0.000 claims description 50
- 238000000354 decomposition reaction Methods 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 229910052785 arsenic Inorganic materials 0.000 claims description 28
- 239000010931 gold Substances 0.000 claims description 27
- 229910052737 gold Inorganic materials 0.000 claims description 26
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 14
- 230000008929 regeneration Effects 0.000 claims description 12
- 238000011069 regeneration method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 9
- 239000001175 calcium sulphate Substances 0.000 claims description 9
- 235000011132 calcium sulphate Nutrition 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 238000009854 hydrometallurgy Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000002506 iron compounds Chemical class 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000000740 bleeding effect Effects 0.000 claims 1
- 230000003028 elevating effect Effects 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 11
- 229910052683 pyrite Inorganic materials 0.000 description 11
- 239000011028 pyrite Substances 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000001117 sulphuric acid Substances 0.000 description 7
- 235000011149 sulphuric acid Nutrition 0.000 description 7
- 229910052925 anhydrite Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 4
- 229940000489 arsenate Drugs 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940000488 arsenic acid Drugs 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052595 hematite Inorganic materials 0.000 description 3
- 239000011019 hematite Substances 0.000 description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910001810 hydroniumjarosite Inorganic materials 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/08—Obtaining noble metals by cyaniding
Definitions
- This invention is directed to a novel environmentally amicable hydrometallurgical process for the recovery of gold from arsenical pyrite concentrate.
- the mineral arsenopyrite is known to contain gold which is in solution in the mineral matrix or is present as fine inclusions. This gold is not available for extraction by hydrometallurgical processes which treat only the mineral surfaces, for example, cyanidation.
- the mineral pyrite is often associated with arsenopyrite and may contain in its matrix finely dispersed gold which is difficult to extract.
- Arsenopyrite and pyrite are the main constituents of arsenical pyrite concentrates.
- the conventional means of liberating gold from arsenical pyrite concentrates is to roast the material and then treat the calcine by cyanidation. This process generates environmental pollution problems due to the airborne emission of sulphur and arsenic oxides.
- the tailings from the calcine cyanidation contain arsenic which is also a potential environmental contaminant.
- Arsenical pyrite concentrates may also be treated for gold recovery through conventional pyrometallurgical processes which include copper smelting, lead smelting and zinc roasting. These processes also produce potentially harmful airborne arsenic emissions from the treatment of these concentrates. Problems associated with the added arsenic burden in the process flows also arise.
- U.S. 3,793,429 discloses a nitric acid leaching process for extracting gold, iron and copper sulphide ores.
- U.S. 2,805,936 discloses a hydrometallurgical process for the recovery of valuable metals as Cu, Ni, Co, As, Au or the like from an arsenical sulphide concentrate, said process comprising the steps:
- An object of the present invention is to provide an environmentally amicable process for decomposing gold-bearing arsenical pyrite concentrates.
- the invention is characterised in that the arsenical sulphide concentrate is arsenical pyrite concentrate containing gold, the acidity of said acidic solution is sufficient to cause arsenic in said concentrate to be oxidized to the +5 oxidation state and to cause nitrogen of said oxidized nitrogen species to be reduced essentially to nitric oxide, gold is extracted from a solid residue formed in step a), arsenic in the precipitated arsenic species of step b) is in the +5 oxidation state and the liquid fraction treated in step b) is separated from the precipitated arsenic species and re-used in step a).
- step a) iron in said concentrate is oxidized to the +3 oxidation state and sulphide in said concentrate is oxidized to sulphate.
- said solid residue formed in step a) is separated from said acidic solution before said dissolved arsenic species is precipitated in step b).
- Arsenopyrite and pyrite are decomposed in acid solutions where the pH is less than 2 by the action of oxidized nitrogen species where the nitrogen has an oxidation state of +3 or greater. These species include nitric acid, nitrous acid and nitrogen dioxide.
- the main products from the decomposition are soluble ferric iron species, soluble arsenate species, soluble sulphate species, elemental sulphur and nitric oxide, as well as nitrogen dioxide.
- Nitrogen dioxide becomes increasingly abundant as a product in the gas phase as the nitric acid concentration increases: see Canadian Patent No. 995,468, Paul B. Queneau et al., August 24, 1976.
- the minor products are arsenic trioxide and nitrous acid.
- the gold contained in the concentrate remains in the solid residue which is composed of elemental sulphur and insoluble gangue minerals. Any silver present in the concentrate would also report to the residue.
- Figure 1 illustrates arsenic concentration as a function of time for three similar experiments with solution composition as a variable.
- the gold in the decomposition residue may be readily extracted by conventional techniques such as cyanidation, following leaching of the residue with sodium hydroxide to dissolve sulfur prior to cyanidation, or treatment with oxidizing chloride lixiviants, such as aqua regia. Silver may also be extracted by these techniques.
- the decomposition solution does not contain significant quantities of species which complex gold, for example, chloride ions. These would put the gold into solution and a separate additional process step would have to be included to extract it.
- the active nitrogen oxides are required only to decompose the minerals in the concentrate.
- the oxidizing nitrogen species should be present in sufficient concentration in the solution to provide an adequate rate of dissolution. Any suitable acid may be used to form the soluble ferric iron species. An adequate rate of dissolution is about 10 to 30 minutes.
- nitrogen dioxide is the decomposition agent for arsenopyrite with sulphuric acid present.
- the sulphuric acid is formed from the decomposition of pyrite.
- the active nitrogen oxides are reduced to nitric oxide which may then be regenerated by an oxidant.
- a useful oxidant is oxygen which reacts with nitric oxide in the presence of water to form nitrogen dioxide, nitrous acid and nitric acid as shown in the reactions set forth below.
- the regeneration of nitric oxide to the higher valence states may be done concurrently with the decomposition or as a separate operation.
- Nitrous oxide is formed by the decomposition of nitric oxide according to the side reaction shown below.
- the active nitrogen oxides can be regenerated during the decomposition step, the quantity of these oxides present at any time may be quite small.
- the criterion is that there must be sufficient acid present in solution to form the soluble ferric iron species. It must be emphasized that it is the oxidized nitrogen species rather than oxygen that are the active decomposition agent. The presence of oxidized nitrogen species with sulphuric acid differentiates the decomposition step described above from the Calera process.
- Figure 1 shows the arsenic concentration as a function of time for three similar experiments in which the only variable is the composition of the solution.
- the three compositions are 3 M acid as HN0 3 ; 2.5 M acid as H 2 SO 4 ; 0.5 M acid as HN0 3 ; and 3.0 M acid as H 2 SO 4 .
- the other conditions are given on Figure 1. It is apparent from the data that the presence of nitric acid greatly speeds the rate of reaction.
- the decomposition and regeneration steps are both exothermic.
- a solution which is three molar in nitric acid is reacted with fine arsenical pyrite concentrate at 15% solids without oxygen present for regeneration
- the temperature increase of the slurry is 40°C.
- oxygen present for generation the temperature increases is 130°C. Since the rates of the decomposition and regeneration reactions increase with temperature the overall reactions appear to accelerate as they proceed. It is possible that controlled cooling may be required to prevent the melting of elemental sulphur and to prevent the precipitation of salts.
- the decomposition step proceeds at any temperature above ambient. However, on a practical basis, the reaction is preferably carried out at temperatures of between 80° and 120°C. It is desirable that sufficient acid be present to form the soluble ferric iron species. Without this acid, compounds will precipitate from solution. If oxygen is used for regeneration, any oxygen pressure above ambient is adequate. Agitation increases the speed of the reactions and improves the quality of the final sulphur-bearing residue.
- the decomposition leach can be carried out over a wide range of solid-liquid ratios. Increasing the ratio of solids to liquids provides economic benefits, but the upper limit of this ratio is reached when the solubility limit of dissolved species is reached.
- the soluble arsenic, iron and sulphur must be removed from solution.
- Arsenic in the pentavalent state as ferric arsenate can be removed from solution with ferric iron.
- the following reaction shows the formation of ferric arsenate from ferric nitrate and arsenate.
- Ferric arsenate is produced virtually quantitatively from an equimolar solution of ferric nitrate and arsenic acid at all temperatures above ambient.
- the rate of precipitation can be controlled by temperature. At room temperature, complete precipitation requires several months; at 100°C precipitation requires one to two hours; and at 200°C precipitation occurs in less than one hour.
- Ferric arsenate can be precipitated rapidly at low temperatures by the neutralization of the acid in the solution. At 25°C the solubility of ferric arsenate between pH 3 and pH 7 is very low. The solids produced at low temperature tend to be colloidal and difficult to filter. The solids can contain ferric hydroxide which also tends to be colloidal,
- a calcium-bearing neutralizing agent such as calcium oxide or calcium carbonate, can be used to neutralize excess acid in solution and to remove sulphate in order to improve ferric arsenate precipitation.
- arsenic trioxide can precipitate when the filtered decomposition solution is cooled.
- arsenate or ferric compounds may be added to the solution.
- Sulphate is removed from solution by the addition of calcium-bearing materials to form calcium sulphate.
- the reaction between calcium carbonate and sulphuric acid is as follows.
- Gypsum CaS0 4 - 2H 2 0
- Gypsum has a low solubility which is virtually unaffected by temperature.
- the solubility ofCaS04 - 2H 2 0 is approximately 0.1 M.
- Anhydrite (CaS0 4 ) forms at temperatures above 60°C (although the crossover point from gypsum may be as high as 110°C due to supersaturation).
- the solubility of anhydrite drops rapidly with temperature. Solubility data for anhydrite in water gives a solubility of 0.02 M at 60°C and .0015 M at 160°C.
- Ferric iron can be removed from solution by the formation of insoluble iron compounds.
- ferric hydroxide Fe(OH) 3
- Fe(OH) 3 ferric hydroxide
- This material may be undesirable as it is colloidal and very difficult to filter.
- the temperature is raised to 100°C, the precipitate is transformed to goethite, a more crystalline ferric iron compound; and as the temperature is raised further to 130°C, hematite (Fe 2 0 3 ) is produced.
- the exact nature of the precipitate is dependent on neutralization history and the duration at temperature.
- a residual iron concentration of 5 g/I can be achieved in the presence of 60 g/I H 2 SO 4 at 150°C. At 200°C, the same residual can be achieved in the presence of 90 g/I H 2 SO 4 .
- hydronium jarosite (H 3 0)Fe 3 (SO Q ) 2 (OH) 6 ) and fibroferrite (Fe(OH)(S0 4 )) are expected to form.
- Hydronium jarosite is the most significant below 150°C.
- Fibroferrite is most significant above 150°C.
- jarosite may be formed by the addition of alkali salts where the alkali metal or radical is NH 4 , Na, K, Ag or Pb. Jarosites are typically formed at 90 to 150°C at a pH of 1.0 to 1.5.
- ferric-sulphate compounds precipitated is difficult to specify as many different species are possible and the factors which govern their formation are complex.
- trace elements such as bismuth or tellurium may be present in the concentrate being treated. While some of these trace elements will report to the leach residue or waste precipitation residues, some may build up in solution and have to be bled-off. When trace elements are present in sufficient concentration, their recovery may be warranted.
- Another possible process for a concentrate that is primarily arsenopyrite is a decomposition step with recycled nitric acid solution containing soluble calcium, using oxygen for regeneration. After leaching, the solution is cooled to precipitate calcium sulphate and a solid-liquid separation is made. The liquid is heated to precipitate ferric arsenate and another solid-liquid separation is made to give a solution to which calcium carbonate is added before reuse.
- one possible process is a decomposition step with a recycled solution, nitric oxide gas and oxygen being used for regeneration. This is followed by another decomposition step without oxygen to convert all the nitrogen oxides to nitric oxide, which is bled off.
- a solid-liquid separation produces a residue for gold treatment. Calcium carbonate is added to the liquid which is then heated to a high temperature to precipitate ferric arsenate, calcium sulphate and hematite. Another solids-liquid separation provides liquid for decomposition.
- the decomposition was rapid and complete.
- Example 2 A test was conducted to demonstrate the decomposition of a pyrite-rich concentrate (as in Example 2) using a ferric nitrate and sulphuric acid solution. This example simulates a decomposition using the product solution from Example 6.
- Example 1 A test was performed to demonstrate the decomposition of an arsenopyrite concentrate (as in Example 1) using nitric oxide gas. Oxygen was added to regenerate the active nitrogen oxides. The nitric oxide gas was produced by the reaction of arsenopyrite with nitric acid as in Example 1.
- a pyrite-rich concentrate can be reacted in a similar manner.
- the decomposition step was the same as for Example 2 using a nitric acid solution and oxygen for regeneration.
- the decomposition step was carried out with a nitric acid and calcium nitrate solution. After decomposition, the slurry was cooled to reduce the solubility of calcium sulphate.
- the decomposition step was as Example 6 using nitric acid solution and oxygen for regeneration.
- a second decomposition step was conducted as in Example 7 using the filtrate from above. Oxygen was not used.
- the solution from the precipitation stage could be reused by the addition of nitrogen oxides, for example, the addition of nitric acid or the addition of nitric oxide and oxygen.
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Claims (22)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US45884683A | 1983-01-18 | 1983-01-18 | |
US458846 | 1983-01-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0119685A1 EP0119685A1 (fr) | 1984-09-26 |
EP0119685B1 true EP0119685B1 (fr) | 1988-08-03 |
Family
ID=23822319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84300292A Expired EP0119685B1 (fr) | 1983-01-18 | 1984-01-18 | Procédé hydrométallurgique pour traiter des arsénopyrites |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0119685B1 (fr) |
AU (1) | AU566135B2 (fr) |
CA (1) | CA1219132A (fr) |
DE (1) | DE3473163D1 (fr) |
ZA (1) | ZA84153B (fr) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7915474B2 (en) | 2009-04-01 | 2011-03-29 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
US7951988B2 (en) | 2009-04-01 | 2011-05-31 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
US8115047B2 (en) | 2009-04-01 | 2012-02-14 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
US8168847B2 (en) | 2009-04-01 | 2012-05-01 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
US8481800B2 (en) | 2009-04-01 | 2013-07-09 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
RU2657254C1 (ru) * | 2017-07-21 | 2018-06-09 | Федеральное государственное унитарное предприятие "Горно-химический комбинат" (ФГУП "ГХК") | Способ извлечения золота из упорных серебросодержащих сульфидных руд концентратов и вторичного сырья |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3534224A1 (de) * | 1985-09-23 | 1987-04-02 | Gock Eberhard Priv Doz Prof Dr | Verfahren zur nasschemischen gewinnung von edelmetallen aus kohlenstoffhaltigen arsenopyritkonzentraten |
AU582961B2 (en) * | 1986-05-29 | 1989-04-13 | Sasox Processing Pty Ltd | Improved hydrometallurgical arsenopyriteprocess |
EP0272060A3 (fr) * | 1986-12-18 | 1990-08-01 | Electrolytic Zinc Company Of Australasia Limited | Récupération hydrométallurgique de métaux et de soufre élémentaire à partir de sulfures métalliques |
AU650802B2 (en) * | 1991-10-25 | 1994-06-30 | Sasox Processing Pty. Limited | Extraction or recovery of metal values |
ZA928157B (en) * | 1991-10-25 | 1993-06-09 | Sasox Processing Pty Ltd | Extraction or recovery of metal values. |
ATE144292T1 (de) * | 1993-01-27 | 1996-11-15 | R & O Mining Processing Ltd | Hydrometallurgisches verfahren zur gewinnung von metallen aus komplexenerzen |
BR9508598A (pt) * | 1994-08-15 | 1997-11-11 | R & O Mining Processing Ltd | Conversão hidrometalúrgica de sulfeto de zinco em sulfato a partir de minérios e concentrados contendo sulfeto de zinco |
RU2114196C1 (ru) * | 1995-09-19 | 1998-06-27 | Клиблей Генри Хадыевич | Способ гидрометаллургического извлечения редких металлов из технологически упорного сырья |
US9272936B2 (en) | 2009-04-01 | 2016-03-01 | Earth Renewal Group, Llc | Waste treatment process |
CN104263962B (zh) * | 2014-09-23 | 2016-08-17 | 铜仁市万山区盛和矿业有限责任公司 | 一种从磁黄铁矿中提取金的方法 |
CN104263963B (zh) * | 2014-09-23 | 2016-08-24 | 铜仁市万山区盛和矿业有限责任公司 | 一种从硫砷铁矿中提取金的方法 |
CN104263961B (zh) * | 2014-09-23 | 2016-03-30 | 铜仁市万山区盛和矿业有限责任公司 | 一种从黄铁矿中提取金的方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE744120C (de) * | 1938-01-25 | 1944-01-10 | Dr Aurel Bognar | Verfahren zur Verarbeitung von Erzen oder sonstigen Bergwerks- und Huettenerzeugnissen |
FR1058809A (fr) * | 1951-01-19 | 1954-03-19 | Chemical Construction Corp | Perfectionnements à la récupération de la teneur en métaux precieux des mineraiscontenant de l'arsenic et de leurs concentrats |
US2805936A (en) * | 1954-08-16 | 1957-09-10 | Felix A Schaufelberger | Leaching of arsenide ores |
US2805940A (en) * | 1954-08-20 | 1957-09-10 | Bennedsen Hans Oluf | Process for extracting cobalt and nickel from their ores |
US2951741A (en) * | 1955-08-05 | 1960-09-06 | Metallurg Resources Inc | Process for treating complex ores |
US3793429A (en) * | 1972-02-18 | 1974-02-19 | Kennecott Copper Corp | Nitric acid process for recovering metal values from sulfide ore materials containing iron sulfides |
-
1983
- 1983-12-20 CA CA000443728A patent/CA1219132A/fr not_active Expired
-
1984
- 1984-01-09 ZA ZA84153A patent/ZA84153B/xx unknown
- 1984-01-16 AU AU23515/84A patent/AU566135B2/en not_active Ceased
- 1984-01-18 EP EP84300292A patent/EP0119685B1/fr not_active Expired
- 1984-01-18 DE DE8484300292T patent/DE3473163D1/de not_active Expired
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7915474B2 (en) | 2009-04-01 | 2011-03-29 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
US7951988B2 (en) | 2009-04-01 | 2011-05-31 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
US8115047B2 (en) | 2009-04-01 | 2012-02-14 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
US8168847B2 (en) | 2009-04-01 | 2012-05-01 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
US8481800B2 (en) | 2009-04-01 | 2013-07-09 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
RU2657254C1 (ru) * | 2017-07-21 | 2018-06-09 | Федеральное государственное унитарное предприятие "Горно-химический комбинат" (ФГУП "ГХК") | Способ извлечения золота из упорных серебросодержащих сульфидных руд концентратов и вторичного сырья |
Also Published As
Publication number | Publication date |
---|---|
ZA84153B (en) | 1985-04-24 |
CA1219132A (fr) | 1987-03-17 |
AU566135B2 (en) | 1987-10-08 |
DE3473163D1 (en) | 1988-09-08 |
AU2351584A (en) | 1984-07-19 |
EP0119685A1 (fr) | 1984-09-26 |
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