CA2008063C - Hydrometallurgical leaching process and apparatus - Google Patents
Hydrometallurgical leaching process and apparatusInfo
- Publication number
- CA2008063C CA2008063C CA002008063A CA2008063A CA2008063C CA 2008063 C CA2008063 C CA 2008063C CA 002008063 A CA002008063 A CA 002008063A CA 2008063 A CA2008063 A CA 2008063A CA 2008063 C CA2008063 C CA 2008063C
- Authority
- CA
- Canada
- Prior art keywords
- column
- leaching
- zone
- ore
- oxygen
- 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
- 238000002386 leaching Methods 0.000 title claims abstract description 226
- 238000000034 method Methods 0.000 title claims abstract description 64
- 230000008569 process Effects 0.000 title claims abstract description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000001301 oxygen Substances 0.000 claims abstract description 134
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 134
- 239000002184 metal Substances 0.000 claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 claims abstract description 79
- 239000007788 liquid Substances 0.000 claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 50
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 21
- 239000011707 mineral Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 86
- 239000000243 solution Substances 0.000 claims description 58
- 239000000543 intermediate Substances 0.000 claims description 41
- 239000012530 fluid Substances 0.000 claims description 35
- 229910052770 Uranium Inorganic materials 0.000 claims description 17
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 17
- 230000001965 increasing effect Effects 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- 238000011144 upstream manufacturing Methods 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims description 9
- 230000005484 gravity Effects 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000010923 batch production Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 239000012633 leachable Substances 0.000 claims description 2
- 230000037452 priming Effects 0.000 claims description 2
- 230000002301 combined effect Effects 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000005352 clarification Methods 0.000 abstract description 47
- 238000013019 agitation Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 18
- 229910052737 gold Inorganic materials 0.000 description 18
- 239000010931 gold Substances 0.000 description 18
- 235000010755 mineral Nutrition 0.000 description 17
- 238000004090 dissolution Methods 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 229910000442 triuranium octoxide Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- -1 hydroxide ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005325 percolation Methods 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron 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
- 239000011133 lead Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052592 oxide mineral Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 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 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052964 arsenopyrite Inorganic materials 0.000 description 1
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052952 pyrrhotite Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YIIYNAOHYJJBHT-UHFFFAOYSA-N uranium;dihydrate Chemical compound O.O.[U] YIIYNAOHYJJBHT-UHFFFAOYSA-N 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A process and apparatus for leaching metal values from a particulate mineral ore containing metal values employs a fluidized bed of the particles; a leaching agent solution containing dissolved oxygen flows upwardly of the bed in a lower leaching zone, to an upper clarification zone; a velocity profile is maintained to promote settling of particles so that the particulate solids remain in the leaching zone and a clarified leachant-containing liquid low in suspended solids rises and collects in the clarifi-cation zone; the process is carried out with a minimum of undissolved gas and avoids the need for mechanical agitation, but the kinetics of the chemical leaching reaction is improved and heat loss via escaping gases is avoided.
Description
20080~3 . ~, This invention relates to the dissolution of metal values from ores, concentrates and calcines, particularly gold, uranium, copper, zinc, nickel and lead.
Hydrometallurgical processes involve the use of water or aqueous solutions into which metal values are leached from ore minerals, and then precipitated as metals after the solutions are suitably purified.
Gold is commonly found as a native metal associated with several sulphide minerals including pyrrhotite, arsenopyrite, pyrite and galena, in a matrix of gangue, generally quartz. A normal practice to dissolve gold is by cyanidation in the presence of oxygen at room temperature. The leaching equipment selection depends on the grade of the ore and the amenability of a particular process to gold leaching.
For gold grades greater than 5 g/ton, aerated leaching vessels are used, the most common designs being: air agitated Pachucas where the aeration serves the dual purposes of a source of dissolved oxygen and a source of undissolved stirring gas; and the combined air and mechanical agitators, which consist of tanks with a central tube open at the bottom through which com-pressed air is admitted, this central tube also serves as a shaft for two agitating arms, one at the top and one at the bottom.
Because sulphide minerals are partially soluble in cyanide solutions, consuming large amounts of oxygen and cyanide from the solution, the leaching rate of gold can be severely limited by lack of oxygen or cyanide; and consequently, a pre-treatment prior to cyanidation is required. The pre-treatment consists of an approximately 24 hours aeration period in which 20~QÇ~
-the ground ore, approximately 80% of which is less than 150 mesh, is mechanically agitated at about 50%
solids and at a pH of 10. Dissolved oxygen enhances the formation of a stable ferric hydroxide film on iron sulphide surfaces. As a consequence cyanide in the leaching step is mostly consumed for the dis-solution of gold. Sometimes, solution replacement is accomplished by dewatering and filtration in order to avoid the negative effect of foreign ions in the cyanidation step.
According to the theory of electrochemical leaching reactions for a given cyanide concentration the leaching rate of gold is controlled by the oxygen diffusion from the bulk to the surface. Many gold plants operate their cyanidation processes at cyanide concentrations which do not limit the gold leaching rate. This means that the rate could be increased by increasing the dissolved oxygen concentration.
The most important uranium ores are pitch-blende (U3O8) and uraninite (UO2) and both require an oxidizing agent for their leaching. As mined, pitch-blende has a grade range of 0.01 to 1% U3O8 but it can be concentrated by gravity methods to 50% U3O8, which concentrate is ground (80% minus lO0 mesh) and sent to the leaching circuit. Pachuca tanks or mechanical agitators using oxygen or other oxidizing agents such as MnO2, NaClO3 or NaNO3 are also commonly used.
In order to dissolve uranium ores it is necessary first to oxidize them to UO3 whereafter they can be leached with acid or alkaline solvents at a temperature of 90C.
~-_ 2~
In the case of copper oxide ores, for example, cuprite Cu2O, tenorite CuO, malachite CuCO3 and Cu(OH)2; and zinc oxide ores, for example, zincite ZnO, smithsonite ZnCO3 and zinc calcine, leaching is performed in the presence of an oxidizing agent usually air or oxygen. Oxidation is required to convert ferrous iron to ferric iron so that iron is precipitated as ferric hydroxide by the addition of hydroxide ions. Leaching is carried out in perco-lation, Pachuca or mechanically agitated tanks, either in batch or continuous operation. Table 1 shows some technical aspects for leaching oxide minerals.
Metal~ Grade~ Leaching Equipment Size TOmp.
Oxide % Agent Distribution C.
;
Cu2O 0.5-H SO Percolation 15mm to size 25 10.0(8u-9~g/1) or Pachuca 80%-150 mesh 25 approx.
ZnO 60 H SO Pachuca 80%-150 mesh 50-70 (as luOg~l or approx.
cal- agitation cine) tanks Table 1. Equipment Operating Conditions for Leaching of Oxide Minerals 20~0~
A sulphide raw material, which is considered submarginal for smelting can be treated by several hydrometallurgical processes to recover the metal value. In the presence of oxygen, sulphate or elemental sulphur is obtained depending on the temperature and pH. Oxidation converts insoluble Co, Ni and Cu sulphides to soluble sulphates, removing the iron as a precipitated ferric oxide. Autoclaves are used at 70-80C. under air pressure of 100 psi for 24 hours.
Typical analysis of an industrial operation is given in Table 2.
Concentrate Residue % %
Ni 10 - 14 0.6 - 1.4 Co 0.3 - 0.4 0.1 - 0.2 Cu l - 2 0.2 - 0.3 Fe 33 - 40 42 - 52 Table 2. Pressure Leaching of Sheritt-Gordon Sulphide Ore.
Another example of dissolution of sulphide ores in the presence of oxygen is leaching of pyrite-containing oxide ores, for example, uranium ores.
This reaction results in the formation of ferric ions and sulphuric acid which is utilized in leaching in uranium. The experimental conditions are a _5_ 2 0 ~ 0~
temperature of 160C using an autoclave at 0.5 to 1 atm. of oxygen pressure; after 6 hours uranium recovery is 90-95%.
Formation of elemental sulphur is produced in the aqueous oxidation of zinc sulphide at 110C
using dilute sulphuric acid and oxygen.
In order to produce elemental sulphur rather than sulphate, oxidation by free oxygen must be avoided, especially if pyrite is present because it gives practically no free sulphur when oxidized in aqueous solution. Thus a moderated oxidizing potential must be used, in the form of as ferric and cupric ions and nitric acid. Leaching of copper, specifically chalcopyrite Cu Fe S2, zinc, nickel and lead sulphides can be performed with these oxidants.
Many different leaching approaches have been used to treat the ores mentioned before. The approach depends on the ore mineralization, size and grade of the ore body, the liberation size and the cost of reagent at the site. The most frequently used pro-cedures being heap leaching, percolation leaching or some form of agitation leaching. In particular reference is made to agitation leaching in con-ventional tanks, namely, Dorr agitators, Pachucas and mechanical mixers.
The Dorr agitator consists of a central, hollow, air lift shaft with a rake at the bottom of the shaft. The whole system turns slowly. The rake moves any settled solids across the bottom of the tank to the central air lift, and the air distributes the pulp uniformly in the tank. The main advantages are the low power consumption and low maintenance.
--6- Z~8~6~
The Pachuca Tank is a large, conical bottomed tank up to about 16m total height and lOm diameter. Compressed air is jetted in at the tank bottom, agitating the slurry and keeping the ore particles suspended in the leach liquor. The nozzle size for the jets varies from 20 to 100 mm diameter, with 25 mm being very common. The major advantage is the simplicity; the air compressor maintenance which does not contact the acid solutions is simple. The main disadvantage is the heat lost to the atmosphere carried by the undissolved nitrogen and air which rises as wet gas bubbles.
The mechanical agitators use different kinds of impellers for particle suspension : the axial flow turbine, the radial flow turbine and the marine type propellor. Agitated tanks are usually baffled to prevent formation of a vortex. At about 50% solids, where hindered settling occurs, power requirements for slurry movement through the tank are reduced. Pulp solids composition in the tank may be different from that in the feed. For a continuous operation, feed and discharge must be identical.
The present invention relates to a process and apparatus for hydrometallurgical leaching of ores, concentrates and calcines, particularly in ground form. The invention seeks:
a) to enhance the kinetics of the process and recovery of metal values;
b) to avoid problems of material handling, during the operation and associated with the removal of exhausted or spent mineral;
~7~ 20080~3 c) to avoid or minimize intermediate solid-liquid separation units in multistage countercurrent leaching;
d) to improve the efficiency of oxygen utilization for a leaching process which requires oxygen as an oxidant; and e) to reduce energy cost.
Broadly described, this invention accomplishes these purposes by contacting a fluidized bed of the finely divided ore material with a leaching agent, typically comprising a solution made up of water and extracting chemicals, the leaching agent containing dissolved oxygen, while maintaining an effective leaching temperature.
In accordance with the invention a sub-stantial relative movement between the leaching solution and the ore particles is obtained by fluidi-zing the particles using the solution. As a con-sequence, the diffusion of reactants and products to or from the reaction surface increases and the kinetics of the reaction increase if the rate control step is mass transport of substances. The con-ventional leaching apparatus produces agitation of the entire solution including fine particles suspended therein.
- 7a - 2 ~ 3 In accordance with one aspect of the invention there is provided a process for recovering a metal from an ore containing the metal, which comprises:
a) forming a slurry, comprising an aqueous solution of particles of said metal-containing ore, leaching agent and dissolved oxygen, said particles of metal-containing ore, comprising a gradated range of unleached particles, partially-leached particles and leached particles, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air, b) priming a vertical column having a lower leaching zone and an upper clarifying zone with said slurry and maintaining a velocity profile in said column spanning said leaching and clarifying zones effective to maintain said unleached and partially leached particles fluidly suspended in said leaching zone and to promote settling of the leached particles from an upper region of said leaching zone such that said clarifying zone comprises an aqueous leachate having not more than 200 g/l of said particles, and c) withdrawing a metal-containing leachate from the clarifying zone.
In accordance with another aspect of the invention there is provided a process for recovering a metal from an ore containing said metal, comprising continuously passing a solution containing dissolved leaching agent and dissolved oxygen, countercurrent through a fluidized column of an aqueous slurry of the ore and metal while introducing the solution into the column at a velocity effective to maintain the bed in a fluidized condition, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is ~, J~f j Il,,' j ~_ _ - 7b - 2008063 dissolved therein, and being present therein in an amount which is greater than that supplied by air.
In accordance with still another aspect of the invention there is provided a process for recovering a metal from an ore containing said metal, comprising:
a) providing in a vertically elongated vessel, having a wall tapering outward, from a floor to an open mouth at the top, a fluid column made up of an aqueous dispersion of said ore, b) continuously feeding into a column an aqueous slurry of the ore as an inflow, c) forming a recycle stream by drawing from an upper part of the column an overflow, adding leaching agent to the recycle stream, dissolving oxygen in the recycle stream and recycling it to a lower part of the column, said oxygen for dissolving having a purity of at least 95%, the dissolved oxygen being present therein in an amount which is greater than that supplied by air, d) maintaining the column at a temperature and a concentration of leaching agent effective for leaching extraction, e) controlling the flow of the recycle stream into the fluid column at a velocity to maintain the bed fluidized and to maintain an upward flow of liquid in contact with the solids of the slurry, whereby a substantially clear liquid is separated from the solids to provide the overflow, f) withdrawing, from an intermediate height in the column, ore slurry which has been treated in the column as an outflow, g) coordinating the inflow and the outflow of the slurry with the inflow of the recycle stream to maintain the column at a predetermined depth, and - - 7c - 200~
h) causing an overflow of low suspended leached solids liquid from the top of the column containing leaching agent.
In accordance with yet another aspect of the invention there is provided a process for leaching a mineral from a mineral ore in a fluidized bed, which comprises passing a solution of a leaching agent and dissolved oxygen upwardly through a bed of the ore at a velocity sufficient to maintain the bed fluidized and recovering a metal-containing leachate from said bed, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air.
In still another aspect of the invention there is provided a process for countercurrent contact of fluids and solids wherein interaction occurs while the solids are exposed at least in part of the fluid, which comprises:
a) passing a flow of a solution containing leaching agent and dissolved oxygen upwardly through a bed of mineral ore having a leachable water soluble component in volume and at a velocity effective to provide a fluid bed surmounted by a supernatent body of a relatively clarified solution containing said water soluble component, b) recycling at least a portion of the relatively purified solution by drawing it from said supernatent body, dissolving oxygen in it and passing it into the bottom of said bed, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air, c) repeating the above steps one or more times until the ore bed is substantially spent, and - 7d - 2008063 d) recovering metal from the solution.
Still further, in accordance with the invention there is provided a process for recovering a metal from an ore containing the metal comprising:
providing a vertical column having a lower leaching zone and an upper clarifying zone, establishing an aqueous slurry of finely divided mineral ore particles in said leaching zone, said slurry comprising an aqueous solution of leaching agent and dissolved oxygen defining a fluid ,, -8- 2 O 08 O~
medium, and finely divided ore particles in said fluid medium, said particles comprising a gradated range of particles extending from dense, metal rich, unleached particles through less dense, partially leached metal containing particles to porous, metal poor, leached particles, maintaining a velocity profile in said column spanning said leaching and clarifying zones effective to maintain said unleached and partially leached particles fluidly suspended in said leaching zone and promote settling of said porous particles from an upper region of said leaching zone such that said clarifying zone comprises an aqueous leachate having not more than 200 mg/l of said particles, and withdrawing a metal pregnant leachate from said clarifying zone.
In another aspect the invention provides an apparatus for carrying out the process.
In this way the recovery of metal values due to the existence of particle elutriation in the fluidized bed is increased. In a multistage counter-current leaching, longer residence time for coarse particles within the column is achieved using an outlet at a certain height of the column in order to control a selective withdrawal of slurry with fine particles. The size distribution in the outlet can also be controlled by varying the ascending flow of liquid stream to obtain a new equilibrium of elutriation. In both cases the longer the residence time for coarse particles, the greater the prospect for dissolution of metal values. On the other hand, from the viewpoint of reagent concentration or solution strength, leaching is more effective for 2~ 0~
coarse particles, when inlet solution enters at the bottom of the column. Therefore recovery of metal values is increased by these two effects.
This invention particularly involves leach-ing minerals such as gold and uranium in the presence of oxygen; the injection of pure oxygen gas increases the dissolved oxygen (D.O.) content in the solution entering the tank. Due to the geometry of the system and the oxygen diffuser device as explained herein below, the efficiency of the oxygen dissolution is much better than with conventional equipment. In Pachuca tanks large amounts of air have to be used in order to suspend solids in the leach liquor, and maximum concentration is proportional to the oxygen partial pressure. In agitation tanks the efficiency of oxygen dissolution is mainly due to the oxygen diffuser design. In the present invention, the static pressure of the column produces a D.O. concentration gradient favoring the kinetics of dissolution at the bottom. On the other hand, due to the simplicity of the system, the top of the column can be sealed hermetically in order to increase the oxygen partial pressure and therefore the D.O.
The invention also seeks to provide a process and apparatus for the leaching of ores which is adaptable to either single stage or multiple stage operation.
Still further the invention seeks to provide a process and apparatus of the above character which also makes use of the leaching liquid injection to fluidize the slurry.
` ~----10- 2~ 0~
In one embodiment of the invention there is provided a multistage countercurrent leaching to transfer slurry directly from one column to another through outlets and inlets at a certain height of the columns. The slope of a transference pipe necessary to flow the slurry between the columns is a function of slurry characteristics and static pressure difference between columns. This gravity trans-portation avoids the use of slurry pump, storage tank and possible solid liquid separations. If the solution in a column needs to be removed, a set of valves can be opened and closed, injecting pure water at the bottom of the column; at the end, the mineral is clean to be mixed with a desired solution. It can occur at the end of preaeration step of gold cyani-dation process. Because in multistage countercurrent leaching the exhausted mineral is removed con-tinuously, the present apparatus does not need a special device for this operation. An auxiliary bottom outlet for slurry can be installed in one of the columns, for cleaning the circuit.
In a particular embodiment of a process and apparatus of the above character, the overflow from the top of each column or tower is essentially clear, by which is intended an average value of less than 200 mg/l, preferably less than 100 mg/l of suspended solid. In order to eliminate intermediate solid-liquid separation, the column presents a cross-sectional area greater at the top than the bottom.
The flow rate per unit area at the bottom is high enough to keep the solids in suspension; at the top of the tower or column flow is sufficiently low that solids settle out and a clear overflow is obtained.
20~Q6~
This condition is achieved by control of the flow at the bottom and top of the column, and this is more especially achieved by the geometry of the column.
In a further embodiment of a single stage or multistage operation the amount of clarified solution in the recycling stream is controlled as overflow for the next column. A valve installed in the recycle line provides the optimum flow according to the residence time in the column and the specific characteristics of leachate and mineral.
In still a further embodiment of the process and apparatus for leaching, an oxygen diffuser device improves the efficiency of oxygen utilization increas-ing the kinetic efficiency and recovery of metal values in gold and uranium ore. Such a device is described in U.S. Patent 4,246,111 (1981) to Canadian Liquid Air Ltd./Air Liquide Canada Ltée.
By means of the hydrometallurgical process and apparatus of the present invention it is possible to minimize capital costs for the leaching equipment and operating costs, and to avoid solid-liquid separation as an intermediate step in the columns.
The invention also provides an improved hydrometallurgical process and apparatus which elimin-ates the need for direct mechanical agitation such as by means of rake arms or impellers.
By means of this invention it is possible to save energy for a leaching process at high temperature using a liquid phase as a fluidizing medium, and to avoid the use of air as in Pachucas, in which most of the air leaves the process and carries large quantities of heat with it. Hence there is an economy -12- 20~
to be gained by eliminating air; the heat lost to atmosphere is saved plus also the energy required to generate compressed air.
In an embodiment of the process and apparatus of the above character, use is made of steam injection or a heating device outside the reactor to achieve an effective leaching temperature. In both cases the heating power is controlled thermostatically by conventional means.
In another embodiment of the invention there is provided a flexible process and apparatus in which the feed material can be fresh ore, concentrate or calcine or can be the product of other metallurgical operations. For example, gold ores containing uranium or copper sulphide are first processed for gold extraction by flotation, then the tail is leached for the two metals in succession. Due to the flexibility of this apparatus in multistage countercurrent leach-ing, the first columns are used to dissolve one metal and the slurry containing the exhausted ore for this metal is leached in the next columns for the remaining metal. Pregnant solutions for each one can be sent to purification/precipitation steps by switching certain valves in the circuit.
In accordance with the invention the dis-solved metal values can be recovered in the recirculation line between the top and bottom of the column. In the specific case of gold a carbon-in-leach process can be performed in the recirculation line by simply installing a recovery bed screen with activated carbon within it in the line. Such a procedure has the advantage that the concentration of leached metal values in the column is maintained low `- 20~)6~
by removal of the leached metal values from the clarified liquid exiting the column before the clarified liquid is reintroduced at the bottom of the column. This shifts the equilibrium in the column in favour of leaching.
It is also possible, in accordance with this invention, to provide an apparatus in which high pressure leaching can be performed in a batch operation. Because liquid injection is used in this apparatus instead of air, the system becomes isolated from the environment simply covering hermetically the clarification zone at the top of the column. This alternative can be applied for leaching of Au, U and sulphide ores which require high oxygen pressure to increase the reaction kinetics.
In accordance with preferred embodiments of the invention a two zone tower is used for the leach-ing process in place of conventional tanks. The tower consists of a tapered cylindrical vessel, with a small diameter at the bottom and larger diameter at the top.
An externally located pump draws clarified liquid flow from the top of the tower, pumps it through an oxygen dissolving device and returns it as a recycled stream to the bottom.
The flow of liquid upwardly in the tower maintains the solids in suspension, as well as trans-ferring oxygen to the solids for the oxidation extraction.
At the bottom of the tower the flow rate per unit of cross-sectional area is maintained high enough to keep the solids in suspension. At the top of the Z0~806~
tower the flow rate is low, so that solids settle out and a clear overflow for recycling through to the pump is obtained.
The ore slurry is added about one third of the tower height from the top and spent ore slurry is removed about one third of the tower height from the bottom.
Leaching agent is added at the bottom of the tower by way of the recycled stream from the top, through the suction of the pump, and is removed at the top.
In the prior art Pachucas, solids build-up occurs on the wall of the vessel, especially in the conical shaped lower portion. This problem can be overcome in the two-zone tower by installing a slow revolving rake that just touches the walls of the tower, suitably the rake may revolve at 1-5 revs./hour.
The process may be carried out batchwise as follows. First the tower is primed by adding to it a charge comprising a slurry of finely divided ore to be leached, or, if several towers are employed, in series, they are all primed in this way.
A leaching agent, for example, in the form of a solution of leaching chemical, is passed into a lower part of the tower, and upwardly through the charge of finely divided ore at a velocity effective to maintain a fluidized bed, leachate is drawn off from an upper zone in the tower and passed through an oxygen dissolving device and recycled into the lower zone of the tower. Pregnant leachate containing the metal values is also drawn off continually until the ore is spent.
-15- ZO ~ 0~
The process is p~eferably carried out with a series of interconnected towers. In this procedure, a fresh leaching chemical is passed into a lower zone of an end tower. Leachate containing residual leaching agent is drawn off, oxygen dissolved in it, and the oxygenated leachate passed back to the lower part of the tower. At the same time, leachate containing residual leaching agent is passed from the end tower to the recycle stream of an intermediate tower, where oxygen is dissolved in it and the resulting stream passed into the bottom zone of the intermediate tower and leachate containing residual leaching agent drawn off from the top of the intermediate tower and passed to the recycle stream of further tower where oxygen is dissolved in it and the oxygen-containing solution passed into a bottom zone of the further tower. In this procedure, when the ore in the end tower is spent, the ore in the intermediate tower becomes spent, the ore in the further tower semi-spent, and the end tower is filled with fresh ore and so on.
The leaching may also be performed in a continuous process in a series of leaching towers, each of which is preferably a vertically elongated vessel having a sidewall defining a vertical treating chamber whose cross-sectional area is greater at the top than at the bottom.
In this arrangement there is an initial tower which has a bottom inlet for fresh ore slurry and an overflow outlet for a final solution of leachate.
2~0~i~
A final tower has a bottom outlet for exhausted ore slurry and a first overflow outlet for a solution of leachate and residual leaching agent to be passed to the preceding tower.
The intermediate towers each have a bottom inlet for recycled solution containing leachate residual leaching agent and dissolved oxygen. The intermediate towers also have a first overflow outlet for leachate and residual leaching agent to be passed to the preceding tower.
Each tower has a recycle system including a line leading from a second overflow outlet for its own leachate, joined by a line for supplementing it, in the case of the end tower, with fresh leaching agent, and in the case of the other towers for supplementing it with overflow solution from the succeeding tower.
If it is necessary, the supplemented solution in the recycle system of each tower is passed through an oxygen-dissolving device and the resulting oxygen-containing solution is passed into the bottom inlet of that tower.
An ore slurry outlet, at an intermediate level, in the initial tower is connected to an ore slurry inlet at a lower level in the adjacent inter-mediate tower, and an ore slurry inlet in the end tower is connected to an ore slurry outlet at a higher level in the adjacent intermediate tower.
A process, according to the invention, employing a series of towers, as described, proceeds as follows, using leaching uranium ore as an example.
First the towers are primed with a charge of slurry.
-17- ~ ~8Q~3 Untreated uranium ore is then fed con-tinuously to the slurry inlet of the initial tower and leached slurry solution is continuously removed from the slurry outlet of the final tower.
Fresh leaching agent, for example, sulfuric acid, is introduced into the system in the end tower along with overflow solution from the tower made up of leaching agent containing a leachate of dissolved uranium and discharged from the overflow at the top of the end tower.
Clarified overflow is recycled in each tower, through the oxygen dissolving device and injected into the bottom of the tower. In the case of the end tower, the recycle overflow solution is supplemented by fresh leaching agent. In the case of the other towers, the recycle solution is supplemented by overflow solution from the succeeding tower.
In this way the solution of leaching agent, containing dissolved oxygen is passed countercurrent to the ore in the successive towers starting with the end tower.
In the case of either the batch or con-tinuous process, the flow rate of liquid in the bottom of each tower is adjusted to fluidize the charge, that is, to maintain the solids in suspension. The upward velocity of the flow is adjusted to balance the tendency of the solid particles to settle under gravity.
Steam is injected into each tower or a heating device controlled by conventional means, preheats the solution to maintain a desired leaching temperature. In the case of uranium, this is suitably in the range of 50C to 100C; in the case of gold -18- 2~ 6~
leaching by cyanidation is generally performed at room temperature. The concentration of the leaching agent, for example, sulfuric acid in the case of uranium, is adjusted in conjunctlon with the temperature, to maintain an efficient leaching solution. The residence time of the ore in the towers is maintained by adjusting the flow rate of the untreated ore to keep pace with the removal rate of the treated ore, whereby the overflow is a substantially clear liquor substantially free of separated solids.
The overflow from the top of each tower is essentially clear having a suspended solids content preferably not more than about 100 mg/l. This condition is achieved by control of the flow rate at the top of the column in the clarifying zone.
Maintaining a low concentration of solids makes recycling possible with minimum damage to the pump.
Slurry is very hard on pumps because of the abrasive nature of the ore particles and the process becomes unworkable if the content of suspended solids in the overflow rises beyond predetermined limits.
The oxidant is pure oxygen, more especially at least 95% oxygen according to standard measurements instead of air. This has the advantage of increasing the amount of dissolved oxidant contained in the solution, eliminates the cost of providing compressed air and eliminates the heat lost in the ballast nitrogen. An increased leaching rate is achieved by the increase of the oxidant in the solution and the countercurrent contact between the solids and the leaching agents in the leaching solution.
-19- ZOG~iQ~
It is also important that the oxygen be thoroughly dissolved, for example, by the use of an oxygen-dissolving device as disclosed in U.S. Patent 4,246,111 (1981) to Canadian Liquid Air Ltd./Air Liquide Canada Ltée, assignee of Guy Savard et al.
This Patent describes means for the efficient dis-solution of oxygen in an aqueous medium.
Thus undissolved oxygen and undissolved gases such as nitrogen are avoided. Undissolved gases would rise through the column conveying or entraining solids and thus disturbing the desired clarification settling in the upper part of the tower. Additionally undissolved gases extract heat from the system.
The temperature of the fluidized column is controlled, for example, by the injection of steam into the bottom of the leaching towers or by preheat-ing the solution using a heating device. The temperature may thus be adjusted to the requirements of the particular ore under the conditions of the invention. The fluidization ensures a homogeneous system maximizing contact between dissolved oxygen, leaching agent and ore particles, while avoiding agitation of the ore particles so that the ore particles may settle under gravity.
As the ore particles are contacted with the leaching solution, they become porous as a result of extraction of metal values, and thus become less dense. By minimizing agitation of the system, while promoting contact of the particles with the leaching solution and dissolved oxygen by fluidization, dis-turbing influences on the clarification by settling are minimized.
-20- 20~
Having thus generally described the invention, it will be referred to in more detail by reference to the accompanying drawings in which:
FIG. 1 illustrates a leaching assembly employing a two-zone tower in accordance with the invention;
FIG. 2 illustrates a multi-tower assembly suitable for a batch process in which an ore slurry moves countercurrent to a solution of leaching chemical and dissolved oxygen;
FIG. 3 illustrates a multi-tower assembly suitable for a continuous process in which several towers are intercon-nected and provision is made for leaching chemical and oxygen to be circulated through the towers;
FIG. 4 illustrates graphically the relation-ship between the bed height and fluid velocity in the leaching and clarification zones for different suspended solids concentrations;
and FIG. 5 illustrates graphically the relation-ship between the fluid velocities in the leaching and clarification zones and the concentration of sus-pended solids in the overflow from the clarification zone for different suspended solids concentrations.
With further reference to Fig. 1, a leaching assembly 10 comprises a two-zone tower 12, a pump 14 and an oxygen dissolving device 16.
-21- 20~6~
Two-zone tower 12 has a fluid inlet 18 and a fluid outlet 20 connected by a recirculation line 22.
Recirculation line 22 includes an influent leach liquor line 24.
Tower 12 further includes an effluent leachate liquor line 26, an ore slurry inlet line 28 and a spent slurry outlet line 30.
Oxygen dissolving device 16 has an oxygen inlet line 32.
Tower 12 has a lower leaching zone 34 and an upper clarification zone 36, and an intermediate zone 35, defined by a tower wall 13. The tower wall 13 converges from top to bottom such that the cross-sectional area of the interior of the tower is greater in the clarification zone 36 than in the leaching zone 34, and additionally the cross-sectional area increases with increased height of tower 12 in the leaching zone 34, in the direction of the clarifi-cation zone 36, and with increased height in the clarification zone 36.
Optionally, line 22 has a pair of branch lines 21 and 23 with metal recovery beds 25 and 27 respectively. Branch line 21 has valves 33 and 37 and branch line 23 have valves 29 and 31. The branch lines 21 and 23 with beds 25 and 27 may be located upstream or downstream of pump 14 but are preferably upstream of oxygen dissolving device 16.
In operation of the leaching assembly 10 of Fig. 1, a slurry of fine ore particles is introduced into tower 12 through ore slurry inlet line 28 and an aqueous leach liquor is introduced into recirculation line 22 through influent line 24. The influent leach -22- 2~Q6~
liquor in recirculation line 22 is pumped by pump 14 along recirculation line 22 and through an oxygen dissolving device 16 and thence into the lower end of tower 12.
Oxygen is fed through oxygen inlet line 32 into oxygen dissolving device 16 which dissolves the oxygen in the aqueous leach liquor to form a leach liquor containing dissolved oxygen. The oxygen dissolving device 16 is operated so that the leach liquor is substantially saturated with oxygen to produce a high dissolved oxygen content, while avoid-ing or minimizing the presence of undissolved oxygen in the leach liquor.
The leach liquor containing dissolved oxygen is pumped into tower 12 by pump 14 at a rate such that the vertically upward flow rate of the liquid in tower 12 is high enough to maintain the fine ore particle solids in fluidized suspended state in the liquid.
The liquid in tower 12 comprises the vehicle of the ore slurry and the leach liquor.
In this way a fluidized suspension of ore particles in the liquid is established in leaching zone 34.
The vertical upward velocity of the liquid decreases with height in the leaching zone 34 as a result of the increasing cross-sectional area of the interior of tower 12 with height, so that more settling rate of the solids occurs with decrease in the liquid velocity whereby the concentration of solids in the leaching zone 34 diminishes with height and is low in the intermediate region 35 adjacent clarification zone 36.
-23- ZO~RQ~
Furthermore, the upward velocity of the liqud in clarification zone 36 decreases with height as a result of the increasing cross-sectional area of this portion of tower 12 with height; the fluid outlet and the effluent leachate liquor line 26 are located in upper regions of clarifying zone 36 in which residual suspended solids are at a minimum as a result of further settling of the less dense porous spent particles in clarification zone 36.
The tower wall 13 in intermediate zone 35 diverges rapidly upwardly in a relatively short height to effect an immediate, substantial reduction in upward velocity of the liquid and a consequent immediate substantial increase in settling of suspended solids, whereby a preliminary clarification is conducted in intermediate zone 35.
In particular the slurry of particles in the tower 12 is exposed to a vertically upward flow force and the vertically downward force consisting essentially of the force of gravity and is not subjected to any significant non-vertical forces or lateral forces. There will, however, be some non-vertical forces acting on the particles as a result of, for example, frictional forces between the flowing liquid and tower wall 13.
In this way there is established in the clarification zone 36, and especially in the upper region of zone 36, a leachate liquor of low suspended solids content. The leachate liquor comprises unused leach liquor, the vehicle of the ore slurry, leachate from the ore and unused dissolved oxygen.
`_ 20~2fQ~
A first portion of the leachate liquor in clarification zone 36 is withdrawn by pump 14 through fluid outlet 20 into recirculation line 22, while a second portion is withdrawn as effluent leachate through effluent leachate liquor line 26.
In the optional case in which recirculation line 22 contains branch lines 21 and 23, valves 29 and 31 are initially closed and valves 33 and 37 are open whereby the recycle stream of leachate liquor passes through recovery bed 25 and metal values in the leachate liquid are retained in bed 25. Thus the liquor re-entering tower 12 at fluid inlet 18 from line 22 is low in metal values so that a low concentration of leached metal values is established in tower 12 thereby favouring the leaching of metal values from the ore particles in tower 12.
Periodically the liquor in branch line 21 upstream and downstream of bed 25 is tested for metal values; when the bed is saturated with metal values, such that the metal value content of the liquor upstream and downstream of bed 25 remains substantially unchanged, valves 33 and 37 are closed and valves 29 and 31 are opened so that the leachate liquor flows through branch line 23 and recovery bed 27.
Metal values are then retained in bed 27 while the metal values held in bed 25 are recovered to regenerate the retaining or absorption capacity of bed 25; this may be achieved by flowing an appropriate liquid through bed 25, by means of a separate circuit (not shown) such liquid having the capacity to remove the metal values held in bed 25. When bed 27 is 20~Q6~
saturated, regenerated bed 25 may then be used to absorb metal values from the leachate while bed 27 is regenerated.
When the metal values comprise gold the beds 25 and 27 suitably comprise activated carbon; and when the metal values comprise uranium the beds 25 and 27 suitably comprise an ion exchange resin.
In this varient it is not necessary to recover metal values form the effluent liquor flowing from line 26.
With further reference to Fig. 2, there is shown a batch leaching assembly 110 having three leaching units 101, 102 and 103 and a recycle line 108.
Each of the leaching units 101, 102 and 103 comprises a leaching assembly similar to that of Fig.
1. For convenience the parts of these leaching units 101, 102 and 103 which correspond to the parts of the leaching assembly 10 of Fig. 1, are given identical numbers raised by 100 in the case of the unit 101, 200 in the case of the unit 102 and 300 in the case of the unit 103.
Thus the batch leaching assembly 110 of Fig.
2 more particularly includes three two-zone towers 112, 212 and 312 respectively, which towers are substantially identical and of the same form as tower 12 of Fig. 1 having a cross-sectional area greater at the top than the bottom defined by tower walls 113, 213 and 313, respectively. The towers 112, 212 and 312 are disposed in series with liquid lines leading to and between them as will be explained more fully in the following description.
_ 200~30~3 The leaching unit 101 comprises two-zone tower 112, a pump 114 and an oxygen dissolving device 116. Tower 112 has a fluid inlet 118 and a fluid outlet 120 interconnected by a recirculation line 122.
Unit 101 further includes an influent leach liquor line 124, an effluent leachate liquor line 126, an oxygen line 132 communicating with oxygen dissolving device 116, and an effluent discharge line 138 in communication with effluent leachate liquor line 126.
Tower 112 further includes an ore slurry inlet line 128 and an ore slurry outlet line 130 and defines a leaching zone 134 and a clarification zone 136. A valve 140 is disposed in influent leach liquor line 124; a valve 142 is disposed in effluent leachate liquor line 126 and a valve 144 is disposed in effluent discharge line 138.
Valves 342 are disposed in recycle line 108.
The units 102 and 103 have parts which correspond to those of the unit 101 and are similarly numbered but increased by a factor of 100 and 200 relative to those of the unit 101. Thus unit 102 has valves 240, 242 and 244, corresponding to valves 140, 142 and 144 of unit 101, whereas unit 103 has valves 340 and 344 corresponding to valves 140 and 144. Unit 103 has valves 342 performing the function of valves 142 and 242 of units 101 and 102, however, valves 342 are in recycle line 108.
The operation of the batch process employed with assembly 110 of Fig. 2 is described as follows:
20Q~306~
_ In starting up the towers 112, 212 and 312 are filled with a slurry of fine particle ore through their respective slurry inlet lines 128, 228 and 328, and are primed with an aqueous solution of leaching agent.
The process is conducted so that in a first stage a fluidized bed of suspended ore particles is established in tower 112 in leaching zone 134, acted on by fresh liquor leaching chemicals entering the bottom of tower 112 through inlet 118 from line 124.
Liquid in tower 112 passes upwardly through leaching zone 134 and leaching of the fine particles of ore occurs in leaching zone 134. The liquid passing upwardly including the resulting leachate flows upwardly into intermediate zone 135 and clarification zone 136 and exits through outlet 120 in clarification zone 136 into recirculation line 122 and is pumped by pump 114 through oxygen dissolving device 116 and thence to inlet 118 and back into tower 112.
A portion of the rising liquid containing leachate exits from clarification zone 136 through effluent leachate liquor line 126 and is pumped by pump 214 into tower 212 vla recirculation line 222, in which it receives fresh dissolved oxygen from oxygen dissolving device 216.
In like manner liquid flows upwardly through leaching zone 234 in tower 212 to establish a fluidized bed of ore, a portion is recycled from clarification zone 236 v1a recirculation line 222 and the balance flows through effluent leachate liquor line 226 into recirculation line 322 and is pumped zo~o~
by pump 314 into tower 312. Oxygen is dissolved in the liquid in recirculation line 322 by means of oxygen dissolving device 316.
At the end of this circuit the overflow of tower 312 is exhausted as a leachate pregnant in metal values through effluent discharge line 338 from where it is fed to a precipitation or electrowinning stage to recover the metal values from the leachate.
The flow rate of the liquid entering the tower 112 via fluid inlet 118 is such as to keep the ore particles suspended under fluidized conditions in leaching zone 134. This procedure is repeated in towers 212 and 312, to establish fluidized bed conditions, until the ore in each tower is spent.
Valves to be described hereinafter and which control the connections between the tower 112, 212 and 312, are manipulated, spent ore from the tower 112 is replenished with fresh ore and the procedure described with respect to tower 112 is carried out with tower 212 until the ore in tower 212 is spent, whereafter the procedure is carried out on tower 312 whereafter the cycle of treatment commences again with tower 112.
More specifically the batch leaching assembly 110 is operated as follows:
In a first stage valves 140 and 142 of unit 101; valve 242 of unit 102 and 344 of unit 102 are open; and valve 144 of unit 101; valves 240 and 244 of unit 102; and valves 340 and 342 of unit 103 are closed. Leaching solution is introduced into tower 112 through influent leach liquor line 124, liquid rising into clarification zone 136 exits through outlet 120 and is pumped by pump 114 along recir-- 200~30/6~
culation line 122 and into tower 112 via inlet 118.
During the process of recirculation via line 122, oxygen is dissolved in the recirculation fluid by oxygen dissolving device 116.
A clarified overflow containing leachate as well as unused leaching agent and dissolved oxygen leaves tower 112 through effluent line 126 and passes through open valve 142 to the recirculation line 222 of tower 212. The overflow in recirculation line 222 passes through oxygen dissolving device 216 wherein oxygen is dissolved in the overflow, and the overflow enters tower 212 via inlet line 218. The overflow rises in tower 212 in contact with the ore therein in leaching zone 234 and leaching of the ore occurs with residual leaching agent present in the overflow from tower 112, in conjunction with the fresh dissolved oxygen introduced by device 216. A portion of the liquid rising in tower 212 into the clarification zone 236 exists via fluid outlet 220 and is recycled through recirculation line 222 to fluid inlet 218. A
second portion of the liquid in clarification zone 236 exits tower 212 via effluent leachate liquor line 226 and flows through open valve 242 into the recir-culation line 322 of unit 103 and is pumped by pump 314 via oxygen dissolving device 316 and via fluid inlet 318 into tower 312. The liquid in tower 312 which comprises leachate from towers 112 and 212 together with residual leaching chemicals from tower 112 and fresh dissolved oxygen from oxygen dissolving device 316 effects leaching of the ore particles in leaching zone 334 of tower 312 and the resulting liquid in clarification zone 336 is partly recycled to 20~
inlet 318 via recirculation line 322 and partly is discharged through effluent discharge line 338. This continues until the ore in tower 112 is spent.
Thus in this first stage leaching is carried out primarily in tower 112 which is the only tower into which fresh leaching agent is fed, however, secondary leaching occurs successively in towers 212 and 312 as a result of unused leaching agent in the overflow from tower 112 and the fresh dissolved oxygen introduced by devices 216 and 316.
In a second stage, the spent ore in tower 112 is replaced with fresh ore. Valves 140 and 142;
244; and 340 and 344 are closed; and valves 144; 240 and 242; and 342 are open.
Fresh leach agent is added through influent leach liquor line 224 and inlet 218 to the bottom of tower 212. Liquid rises in tower 212 as described previously for tower 112, leaching occurs in the resulting fluidized bed and a rislng clarified liquid collects in clarification zone 236, which liquid comprises leachate, unused leaching agent and possibly unused dissolved oxygen. A portion of this liquid in clarification zone 236 passes through outlet 220 into recirculation line 222 and is pumped by pump 214 through oxygen dissolving device 216 and back into tower 212 via inlet 218. An overflow portion of the liquid in clarification zone 236 exits through effluent leachate liquor line 226 and enters recir-culation line 322 of unit 103. The liquid rises through the fluidized bed in leaching zone 334 of tower 312 to form a liquid containing leachate in clarification zone 336, and overflow from zone 336 exits tower 312 via effluent leachate liquor line 326 2~
and passes along recycle ,line 108 into recirculation line 122 of unit 101 and thence into tower 112 from which overflow in clarification zone 136 exits via effluent discharge line 138.
Thus in this second stage primary leaching occurs in tower 212 of unit 102 which is the only tower into which fresh leaching agent is added, however, secondary leaching occurs in towers 312 and 112 successively with leaching chemicals present in the discharge from tower 212. The second stage continues until the ore in tower 212 is spent.
In a third stage of the process, valves 140 and 144; 240 and 242; and 344 are closed and valves 142; 244; and 340 and 342 are open. Spent ore in tower 312 is replaced with fresh ore.
Fresh leaching chemical is added through influent leach liquid line 324 and inlet 318 into tower 312 in which a fluidized bed of the ore is established. Liquid rising into clarification zone 336 exits via outlet 320 into recirculation line 322 and is pumped by pump 314 through oxygen dissolving device 316 and back into tower 312 via inlet 318. An overflow of clarified liquid in clarification zone 336 exits via effluent leachate line 326 and flows into recycle line 108 to the recirculation line 122 of unit 101 from which it is pumped by pump 114 through oxygen dissolving device 116 into tower 112 via inlet 118.
Liquid rises in tower 112 and the overflow from clarification zone 136 exits via effluent leachate line 126 and thence into recirculation line 222 of unit 102 where it is pumped by pump 214 through oxygen dissolving device 216 into tower 212 via inlet 218.
Liquid rises in tower 212 and the overflow in clarifi-20~,Q~
cation zone 236 exits via effluent leachate liquorline 226 and is discharged via effluent discharge line 238. Thus in the third stage of the process leaching is carried out primarily in tower 312 which is the only tower into which fresh leaching agent is fed, however, secondary leaching occurs successively in towers 112 and 212 as a result of unused leaching agent in the overflow from tower 312 and the fresh dissolved oxygen introduced by devices 116 and 216.
It will be understood that in all three stages recirculation of liquid occurs from the clarification zones 136, 236 and 336, via recir-culation lines 112, 222 and 322, and thus recycling within the units 101, 102 and 103 occurs in the primary and secondary leaching operations in the first, second and third stages to enhance the efficiency.
With further reference to Fig. 3, a leaching installation for continuous leaching comprises a leaching assembly 410 having leaching units 401, 402 and 403.
The leaching units 401, 402 and 403 are similar in many respect to the leaching units 101, 102 and 103 of Fig. 2 and the leaching assembly 10 of Fig.
1. Parts of the leaching assembly 410 which are the same as or function in a manner similar to those of leaching assembly 110 of Fig. 2 are identified by similar integers raised to the 400, 500 and 600 series for units 401, 402 and 403 respectively.
Thus, leaching unit 401 comprises a two-zone tower 412, a pump 414 and a oxygen dissolving device 416.
20~0~
Two-zone tower 412 has a fluid inlet 418 and a fluid outlet 420 connected by a recirculation line 42Z.
Tower 412 further includes an effluent leachate discharge line 438, an ore slurry inlet line 428 and a slurry outlet line 430.
Oxygen dissolving device 416 has an oxygen inlet line 432.
Tower 412 has a leaching zone 434 and intermediate zone 435 and a clarification zone 436.
The tower 412 is of the same form as the tower 12 of Fig. 1 and the towers 112, 212 and 312 of Fig. 2.
Thus the tower 412 converges from top to bottom such that the cross-sectional area of the interior of the tower is greater in the clarification zone 436 than in the leaching zone 434 and additionally the cross-sectional area increases with increased height of tower 412 in the zones 434, 435 and 436.
Unit 402 is similar to unit 401 with effluent discharge line 538 communicating with recir-culation line 422 upstream of pump 414.
A gravitational flow line 442 interconnects slurry outlet 430 of tower 412 and slurry inlet 528 of tower 512.
Unit 403 is similar to units 401 and 402.
Effluent liquid discharge line 638 of unit 403 communicates with recirculation line 522 of unit 402 upstream of pump 514, and a gravitational flow line (not shown) interconnects slurry outlet 530 of tower 512 and slurry inlet 628 of tower 612.
Slurry outlet 630 of unit 403 communicates with a waste line 644.
20~18Q6`~
-An influent leach liquor line 624 communicates with recirculation line 622 upstream of pump 614.
The leaching unit 401, 402 and 403 are shown in sequence for carrying out a continuous process for recovering a metal value from a mineral ore.
Units 401 and 403 represent initial and final units respectively with unit 402 being an intermediate unit. There may be one intermediate unit 402 or several such intermediate units, or inter-mediate unit 402 may be dispensed with so that there are only units 401 and 403.
The general operation of leaching assembly 410 is similar to the operation described with respect to Figs. 1 and 2 except that liquor moves con-tinuously through the assembly 410 from a source connected to influent leach liquor line 624, sequentially through towers 612, 512 and 412, with final leachate being discharged through effluent leachate discharge line 438. Fine particle mineral ore, on the other hand, moves generally in counterflow to the liquor from a source into slurry inlet 428 and sequentially through towers 412, 512 and 612, with the spent ore slurry being discharged through waste line 644.
More especially an established continuous leaching operation in leaching assembly 410 functions as follows.
Fresh slurry of particulate mineral ore containing a metal value to be leached enters tower 412 through slurry inlet 428. Liquid comprising 2C~ )6~s leaching agent, dissolved oxygen and a leachate from towers 512 and 612 is introduced into tower 412 through inlet 418.
The flow of the liquid through inlet 418 and the slurry through slurry inlet 428 is controlled to establish a fluidized suspension of the mineral ore particles in leaching zone 434.
Leaching of the mineral ore occurs in leaching zone 434 and a clarified liquid or pool comprising leachates, unused leaching agents and dissolved oxygen collects in clarification zone 436.
A portion of the liquid in clarification zone 436 exits through outlet 420 into recirculation line 422 and is pumped by pump 414 through oxygen dissolving device 416 and back into tower 412. The leaching agent present in the liquid recycled from outlet 420 of tower 412 is supplemented by leachate from effluent discharge line 538 of tower 512.
An overflow portion of the liquid in clarification zone 436 is discharged as leachate through effluent discharge line 438 and passes to an appropriate treatment stage for recovery of metal values from the leachate.
Slurry outlet 430 is at an approximate midpoint of leaching zone 434 and delivers partly leached ore slurry from tower 412 through gravitational flow line 442 to slurry inlet 528 of tower 512.
The leaching operation in tower 512 is sub-stantially the same as that in tower 412 with recycl-ing of clarified liquid containing leachate and unused leaching agent through outlet 520 and recirculation line 522, the recycling liquid being supplemented by 2~Q6;~
leachate in effluent discharge line 638 from tower 612. The overflow liquid from clarification zone 536 is discharged through effluent leachate discharge line 538, the leachate being, as described above, dis-charged into recirculation line 422 upstream of pump 414.
The partly leached high solids slurry flows along line 442 by gravity from tower 412 to tower 512 and similarly flows by gravity through a similar line (not shown) from tower 512 to tower 612 through slurry outlet 530 of tower 512 and slurry inlet 628 of tower 612, respectively. The liquid rising in tower 612 into clarification zone 636 is recycled through recirculation line 622 and supplemented with fresh leaching agent via influent leach liquor line 624.
The overflow liquid of clarification zone 636 flows through effluent discharge line 638 into recirculation line 522 of tower 512.
In this way the leaching agent flows sequentially through towers 612, 512 and 412 and the ore slurry flows in countercurrent direction sequentially through towers 412, 512 and 612.
With further reference to Fig. 4 there is shown graphically the relationship between the height of the fluidised bed in the tower and the fluid velocity in the leaching and clarification zones for different concentrations of suspended solids. By reference to Fig. 4 it is possible to determine for a particular slurry concentration the velocity profile required in the leaching zone and the clarification zone and these parameters can be obtained by appropriate design of the tower, and in particular 2~Q~Q6~
-change in cross-sectional area of the tower with increase in height, in conjunction with the inlet flow rate of leaching liquor.
Similarly by reference to Fig. 5 the sus-pended solids in the overflow is identified for different velocity profiles in the leaching zone and clarifications zone, for different ore concentrations and based on such a plot appropriate velocity para-meters for a particular ore concentration can be determined to achieve clarified liquid of satisfactory low solids content.
Thus, based on the information in Figs. 4 and 5 appropriate design of the towers and the flow parameters can be developed to produce a clarified leachate of a desired low suspended solids content.
Hydrometallurgical processes involve the use of water or aqueous solutions into which metal values are leached from ore minerals, and then precipitated as metals after the solutions are suitably purified.
Gold is commonly found as a native metal associated with several sulphide minerals including pyrrhotite, arsenopyrite, pyrite and galena, in a matrix of gangue, generally quartz. A normal practice to dissolve gold is by cyanidation in the presence of oxygen at room temperature. The leaching equipment selection depends on the grade of the ore and the amenability of a particular process to gold leaching.
For gold grades greater than 5 g/ton, aerated leaching vessels are used, the most common designs being: air agitated Pachucas where the aeration serves the dual purposes of a source of dissolved oxygen and a source of undissolved stirring gas; and the combined air and mechanical agitators, which consist of tanks with a central tube open at the bottom through which com-pressed air is admitted, this central tube also serves as a shaft for two agitating arms, one at the top and one at the bottom.
Because sulphide minerals are partially soluble in cyanide solutions, consuming large amounts of oxygen and cyanide from the solution, the leaching rate of gold can be severely limited by lack of oxygen or cyanide; and consequently, a pre-treatment prior to cyanidation is required. The pre-treatment consists of an approximately 24 hours aeration period in which 20~QÇ~
-the ground ore, approximately 80% of which is less than 150 mesh, is mechanically agitated at about 50%
solids and at a pH of 10. Dissolved oxygen enhances the formation of a stable ferric hydroxide film on iron sulphide surfaces. As a consequence cyanide in the leaching step is mostly consumed for the dis-solution of gold. Sometimes, solution replacement is accomplished by dewatering and filtration in order to avoid the negative effect of foreign ions in the cyanidation step.
According to the theory of electrochemical leaching reactions for a given cyanide concentration the leaching rate of gold is controlled by the oxygen diffusion from the bulk to the surface. Many gold plants operate their cyanidation processes at cyanide concentrations which do not limit the gold leaching rate. This means that the rate could be increased by increasing the dissolved oxygen concentration.
The most important uranium ores are pitch-blende (U3O8) and uraninite (UO2) and both require an oxidizing agent for their leaching. As mined, pitch-blende has a grade range of 0.01 to 1% U3O8 but it can be concentrated by gravity methods to 50% U3O8, which concentrate is ground (80% minus lO0 mesh) and sent to the leaching circuit. Pachuca tanks or mechanical agitators using oxygen or other oxidizing agents such as MnO2, NaClO3 or NaNO3 are also commonly used.
In order to dissolve uranium ores it is necessary first to oxidize them to UO3 whereafter they can be leached with acid or alkaline solvents at a temperature of 90C.
~-_ 2~
In the case of copper oxide ores, for example, cuprite Cu2O, tenorite CuO, malachite CuCO3 and Cu(OH)2; and zinc oxide ores, for example, zincite ZnO, smithsonite ZnCO3 and zinc calcine, leaching is performed in the presence of an oxidizing agent usually air or oxygen. Oxidation is required to convert ferrous iron to ferric iron so that iron is precipitated as ferric hydroxide by the addition of hydroxide ions. Leaching is carried out in perco-lation, Pachuca or mechanically agitated tanks, either in batch or continuous operation. Table 1 shows some technical aspects for leaching oxide minerals.
Metal~ Grade~ Leaching Equipment Size TOmp.
Oxide % Agent Distribution C.
;
Cu2O 0.5-H SO Percolation 15mm to size 25 10.0(8u-9~g/1) or Pachuca 80%-150 mesh 25 approx.
ZnO 60 H SO Pachuca 80%-150 mesh 50-70 (as luOg~l or approx.
cal- agitation cine) tanks Table 1. Equipment Operating Conditions for Leaching of Oxide Minerals 20~0~
A sulphide raw material, which is considered submarginal for smelting can be treated by several hydrometallurgical processes to recover the metal value. In the presence of oxygen, sulphate or elemental sulphur is obtained depending on the temperature and pH. Oxidation converts insoluble Co, Ni and Cu sulphides to soluble sulphates, removing the iron as a precipitated ferric oxide. Autoclaves are used at 70-80C. under air pressure of 100 psi for 24 hours.
Typical analysis of an industrial operation is given in Table 2.
Concentrate Residue % %
Ni 10 - 14 0.6 - 1.4 Co 0.3 - 0.4 0.1 - 0.2 Cu l - 2 0.2 - 0.3 Fe 33 - 40 42 - 52 Table 2. Pressure Leaching of Sheritt-Gordon Sulphide Ore.
Another example of dissolution of sulphide ores in the presence of oxygen is leaching of pyrite-containing oxide ores, for example, uranium ores.
This reaction results in the formation of ferric ions and sulphuric acid which is utilized in leaching in uranium. The experimental conditions are a _5_ 2 0 ~ 0~
temperature of 160C using an autoclave at 0.5 to 1 atm. of oxygen pressure; after 6 hours uranium recovery is 90-95%.
Formation of elemental sulphur is produced in the aqueous oxidation of zinc sulphide at 110C
using dilute sulphuric acid and oxygen.
In order to produce elemental sulphur rather than sulphate, oxidation by free oxygen must be avoided, especially if pyrite is present because it gives practically no free sulphur when oxidized in aqueous solution. Thus a moderated oxidizing potential must be used, in the form of as ferric and cupric ions and nitric acid. Leaching of copper, specifically chalcopyrite Cu Fe S2, zinc, nickel and lead sulphides can be performed with these oxidants.
Many different leaching approaches have been used to treat the ores mentioned before. The approach depends on the ore mineralization, size and grade of the ore body, the liberation size and the cost of reagent at the site. The most frequently used pro-cedures being heap leaching, percolation leaching or some form of agitation leaching. In particular reference is made to agitation leaching in con-ventional tanks, namely, Dorr agitators, Pachucas and mechanical mixers.
The Dorr agitator consists of a central, hollow, air lift shaft with a rake at the bottom of the shaft. The whole system turns slowly. The rake moves any settled solids across the bottom of the tank to the central air lift, and the air distributes the pulp uniformly in the tank. The main advantages are the low power consumption and low maintenance.
--6- Z~8~6~
The Pachuca Tank is a large, conical bottomed tank up to about 16m total height and lOm diameter. Compressed air is jetted in at the tank bottom, agitating the slurry and keeping the ore particles suspended in the leach liquor. The nozzle size for the jets varies from 20 to 100 mm diameter, with 25 mm being very common. The major advantage is the simplicity; the air compressor maintenance which does not contact the acid solutions is simple. The main disadvantage is the heat lost to the atmosphere carried by the undissolved nitrogen and air which rises as wet gas bubbles.
The mechanical agitators use different kinds of impellers for particle suspension : the axial flow turbine, the radial flow turbine and the marine type propellor. Agitated tanks are usually baffled to prevent formation of a vortex. At about 50% solids, where hindered settling occurs, power requirements for slurry movement through the tank are reduced. Pulp solids composition in the tank may be different from that in the feed. For a continuous operation, feed and discharge must be identical.
The present invention relates to a process and apparatus for hydrometallurgical leaching of ores, concentrates and calcines, particularly in ground form. The invention seeks:
a) to enhance the kinetics of the process and recovery of metal values;
b) to avoid problems of material handling, during the operation and associated with the removal of exhausted or spent mineral;
~7~ 20080~3 c) to avoid or minimize intermediate solid-liquid separation units in multistage countercurrent leaching;
d) to improve the efficiency of oxygen utilization for a leaching process which requires oxygen as an oxidant; and e) to reduce energy cost.
Broadly described, this invention accomplishes these purposes by contacting a fluidized bed of the finely divided ore material with a leaching agent, typically comprising a solution made up of water and extracting chemicals, the leaching agent containing dissolved oxygen, while maintaining an effective leaching temperature.
In accordance with the invention a sub-stantial relative movement between the leaching solution and the ore particles is obtained by fluidi-zing the particles using the solution. As a con-sequence, the diffusion of reactants and products to or from the reaction surface increases and the kinetics of the reaction increase if the rate control step is mass transport of substances. The con-ventional leaching apparatus produces agitation of the entire solution including fine particles suspended therein.
- 7a - 2 ~ 3 In accordance with one aspect of the invention there is provided a process for recovering a metal from an ore containing the metal, which comprises:
a) forming a slurry, comprising an aqueous solution of particles of said metal-containing ore, leaching agent and dissolved oxygen, said particles of metal-containing ore, comprising a gradated range of unleached particles, partially-leached particles and leached particles, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air, b) priming a vertical column having a lower leaching zone and an upper clarifying zone with said slurry and maintaining a velocity profile in said column spanning said leaching and clarifying zones effective to maintain said unleached and partially leached particles fluidly suspended in said leaching zone and to promote settling of the leached particles from an upper region of said leaching zone such that said clarifying zone comprises an aqueous leachate having not more than 200 g/l of said particles, and c) withdrawing a metal-containing leachate from the clarifying zone.
In accordance with another aspect of the invention there is provided a process for recovering a metal from an ore containing said metal, comprising continuously passing a solution containing dissolved leaching agent and dissolved oxygen, countercurrent through a fluidized column of an aqueous slurry of the ore and metal while introducing the solution into the column at a velocity effective to maintain the bed in a fluidized condition, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is ~, J~f j Il,,' j ~_ _ - 7b - 2008063 dissolved therein, and being present therein in an amount which is greater than that supplied by air.
In accordance with still another aspect of the invention there is provided a process for recovering a metal from an ore containing said metal, comprising:
a) providing in a vertically elongated vessel, having a wall tapering outward, from a floor to an open mouth at the top, a fluid column made up of an aqueous dispersion of said ore, b) continuously feeding into a column an aqueous slurry of the ore as an inflow, c) forming a recycle stream by drawing from an upper part of the column an overflow, adding leaching agent to the recycle stream, dissolving oxygen in the recycle stream and recycling it to a lower part of the column, said oxygen for dissolving having a purity of at least 95%, the dissolved oxygen being present therein in an amount which is greater than that supplied by air, d) maintaining the column at a temperature and a concentration of leaching agent effective for leaching extraction, e) controlling the flow of the recycle stream into the fluid column at a velocity to maintain the bed fluidized and to maintain an upward flow of liquid in contact with the solids of the slurry, whereby a substantially clear liquid is separated from the solids to provide the overflow, f) withdrawing, from an intermediate height in the column, ore slurry which has been treated in the column as an outflow, g) coordinating the inflow and the outflow of the slurry with the inflow of the recycle stream to maintain the column at a predetermined depth, and - - 7c - 200~
h) causing an overflow of low suspended leached solids liquid from the top of the column containing leaching agent.
In accordance with yet another aspect of the invention there is provided a process for leaching a mineral from a mineral ore in a fluidized bed, which comprises passing a solution of a leaching agent and dissolved oxygen upwardly through a bed of the ore at a velocity sufficient to maintain the bed fluidized and recovering a metal-containing leachate from said bed, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air.
In still another aspect of the invention there is provided a process for countercurrent contact of fluids and solids wherein interaction occurs while the solids are exposed at least in part of the fluid, which comprises:
a) passing a flow of a solution containing leaching agent and dissolved oxygen upwardly through a bed of mineral ore having a leachable water soluble component in volume and at a velocity effective to provide a fluid bed surmounted by a supernatent body of a relatively clarified solution containing said water soluble component, b) recycling at least a portion of the relatively purified solution by drawing it from said supernatent body, dissolving oxygen in it and passing it into the bottom of said bed, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air, c) repeating the above steps one or more times until the ore bed is substantially spent, and - 7d - 2008063 d) recovering metal from the solution.
Still further, in accordance with the invention there is provided a process for recovering a metal from an ore containing the metal comprising:
providing a vertical column having a lower leaching zone and an upper clarifying zone, establishing an aqueous slurry of finely divided mineral ore particles in said leaching zone, said slurry comprising an aqueous solution of leaching agent and dissolved oxygen defining a fluid ,, -8- 2 O 08 O~
medium, and finely divided ore particles in said fluid medium, said particles comprising a gradated range of particles extending from dense, metal rich, unleached particles through less dense, partially leached metal containing particles to porous, metal poor, leached particles, maintaining a velocity profile in said column spanning said leaching and clarifying zones effective to maintain said unleached and partially leached particles fluidly suspended in said leaching zone and promote settling of said porous particles from an upper region of said leaching zone such that said clarifying zone comprises an aqueous leachate having not more than 200 mg/l of said particles, and withdrawing a metal pregnant leachate from said clarifying zone.
In another aspect the invention provides an apparatus for carrying out the process.
In this way the recovery of metal values due to the existence of particle elutriation in the fluidized bed is increased. In a multistage counter-current leaching, longer residence time for coarse particles within the column is achieved using an outlet at a certain height of the column in order to control a selective withdrawal of slurry with fine particles. The size distribution in the outlet can also be controlled by varying the ascending flow of liquid stream to obtain a new equilibrium of elutriation. In both cases the longer the residence time for coarse particles, the greater the prospect for dissolution of metal values. On the other hand, from the viewpoint of reagent concentration or solution strength, leaching is more effective for 2~ 0~
coarse particles, when inlet solution enters at the bottom of the column. Therefore recovery of metal values is increased by these two effects.
This invention particularly involves leach-ing minerals such as gold and uranium in the presence of oxygen; the injection of pure oxygen gas increases the dissolved oxygen (D.O.) content in the solution entering the tank. Due to the geometry of the system and the oxygen diffuser device as explained herein below, the efficiency of the oxygen dissolution is much better than with conventional equipment. In Pachuca tanks large amounts of air have to be used in order to suspend solids in the leach liquor, and maximum concentration is proportional to the oxygen partial pressure. In agitation tanks the efficiency of oxygen dissolution is mainly due to the oxygen diffuser design. In the present invention, the static pressure of the column produces a D.O. concentration gradient favoring the kinetics of dissolution at the bottom. On the other hand, due to the simplicity of the system, the top of the column can be sealed hermetically in order to increase the oxygen partial pressure and therefore the D.O.
The invention also seeks to provide a process and apparatus for the leaching of ores which is adaptable to either single stage or multiple stage operation.
Still further the invention seeks to provide a process and apparatus of the above character which also makes use of the leaching liquid injection to fluidize the slurry.
` ~----10- 2~ 0~
In one embodiment of the invention there is provided a multistage countercurrent leaching to transfer slurry directly from one column to another through outlets and inlets at a certain height of the columns. The slope of a transference pipe necessary to flow the slurry between the columns is a function of slurry characteristics and static pressure difference between columns. This gravity trans-portation avoids the use of slurry pump, storage tank and possible solid liquid separations. If the solution in a column needs to be removed, a set of valves can be opened and closed, injecting pure water at the bottom of the column; at the end, the mineral is clean to be mixed with a desired solution. It can occur at the end of preaeration step of gold cyani-dation process. Because in multistage countercurrent leaching the exhausted mineral is removed con-tinuously, the present apparatus does not need a special device for this operation. An auxiliary bottom outlet for slurry can be installed in one of the columns, for cleaning the circuit.
In a particular embodiment of a process and apparatus of the above character, the overflow from the top of each column or tower is essentially clear, by which is intended an average value of less than 200 mg/l, preferably less than 100 mg/l of suspended solid. In order to eliminate intermediate solid-liquid separation, the column presents a cross-sectional area greater at the top than the bottom.
The flow rate per unit area at the bottom is high enough to keep the solids in suspension; at the top of the tower or column flow is sufficiently low that solids settle out and a clear overflow is obtained.
20~Q6~
This condition is achieved by control of the flow at the bottom and top of the column, and this is more especially achieved by the geometry of the column.
In a further embodiment of a single stage or multistage operation the amount of clarified solution in the recycling stream is controlled as overflow for the next column. A valve installed in the recycle line provides the optimum flow according to the residence time in the column and the specific characteristics of leachate and mineral.
In still a further embodiment of the process and apparatus for leaching, an oxygen diffuser device improves the efficiency of oxygen utilization increas-ing the kinetic efficiency and recovery of metal values in gold and uranium ore. Such a device is described in U.S. Patent 4,246,111 (1981) to Canadian Liquid Air Ltd./Air Liquide Canada Ltée.
By means of the hydrometallurgical process and apparatus of the present invention it is possible to minimize capital costs for the leaching equipment and operating costs, and to avoid solid-liquid separation as an intermediate step in the columns.
The invention also provides an improved hydrometallurgical process and apparatus which elimin-ates the need for direct mechanical agitation such as by means of rake arms or impellers.
By means of this invention it is possible to save energy for a leaching process at high temperature using a liquid phase as a fluidizing medium, and to avoid the use of air as in Pachucas, in which most of the air leaves the process and carries large quantities of heat with it. Hence there is an economy -12- 20~
to be gained by eliminating air; the heat lost to atmosphere is saved plus also the energy required to generate compressed air.
In an embodiment of the process and apparatus of the above character, use is made of steam injection or a heating device outside the reactor to achieve an effective leaching temperature. In both cases the heating power is controlled thermostatically by conventional means.
In another embodiment of the invention there is provided a flexible process and apparatus in which the feed material can be fresh ore, concentrate or calcine or can be the product of other metallurgical operations. For example, gold ores containing uranium or copper sulphide are first processed for gold extraction by flotation, then the tail is leached for the two metals in succession. Due to the flexibility of this apparatus in multistage countercurrent leach-ing, the first columns are used to dissolve one metal and the slurry containing the exhausted ore for this metal is leached in the next columns for the remaining metal. Pregnant solutions for each one can be sent to purification/precipitation steps by switching certain valves in the circuit.
In accordance with the invention the dis-solved metal values can be recovered in the recirculation line between the top and bottom of the column. In the specific case of gold a carbon-in-leach process can be performed in the recirculation line by simply installing a recovery bed screen with activated carbon within it in the line. Such a procedure has the advantage that the concentration of leached metal values in the column is maintained low `- 20~)6~
by removal of the leached metal values from the clarified liquid exiting the column before the clarified liquid is reintroduced at the bottom of the column. This shifts the equilibrium in the column in favour of leaching.
It is also possible, in accordance with this invention, to provide an apparatus in which high pressure leaching can be performed in a batch operation. Because liquid injection is used in this apparatus instead of air, the system becomes isolated from the environment simply covering hermetically the clarification zone at the top of the column. This alternative can be applied for leaching of Au, U and sulphide ores which require high oxygen pressure to increase the reaction kinetics.
In accordance with preferred embodiments of the invention a two zone tower is used for the leach-ing process in place of conventional tanks. The tower consists of a tapered cylindrical vessel, with a small diameter at the bottom and larger diameter at the top.
An externally located pump draws clarified liquid flow from the top of the tower, pumps it through an oxygen dissolving device and returns it as a recycled stream to the bottom.
The flow of liquid upwardly in the tower maintains the solids in suspension, as well as trans-ferring oxygen to the solids for the oxidation extraction.
At the bottom of the tower the flow rate per unit of cross-sectional area is maintained high enough to keep the solids in suspension. At the top of the Z0~806~
tower the flow rate is low, so that solids settle out and a clear overflow for recycling through to the pump is obtained.
The ore slurry is added about one third of the tower height from the top and spent ore slurry is removed about one third of the tower height from the bottom.
Leaching agent is added at the bottom of the tower by way of the recycled stream from the top, through the suction of the pump, and is removed at the top.
In the prior art Pachucas, solids build-up occurs on the wall of the vessel, especially in the conical shaped lower portion. This problem can be overcome in the two-zone tower by installing a slow revolving rake that just touches the walls of the tower, suitably the rake may revolve at 1-5 revs./hour.
The process may be carried out batchwise as follows. First the tower is primed by adding to it a charge comprising a slurry of finely divided ore to be leached, or, if several towers are employed, in series, they are all primed in this way.
A leaching agent, for example, in the form of a solution of leaching chemical, is passed into a lower part of the tower, and upwardly through the charge of finely divided ore at a velocity effective to maintain a fluidized bed, leachate is drawn off from an upper zone in the tower and passed through an oxygen dissolving device and recycled into the lower zone of the tower. Pregnant leachate containing the metal values is also drawn off continually until the ore is spent.
-15- ZO ~ 0~
The process is p~eferably carried out with a series of interconnected towers. In this procedure, a fresh leaching chemical is passed into a lower zone of an end tower. Leachate containing residual leaching agent is drawn off, oxygen dissolved in it, and the oxygenated leachate passed back to the lower part of the tower. At the same time, leachate containing residual leaching agent is passed from the end tower to the recycle stream of an intermediate tower, where oxygen is dissolved in it and the resulting stream passed into the bottom zone of the intermediate tower and leachate containing residual leaching agent drawn off from the top of the intermediate tower and passed to the recycle stream of further tower where oxygen is dissolved in it and the oxygen-containing solution passed into a bottom zone of the further tower. In this procedure, when the ore in the end tower is spent, the ore in the intermediate tower becomes spent, the ore in the further tower semi-spent, and the end tower is filled with fresh ore and so on.
The leaching may also be performed in a continuous process in a series of leaching towers, each of which is preferably a vertically elongated vessel having a sidewall defining a vertical treating chamber whose cross-sectional area is greater at the top than at the bottom.
In this arrangement there is an initial tower which has a bottom inlet for fresh ore slurry and an overflow outlet for a final solution of leachate.
2~0~i~
A final tower has a bottom outlet for exhausted ore slurry and a first overflow outlet for a solution of leachate and residual leaching agent to be passed to the preceding tower.
The intermediate towers each have a bottom inlet for recycled solution containing leachate residual leaching agent and dissolved oxygen. The intermediate towers also have a first overflow outlet for leachate and residual leaching agent to be passed to the preceding tower.
Each tower has a recycle system including a line leading from a second overflow outlet for its own leachate, joined by a line for supplementing it, in the case of the end tower, with fresh leaching agent, and in the case of the other towers for supplementing it with overflow solution from the succeeding tower.
If it is necessary, the supplemented solution in the recycle system of each tower is passed through an oxygen-dissolving device and the resulting oxygen-containing solution is passed into the bottom inlet of that tower.
An ore slurry outlet, at an intermediate level, in the initial tower is connected to an ore slurry inlet at a lower level in the adjacent inter-mediate tower, and an ore slurry inlet in the end tower is connected to an ore slurry outlet at a higher level in the adjacent intermediate tower.
A process, according to the invention, employing a series of towers, as described, proceeds as follows, using leaching uranium ore as an example.
First the towers are primed with a charge of slurry.
-17- ~ ~8Q~3 Untreated uranium ore is then fed con-tinuously to the slurry inlet of the initial tower and leached slurry solution is continuously removed from the slurry outlet of the final tower.
Fresh leaching agent, for example, sulfuric acid, is introduced into the system in the end tower along with overflow solution from the tower made up of leaching agent containing a leachate of dissolved uranium and discharged from the overflow at the top of the end tower.
Clarified overflow is recycled in each tower, through the oxygen dissolving device and injected into the bottom of the tower. In the case of the end tower, the recycle overflow solution is supplemented by fresh leaching agent. In the case of the other towers, the recycle solution is supplemented by overflow solution from the succeeding tower.
In this way the solution of leaching agent, containing dissolved oxygen is passed countercurrent to the ore in the successive towers starting with the end tower.
In the case of either the batch or con-tinuous process, the flow rate of liquid in the bottom of each tower is adjusted to fluidize the charge, that is, to maintain the solids in suspension. The upward velocity of the flow is adjusted to balance the tendency of the solid particles to settle under gravity.
Steam is injected into each tower or a heating device controlled by conventional means, preheats the solution to maintain a desired leaching temperature. In the case of uranium, this is suitably in the range of 50C to 100C; in the case of gold -18- 2~ 6~
leaching by cyanidation is generally performed at room temperature. The concentration of the leaching agent, for example, sulfuric acid in the case of uranium, is adjusted in conjunctlon with the temperature, to maintain an efficient leaching solution. The residence time of the ore in the towers is maintained by adjusting the flow rate of the untreated ore to keep pace with the removal rate of the treated ore, whereby the overflow is a substantially clear liquor substantially free of separated solids.
The overflow from the top of each tower is essentially clear having a suspended solids content preferably not more than about 100 mg/l. This condition is achieved by control of the flow rate at the top of the column in the clarifying zone.
Maintaining a low concentration of solids makes recycling possible with minimum damage to the pump.
Slurry is very hard on pumps because of the abrasive nature of the ore particles and the process becomes unworkable if the content of suspended solids in the overflow rises beyond predetermined limits.
The oxidant is pure oxygen, more especially at least 95% oxygen according to standard measurements instead of air. This has the advantage of increasing the amount of dissolved oxidant contained in the solution, eliminates the cost of providing compressed air and eliminates the heat lost in the ballast nitrogen. An increased leaching rate is achieved by the increase of the oxidant in the solution and the countercurrent contact between the solids and the leaching agents in the leaching solution.
-19- ZOG~iQ~
It is also important that the oxygen be thoroughly dissolved, for example, by the use of an oxygen-dissolving device as disclosed in U.S. Patent 4,246,111 (1981) to Canadian Liquid Air Ltd./Air Liquide Canada Ltée, assignee of Guy Savard et al.
This Patent describes means for the efficient dis-solution of oxygen in an aqueous medium.
Thus undissolved oxygen and undissolved gases such as nitrogen are avoided. Undissolved gases would rise through the column conveying or entraining solids and thus disturbing the desired clarification settling in the upper part of the tower. Additionally undissolved gases extract heat from the system.
The temperature of the fluidized column is controlled, for example, by the injection of steam into the bottom of the leaching towers or by preheat-ing the solution using a heating device. The temperature may thus be adjusted to the requirements of the particular ore under the conditions of the invention. The fluidization ensures a homogeneous system maximizing contact between dissolved oxygen, leaching agent and ore particles, while avoiding agitation of the ore particles so that the ore particles may settle under gravity.
As the ore particles are contacted with the leaching solution, they become porous as a result of extraction of metal values, and thus become less dense. By minimizing agitation of the system, while promoting contact of the particles with the leaching solution and dissolved oxygen by fluidization, dis-turbing influences on the clarification by settling are minimized.
-20- 20~
Having thus generally described the invention, it will be referred to in more detail by reference to the accompanying drawings in which:
FIG. 1 illustrates a leaching assembly employing a two-zone tower in accordance with the invention;
FIG. 2 illustrates a multi-tower assembly suitable for a batch process in which an ore slurry moves countercurrent to a solution of leaching chemical and dissolved oxygen;
FIG. 3 illustrates a multi-tower assembly suitable for a continuous process in which several towers are intercon-nected and provision is made for leaching chemical and oxygen to be circulated through the towers;
FIG. 4 illustrates graphically the relation-ship between the bed height and fluid velocity in the leaching and clarification zones for different suspended solids concentrations;
and FIG. 5 illustrates graphically the relation-ship between the fluid velocities in the leaching and clarification zones and the concentration of sus-pended solids in the overflow from the clarification zone for different suspended solids concentrations.
With further reference to Fig. 1, a leaching assembly 10 comprises a two-zone tower 12, a pump 14 and an oxygen dissolving device 16.
-21- 20~6~
Two-zone tower 12 has a fluid inlet 18 and a fluid outlet 20 connected by a recirculation line 22.
Recirculation line 22 includes an influent leach liquor line 24.
Tower 12 further includes an effluent leachate liquor line 26, an ore slurry inlet line 28 and a spent slurry outlet line 30.
Oxygen dissolving device 16 has an oxygen inlet line 32.
Tower 12 has a lower leaching zone 34 and an upper clarification zone 36, and an intermediate zone 35, defined by a tower wall 13. The tower wall 13 converges from top to bottom such that the cross-sectional area of the interior of the tower is greater in the clarification zone 36 than in the leaching zone 34, and additionally the cross-sectional area increases with increased height of tower 12 in the leaching zone 34, in the direction of the clarifi-cation zone 36, and with increased height in the clarification zone 36.
Optionally, line 22 has a pair of branch lines 21 and 23 with metal recovery beds 25 and 27 respectively. Branch line 21 has valves 33 and 37 and branch line 23 have valves 29 and 31. The branch lines 21 and 23 with beds 25 and 27 may be located upstream or downstream of pump 14 but are preferably upstream of oxygen dissolving device 16.
In operation of the leaching assembly 10 of Fig. 1, a slurry of fine ore particles is introduced into tower 12 through ore slurry inlet line 28 and an aqueous leach liquor is introduced into recirculation line 22 through influent line 24. The influent leach -22- 2~Q6~
liquor in recirculation line 22 is pumped by pump 14 along recirculation line 22 and through an oxygen dissolving device 16 and thence into the lower end of tower 12.
Oxygen is fed through oxygen inlet line 32 into oxygen dissolving device 16 which dissolves the oxygen in the aqueous leach liquor to form a leach liquor containing dissolved oxygen. The oxygen dissolving device 16 is operated so that the leach liquor is substantially saturated with oxygen to produce a high dissolved oxygen content, while avoid-ing or minimizing the presence of undissolved oxygen in the leach liquor.
The leach liquor containing dissolved oxygen is pumped into tower 12 by pump 14 at a rate such that the vertically upward flow rate of the liquid in tower 12 is high enough to maintain the fine ore particle solids in fluidized suspended state in the liquid.
The liquid in tower 12 comprises the vehicle of the ore slurry and the leach liquor.
In this way a fluidized suspension of ore particles in the liquid is established in leaching zone 34.
The vertical upward velocity of the liquid decreases with height in the leaching zone 34 as a result of the increasing cross-sectional area of the interior of tower 12 with height, so that more settling rate of the solids occurs with decrease in the liquid velocity whereby the concentration of solids in the leaching zone 34 diminishes with height and is low in the intermediate region 35 adjacent clarification zone 36.
-23- ZO~RQ~
Furthermore, the upward velocity of the liqud in clarification zone 36 decreases with height as a result of the increasing cross-sectional area of this portion of tower 12 with height; the fluid outlet and the effluent leachate liquor line 26 are located in upper regions of clarifying zone 36 in which residual suspended solids are at a minimum as a result of further settling of the less dense porous spent particles in clarification zone 36.
The tower wall 13 in intermediate zone 35 diverges rapidly upwardly in a relatively short height to effect an immediate, substantial reduction in upward velocity of the liquid and a consequent immediate substantial increase in settling of suspended solids, whereby a preliminary clarification is conducted in intermediate zone 35.
In particular the slurry of particles in the tower 12 is exposed to a vertically upward flow force and the vertically downward force consisting essentially of the force of gravity and is not subjected to any significant non-vertical forces or lateral forces. There will, however, be some non-vertical forces acting on the particles as a result of, for example, frictional forces between the flowing liquid and tower wall 13.
In this way there is established in the clarification zone 36, and especially in the upper region of zone 36, a leachate liquor of low suspended solids content. The leachate liquor comprises unused leach liquor, the vehicle of the ore slurry, leachate from the ore and unused dissolved oxygen.
`_ 20~2fQ~
A first portion of the leachate liquor in clarification zone 36 is withdrawn by pump 14 through fluid outlet 20 into recirculation line 22, while a second portion is withdrawn as effluent leachate through effluent leachate liquor line 26.
In the optional case in which recirculation line 22 contains branch lines 21 and 23, valves 29 and 31 are initially closed and valves 33 and 37 are open whereby the recycle stream of leachate liquor passes through recovery bed 25 and metal values in the leachate liquid are retained in bed 25. Thus the liquor re-entering tower 12 at fluid inlet 18 from line 22 is low in metal values so that a low concentration of leached metal values is established in tower 12 thereby favouring the leaching of metal values from the ore particles in tower 12.
Periodically the liquor in branch line 21 upstream and downstream of bed 25 is tested for metal values; when the bed is saturated with metal values, such that the metal value content of the liquor upstream and downstream of bed 25 remains substantially unchanged, valves 33 and 37 are closed and valves 29 and 31 are opened so that the leachate liquor flows through branch line 23 and recovery bed 27.
Metal values are then retained in bed 27 while the metal values held in bed 25 are recovered to regenerate the retaining or absorption capacity of bed 25; this may be achieved by flowing an appropriate liquid through bed 25, by means of a separate circuit (not shown) such liquid having the capacity to remove the metal values held in bed 25. When bed 27 is 20~Q6~
saturated, regenerated bed 25 may then be used to absorb metal values from the leachate while bed 27 is regenerated.
When the metal values comprise gold the beds 25 and 27 suitably comprise activated carbon; and when the metal values comprise uranium the beds 25 and 27 suitably comprise an ion exchange resin.
In this varient it is not necessary to recover metal values form the effluent liquor flowing from line 26.
With further reference to Fig. 2, there is shown a batch leaching assembly 110 having three leaching units 101, 102 and 103 and a recycle line 108.
Each of the leaching units 101, 102 and 103 comprises a leaching assembly similar to that of Fig.
1. For convenience the parts of these leaching units 101, 102 and 103 which correspond to the parts of the leaching assembly 10 of Fig. 1, are given identical numbers raised by 100 in the case of the unit 101, 200 in the case of the unit 102 and 300 in the case of the unit 103.
Thus the batch leaching assembly 110 of Fig.
2 more particularly includes three two-zone towers 112, 212 and 312 respectively, which towers are substantially identical and of the same form as tower 12 of Fig. 1 having a cross-sectional area greater at the top than the bottom defined by tower walls 113, 213 and 313, respectively. The towers 112, 212 and 312 are disposed in series with liquid lines leading to and between them as will be explained more fully in the following description.
_ 200~30~3 The leaching unit 101 comprises two-zone tower 112, a pump 114 and an oxygen dissolving device 116. Tower 112 has a fluid inlet 118 and a fluid outlet 120 interconnected by a recirculation line 122.
Unit 101 further includes an influent leach liquor line 124, an effluent leachate liquor line 126, an oxygen line 132 communicating with oxygen dissolving device 116, and an effluent discharge line 138 in communication with effluent leachate liquor line 126.
Tower 112 further includes an ore slurry inlet line 128 and an ore slurry outlet line 130 and defines a leaching zone 134 and a clarification zone 136. A valve 140 is disposed in influent leach liquor line 124; a valve 142 is disposed in effluent leachate liquor line 126 and a valve 144 is disposed in effluent discharge line 138.
Valves 342 are disposed in recycle line 108.
The units 102 and 103 have parts which correspond to those of the unit 101 and are similarly numbered but increased by a factor of 100 and 200 relative to those of the unit 101. Thus unit 102 has valves 240, 242 and 244, corresponding to valves 140, 142 and 144 of unit 101, whereas unit 103 has valves 340 and 344 corresponding to valves 140 and 144. Unit 103 has valves 342 performing the function of valves 142 and 242 of units 101 and 102, however, valves 342 are in recycle line 108.
The operation of the batch process employed with assembly 110 of Fig. 2 is described as follows:
20Q~306~
_ In starting up the towers 112, 212 and 312 are filled with a slurry of fine particle ore through their respective slurry inlet lines 128, 228 and 328, and are primed with an aqueous solution of leaching agent.
The process is conducted so that in a first stage a fluidized bed of suspended ore particles is established in tower 112 in leaching zone 134, acted on by fresh liquor leaching chemicals entering the bottom of tower 112 through inlet 118 from line 124.
Liquid in tower 112 passes upwardly through leaching zone 134 and leaching of the fine particles of ore occurs in leaching zone 134. The liquid passing upwardly including the resulting leachate flows upwardly into intermediate zone 135 and clarification zone 136 and exits through outlet 120 in clarification zone 136 into recirculation line 122 and is pumped by pump 114 through oxygen dissolving device 116 and thence to inlet 118 and back into tower 112.
A portion of the rising liquid containing leachate exits from clarification zone 136 through effluent leachate liquor line 126 and is pumped by pump 214 into tower 212 vla recirculation line 222, in which it receives fresh dissolved oxygen from oxygen dissolving device 216.
In like manner liquid flows upwardly through leaching zone 234 in tower 212 to establish a fluidized bed of ore, a portion is recycled from clarification zone 236 v1a recirculation line 222 and the balance flows through effluent leachate liquor line 226 into recirculation line 322 and is pumped zo~o~
by pump 314 into tower 312. Oxygen is dissolved in the liquid in recirculation line 322 by means of oxygen dissolving device 316.
At the end of this circuit the overflow of tower 312 is exhausted as a leachate pregnant in metal values through effluent discharge line 338 from where it is fed to a precipitation or electrowinning stage to recover the metal values from the leachate.
The flow rate of the liquid entering the tower 112 via fluid inlet 118 is such as to keep the ore particles suspended under fluidized conditions in leaching zone 134. This procedure is repeated in towers 212 and 312, to establish fluidized bed conditions, until the ore in each tower is spent.
Valves to be described hereinafter and which control the connections between the tower 112, 212 and 312, are manipulated, spent ore from the tower 112 is replenished with fresh ore and the procedure described with respect to tower 112 is carried out with tower 212 until the ore in tower 212 is spent, whereafter the procedure is carried out on tower 312 whereafter the cycle of treatment commences again with tower 112.
More specifically the batch leaching assembly 110 is operated as follows:
In a first stage valves 140 and 142 of unit 101; valve 242 of unit 102 and 344 of unit 102 are open; and valve 144 of unit 101; valves 240 and 244 of unit 102; and valves 340 and 342 of unit 103 are closed. Leaching solution is introduced into tower 112 through influent leach liquor line 124, liquid rising into clarification zone 136 exits through outlet 120 and is pumped by pump 114 along recir-- 200~30/6~
culation line 122 and into tower 112 via inlet 118.
During the process of recirculation via line 122, oxygen is dissolved in the recirculation fluid by oxygen dissolving device 116.
A clarified overflow containing leachate as well as unused leaching agent and dissolved oxygen leaves tower 112 through effluent line 126 and passes through open valve 142 to the recirculation line 222 of tower 212. The overflow in recirculation line 222 passes through oxygen dissolving device 216 wherein oxygen is dissolved in the overflow, and the overflow enters tower 212 via inlet line 218. The overflow rises in tower 212 in contact with the ore therein in leaching zone 234 and leaching of the ore occurs with residual leaching agent present in the overflow from tower 112, in conjunction with the fresh dissolved oxygen introduced by device 216. A portion of the liquid rising in tower 212 into the clarification zone 236 exists via fluid outlet 220 and is recycled through recirculation line 222 to fluid inlet 218. A
second portion of the liquid in clarification zone 236 exits tower 212 via effluent leachate liquor line 226 and flows through open valve 242 into the recir-culation line 322 of unit 103 and is pumped by pump 314 via oxygen dissolving device 316 and via fluid inlet 318 into tower 312. The liquid in tower 312 which comprises leachate from towers 112 and 212 together with residual leaching chemicals from tower 112 and fresh dissolved oxygen from oxygen dissolving device 316 effects leaching of the ore particles in leaching zone 334 of tower 312 and the resulting liquid in clarification zone 336 is partly recycled to 20~
inlet 318 via recirculation line 322 and partly is discharged through effluent discharge line 338. This continues until the ore in tower 112 is spent.
Thus in this first stage leaching is carried out primarily in tower 112 which is the only tower into which fresh leaching agent is fed, however, secondary leaching occurs successively in towers 212 and 312 as a result of unused leaching agent in the overflow from tower 112 and the fresh dissolved oxygen introduced by devices 216 and 316.
In a second stage, the spent ore in tower 112 is replaced with fresh ore. Valves 140 and 142;
244; and 340 and 344 are closed; and valves 144; 240 and 242; and 342 are open.
Fresh leach agent is added through influent leach liquor line 224 and inlet 218 to the bottom of tower 212. Liquid rises in tower 212 as described previously for tower 112, leaching occurs in the resulting fluidized bed and a rislng clarified liquid collects in clarification zone 236, which liquid comprises leachate, unused leaching agent and possibly unused dissolved oxygen. A portion of this liquid in clarification zone 236 passes through outlet 220 into recirculation line 222 and is pumped by pump 214 through oxygen dissolving device 216 and back into tower 212 via inlet 218. An overflow portion of the liquid in clarification zone 236 exits through effluent leachate liquor line 226 and enters recir-culation line 322 of unit 103. The liquid rises through the fluidized bed in leaching zone 334 of tower 312 to form a liquid containing leachate in clarification zone 336, and overflow from zone 336 exits tower 312 via effluent leachate liquor line 326 2~
and passes along recycle ,line 108 into recirculation line 122 of unit 101 and thence into tower 112 from which overflow in clarification zone 136 exits via effluent discharge line 138.
Thus in this second stage primary leaching occurs in tower 212 of unit 102 which is the only tower into which fresh leaching agent is added, however, secondary leaching occurs in towers 312 and 112 successively with leaching chemicals present in the discharge from tower 212. The second stage continues until the ore in tower 212 is spent.
In a third stage of the process, valves 140 and 144; 240 and 242; and 344 are closed and valves 142; 244; and 340 and 342 are open. Spent ore in tower 312 is replaced with fresh ore.
Fresh leaching chemical is added through influent leach liquid line 324 and inlet 318 into tower 312 in which a fluidized bed of the ore is established. Liquid rising into clarification zone 336 exits via outlet 320 into recirculation line 322 and is pumped by pump 314 through oxygen dissolving device 316 and back into tower 312 via inlet 318. An overflow of clarified liquid in clarification zone 336 exits via effluent leachate line 326 and flows into recycle line 108 to the recirculation line 122 of unit 101 from which it is pumped by pump 114 through oxygen dissolving device 116 into tower 112 via inlet 118.
Liquid rises in tower 112 and the overflow from clarification zone 136 exits via effluent leachate line 126 and thence into recirculation line 222 of unit 102 where it is pumped by pump 214 through oxygen dissolving device 216 into tower 212 via inlet 218.
Liquid rises in tower 212 and the overflow in clarifi-20~,Q~
cation zone 236 exits via effluent leachate liquorline 226 and is discharged via effluent discharge line 238. Thus in the third stage of the process leaching is carried out primarily in tower 312 which is the only tower into which fresh leaching agent is fed, however, secondary leaching occurs successively in towers 112 and 212 as a result of unused leaching agent in the overflow from tower 312 and the fresh dissolved oxygen introduced by devices 116 and 216.
It will be understood that in all three stages recirculation of liquid occurs from the clarification zones 136, 236 and 336, via recir-culation lines 112, 222 and 322, and thus recycling within the units 101, 102 and 103 occurs in the primary and secondary leaching operations in the first, second and third stages to enhance the efficiency.
With further reference to Fig. 3, a leaching installation for continuous leaching comprises a leaching assembly 410 having leaching units 401, 402 and 403.
The leaching units 401, 402 and 403 are similar in many respect to the leaching units 101, 102 and 103 of Fig. 2 and the leaching assembly 10 of Fig.
1. Parts of the leaching assembly 410 which are the same as or function in a manner similar to those of leaching assembly 110 of Fig. 2 are identified by similar integers raised to the 400, 500 and 600 series for units 401, 402 and 403 respectively.
Thus, leaching unit 401 comprises a two-zone tower 412, a pump 414 and a oxygen dissolving device 416.
20~0~
Two-zone tower 412 has a fluid inlet 418 and a fluid outlet 420 connected by a recirculation line 42Z.
Tower 412 further includes an effluent leachate discharge line 438, an ore slurry inlet line 428 and a slurry outlet line 430.
Oxygen dissolving device 416 has an oxygen inlet line 432.
Tower 412 has a leaching zone 434 and intermediate zone 435 and a clarification zone 436.
The tower 412 is of the same form as the tower 12 of Fig. 1 and the towers 112, 212 and 312 of Fig. 2.
Thus the tower 412 converges from top to bottom such that the cross-sectional area of the interior of the tower is greater in the clarification zone 436 than in the leaching zone 434 and additionally the cross-sectional area increases with increased height of tower 412 in the zones 434, 435 and 436.
Unit 402 is similar to unit 401 with effluent discharge line 538 communicating with recir-culation line 422 upstream of pump 414.
A gravitational flow line 442 interconnects slurry outlet 430 of tower 412 and slurry inlet 528 of tower 512.
Unit 403 is similar to units 401 and 402.
Effluent liquid discharge line 638 of unit 403 communicates with recirculation line 522 of unit 402 upstream of pump 514, and a gravitational flow line (not shown) interconnects slurry outlet 530 of tower 512 and slurry inlet 628 of tower 612.
Slurry outlet 630 of unit 403 communicates with a waste line 644.
20~18Q6`~
-An influent leach liquor line 624 communicates with recirculation line 622 upstream of pump 614.
The leaching unit 401, 402 and 403 are shown in sequence for carrying out a continuous process for recovering a metal value from a mineral ore.
Units 401 and 403 represent initial and final units respectively with unit 402 being an intermediate unit. There may be one intermediate unit 402 or several such intermediate units, or inter-mediate unit 402 may be dispensed with so that there are only units 401 and 403.
The general operation of leaching assembly 410 is similar to the operation described with respect to Figs. 1 and 2 except that liquor moves con-tinuously through the assembly 410 from a source connected to influent leach liquor line 624, sequentially through towers 612, 512 and 412, with final leachate being discharged through effluent leachate discharge line 438. Fine particle mineral ore, on the other hand, moves generally in counterflow to the liquor from a source into slurry inlet 428 and sequentially through towers 412, 512 and 612, with the spent ore slurry being discharged through waste line 644.
More especially an established continuous leaching operation in leaching assembly 410 functions as follows.
Fresh slurry of particulate mineral ore containing a metal value to be leached enters tower 412 through slurry inlet 428. Liquid comprising 2C~ )6~s leaching agent, dissolved oxygen and a leachate from towers 512 and 612 is introduced into tower 412 through inlet 418.
The flow of the liquid through inlet 418 and the slurry through slurry inlet 428 is controlled to establish a fluidized suspension of the mineral ore particles in leaching zone 434.
Leaching of the mineral ore occurs in leaching zone 434 and a clarified liquid or pool comprising leachates, unused leaching agents and dissolved oxygen collects in clarification zone 436.
A portion of the liquid in clarification zone 436 exits through outlet 420 into recirculation line 422 and is pumped by pump 414 through oxygen dissolving device 416 and back into tower 412. The leaching agent present in the liquid recycled from outlet 420 of tower 412 is supplemented by leachate from effluent discharge line 538 of tower 512.
An overflow portion of the liquid in clarification zone 436 is discharged as leachate through effluent discharge line 438 and passes to an appropriate treatment stage for recovery of metal values from the leachate.
Slurry outlet 430 is at an approximate midpoint of leaching zone 434 and delivers partly leached ore slurry from tower 412 through gravitational flow line 442 to slurry inlet 528 of tower 512.
The leaching operation in tower 512 is sub-stantially the same as that in tower 412 with recycl-ing of clarified liquid containing leachate and unused leaching agent through outlet 520 and recirculation line 522, the recycling liquid being supplemented by 2~Q6;~
leachate in effluent discharge line 638 from tower 612. The overflow liquid from clarification zone 536 is discharged through effluent leachate discharge line 538, the leachate being, as described above, dis-charged into recirculation line 422 upstream of pump 414.
The partly leached high solids slurry flows along line 442 by gravity from tower 412 to tower 512 and similarly flows by gravity through a similar line (not shown) from tower 512 to tower 612 through slurry outlet 530 of tower 512 and slurry inlet 628 of tower 612, respectively. The liquid rising in tower 612 into clarification zone 636 is recycled through recirculation line 622 and supplemented with fresh leaching agent via influent leach liquor line 624.
The overflow liquid of clarification zone 636 flows through effluent discharge line 638 into recirculation line 522 of tower 512.
In this way the leaching agent flows sequentially through towers 612, 512 and 412 and the ore slurry flows in countercurrent direction sequentially through towers 412, 512 and 612.
With further reference to Fig. 4 there is shown graphically the relationship between the height of the fluidised bed in the tower and the fluid velocity in the leaching and clarification zones for different concentrations of suspended solids. By reference to Fig. 4 it is possible to determine for a particular slurry concentration the velocity profile required in the leaching zone and the clarification zone and these parameters can be obtained by appropriate design of the tower, and in particular 2~Q~Q6~
-change in cross-sectional area of the tower with increase in height, in conjunction with the inlet flow rate of leaching liquor.
Similarly by reference to Fig. 5 the sus-pended solids in the overflow is identified for different velocity profiles in the leaching zone and clarifications zone, for different ore concentrations and based on such a plot appropriate velocity para-meters for a particular ore concentration can be determined to achieve clarified liquid of satisfactory low solids content.
Thus, based on the information in Figs. 4 and 5 appropriate design of the towers and the flow parameters can be developed to produce a clarified leachate of a desired low suspended solids content.
Claims (25)
1. A process for recovering a metal from an ore containing the metal, which comprises:
a) forming a slurry, comprising an aqueous solution of particles of said metal-containing ore, leaching agent and dissolved oxygen, said particles of metal-containing ore, comprising a gradated range of unleached particles, partially-leached particles and leached particles, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air, b) priming a vertical column having a lower leaching zone and an upper clarifying zone with said slurry and maintaining a velocity profile in said column spanning said leaching and clarifying zones effective to maintain said unleached and partially leached particles fluidly suspended in said leaching zone and to promote settling of said leached particles from an upper region of said leaching zone such that said clarifying zone comprises an aqueous leachate having not more than 200 g/l of said particles, and c) withdrawing a metal-containing leachate from the clarifying zone.
a) forming a slurry, comprising an aqueous solution of particles of said metal-containing ore, leaching agent and dissolved oxygen, said particles of metal-containing ore, comprising a gradated range of unleached particles, partially-leached particles and leached particles, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air, b) priming a vertical column having a lower leaching zone and an upper clarifying zone with said slurry and maintaining a velocity profile in said column spanning said leaching and clarifying zones effective to maintain said unleached and partially leached particles fluidly suspended in said leaching zone and to promote settling of said leached particles from an upper region of said leaching zone such that said clarifying zone comprises an aqueous leachate having not more than 200 g/l of said particles, and c) withdrawing a metal-containing leachate from the clarifying zone.
2. A process according to claim 1, wherein said velocity profile is such that said clarifying zone comprises an aqueous leachate having not more than 100 mg/l of said particles.
3. A process according to claim 1 or 2, wherein said slurry is substantially free of undissolved gases.
4. A process according to claim 3, wherein said slurry is initially saturated with oxygen.
5. A process according to claim 1, 2 or 4, wherein said slurry is exposed to forces consisting essentially of a vertically upward flow force and the vertically downward force of gravity.
6. A process for recovering a metal from an ore containing said metal, comprising continuously passing a solution containing dissolved leaching agent and dissolved oxygen, countercurrent through a fluidized column of an aqueous slurry of the ore and metal while introducing the solution into the column at a velocity effective to maintain the bed in a fluidized condition, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air.
7. A process as defined in claim 6, in which the column increases in cross-section from a lower solution-introduction zone to an upper leachate recovery zone.
8. A process as defined in claim 6 or 7, which is a batch process.
9. A process as defined in claim 6 or 7, in which leachate is drawn off from an upper part of the column and combined with further dissolved oxygen and leaching chemical and introduced as a recycle stream into a lower part of the column.
10. A process as defined in claim 6, there being a plurality of fluidized columns in series, including an initial column and a final column and at least one intermediate fluidized column, and in which fresh ore is added to the initial column and passed, as partly leached ore, to the at least one intermediate column and thence to the final column where it is recovered as spent ore, fresh leaching chemical is added to a lower part of the final column in a solution containing dissolved oxygen, leachate containing leaching chemical being passed from a top zone in final column and into a lower part of an intermediate column, leachate containing leaching chemical being passed from a top zone in the intermediate column and passed into a lower part of the initial column, combined with a solution containing dissolved oxygen, and leachate being recovered from an upper zone in the initial column.
11. A process according to claim 10, wherein a portion of the leachate in the top zone of each of said initial, intermediate and final columns is returned to the lower part of the same column as part of the said solution containing dissolved oxygen.
12. A process according to claim 10, including:
combining the portion of the leachate from the top zone of said final column with said fresh leaching chemical to form a combined final stream, dissolving oxygen in said combined final stream and passing said combined final stream containing dis-solved oxygen into said lower part of said final column, combining the portion of leachate from the top zone of said intermediate column with said leachate passed from said top zone of said final column to form a combined intermediate stream, dis-solving oxygen in the combined intermediate stream and passing the combined intermediate stream containing dissolved oxygen into the lower part of the inter-mediate column, and combining the portion of leachate from the top zone of said initial column with said leachate passed from said top zone of said intermediate column to form a combined initial stream, dissolving oxygen in the combined initial stream and passing the com-bined initial stream containing dissolved oxygen into the lower part of the initial column.
combining the portion of the leachate from the top zone of said final column with said fresh leaching chemical to form a combined final stream, dissolving oxygen in said combined final stream and passing said combined final stream containing dis-solved oxygen into said lower part of said final column, combining the portion of leachate from the top zone of said intermediate column with said leachate passed from said top zone of said final column to form a combined intermediate stream, dis-solving oxygen in the combined intermediate stream and passing the combined intermediate stream containing dissolved oxygen into the lower part of the inter-mediate column, and combining the portion of leachate from the top zone of said initial column with said leachate passed from said top zone of said intermediate column to form a combined initial stream, dissolving oxygen in the combined initial stream and passing the com-bined initial stream containing dissolved oxygen into the lower part of the initial column.
13. A process for recovering a metal from an ore containing said metal, comprising:
a) providing in a vertically elongated vessel, having a wall tapering outward, from a floor to an open mouth at the top, a fluid column made up of an aqueous dispersion of said ore, b) continuously feeding into a column an aqueous slurry of the ore as an inflow, c) forming a recycle stream by drawing from an upper part of the column an overflow, adding leaching agent to the recycle stream, dissolving oxygen in the recycle stream and recycling it to a lower part of the column, said oxygen for dissolving having a purity of at least 95%, the dissolved oxygen being present therein in an amount which is greater than that supplied by air, d) maintaining the column at a temperature and a concentration of leaching agent effective for leaching extraction, e) controlling the flow of the recycle stream into the fluid column at a velocity to maintain the bed fluidized and to maintain an upward flow of liquid in contact with the solids of the slurry, whereby a substantially clear liquid is separated from the solids to provide the overflow, f) withdrawing, from an intermediate height in the column, ore slurry which has been treated in the column as an outflow, g) coordinating the inflow and the outflow of the slurry with the inflow of the recycle stream to maintain the column at a predetermined depth, and h) causing an overflow of low suspended leached solids liquid from the top of the column containing leaching agent.
a) providing in a vertically elongated vessel, having a wall tapering outward, from a floor to an open mouth at the top, a fluid column made up of an aqueous dispersion of said ore, b) continuously feeding into a column an aqueous slurry of the ore as an inflow, c) forming a recycle stream by drawing from an upper part of the column an overflow, adding leaching agent to the recycle stream, dissolving oxygen in the recycle stream and recycling it to a lower part of the column, said oxygen for dissolving having a purity of at least 95%, the dissolved oxygen being present therein in an amount which is greater than that supplied by air, d) maintaining the column at a temperature and a concentration of leaching agent effective for leaching extraction, e) controlling the flow of the recycle stream into the fluid column at a velocity to maintain the bed fluidized and to maintain an upward flow of liquid in contact with the solids of the slurry, whereby a substantially clear liquid is separated from the solids to provide the overflow, f) withdrawing, from an intermediate height in the column, ore slurry which has been treated in the column as an outflow, g) coordinating the inflow and the outflow of the slurry with the inflow of the recycle stream to maintain the column at a predetermined depth, and h) causing an overflow of low suspended leached solids liquid from the top of the column containing leaching agent.
14. A process as defined in claim 13, in which there is employed a plurality of said vertically elongated vessels in series, each provided with a fluid column, the vessels being made up of a first vessel, at least one intermediate vessel, and a terminal vessel, comprising the continuous steps in which:
raw ore slurry is fed to the first column, leached slurry is withdrawn from the terminal column, partially leached slurry is passed from the first column serially to the subsequent columns, fresh leaching chemical is provided to the recycle stream of the terminal column, the recycle stream of the intermediate and first columns receiving their supply of leaching chemical in low solids liquid overflowing from the succeeding column, the leaching chemical is discharged in the low solids overflow from the first column.
raw ore slurry is fed to the first column, leached slurry is withdrawn from the terminal column, partially leached slurry is passed from the first column serially to the subsequent columns, fresh leaching chemical is provided to the recycle stream of the terminal column, the recycle stream of the intermediate and first columns receiving their supply of leaching chemical in low solids liquid overflowing from the succeeding column, the leaching chemical is discharged in the low solids overflow from the first column.
15. A process as defined in claim 13 or 14, in which the ore contains uranium.
16. A process as defined in claim 13 or 14, in which the ore contains uranium and the leaching chemical comprises sulphuric acid.
17. A process for leaching a mineral from a mineral ore in a fluidized bed, which comprises passing a solution of a leaching agent and dissolved oxygen upwardly through a bed of the ore at a velocity sufficient to maintain the bed fluidized and recovering a metal-containing leachate from said bed, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air.
18. A process for countercurrent contact of fluids and solids wherein interaction occurs while the solids are exposed at least in part of the fluid, which comprises:
a) passing a flow of a solution containing leaching agent and dissolved oxygen upwardly through a bed of mineral ore having a leachable water soluble component in volume and at a velocity effective to provide a fluid bed surmounted by a supernatent body of a relatively clarified solution containing said water soluble component, b) recycling at least a portion of the relatively purified solution by drawing it from said supernatent body, dissolving oxygen in it and passing it into the bottom of said bed, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air, c) repeating the above steps one or more times until the ore bed is substantially spent, and d) recovering metal from the solution.
a) passing a flow of a solution containing leaching agent and dissolved oxygen upwardly through a bed of mineral ore having a leachable water soluble component in volume and at a velocity effective to provide a fluid bed surmounted by a supernatent body of a relatively clarified solution containing said water soluble component, b) recycling at least a portion of the relatively purified solution by drawing it from said supernatent body, dissolving oxygen in it and passing it into the bottom of said bed, said dissolved oxygen being supplied by oxygen gas of at least 95% purity which is dissolved therein, and being present therein in an amount which is greater than that supplied by air, c) repeating the above steps one or more times until the ore bed is substantially spent, and d) recovering metal from the solution.
19. A process according to claim 1, 2 or 4, comprising establishing a recycle stream of at least a portion of said aqueous leachate, said recycle stream exiting said column at said upper clarifying zone and re-entering said column at said lower leaching zone.
20. A process according to claim 3, comprising establishing a recycle stream of at least a portion of said aqueous leachate, said recycle stream exiting said column at said upper clarifying zone and re-entering said column at said lower leaching zone.
21. A process according to claim 19, comprising flowing said recycle stream though a metal recovery bed upstream of the re-entry of said column to remove metal from the recycle stream prior to re-entry into said column.
22. A process according to claim 20, comprising flowing said recycle stream though a metal recovery bed upstream of the re-entry of said column to remove metal from the recycle stream prior to re-entry into said column.
23. An apparatus for leaching metal from ore, comprising:
a vertical column having a lower leaching zone and an upper clarifying zone, an inlet in said leaching zone for ore slurry, an outlet in said leaching zone for spent slurry, a fluid inlet in said leaching zone, a fluid outlet in said clarifying zone, a recirculation line connecting said fluid inlet and fluid outlet, a pump in said recirculation line for pumping liquid in said line to said fluid inlet, an influent line for leaching agent communication with said recirculation line, and an oxygen dissolving device in said recirculation line downstream of said influent line, said column having a cross-section area increasing from said leaching zone to said clarifying zone effective in the establishment of a fluidized bed of ore particles in said leaching zone, and in the promotion of settling of particles in said column away from said clarifying zone.
a vertical column having a lower leaching zone and an upper clarifying zone, an inlet in said leaching zone for ore slurry, an outlet in said leaching zone for spent slurry, a fluid inlet in said leaching zone, a fluid outlet in said clarifying zone, a recirculation line connecting said fluid inlet and fluid outlet, a pump in said recirculation line for pumping liquid in said line to said fluid inlet, an influent line for leaching agent communication with said recirculation line, and an oxygen dissolving device in said recirculation line downstream of said influent line, said column having a cross-section area increasing from said leaching zone to said clarifying zone effective in the establishment of a fluidized bed of ore particles in said leaching zone, and in the promotion of settling of particles in said column away from said clarifying zone.
24. An apparatus for leaching a metal of an ore, comprising:
a system comprising a plurality of vessels, including an initial vessel, at least one intermediate vessel and a terminal vessel, arranged for downstream flow of leaching agent from said terminal vessel to said initial vessel via said at least one intermediate vessel;
each of said vessels being provided with a recycle line leading from an overflow zone to the bottom of the vessel, said recycle line including an inlet for leaching agent, and an oxygen dissolving device whereby a solution of leaching agent containing dissolved oxygen is introduced into the bottom of the vessel, each of the terminal and intermediate vessels being provided with an outlet line leading from an overflow zone to the recycle line of an adjacent downstream vessel, the initial vessel being provided with an outlet line leading from an overflow zone to leave the system, the terminal vessel having at its bottom an ore slurry outlet, the initial vessel having at its bottom an ore slurry inlet, the initial and intermediate vessels each having an ore slurry line leading from a mid-zone in the slurry for a mid-zone in the slurry of the adjacent upstream vessel.
a system comprising a plurality of vessels, including an initial vessel, at least one intermediate vessel and a terminal vessel, arranged for downstream flow of leaching agent from said terminal vessel to said initial vessel via said at least one intermediate vessel;
each of said vessels being provided with a recycle line leading from an overflow zone to the bottom of the vessel, said recycle line including an inlet for leaching agent, and an oxygen dissolving device whereby a solution of leaching agent containing dissolved oxygen is introduced into the bottom of the vessel, each of the terminal and intermediate vessels being provided with an outlet line leading from an overflow zone to the recycle line of an adjacent downstream vessel, the initial vessel being provided with an outlet line leading from an overflow zone to leave the system, the terminal vessel having at its bottom an ore slurry outlet, the initial vessel having at its bottom an ore slurry inlet, the initial and intermediate vessels each having an ore slurry line leading from a mid-zone in the slurry for a mid-zone in the slurry of the adjacent upstream vessel.
25. An apparatus according to claim 23, including a metal recovery bed in said recirculation line upstream of said oxygen dissolving device.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002008063A CA2008063C (en) | 1990-01-18 | 1990-01-18 | Hydrometallurgical leaching process and apparatus |
ZA91333A ZA91333B (en) | 1990-01-18 | 1991-01-16 | Hydrometallurgical leaching process and apparatus |
AU69426/91A AU642951B2 (en) | 1990-01-18 | 1991-01-17 | Hydrometallurgical leaching process and apparatus |
US07/933,904 US5250273A (en) | 1990-01-18 | 1992-08-27 | Hydrometallurgical leaching process and apparatus |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002008063A CA2008063C (en) | 1990-01-18 | 1990-01-18 | Hydrometallurgical leaching process and apparatus |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2008063A1 CA2008063A1 (en) | 1991-07-18 |
CA2008063C true CA2008063C (en) | 1996-07-23 |
Family
ID=4144056
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002008063A Expired - Fee Related CA2008063C (en) | 1990-01-18 | 1990-01-18 | Hydrometallurgical leaching process and apparatus |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU642951B2 (en) |
CA (1) | CA2008063C (en) |
ZA (1) | ZA91333B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010037169A1 (en) * | 2008-10-01 | 2010-04-08 | The University Of Queensland | Process for extraction of mined material |
EP3967661B1 (en) | 2020-09-09 | 2023-07-26 | Northvolt AB | Process for preparing battery grade metal sulphate solutions |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AUPP696798A0 (en) * | 1998-11-06 | 1998-12-03 | Bactech (Australia) Pty Limited | Improved reactor |
DE102018208043A1 (en) * | 2018-05-23 | 2019-11-28 | Robert Bosch Gmbh | Method and apparatus for recovering gold, silver and platinum metals |
CN113173668B (en) * | 2021-06-01 | 2023-04-18 | 中国海洋大学 | Automatic material-supplementing type seawater desalination water mineralization tower |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU552286B2 (en) * | 1982-06-09 | 1986-05-29 | Moskovsky Institut Stali I Splavov | Plant for the recovery of non-ferrous metals by sulphuric acid leaching |
AU3774689A (en) * | 1989-03-30 | 1990-11-05 | Nauchno-Proizvodstvennoe Obiedinenie "Energostal" | Method of extracting iron from a pulp containing compounds of heavy non-ferrous metals |
-
1990
- 1990-01-18 CA CA002008063A patent/CA2008063C/en not_active Expired - Fee Related
-
1991
- 1991-01-16 ZA ZA91333A patent/ZA91333B/en unknown
- 1991-01-17 AU AU69426/91A patent/AU642951B2/en not_active Ceased
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010037169A1 (en) * | 2008-10-01 | 2010-04-08 | The University Of Queensland | Process for extraction of mined material |
EP3967661B1 (en) | 2020-09-09 | 2023-07-26 | Northvolt AB | Process for preparing battery grade metal sulphate solutions |
Also Published As
Publication number | Publication date |
---|---|
AU642951B2 (en) | 1993-11-04 |
ZA91333B (en) | 1991-11-27 |
CA2008063A1 (en) | 1991-07-18 |
AU6942691A (en) | 1991-07-25 |
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