US20050069473A1 - Integration processes of the treatments of zinc silicate concentrates or zinc silicate ore and roasted concentrates of zinc sulphides - Google Patents
Integration processes of the treatments of zinc silicate concentrates or zinc silicate ore and roasted concentrates of zinc sulphides Download PDFInfo
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- US20050069473A1 US20050069473A1 US10/497,133 US49713304A US2005069473A1 US 20050069473 A1 US20050069473 A1 US 20050069473A1 US 49713304 A US49713304 A US 49713304A US 2005069473 A1 US2005069473 A1 US 2005069473A1
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- zinc
- concentrates
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- silicate
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- 239000012141 concentrate Substances 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 93
- 230000008569 process Effects 0.000 title claims abstract description 91
- 230000010354 integration Effects 0.000 title claims abstract description 70
- 238000011282 treatment Methods 0.000 title claims abstract description 57
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical class [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 235000019352 zinc silicate Nutrition 0.000 title claims abstract description 52
- 239000004110 Zinc silicate Substances 0.000 title claims description 20
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 title 2
- 238000002386 leaching Methods 0.000 claims abstract description 82
- 239000011701 zinc Substances 0.000 claims abstract description 66
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 63
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 62
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001556 precipitation Methods 0.000 claims abstract description 30
- 230000007935 neutral effect Effects 0.000 claims abstract description 28
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 13
- 239000011707 mineral Substances 0.000 claims abstract description 13
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 150000004760 silicates Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001033 granulometry Methods 0.000 claims description 2
- 239000008235 industrial water Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011449 brick Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000000746 purification Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 239000011686 zinc sulphate Substances 0.000 description 5
- 235000009529 zinc sulphate Nutrition 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- -1 ZINC SILICATES Chemical class 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
Definitions
- This invention aims to supply several processes of integration and unification in the treatment of zinc silicate ores and concentrates with the calcine obtained from the sulphides roasting, defined by joint or interconnected leaching of these several sources of zinc, their filtrations and joint purification of the solutions of the obtained zinc sulphate.
- results are options of simplified processes with elevated performances of recovery of zinc, mainly from the silicate concentrates and ores (increase from 88% to 97% in zinc solution, in the treatment of the silicates).
- the extraction of magnesium, a chemical element, with high levels in ores and zinc silicate concentrates, is obtained using the magnesium treatment system described in all integration operations.
- the invention also includes processes for purging undesirable elements during zinc production, such as fluorides and chlorides.
- the Petitioner has developed integration and unification processes of the treatments of concentrates or zinc silicate ore and roasted concentrates of zinc sulphides characterized by joint leaching from the many sources of zinc, its filtrations and the unique purification obtained.
- the integration can be obtained in eight distinct processes, as follows:
- Integration Process I shown in the blocks flowchart of FIG. 1 .
- FIG. I shows the option of integration of the treatment processes of sulphide concentrate and silicate (or ore) zinc concentrate, where the integration or linking of the processes occurs in the Neutral Leaching stage ( 5 ).
- the silicate cake is pre-leached ( 4 ).
- the carbonates present in the concentrate are dissolved and the acid pulp is driven to the Neutral Leaching ( 5 ) of the calcine (arising from the Roasting of the sulphide concentrate), where it is integrated into the joint zinc extraction process of the two sources of Zinc.
- the operational conditions, for each stage of this process are described hereinbelow:
- Repulping Stage ( 1 ) This stage consists of the repulping of the zinc silicate concentrate with washing waters of the leaching residues, residual waters of the plant or simply industrial water.
- the operation parameter in this phase of the process is the concentration of the solids, to be kept from 45% to 60%.
- the repulping tank is to be coated with an anti-acid material, to resist the chemical effect, when liquids of high degree of acidity are used.
- the spent solution arising from the stage of the zinc electrolysis is added to the ore pulp/zinc silicated concentrate, so as to maintain the pH ranging from 4.0 to 4.5.
- Direct or indirect steam is injected in the tanks to maintain a temperature ranging from 75 to 85° C.
- part of the magnesium and of the zinc contained in the silicate ore is added to the solution.
- it is executed the selective precipitation of the zinc in relation to the magnesium, by adjusting the pH parameters, temperature and residence time.
- the zinc concentrations are lesser than 10.0 g/l, it is performed the separation solid/liquid, where the liquid is sent to the stage of recuperation of zinc and the solid part to the ore's or silicates concentrate's pre-leaching stage.
- the water balance in the plant is done by virtue of a greater or lesser amount of solution spent in this stage.
- the balance of water in the plant is unfavorable (increase of the general volume) it is increased the amount of spent solution introduced in this stage and vice-versa, and the favorable balance of water decreases the quantity of spent solution.
- the pH, in this stage, is kept within the range from 3.0 to 3.5, through the addition of spent solution arising from the zinc electrolysis.
- the residence time ranges from 3 to 6 hours and varies according to the physical & chemical characteristics of the silicate that is being treated.
- Stage of neutral leaching ( 5 )—It is in this stage that the integration of the process occurs.
- the two ores (the silicated ore and the zinc sulphide already duly calcined) are leached together.
- the leaching is to be performed so as to be obtained the zinc's maximum extraction and the silica coagulation, so that the obtained pulp may be decanted, filtered or centrifuged.
- the most important to obtain a maximum extraction of zinc and coagulation of the silica were:
- the zinc extraction efficiency in this stage is 80%.
- the concentration of soluble silica in the industrial tests was around 60 to 80 mg/l in the zinc sulphate solution, which is sent for purification. This concentration of silica didn't harm or decrease the efficiency of the processes of solid/liquid separation of the pulp.
- the pulp obtained in the last tank of Neutral Leaching ( 7 ) is thickened, so that an overflow be obtained, such overflow constituted of a zinc sulphate with traces of cadmium, copper, cobalt, nickel, arsenic, germanium, antimony, which goes to the stages of Purification, Electrolysis and Casting. These last phases of the process are not the subject of the Patent.
- the underflow goes to the Acid Leaching unit ( 7 ), for leaching of the zinc ferrites from the Roaster's calcine, whose later phases are not the subjects of this Patent, as well.
- FIG. II exhibits another option of connection of the processes of treatment of the zinc sources.
- the interlinking occurs in the stages of Acid Leaching of the calcine ( 7 ) and/or precipitation of iron ( 11 ), instead of the stage of Neutral Leaching of the previous option.
- the amount of concentrate or silicated ore in each stage may range from zero to one hundred percent.
- the option to use the integration process I or II depends on:
- Integration Process III shown in the blocks flowchart of FIG. III.
- FIG. III presents the integrated process for the obtainment of zinc, where the silicate concentrate or ore is fully leached ( 4 ) and the obtained pulp is sent to the Neutral Leaching of the Calcine of sulphide zinc concentrate ( 5 ).
- the silicate acid leaching ( 4 ) is made with a solution denominated leaching solution, which is a mixture of Concentrated Sulfuric Acid with spent solution from the electrolysis.
- the concentration of acid in the leaching solution may range from 150 to 250 g/l and such variation is due to the balance of sulphate in the process.
- the residence time ranges from 5 to 8 hours and basically depends on the efficiency of agitation in the tanks, granulometry of the ore/concentrate, temperature and the grade of the minerals contained in the source of silicate zinc.
- the purpose of this stage is to extract the maximum possible of the zinc contained in the silicate source and the parameter to evaluate the efficiency of this stage is the content of zinc soluble in acid (zinc content not leached) discarded in the subsequent stage, which is the separation solid/liquid.
- the value deemed optimal is ZnH+ ⁇ 0.5%.
- the process of integration of the two plants is made through the liquid obtained in the stage of separation solid/liquid ( 14 ), which is sent to the neutral leaching ( 5 ).
- the conditions of the neutral leaching operations are the same ones already described in the item “Integration Process I”.
- the obtained solid residue is sent to the filtration ( 15 ) where the residue washing is accomplished to recover the soluble zinc.
- the washing is performed in two stages, re-pulping and displacement and the soluble zinc content contained in the discarded residue is lesser than 0.5%.
- Integration Process IV shown in the blocks flowchart of FIG. IV.
- FIG. IV shows the integration process which has also been industrially tested and contemplates the calcination of the silicate concentrate, aiming at the decomposition of the organic substances and the carbonates contained in the concentrate.
- the calcination may be acomplished, by using horizontal or vertical batch or continuous kiln, by using BPF oil of any type, gasogene, natural gas, coal fines, etc.
- BPF oil of any type, gasogene, natural gas, coal fines, etc.
- the use of the previously calcinated silicate concentrate eliminates the silicate's pre-leaching step, whose purpose was precisely to promote the decomposition of the carbonates through the chemical process.
- FIGS. V to VIII Process for integration and removal of halogens, such as fluorides and chlorides are shown in FIGS. V to VIII, attached. They include implementing additional neutralization steps in general before filtration of the pulp leached of silicates.
- the basis for removing fluoride is based on precipitation with lime, to form a stable compound of calcium fluoride (CaF2), with a pH of around 4.0 to 4.7. In this case, the pH control must be strict to not pass 5.0 avoiding zinc precipitation and loss of plant yields.
- FIG. IX attached presents the comparative results of the calcination of the concentrate at 900° C. versus raw concentrate as to the parameters loss of ignition, zinc content, carbonate content and foam formation.
- FIG. IX shows that it was possible to completely eliminate the foam with the increase of the Zn content in the concentrate, from 40% to 44% (in the calcined concentrate) and mass reduction (loss of ignition) of 20%, referring to the elimination of the carbonates ( ⁇ 0.2%) and moisture, either in bench or at industrial tests.
- FIG. X shows the results of tests of zinc selective precipitation with silicate calcined concentrate on a zinc solution with the silicates calcined concentrate on a solution of 17 g/l of zinc and 2.1-2.4 g/l of Mg (magnesium).
- the results demonstrate that, at temperatures of 90-95° C. and residence time of five hours, the zinc precipitates to 2.7-4.3 g/l, which represents an efficiency of about 80% for zinc precipitation (17- ⁇ fraction (4/17) ⁇ 100), and the magnesium concentration increased from 2.4 to 4.0 g/l, demonstrating an expressive capacity of magnesium purge.
- FIG. XI shows that the calcination of the silicates concentrate drastically reduced the residence time, during the leaching, due to the reduction in the formation of foam, from 4 to 1 hour and 30 minutes. This rendered it possible to reduce the necessary volume to perform the leaching of the sources of zinc.
- FIG. XII attached presents the results of the effect of calcination on the purification of the solutions of zinc sulphate, where there is a reduction of more than 1% in the consumption of zinc dust in relation to the cathode produced when the solution was obtained through the calcined concentrate, from 4.12to 2.95%.
- FIG. XIII attached presents the leaching and filtration efficiency of the calcined ore of zinc sulphide where it increased from 96% to 99%, according to the results obtained with the feeding of the calcined ore/concentrate of silicates, at the end of the acid leaching or beginning of the neutralization of the iron precipitation.
- the tests were made on benches, in volumes of 50 liters, according to the operational conditions shown in FIG. XIII.
- FIG. XV attached presents the results of integration industrial tests where it confirms the performance of zinc selective precipitation, already shown in FIG. X.
- This figure shows that the zinc content, in the liquid part of the solution was, generally, in an average of 5 g/l when it was used a washing solution with Zn 17-25 g/l and silicate concentrate for the selective precipitation of zinc.
- FIG. XVI attache presents the results of industrial tests, when it was used the calcined silicate concentrate and the integration process of FIG. IV.
- FIG. XVII attached presents the results of industrial tests to remove fluorides from solutions obtained from leaching de silicate concentrates.
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Abstract
Description
- This invention aims to supply several processes of integration and unification in the treatment of zinc silicate ores and concentrates with the calcine obtained from the sulphides roasting, defined by joint or interconnected leaching of these several sources of zinc, their filtrations and joint purification of the solutions of the obtained zinc sulphate.
- The well-known hydrometallurgic processes of obtainment of zinc in solution consist in the treatment of Sulphide Roaster calcine by neutral leaching through several Teachings stages of the ferrites and consequent removal of iron, either by precipitation as jarosite, paragoethite, goethite, haematite or iron slag. The
patents GB 2 114 966 A “Recovery of zinc from sulphidic material”, U.S. Pat. No. 5,120,353 “Hidrometallurgic method for processing raw materials containing zinc sulphide”, U.S. Pat. No. 5,585,079 “Method for leaching material containing zinc oxide and zinc silicate” and the Brazilian Patent PI 9407223-0 A “Processes for extraction of Zinc from Concentrates of Zinc Sulphide, and for the leaching of zinc ferrite, jointly with a sulphided material containing zinc sulphide”, refer to these processes. - The results are options of simplified processes with elevated performances of recovery of zinc, mainly from the silicate concentrates and ores (increase from 88% to 97% in zinc solution, in the treatment of the silicates).
- The use of only one acid leaching for the zinc ferrites has also been achieved through the integrated process with the silicate ores and concentrates, allowing for the obtainment of up to 99.3% of a zinc solution in relation to this Zinc source.
- The extraction of magnesium, a chemical element, with high levels in ores and zinc silicate concentrates, is obtained using the magnesium treatment system described in all integration operations. The invention also includes processes for purging undesirable elements during zinc production, such as fluorides and chlorides.
- The Petitioner has developed integration and unification processes of the treatments of concentrates or zinc silicate ore and roasted concentrates of zinc sulphides caracterized by joint leaching from the many sources of zinc, its filtrations and the unique purification obtained. The integration can be obtained in eight distinct processes, as follows:
-
- (i) The Integration process is characterized by the use of raw or zinc silicate ore concentrates supplied by several ore sources which are leached jointly with the calcine from the zinc sulphide roaster, in the Neutral Leaching process, as shown in the flowchart of
FIG. 1 attached; - (ii) Integration process characterized by the use of raw concentrates or zinc silicate ores, interlinked with treatment of the zinc sulphide roaster calcine, in the Acid Ferrite Leaching or calcine (7) and Iron Precipitation (11) process, in accordance with the flowchart of FIG. II attached;
- (iii) Integration process, characterized by use of raw concentrates or zinc silicate ores from several mineral sources, interlinked using treatment with the zinc sulphide roasted calcine in the Neutral Leaching stage (5), after silicate leaching in accordance with the flowchart in FIG. III attached;
- (iv) Integration process, characterized by the use of calcines of silicate concentrates or silicate ores (obtained at 600-900° C.), with selective zinc precipitation in the Magnesium treatment, and integration with the product of the Zinc Sulphide Roaster in the Neutral Leaching, Ferrite Acid Leaching or iron Precipitation stages, in accordance with the flowchart in FIG. IV attached;
- (v) Integration process, characterized by the use of raw concentrates or zinc silicate ores from several mineral sources, which are leached together with the calcine from the zinc sulphide roaster, during the Neutral Leaching stage including the removal of halogens such as: fluorides and chlorides, in accordance with the flowchart in FIG. V attached;
- (vi) Integration process, characterized by the use of raw concentrates or zinc silicate ores from several mineral sources, interlinked with the treatment with the calcine from the zinc sulphide roaster, in the Acid Leaching and Iron Precipitation stage including the stages of halogen removal, such as fluorides and chlorides, in accordance with the flowchart in FIG. VI attached;
- (vii) Integration process, characterized by the use of concentrates raw concentrates or zinc silicate ores from several mineral sources, interlinked with the treatment with the calcine from the zinc sulphide roaster in the Neutral Leaching stage after silicate leaching, including the stages of halogen removal, such as fluorides and chlorides, in accordance with the flowchart in FIG. VII attached;
- (viii) Integration process, characterized by the use of calcine (obtained at 600-900° C.) of silicate concentrates or silicate ores with selective precipitation of zinc in the Magnesium treatment and integration with the product of the Zinc Sulphide Roaster either in the Neutral Leaching, Acid Leaching of ferrites or Iron Precipitation stages, including the stages of halogen removal, such as fluorides and chlorides, in accordance with the flowchart in FIG. VIII attached;
Integration process I—shown in the blocks flowchart of FIG. I, attached.
- (i) The Integration process is characterized by the use of raw or zinc silicate ore concentrates supplied by several ore sources which are leached jointly with the calcine from the zinc sulphide roaster, in the Neutral Leaching process, as shown in the flowchart of
- Integration Process I—shown in the blocks flowchart of
FIG. 1 . - FIG. I shows the option of integration of the treatment processes of sulphide concentrate and silicate (or ore) zinc concentrate, where the integration or linking of the processes occurs in the Neutral Leaching stage (5). After the magnesium treatment of the concentrate or silicate ore (2), to extract the magnesium present in the concentrate and in the spent solution from the electrolysis (13), the silicate cake is pre-leached (4). In the pre-leaching stage(4), the carbonates present in the concentrate are dissolved and the acid pulp is driven to the Neutral Leaching (5) of the calcine (arising from the Roasting of the sulphide concentrate), where it is integrated into the joint zinc extraction process of the two sources of Zinc. The operational conditions, for each stage of this process are described hereinbelow:
- Repulping Stage (1)—This stage consists of the repulping of the zinc silicate concentrate with washing waters of the leaching residues, residual waters of the plant or simply industrial water. The operation parameter in this phase of the process is the concentration of the solids, to be kept from 45% to 60%. The repulping tank is to be coated with an anti-acid material, to resist the chemical effect, when liquids of high degree of acidity are used.
- Stage of Magnesium Treatment (2)—Its purpose is to eliminate part of the magnesium contained in the source of silicates zinc and in the spent solution from the electrolysis. It is suited to control the balance of the plant waters.
- The spent solution arising from the stage of the zinc electrolysis is added to the ore pulp/zinc silicated concentrate, so as to maintain the pH ranging from 4.0 to 4.5. Direct or indirect steam is injected in the tanks to maintain a temperature ranging from 75 to 85° C. Upon such conditions, part of the magnesium and of the zinc contained in the silicate ore is added to the solution. Next, in a series of cascade tanks, it is executed the selective precipitation of the zinc in relation to the magnesium, by adjusting the pH parameters, temperature and residence time. When the zinc concentrations are lesser than 10.0 g/l, it is performed the separation solid/liquid, where the liquid is sent to the stage of recuperation of zinc and the solid part to the ore's or silicates concentrate's pre-leaching stage.
- The water balance in the plant is done by virtue of a greater or lesser amount of solution spent in this stage. When the balance of water in the plant is unfavorable (increase of the general volume) it is increased the amount of spent solution introduced in this stage and vice-versa, and the favorable balance of water decreases the quantity of spent solution.
- Pre-leaching stage of ore/silicate concentrate(4)—This stage consists of the pre-leaching of the pulp with a view to promote the dissociation of the carbonates contained in the silicate ore/concentrate, according to reaction:
MeCO3+H2SO4 - - - MeSO4+CO2+H2O, where Me=Ca, Mg, Zn, etc. - The pH, in this stage, is kept within the range from 3.0 to 3.5, through the addition of spent solution arising from the zinc electrolysis. The residence time ranges from 3 to 6 hours and varies according to the physical & chemical characteristics of the silicate that is being treated.
- Stage of neutral leaching (5)—It is in this stage that the integration of the process occurs. The two ores (the silicated ore and the zinc sulphide already duly calcined) are leached together. The leaching is to be performed so as to be obtained the zinc's maximum extraction and the silica coagulation, so that the obtained pulp may be decanted, filtered or centrifuged. Of the several studied parameters it was verified that the most important to obtain a maximum extraction of zinc and coagulation of the silica were:
-
- pH—3.2 to 3.8.
- Temperature—70 to 75° C.
- Residence Time: from 4 to 5 hours.
- The zinc extraction efficiency in this stage is 80%.
- The concentration of soluble silica in the industrial tests was around 60 to 80 mg/l in the zinc sulphate solution, which is sent for purification. This concentration of silica didn't harm or decrease the efficiency of the processes of solid/liquid separation of the pulp.
- Yet in this stage it is made the purification of the elements deemed dangerous to the stage of the electrolysis of the zinc. This purification is made through the precipitation of the iron contained in the solution, in the form of ferric hydroxide. Chemical elements as As, Ge, Sb, Se and Te are purified in this stage. The iron in the first tank has to be kept ranging from 0.5 to 3.0 g/l and this variation is in accordance with the concentration of these elements deemed dangerous in the ores/concentrates which are being processed. The adjustment of the concentration of iron in the first tank is made by using the liquid from the acid leaching stage. Anode mud containing manganese dioxide is also added in this tank for the oxidation of the Fe++ to Fe+++.
- The pulp obtained in the last tank of Neutral Leaching (7) is thickened, so that an overflow be obtained, such overflow constituted of a zinc sulphate with traces of cadmium, copper, cobalt, nickel, arsenic, germanium, antimony, which goes to the stages of Purification, Electrolysis and Casting. These last phases of the process are not the subject of the Patent.
- The underflow goes to the Acid Leaching unit (7), for leaching of the zinc ferrites from the Roaster's calcine, whose later phases are not the subjects of this Patent, as well.
- Integration Process II—shown in the blocks flowchart of FIG. II.
- FIG. II exhibits another option of connection of the processes of treatment of the zinc sources. In this case, the interlinking occurs in the stages of Acid Leaching of the calcine (7) and/or precipitation of iron (11), instead of the stage of Neutral Leaching of the previous option.
- The amount of concentrate or silicated ore in each stage may range from zero to one hundred percent. The option to use the integration process I or II depends on:
-
- whether the plant is already in operation: the availability of equipments in each stage; complexity of lay-out change; physical space for the adaptation; cost/benefit.
- If a new plant: it depends more on the cost/benefit.
- Integration Process III—shown in the blocks flowchart of FIG. III.
- FIG. III presents the integrated process for the obtainment of zinc, where the silicate concentrate or ore is fully leached (4) and the obtained pulp is sent to the Neutral Leaching of the Calcine of sulphide zinc concentrate (5).
- In this process it is introduced a step denominated silicate leaching followed by a solid/liquid separation. The silicate acid leaching (4) is made with a solution denominated leaching solution, which is a mixture of Concentrated Sulfuric Acid with spent solution from the electrolysis. The concentration of acid in the leaching solution may range from 150 to 250 g/l and such variation is due to the balance of sulphate in the process. The residence time ranges from 5 to 8 hours and basically depends on the efficiency of agitation in the tanks, granulometry of the ore/concentrate, temperature and the grade of the minerals contained in the source of silicate zinc. The purpose of this stage is to extract the maximum possible of the zinc contained in the silicate source and the parameter to evaluate the efficiency of this stage is the content of zinc soluble in acid (zinc content not leached) discarded in the subsequent stage, which is the separation solid/liquid. The value deemed optimal is ZnH+≦0.5%. The process of integration of the two plants is made through the liquid obtained in the stage of separation solid/liquid (14), which is sent to the neutral leaching (5). The conditions of the neutral leaching operations are the same ones already described in the item “Integration Process I”. The obtained solid residue is sent to the filtration (15) where the residue washing is accomplished to recover the soluble zinc.
- The washing is performed in two stages, re-pulping and displacement and the soluble zinc content contained in the discarded residue is lesser than 0.5%.
- Integration Process IV—shown in the blocks flowchart of FIG. IV.
- FIG. IV shows the integration process which has also been industrially tested and contemplates the calcination of the silicate concentrate, aiming at the decomposition of the organic substances and the carbonates contained in the concentrate. The calcination may be acomplished, by using horizontal or vertical batch or continuous kiln, by using BPF oil of any type, gasogene, natural gas, coal fines, etc. The use of the previously calcinated silicate concentrate eliminates the silicate's pre-leaching step, whose purpose was precisely to promote the decomposition of the carbonates through the chemical process.
- The integration of the process can be made:
-
- By directly adding the silicate calcinate in the stage of neutral leaching(5), or
- By adding the silicate calcinate in the acid leaching stage(7), or
- By adding the silicate calcine in the Precipitation of Iron/Paragoetite phase (11), or
- By simultaneously adding the silicate calcine in the two or three phases.
- For all the options above, the silicate calcine may or may not be submitted to the magnesium treatment, jointly with the secondary filtrate from the residue washing or other plant's washing waters. This depends on the plant's magnesium balance. FIG. IV shows the magnesium treatment in all its options.
- The operational conditions of the stages where the silicate ore/concentrate is added are the same ones already described in the integration processes I, II, III. The option of using the calcined silicate ore/concentrate is taken in accordance with the cost/benefit studies.
- Process for integration and removal of halogens, such as fluorides and chlorides are shown in FIGS. V to VIII, attached. They include implementing additional neutralization steps in general before filtration of the pulp leached of silicates. The basis for removing fluoride is based on precipitation with lime, to form a stable compound of calcium fluoride (CaF2), with a pH of around 4.0 to 4.7. In this case, the pH control must be strict to not pass 5.0 avoiding zinc precipitation and loss of plant yields.
- The processes, according to this invention, are illustrated by the non-limitative examples of practical realization hereinafter, and the following data were extracted from pilot tests and/or realizations of industrial scales:
- Integration Process III:
- INCREASE OF THE RECOVERY OF THE PLANT WITH THE INTEGRATION BY PROCESS III
- The concentrates were treated according to the flowchart of FIG. III.
- Treated amounts:
-
- Sulphide concentrates=10212.332 t
- Silicated concentrates=13291.000 t
- Leaching efficiency of the silicate concentrate=94.30%
- Content of Zn soluble in acid=1.79%
- Clear height in the thickening of the leached silicates concentrate=1.4 m
- Consumption of zinc powder in relation to the produced cathode=2.94%
- Production of cathodes=9641.430 t
- Problems occurred with this process:
-
- Since the silicate concentrate is obtained by flotation, during the period in which this process was used, an expressive foam during the leaching occurred and the tanks overflew. The way to minimize such overflows was to accomplish a weak leaching, with a greater number of reactors and using floor pump to return the overflow to the origin tanks. Another solution to the problem is the Integrated Process IV.
- The current efficiency (Faraday) is decreased when the total content of organic matter exceeds 3 mg/l. This parameter was controlled in the concentration Plant of the minerals of silicates, with more precise controls in the consumption of flotation or implementing the Integrated Process IV (FIG. IV).
- Integrated Process IV:
- INCREASE IN THE LEACHING EFFICIENCY OF THE CALCINED CONCENTRATES OF ZINC SILICATES AND INCREASE OF LEACHING EFFICIENCY OF THE CALCINE FROM SULPHIDE CONCENTRATES, WITH THE INTRODUCTION OF THE CALCINED SILICATE CONCENTRATE, AT THE END OF THE HOT ACID LEACHING.
- Process IV, (attached FIG. IV), was tested at bench, pilot & industrial plant. The obtained results are shown as follows:
- RESULTS OF TESTS OBTAINED IN A PILOT PLANT(examples 2 to 8):
- FIG. IX attached presents the comparative results of the calcination of the concentrate at 900° C. versus raw concentrate as to the parameters loss of ignition, zinc content, carbonate content and foam formation. FIG. IX shows that it was possible to completely eliminate the foam with the increase of the Zn content in the concentrate, from 40% to 44% (in the calcined concentrate) and mass reduction (loss of ignition) of 20%, referring to the elimination of the carbonates (<0.2%) and moisture, either in bench or at industrial tests.
- FIG. X shows the results of tests of zinc selective precipitation with silicate calcined concentrate on a zinc solution with the silicates calcined concentrate on a solution of 17 g/l of zinc and 2.1-2.4 g/l of Mg (magnesium). The results demonstrate that, at temperatures of 90-95° C. and residence time of five hours, the zinc precipitates to 2.7-4.3 g/l, which represents an efficiency of about 80% for zinc precipitation (17-{fraction (4/17)}×100), and the magnesium concentration increased from 2.4 to 4.0 g/l, demonstrating an expressive capacity of magnesium purge.
- FIG. XI shows that the calcination of the silicates concentrate drastically reduced the residence time, during the leaching, due to the reduction in the formation of foam, from 4 to 1 hour and 30 minutes. This rendered it possible to reduce the necessary volume to perform the leaching of the sources of zinc.
- FIG. XII attached presents the results of the effect of calcination on the purification of the solutions of zinc sulphate, where there is a reduction of more than 1% in the consumption of zinc dust in relation to the cathode produced when the solution was obtained through the calcined concentrate, from 4.12to 2.95%.
- FIG. XIII attached presents the leaching and filtration efficiency of the calcined ore of zinc sulphide where it increased from 96% to 99%, according to the results obtained with the feeding of the calcined ore/concentrate of silicates, at the end of the acid leaching or beginning of the neutralization of the iron precipitation. The tests were made on benches, in volumes of 50 liters, according to the operational conditions shown in FIG. XIII.
- The results of the bench test for reducing the fluoride levels from concentrated silicate leaching, can be found in FIG. XIV, attached.
- RESULTS OBTAINED IN TESTS OF INDUSTRIAL SCALE (examples 8 to 10)
- Calcination of the Silicates concentrates in Rotary Kiln
- Temperatures=600-900° C.
- Residual content of carbonates=2% or Total Carbon=0.3% maximum
- FIG. XV attached presents the results of integration industrial tests where it confirms the performance of zinc selective precipitation, already shown in FIG. X. This figure shows that the zinc content, in the liquid part of the solution was, generally, in an average of 5 g/l when it was used a washing solution with Zn=17-25 g/l and silicate concentrate for the selective precipitation of zinc.
- FIG. XVI attache, presents the results of industrial tests, when it was used the calcined silicate concentrate and the integration process of FIG. IV. The obtained leaching & filtration average efficiency ranged from 95 to 99%, being the main impediments to keep the elevated efficiency were the low efficiency of the press-filters used for the extraction of water-soluble zinc.
- FIG. XVII attached, presents the results of industrial tests to remove fluorides from solutions obtained from leaching de silicate concentrates.
- It was found that the level fell from 27 to 17 mg/l, allowing for automatic removal in electrolysis rooms.
Claims (29)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0106186A BRPI0106186B1 (en) | 2001-11-27 | 2001-11-27 | integration processes for the treatment of zinc silicate and sulfate zinc silicate concentrates or ores, whose integration takes place in the neutral leaching step, and / or in the acid leaching step and / or the iron / papagoetite precipitation step |
| BRPI0106186-0 | 2001-11-27 | ||
| PCT/BR2002/000149 WO2003046232A1 (en) | 2001-11-27 | 2002-11-07 | Integration processes of the treatments of zinc silicate concentrates or zinc silicate ore and roasted concentrates of zinc sulphides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20050069473A1 true US20050069473A1 (en) | 2005-03-31 |
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ID=3948175
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/497,133 Abandoned US20050069473A1 (en) | 2001-11-27 | 2002-11-07 | Integration processes of the treatments of zinc silicate concentrates or zinc silicate ore and roasted concentrates of zinc sulphides |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20050069473A1 (en) |
| CN (1) | CN1571853B (en) |
| AU (1) | AU2002336830B2 (en) |
| BR (1) | BRPI0106186B1 (en) |
| WO (1) | WO2003046232A1 (en) |
| ZA (1) | ZA200304930B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014000021A1 (en) * | 2012-06-26 | 2014-01-03 | Metaleach Limited | Method for leaching zinc silicate ores |
| CN109097557A (en) * | 2018-08-03 | 2018-12-28 | 中南大学 | A method of recycling zinc from willemite resource |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129560B (en) * | 2019-06-19 | 2021-05-11 | 个旧兴华锌业有限公司 | Process for extracting zinc ingot from high-silicon zinc oxide ore and high-impurity secondary zinc oxide powder |
| CN110560070B (en) * | 2019-08-09 | 2020-09-25 | 红河学院 | A kind of method for preparing doped nano zinc ferrite with iron-containing waste |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120353A (en) * | 1990-02-16 | 1992-06-09 | Outokumpu Oy | Hydrometallurgic method for processing raw materials containing zinc sulphide |
| US5585079A (en) * | 1993-06-24 | 1996-12-17 | Outokumpu Engineering Contracters Oy | Method for leaching material containing zinc oxide and zinc silicate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB145085A (en) * | 1920-06-17 | 1921-09-01 | Metallbank & Metallurg Ges Ag | Process for treating sal ammoniac skimmings |
| CN1030258A (en) * | 1988-02-10 | 1989-01-11 | 昆明冶金研究所 | The treatment process of ore of zinc silicate |
| BRPI9904195A2 (en) * | 1999-02-05 | 2016-09-27 | Companhia Mineira De Metais | processes for integrating the treatment of zinc silicate concentrates or ores of sulphide zinc |
-
2001
- 2001-11-27 BR BRPI0106186A patent/BRPI0106186B1/en not_active IP Right Cessation
-
2002
- 2002-11-07 WO PCT/BR2002/000149 patent/WO2003046232A1/en not_active Ceased
- 2002-11-07 AU AU2002336830A patent/AU2002336830B2/en not_active Expired
- 2002-11-07 CN CN028206029A patent/CN1571853B/en not_active Expired - Lifetime
- 2002-11-07 US US10/497,133 patent/US20050069473A1/en not_active Abandoned
-
2003
- 2003-06-25 ZA ZA200304930A patent/ZA200304930B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120353A (en) * | 1990-02-16 | 1992-06-09 | Outokumpu Oy | Hydrometallurgic method for processing raw materials containing zinc sulphide |
| US5585079A (en) * | 1993-06-24 | 1996-12-17 | Outokumpu Engineering Contracters Oy | Method for leaching material containing zinc oxide and zinc silicate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014000021A1 (en) * | 2012-06-26 | 2014-01-03 | Metaleach Limited | Method for leaching zinc silicate ores |
| CN109097557A (en) * | 2018-08-03 | 2018-12-28 | 中南大学 | A method of recycling zinc from willemite resource |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1071169A1 (en) | 2005-07-08 |
| AU2002336830A1 (en) | 2003-06-10 |
| BR0106186A (en) | 2003-09-23 |
| WO2003046232A1 (en) | 2003-06-05 |
| BRPI0106186B1 (en) | 2017-04-25 |
| CN1571853B (en) | 2010-05-26 |
| ZA200304930B (en) | 2004-08-25 |
| CN1571853A (en) | 2005-01-26 |
| AU2002336830B2 (en) | 2007-03-22 |
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