AU2017403278A1 - Method for recycling wrapped complex copper oxide ores - Google Patents
Method for recycling wrapped complex copper oxide ores Download PDFInfo
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- AU2017403278A1 AU2017403278A1 AU2017403278A AU2017403278A AU2017403278A1 AU 2017403278 A1 AU2017403278 A1 AU 2017403278A1 AU 2017403278 A AU2017403278 A AU 2017403278A AU 2017403278 A AU2017403278 A AU 2017403278A AU 2017403278 A1 AU2017403278 A1 AU 2017403278A1
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- Prior art keywords
- copper
- copper oxide
- wrapped
- ores
- flotation
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 55
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000010949 copper Substances 0.000 claims abstract description 73
- 229910052802 copper Inorganic materials 0.000 claims abstract description 73
- 238000005188 flotation Methods 0.000 claims abstract description 58
- 238000002386 leaching Methods 0.000 claims abstract description 34
- 239000012141 concentrate Substances 0.000 claims abstract description 33
- 229910052626 biotite Inorganic materials 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 19
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012991 xanthate Substances 0.000 claims abstract description 12
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 32
- 239000011707 mineral Substances 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052595 hematite Inorganic materials 0.000 claims description 15
- 239000011019 hematite Substances 0.000 claims description 15
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 229910001608 iron mineral Inorganic materials 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000006148 magnetic separator Substances 0.000 claims description 5
- 230000002000 scavenging effect Effects 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical compound CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 206010037660 Pyrexia Diseases 0.000 claims description 3
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000007885 magnetic separation Methods 0.000 abstract description 4
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- -1 fatty acid salt Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- 239000002918 waste heat Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 11
- 229910000010 zinc carbonate Inorganic materials 0.000 description 8
- 238000005987 sulfurization reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 108091005950 Azurite Proteins 0.000 description 2
- 241000907663 Siproeta stelenes Species 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001748 carbonate mineral Inorganic materials 0.000 description 2
- 229910001779 copper mineral Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- GWBUNZLLLLDXMD-UHFFFAOYSA-H tricopper;dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[O-]C([O-])=O.[O-]C([O-])=O GWBUNZLLLLDXMD-UHFFFAOYSA-H 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
-
- 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
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for recycling wrapped complex copper oxide ores. A wrapped copper oxide ore which is difficult to recycle by floatation and has a low direct acid leaching rate is subjected to a combination of vulcanization, xanthate, fatty acid salt, and hydroximic acid to float free copper oxide, ferrous and biotite ores wrapping a copper ore in ores are recycled by magnetic separation, and a large amount of low-grade copper-containing tailings are separated. Copper resources in a rough concentrate containing wrapped copper are recycled by high-temperature pressurizing, stirring, leaching and intensifying, ore pulp is leached out at high temperature and is mixed with low-grade copper-containing tailings to continue leaching by waste heat and waste acid to obtain the copper ore in tailings, the wrapped copper oxide ores which cannot be recycled by flotation directly and acid leaching directly are efficiently recycled. The technical difficulties of processing and using of wrapped complex copper oxide ore resources are economically and effectively resolved.
Description
The present invention relates to a method for recycling wrapped complex copper oxide ores, and belongs to technical field of mineral beneficiation and metallurgy.
Prior Art Discussion
Copper oxide minerals mainly include malachite, chrysocolla, azurite, cuprite, tenorite, pseudo-malachite, and bound copper, etc., and mainly coexist in association with gangue minerals including silicates, carbonates, and iron oxides, etc. Independent copper oxide ores, such as malachite, chrysocolla, azurite, cuprite, and tenorite, etc., may be recycled by sulfurization and xanthate flotation method; high-binding-ratio copper oxide ores coexisting densely with silicate minerals may be recycled by means of sulfuric acid leaching, solid-liquid separation, extraction, and electro-deposition; low-binding-ratio copper oxide ores coexisting densely with carbonate minerals may be recycled by means of ammonia leaching, solid-liquid separation, extraction, and electro-deposition. However, for copper oxide ores that mainly consist of pseudomalachite, partially densely coexist with limonite, hematite and biotite and are partially wrapped by iron and silicate minerals, there is no efficient recycling method yet up to now. Consequently, those copper oxide ore resources have not been recycled effectively at present.
It is difficult to recycle such copper oxide minerals with the conventional sulfurization - xanthate flotation method, because it is difficult for the sulfurizing agent and xanthate collecting agent to contact with the surfaces of the copper oxide minerals owing to the fact that the copper oxide ores are wrapped by hematite, limonite or biotite partially, the monomers of copper oxide mineral cannot be separated and consequently the part of copper oxide mineral cannot be recycled by flotation. That part of copper oxide ores cannot be recycled effectively with the conventional ammonia leaching - extraction electro-deposition technique, because it is difficult for ammonia to destroy the structures of iron oxide ores and biotite and contact with the wrapped copper oxide mineral, and consequently that part of copper oxide ores cannot be leached out effectively. When the conventional acid leaching technique is used to treat such copper oxide ores, since the sulfuric acid can diffuse into the hematite, limonite and biotite and leach out the wrapped copper oxide mineral only if heating is applied through the pulp to promote lattice deformation of the hematite and biotite minerals, the leaching cost is high and no economic benefit can be attained if the pulp is heated up to 60°C or a higher temperature owing to the low grade and huge quantity of raw ores.
The Patent Application No. CN201010178875.2 has disclosed a beneficiation and metallurgy method for high-binding-ratio carbonate gangue-type oxygen-sulfur mixed copper ores, which is oriented to high-binding-ratio oxygen-sulfur mixed copper ores with high content of calcium-magnesium carbonate gangue minerals. In the method, firstly, the copper sulfide mineral and free copper oxide mineral are recycled by flotation, and the calcium-magnesium carbonate minerals in the flotation tailing are treated by reverse flotation with aliphatic acid, to obtain middlings that contain bound copper and has low content of calcium-magnesium carbonate minerals; and then, sulfuric acid is added to the middling and the mixture is agitated to leach out the bound copper, and then a copper product is obtained through a metallurgical method from the copper-containing solution after solid-liquid separation. This method also cannot be used to treat such wrapped copper oxide ores, because a good effect cannot be achieved if sulfurization - xanthate flotation is used owing to the fact that there is little free copper oxide mineral in the wrapped copper oxide ores and a part of the iron-bearing mineral may enter into the carbonate mineral and result in loss of the copper mineral if calciummagnesium reversed flotation is used.
The Patent Application No. CN201210201306.4 has disclosed a macromolecular bridging flotation method for bound opper impregnated bodies, which is oriented to bound copper impregnated bodies that cannot be recycled by conventional flotation, and employs macromolecular bridging agent, bridging copper ions, and xanthate bringing collecting agent, wherein, polyatomic adsorption happens on the surfaces of the bound copper impregnated bodies by means of ions of the macromolecular bridging agent, the copper ions are reabsorbed on the bridging agent that is absorbed to the surface, the collecting agent of xanthate negative ions are absorbed on the bridging copper ions, so that the surfaces of the bound copper impregnated bodies become hydrophobic and thereby flotation is realized. This method also cannot be effectively used to recycle such wrapped copper oxide ores, because the molecules of the macromolecular bridging agent cannot interact with the copper oxide ores wrapped by gangue minerals such as hematite, limonite, and biotite, etc., and consequently it is difficult to recycle the copper oxide mineral by means of bridging flotation.
For some refractory minerals, a good effect is attained by means of heating flotation. For example, Xianyang Qiu, et al. studied heating sulfurization and flotation dynamics of smithsonite, and have concluded that the surface properties of smithsonite can be modified directly through a heating sulfurization process and zinc sulfide surface is formed on partial surface of smithsonite and is beneficial for adsorption of an amine collecting agent to the surface of smithsonite. Heating can accelerate sulfurization and flotation of smithsonite, shorten flotation time, reduce reagent usage, and improve floatability and recycling ratio [Xianyang Qiu, et al., “Study of Heating Surface Sulfurized Flotation Dynamics of Smithsonite, Nonferrous Metals (Mineral Separation Section), 2007(1): 24-26]. Jianguang Guo, et al. renovated the heating flotation process of tungsten ores in Shizhuyuan, Hunan. It is proven that after the new heating flotation method is applied, the flow structure becomes more reasonable, the operation of the process becomes simpler, and the reagent removal and desulfurization procedures are canceled. With the new method, power consumption can be saved greatly every year, the metal loss during reagent removal is eliminated thoroughly, and the quality and recycling ratio of scheelite concentrate are improved [Jianguang Guo, et al., Practice of Renovation of Heating Flotation Process of Tungsten Ores in Shizhuyuan, Nonferrous Metals (Mineral Separation Section), 2002(6), 13-14],
Ore slime dispersion and control is helpful for performing flotation and improving flotation effect. Congjie Zhu studied the influence of ore slime on the behaviors of flotation of zinc oxide mineral. Ore slime has an influence on the up-floating of smithsonite by means of adsorption of the flotation reagent, coverage on the surface of smithsonite, and slight dissolution, and ore slime with a size of smaller than 5 pm has the highest influence. Besides, he has concluded that the influence of ore slime may be reduced by adding sodium hexametaphosphate and water glass in a small quantity and utilizing ultrasonic treatment [Congjie Zhu, ''Study on the Effect of Slimes on Flotation of Zinc Oxide Mineral, Comprehensive Utilization of Mineral Products, 2005(2):
7-11]. Qicheng Feng, et al. carried out flotation tests for argillaceous refractory copper oxide ores in Xinjiang, and has concluded: by adding an efficient combined ore slime inhibitor CHO+A22, the up-floating of ore slime in the flotation process is effectively inhibited, and the problem of frothy and highly-viscous pulp in the flotation process is solved. As a result, the entire flotation process is carried out smoothly, and finally indexes of 18.18% copper grade and 75.04% copper recycling ratio are achieved [Qicheng Feng, et al., Comprehensive Utilization of Mineral Products, 2011(6): 21-24, 49],
However, the wrapped copper oxide ores involved in the present invention are very refractory, and a satisfactory effect cannot be attained merely by heating or ore slime dispersion and inhibition.
The object of the present invention is to provide a method for recycling wrapped complex copper oxide ores, in which, for wrapped complex copper oxide ores that are difficult to be recycled by flotation and can be leached only at a poor leaching ratio by direct acid leaching, the free copper oxide mineral in the wrapped complex copper oxide ores is recycled by sulfurization and combined flotation with xanthate and aliphatic acid, and the copper-containing iron minerals and biotite mineral are recycled by magnetic separation, while low-grade copper-containing tailing is obtained at the same time; the copper mineral resource in the wrapped copper-containing rough concentrate is recycled by pressurized leaching at a high temperature; the copper in the low-grade copper-containing tailing is further leached out and recycled by means of the residual heat and the residual acid in the procedure of high-temperature pressurized leaching of pulp; thus, the wrapped complex copper oxide ores that cannot be recycled by direct flotation and direct acid leaching are recycled efficiently.
Summary of the Invention
The object of the present invention is attained with the following technical scheme:
a method for recycling wrapped complex copper oxide ores, comprising the following steps:
(1) for wrapped complex copper oxide ores with a binding ratio of less than 10%, with a copper distribution ratio of less than 40% in free copper oxide ore and a wrapped copper distribution ratio of 40%~50% in limonite, hematite and biotite, first, crushing and grinding the ores, wherein, grinding fineness is -0.074mm and the mass percentage is 75%~90%; then, loading the pulp produced in the grinding into an agitating vessel for size mixing to attain pulp having 35%~40% mass percentage concentration, adding 600~800g sodium sulfide and 1,000-1,500g water glass inhibitor per ton of dry ores, agitating for 4-6 min, adding 200~400g xanthate collecting agent, 200-3OOg hydroximic acid, and 3 00-5 OOg aliphatic acid collecting agent (sodium oleate or oxidized paraffin soap), agitating for 4-6 min, and carrying out rough flotation once and scavenging twice to produce rough flotation concentrate and flotation tailing;
(2) recycling the copper-wrapping iron minerals and biotite mineral in the flotation tailing obtained in the step (1) with a high-intensity magnetic field magnetic separator that has 1.0-1.6T magnetic induction intensity, to obtain magnetically separated concentrate, and obtain low-grade copper-containing magnetic-separating tailing at the same time;
(3) combining the rough flotation concentrate obtained in the step (1) and the magnetically separated concentrate obtained in the step (2) to obtain copper-containing rough concentrate, treating the copper-containing rough concentrate by sulfuric acid leaching in an autoclave under a condition of 2-3:1 liquid-to-solid ratio and controlling the pH value of the leach pulp at 1.0-1.5, charging high-temperature and high-pressure steam from the bottom of the autoclave for heating, controlling the pulp temperature at 100-130°C by controlling the amount of addition of the steam, and leaching for 90~120min.;
(4) discharging the leach pulp in the step (3) from the top of the autoclave, mixing the leach pulp with the low-grade copper-containing magnetically separated tailing, agitating the pulp further for 60~90min to leach out copper oxide, carrying out solidliquid separation after the leaching is completed, and treating the leachate by extraction and electro-deposition to obtain electro-deposited copper.
The hematite, limonite, and biotite inclusions contain 1.6-2.8% copper.
The copper grade in the wrapped copper oxide ores is 1.0%~2.0%.
The xanthate comprises isopentyl xanthate and butyl xanthate.
The pulp heating in the autoclave is realized by means of charging high-temperature and high-pressure steam from the bottom of the autoclave.
The present invention has the following advantages and beneficial effects:
(1) Free copper oxide mineral and copper-containing iron minerals can be recycled in one flotation cycle with a combined collecting agent;
(2) A part of weakly magnetic iron minerals and biotite that wrap the copper can be recycled by strong magnetic separation;
(3) A large quantity of low-grade copper-containing tailing can be separated by means of flotation and magnetic separation in combination, so that the quantity of ores entering into the high-temperature pressurized acid leaching process is reduced, and sulfuric acid consumption and heating cost are reduced;
(4) The high-temperature pressurized leach pulp is mixed with the low-grade coppercontaining tailing and the mixture is further leached, and the residual heat and residual acid from the high-temperature pressurized leaching are fully utilized to further recycle the copper resource lost in the tailing, and thereby the recycling ratio of copper is improved.
Brief Description of the Drawings
Fig. 1 is a flow chart of the process according to the present invention.
Detailed Description of the Drawings
Those skilled in the art should appreciate that the following examples are provided only to explain the present invention and shall not be deemed as limitation to the scope of the present invention. If no specific technique or condition is indicated in the example, the example is carried out by utilizing techniques or conditions described in available literature in the art or according to the product specification. Any reagent or instrument for which the manufacturer is not indicated is a conventional product that is commercially available.
Example 1:
For the wrapped complex copper oxide ores, the binding ratio is less than 10%, copper grade is 2.0%, the distribution ratio of copper in free copper oxide is 35%, copper content in hematite, limonite and biotite inclusions is 2.0-2.8%, the distribution ratio of copper in hematite, limonite and biotite is 50%, with quartz and kaolinite as main gangue minerals.
(1) First, the ores are crushed and ground, grinding fineness is -0.074mm and the mass percentage is 75%; then, the pulp produced in the grinding is loaded into an agitating vessel for size mixing, mass percentage concentration of pulp is 35%, 800g sodium sulfide and l,000g water glass inhibitor are added per ton of dry ores, the mixture is agitated for 4~6min, 400g isopentyl xanthate collecting agent, 300g hydroximic acid, and 500g sodium oleate are added, and the mixture is agitated for 4~6min; rough flotation is carried out once, and scavenging is carried out twice, so that rough flotation concentrate and flotation tailing are obtained finally.
(2) The iron minerals in the flotation tailing obtained in the step (1), which have not been recycled in the flotation, are recycled in a high-intensity magnetic field magnetic separator with 1.6T magnetic induction intensity, to obtain magnetically separated concentrate, and to obtain magnetic-separating tailing that contains 0.5% copper at the same time.
(3) The rough flotation concentrate obtained in the step (1) and the magnetically separated concentrate obtained in the step (2) are combined to obtain copper-containing rough concentrate, the copper-containing rough concentrate is treated by sulfuric acid leaching in a autoclave under a condition of 2:1 liquid-to-solid ratio, and the pH value of the leach pulp is controlled at 1.0-1.2, high-temperature and high-pressure steam is charged from the bottom of the autoclave for heating, the pulp temperature is controlled at 120~130°Cby controlling the amount of addition of the steam, and leaching is carried out for 120min.
(4) The leach pulp is discharged from the top of the autoclave and mixed with the lowgrade copper-containing tailing, the mixture is agitated for 90min for further leaching, solid-liquid separation is carried out after the leaching is completed, and the leachate is treated by extraction and electro-deposition to obtain electro-deposited copper.
The overall recycling ratio of copper is 90%.
Example 2:
For the wrapped complex copper oxide ores, the binding ratio is less than 10%, copper grade is 1.5%, the distribution ratio of copper in free copper oxide is 30%, copper content in hematite, limonite and biotite inclusions is 1.8-2.5%, the distribution ratio of copper in hematite, limonite and biotite is 47%, with quartz and kaolinite as main gangue minerals.
(1) First, the ores are crushed and ground, grinding fineness is -0.074mm and the mass percentage is 80%; then, the pulp produced in the grinding is loaded into an agitating vessel for size mixing, mass percentage concentration of pulp is 38%, 700g sodium sulfide and 1,200g water glass inhibitor are added per ton of dry ores, the mixture is agitated for 4~6min, 300g butyl xanthate collecting agent, 25 Og hydroximic acid, and 400g oxidized paraffin soap are added, and the mixture is agitated for 4~6min; rough flotation is carried out once, and scavenging is carried out twice, so that rough flotation concentrate and flotation tailing are obtained finally.
(2) The iron minerals in the flotation tailing are recycled in a high-intensity magnetic field magnetic separator with 1,4T magnetic induction intensity, to obtain magnetically separated concentrate, and to obtain magnetic-separating tailing that contains 0.4% copper at the same time.
(3) The rough flotation concentrate and the magnetically separated concentrate are combined to obtain copper-containing rough concentrate, the copper-containing rough concentrate is treated by sulfuric acid leaching in a autoclave under a condition of 2.5:1 liquid-to-solid ratio, and the pH value of the leach pulp is controlled at 1.2-1.3, hightemperature and high-pressure steam is charged from the bottom of the autoclave for heating, the pulp temperature is controlled at 110~120°Cby controlling the amount of addition of the steam, and leaching is carried out for lOOmin.
(4) The leach pulp is discharged from the top of the autoclave and mixed with the lowgrade copper-containing tailing, the mixture is agitated for 80min for further leaching, solid-liquid separation is carried out after the leaching is completed, and the leachate is treated by extraction and electro-deposition to obtain electro-deposited copper.
The overall recycling ratio of copper is 86%.
Example 3:
For the wrapped complex copper oxide ores, the binding ratio is less than 10%, copper grade is 1.5%, the distribution ratio of copper in free copper oxide is 39%, copper content in hematite, limonite and biotite inclusions is 1.6-2.0%, the distribution ratio of copper in hematite, limonite and biotite is 40%, with quartz and kaolinite as main gangue minerals.
(1) First, the ores are crushed and ground, grinding fineness is -0.074mm and the mass percentage is 90%; then, the pulp produced in the grinding is loaded into an agitating vessel for size mixing, mass percentage concentration of pulp is 40%, 600g sodium sulfide and l,000g water glass inhibitor are added per ton of dry ores, the mixture is agitated for 4~6min, 200g isopentyl xanthate collecting agent, 200g hydroximic acid, and 300g oxidized paraffin soap are added, and the mixture is agitated for 4~6min; rough flotation is carried out once, and scavenging is carried out twice, so that rough flotation concentrate and flotation tailing are obtained finally.
(2) The iron minerals in the flotation tailing, which have not been recycled in the flotation, are recycled in a high-intensity magnetic field magnetic separator with 1.0T magnetic induction intensity, to obtain magnetically separated concentrate, and to obtain magnetic-separating tailing that contains 0.3% copper at the same time.
(3) The rough flotation concentrate and the magnetically separated concentrate are combined to obtain copper-containing rough concentrate, the copper-containing rough concentrate is treated by sulfuric acid leaching in a autoclave under a condition of 3:1 liquid-to-solid ratio, and the pH value of the leach pulp is controlled at 1.3-1.5, hightemperature and high-pressure steam is charged from the bottom of the autoclave for heating, the pulp temperature is controlled at 100-110°C by controlling the amount of addition of the steam, and leaching is carried out for 90min.
(4) The leach pulp is discharged from the top of the autoclave and mixed with the lowgrade copper-containing tailing, the mixture is agitated for 60min for further leaching, solid-liquid separation is carried out after the leaching is completed, and the leachate is treated by extraction and electro-deposition to obtain electro-deposited copper.
The overall recycling ratio of copper is 80%.
The basic principle, main features and advantages of the present invention are illustrated and described above. Those skilled in the art should appreciate that the present invention is not limited to those examples. Those examples and description are provided only to explain the principle of the present invention. Various modifications and variations can be made to the present invention without departing from the spirit and scope of the present invention, and all of such modifications and variations shall be deemed as falling into the scope of protection of the present invention. The scope of protection of the present invention is only defined by the attached claims and their equivalents.
Claims (5)
- (1) for wrapped complex copper oxide ores with a binding ratio of less than 10%, with a copper distribution ratio of less than 40% in free copper oxide ore and a wrapped copper distribution ratio of 40%~50% in limonite, hematite and biotite, first, crushing and grinding the ores, wherein, grinding fineness is 0.074mm and the mass percentage is 75%~90%; then, loading the pulp produced in the grinding into an agitating vessel for size mixing to attain pulp having 35%~40% mass percentage concentration, adding 600~800g sodium sulfide and 1,000-1,500g water glass inhibitor per ton of dry ores, agitating for 4-6 min, adding 200~400g xanthate collecting agent, 200-3OOg hydroximic acid, and 3 00-5 OOg aliphatic acid collecting agent, agitating for 4-6 min, and carrying out rough flotation once and scavenging twice to produce rough flotation concentrate and flotation tailing;1. A method for recycling wrapped complex copper oxide ores, comprising the following steps:
- 2. The method for recycling wrapped complex copper oxide ores according to claim 1, wherein, the hematite, limonite, and biotite inclusions contain 1.6-2.8% copper.(2) recycling the copper-wrapping iron minerals and biotite mineral in the flotation tailing obtained in the step (1) with a high-intensity magnetic field magnetic separator that has 1.0-1.6T magnetic induction intensity, to obtain magnetically separated concentrate, and obtain low-grade copper-containing magnetic-separating tailing at the same time;
- 3. The method for recycling wrapped complex copper oxide ores according to claim 1, wherein, the copper grade in the wrapped copper oxide ores is 1.0%~2.0%.(3) combining the rough flotation concentrate obtained in the step (1) and the magnetically separated concentrate obtained in the step (2) to obtain coppercontaining rough concentrate, treating the copper-containing rough concentrate by sulfuric acid leaching in an autoclave under a condition of 2-3:1 liquid-to-solid ratio and controlling the pH value of the leach pulp at 1.0-1.5, controlling the pulp temperature at 100~103°C, and leaching for 90~120min.;
- 4. The method for recycling wrapped complex copper oxide ores according to claim 1, wherein, the xanthate comprises isopentyl xanthate and butyl xanthate.(4) discharging the leach pulp in the step (3) from the top of the autoclave, mixing the leach pulp with the low-grade copper-containing tailing, agitating for 60~90min to leach out, carrying out solid-liquid separation after the leaching is completed, and treating the leachate by extraction and electro-deposition to obtain electro-deposited copper.
- 5. The method for recycling wrapped complex copper oxide ores according to claim 1, wherein, the pulp heating in the autoclave is realized by means of charging hightemperature and high-pressure steam from the bottom of the autoclave.
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| PCT/CN2017/114280 WO2018161653A1 (en) | 2017-03-09 | 2017-12-01 | Method for recycling wrapped complex copper oxide ores |
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| CN115532427A (en) * | 2022-09-21 | 2022-12-30 | 中国地质科学院矿产综合利用研究所 | Method for echelon recycling and large-scale absorption of copper ore tailings |
| CN115747507A (en) * | 2022-12-01 | 2023-03-07 | 中铁资源集团有限公司 | Hydrometallurgical method for recovering copper from copper oxide ore |
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| CN106944244B (en) * | 2017-03-09 | 2018-01-12 | 昆明理工大学 | A kind of method that coated complex copper oxide ore recycles |
| CN107362901A (en) * | 2017-09-18 | 2017-11-21 | 万宝矿产有限公司 | A kind of flotation acidleach method for handling high-carbon hydrochlorate cupric oxide ore |
| CN107971123B (en) * | 2017-11-17 | 2020-01-10 | 昆明理工大学 | Dressing and smelting method of iron coated mixed copper ore |
| CN108160311B (en) * | 2017-11-24 | 2020-01-10 | 昆明理工大学 | Method for dressing and smelting weakly magnetic mineral coated sulfur-oxygen mixed zinc ore |
| CN110681477B (en) * | 2018-07-06 | 2021-08-10 | 厦门紫金矿冶技术有限公司 | Dressing and smelting combined treatment method for recovering complex copper oxide ore |
| CN109261343A (en) * | 2018-08-28 | 2019-01-25 | 昆明冶金高等专科学校 | A kind of method of complexity boleite selecting smelting combination separation |
| CN111266195B (en) * | 2020-03-05 | 2021-09-07 | 中南大学 | A combined collector for zinc oxide ore flotation and its application |
| CN113634375A (en) * | 2021-08-13 | 2021-11-12 | 西安建筑科技大学 | A kind of beneficiation method of low-grade mixed copper oxide ore |
| CN114522796B (en) * | 2022-02-23 | 2023-09-29 | 西部矿业股份有限公司 | Mineral separation method for pre-separation decalcification of low-grade marble copper oxide ore |
| CN114669398B (en) * | 2022-02-28 | 2023-08-18 | 玉溪大红山矿业有限公司 | Outdoor low-grade copper ore floatation process |
| CN115487932B (en) * | 2022-09-26 | 2024-04-09 | 昆明理工大学 | Method for surface pretreatment-xanthate flotation of silicate copper oxide ore |
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| RU2376069C2 (en) * | 2008-02-11 | 2009-12-20 | Общество с ограниченной ответственностью "Нординвэс" | Dressing module |
| CN101831559B (en) * | 2010-05-21 | 2012-05-30 | 昆明理工大学 | A kind of beneficiation and smelting method of carbonate gangue type oxygen-sulfur mixed copper ore with high binding rate |
| CN102051491B (en) * | 2010-11-19 | 2012-10-24 | 中南大学 | Method for concentrating gold from pyrite inclusion-type gold ore |
| JP2012139609A (en) * | 2010-12-28 | 2012-07-26 | Hirabayashi Kinzoku Kk | Sorting method of mixed metal |
| CN102266818A (en) * | 2011-07-09 | 2011-12-07 | 云南迪庆矿业开发有限责任公司 | Comprehensive treatment method for mixed copper mine |
| CN102688808B (en) * | 2012-06-19 | 2013-04-03 | 昆明理工大学 | Macromolecule bridging flotation method for combined copper disseminated body |
| DE102014200415A1 (en) * | 2013-12-20 | 2015-06-25 | Siemens Aktiengesellschaft | Process for the separation of a defined mineral substance phase from a ground ore |
| CN104815746A (en) * | 2015-04-09 | 2015-08-05 | 湖南有色金属研究院 | Recovery method of high-iron highly-argillaceous alkaline gangue refractory oxide copper ore |
| MX2017013512A (en) * | 2015-04-22 | 2018-04-24 | Anglo American Services Uk Ltd | Process for recovering value metals from ore. |
| CN105413854B (en) * | 2015-12-23 | 2018-02-13 | 中国地质科学院矿产综合利用研究所 | Beneficiation method for high-oxidation-rate copper-molybdenum paragenic ore |
| CN105420488A (en) * | 2015-12-30 | 2016-03-23 | 核工业北京化工冶金研究院 | Method for preprocessing wrapped uranium-molybdenum ores through oxidizing roasting |
| CN106944244B (en) * | 2017-03-09 | 2018-01-12 | 昆明理工大学 | A kind of method that coated complex copper oxide ore recycles |
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| CN115532427A (en) * | 2022-09-21 | 2022-12-30 | 中国地质科学院矿产综合利用研究所 | Method for echelon recycling and large-scale absorption of copper ore tailings |
| CN115747507A (en) * | 2022-12-01 | 2023-03-07 | 中铁资源集团有限公司 | Hydrometallurgical method for recovering copper from copper oxide ore |
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