WO2018161653A1 - 一种包裹型复杂氧化铜矿回收利用的方法 - Google Patents
一种包裹型复杂氧化铜矿回收利用的方法 Download PDFInfo
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- WO2018161653A1 WO2018161653A1 PCT/CN2017/114280 CN2017114280W WO2018161653A1 WO 2018161653 A1 WO2018161653 A1 WO 2018161653A1 CN 2017114280 W CN2017114280 W CN 2017114280W WO 2018161653 A1 WO2018161653 A1 WO 2018161653A1
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- WIPO (PCT)
- Prior art keywords
- copper
- copper oxide
- leaching
- minutes
- wrapped
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 53
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000010949 copper Substances 0.000 claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 claims abstract description 77
- 238000005188 flotation Methods 0.000 claims abstract description 51
- 238000002386 leaching Methods 0.000 claims abstract description 47
- 239000012141 concentrate Substances 0.000 claims abstract description 33
- 229910052626 biotite Inorganic materials 0.000 claims abstract description 20
- 238000007885 magnetic separation Methods 0.000 claims abstract description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000012991 xanthate Substances 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000194 fatty acid Substances 0.000 claims abstract description 5
- 229930195729 fatty acid Natural products 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 33
- 239000011707 mineral Substances 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 229910052595 hematite Inorganic materials 0.000 claims description 13
- 239000011019 hematite Substances 0.000 claims description 13
- 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 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005363 electrowinning Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000003814 drug Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 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
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 5
- 239000006148 magnetic separator Substances 0.000 claims description 5
- 238000002156 mixing Methods 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
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000010408 sweeping Methods 0.000 claims 1
- -1 fatty acid salt Chemical class 0.000 abstract description 3
- 239000002918 waste heat Substances 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 11
- 229910001608 iron mineral Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 241000907663 Siproeta stelenes Species 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical compound CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 description 2
- 108091005950 Azurite Proteins 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 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
- 238000010792 warming Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 229910001779 copper mineral Inorganic materials 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
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010802 sludge Substances 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 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
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
Images
Classifications
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- 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
Definitions
- the invention relates to a method for recycling and utilizing a wrapped complex copper oxide ore, belonging to the technical field of ore metallurgy.
- Copper oxide minerals mainly include malachite, chrysocolla, azurite, cuprite, ferrous copper, imaginary malachite, combined copper, etc., mainly with gangue minerals such as silicate, carbonate and iron oxide.
- gangue minerals such as silicate, carbonate and iron oxide.
- For independent oxidized copper ore such as malachite, chrysocolla, azurite, cuprite, epochrite, etc., it can be recovered by flotation of sulphide xanthate, which has high binding rate and dense symbiosis with silicate minerals. Copper ore can be recovered by means of sulfuric acid leaching, solid-liquid separation and extraction electrowinning.
- ammonia leaching, solid-liquid separation and extraction electrowinning can be used.
- Method of recycling For the illusion of malachite, part of the copper oxide ore is closely symbiotic with limonite, hematite and biotite, and some copper oxide ore is surrounded by iron and silicate minerals. The method utilized makes this part of the copper oxide ore resources not effectively recycled.
- Conventional vulcanization-xanthate flotation method is difficult to recover such copper oxide minerals because part of the copper oxide ore is encapsulated by hematite, limonite, biotite, and copper oxide minerals cannot be dissociated by monomers, vulcanizing agents and The collector xanthate is difficult to contact with the surface of the copper oxide mineral and cannot be floated to recover this part of the copper oxide mineral.
- Conventional ammonia leaching-extraction-electrowinning technology cannot effectively recover this part of copper oxide ore because ammonia cannot damage the structure of iron oxide ore and biotite, and it is difficult to contact with the encapsulated copper oxide mineral, and it is not effective to leach this part of copper oxide. mine.
- Application method of high-integration rate carbonate gangue type oxygen-sulfur mixed copper with application number 201010178875.2 is for oxygen-sulfur mixed copper ore with high bonding rate and high content of calcium-magnesium carbonate gangue minerals.
- the method can also not be used to treat the encapsulated copper oxide ore because the free copper oxide mineral in the encapsulated copper oxide ore is rare, and the sulfide yellow drug flotation has no good effect, while the calcium and magnesium are floating.
- the selection will cause some of the iron-containing minerals to enter the carbonate minerals, resulting in the loss of copper minerals.
- a polymer bridge flotation method combining copper impregnation body is a combined copper impregnation body which cannot be recovered by conventional flotation, and adopts polymer bridging agent, copper ion bridge ion and xanthate bridge.
- the collector is adsorbed by the polymer bridge ion on the surface of the copper-impregnated body, and the copper ion is adsorbed on the bridged adsorbent on the surface, and the collector xanthate anion is adsorbed on the bridged copper ion.
- the surface of the copper-impregnated body is made hydrophobic to achieve flotation. This method can not be effectively used for the recovery and utilization of the encapsulated copper oxide ore. The reason is that the polymer of the compound of the overseas Chinese cannot be combined with the copper oxide ore which is surrounded by gangue minerals such as hematite, limonite and biotite.
- the HSC flotation method recovers the copper oxide mineral.
- Some refractory minerals have achieved good results through warming flotation.
- Qiu Xianyang et al. studied the kinetics of refining and flocculation of rhombohedrite.
- Changing the surface properties of the smithsonite, forming a part of the surface of the zinc sulfide on the surface, is beneficial to the adsorption of the amine collector on the surface; heating can accelerate the flotation rate of the renosol, shorten the flotation time, and reduce the dosage of the agent.
- the dispersion and control of the slime is beneficial to the flotation and the flotation effect.
- Zhu Congjie studied the effect of slime on the flotation behavior of zinc oxide minerals. The sludge was adsorbed by flotation reagents, and the cover on the surface of the zinc ore and the micro-dissolution affected the uplift of the sphalerite, and the effect was less than 5 micron. For the biggest.
- the object of the present invention is to provide a method for recycling and utilizing a packaged complex copper oxide ore.
- a packaged complex copper oxide ore which is difficult to float and recover and has a low direct acid leaching rate, a vulcanization, a yellow drug flotation, a fatty acid combined flotation is used.
- Free copper oxide, magnetic recovery of copper-bearing iron minerals and biotite minerals, while obtaining low-grade copper-bearing tailings, and copper-containing coarse concentrates are recovered by high temperature pressure leaching to recover copper resources.
- the copper in the low-grade copper-containing tailings is recovered by the waste heat and residual acid of the high-temperature pressure leaching slurry, and the high-efficiency recycling of the wrapped complex copper oxide ore which cannot be directly floated and directly acid-leached is realized.
- a method for recycling a packaged complex copper oxide ore is carried out as follows:
- the distribution ratio of copper in the free copper oxide ore is less than 40%, and the distribution ratio of copper wrapped in limonite, hematite and biotite is 40% to 50%.
- the ore is firstly crushed and ground. The fineness of the grinding is -0.074mm, and the mass percentage is 75% to 90%.
- the slurry after grinding enters the mixing tank to adjust the pulp. The concentration of the pulp is 35% ⁇ 40.
- step (2) recovering the copper-coated iron and biotite minerals from the flotation tailings of step (1) with a strong magnetic field magnetic separator with a magnetic induction strength of 1.0T to 1.6T, and obtaining a low-grade copper-containing concentrate.
- Magnetic separation tailings
- step (3) Combining the flotation coarse concentrate of step (1) with the magnetic separation concentrate of step (2) to obtain a copper-containing coarse concentrate, and the copper-containing coarse concentrate is in a liquid-solid ratio of 2 to 3:1.
- Sulfuric acid leaching in the autoclave the pH value of the leaching slurry is controlled at 1.0 to 1.5, and high temperature and high pressure steam is introduced from the bottom of the autoclave for heating, and the temperature of the slurry is controlled by the amount of steam to be 100 to 130 degrees Celsius, and the leaching time is 90. Minutes to 120 minutes;
- step (3) The leaching slurry of step (3) is discharged from the top of the pressurized kettle, mixed with the low-grade copper-containing magnetic separation tailings, and the slurry is continuously stirred to leaching the copper oxide for 60 minutes to 90 minutes, the leaching is finished, the solid-liquid separation, the leaching solution
- the electrowinning copper is obtained by extracting electrowinning.
- the hematite, limonite, and biotite inclusions contain 1.6 to 2.8% of copper.
- the encapsulated copper oxide ore has a copper grade of 1.0% to 2.0%.
- the xanthate is isoamyl and butyl xanthate.
- the slurry heating in the autoclave is achieved by passing high temperature and high pressure steam to the bottom of the autoclave.
- the free copper oxide ore and copper-bearing iron mineral can be floated at one time by using a combined collector;
- the high-temperature pressure leaching slurry is mixed with the low-grade copper-containing tailings, and the leaching is continued, and the waste heat and residual acid of the high-temperature pressure leaching are fully utilized to further recover the copper resources lost in the tailings and improve the recovery rate of copper.
- Figure 1 is a process flow diagram of the present invention.
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- the combined rate of encapsulated complex copper oxide ore is less than 10%, the copper grade is 2.0%, the distribution of copper in free copper oxide is 35%, and the hematite, limonite and biotite inclusions contain 2.0 to 2.8% of copper.
- the distribution of copper in hematite, limonite and biotite is 50%, and quartz and kaolinite are the main gangue minerals.
- the fineness of grinding is -0.074mm, and the mass percentage is 75%.
- the slurry after grinding enters the mixing tank to adjust the pulp.
- the concentration of pulp is 35%, and it is dry per ton.
- the amount of minerals is first added with 800 g of sodium sulfide, 1000 g of inhibitor water glass is added, and the mixture is stirred for 4 minutes to 6 minutes.
- the collector is 400 g of isoamyl xanthate, 300 g of hydroxamic acid, 500 g of sodium oleate, and stirred for 4 minutes. ⁇ 6 minutes, after a rough selection and a second sweep, the flotation coarse concentrate and flotation tailings are finally produced.
- step (1) The flotation tailings of step (1) are recovered by a strong magnetic field magnetic separator with a magnetic induction intensity of 1.6T.
- the unselected iron mineral was selected to obtain a magnetic separation concentrate, and at the same time, a magnetic separation tailing of 0.5% copper was obtained.
- step (3) Combining the flotation coarse concentrate of step (1) with the step (2) magnetic separation concentrate to obtain a copper-containing coarse concentrate, and the copper-containing coarse concentrate is pressurized under the condition of a liquid-solid ratio of 2:1.
- the sulfuric acid leaching is carried out in the kettle, and the pH value of the leaching slurry is controlled at 1.0 to 1.2.
- the high temperature and high pressure steam is introduced from the bottom of the pressure vessel to be heated, and the temperature of the slurry is controlled by the steam addition amount to 120 to 130 degrees Celsius, and the leaching time is 120 minutes.
- the top of the leaching slurry pressurizer is discharged, mixed with the low-grade copper-containing tailings, and the leaching is continued for 90 minutes.
- the leaching is completed, the solid-liquid separation is performed, and the leaching solution is obtained by extracting electrowinning.
- the overall recovery rate of copper is 90%.
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- the combined rate of encapsulated complex copper oxide ore is less than 10%, the copper grade is 1.5%, the distribution of copper in free copper oxide is 30%, hematite, limonite, biotite contains 1.8 to 2.5% copper, and red iron The distribution of copper in ore, limonite and biotite is 47%, and quartz and kaolinite are the main gangue minerals.
- the fineness of grinding is -0.074mm, and the mass percentage is 80%.
- the slurry after grinding enters the mixing tank to adjust the pulp.
- the mass concentration of the pulp is 38%, and it is dry per ton.
- the amount of minerals is first added with 700 g of sodium sulfide, 1200 g of inhibitor water glass is added, stirred for 4 minutes to 6 minutes, collector butyl xanthate 300 g, hydroxamic acid 250 g, oxidized paraffin soap 400 g, stirred for 4 minutes ⁇ After 6 minutes, after a rough selection and a second sweep, the flotation coarse concentrate and flotation tailings are finally produced.
- the copper-bearing coarse concentrate is leached in the autoclave under the condition of liquid-solid ratio of 2.5:1, and the pH of the slurry is leached.
- the value is controlled at 1.2 to 1.3, and the high temperature and high pressure steam is introduced from the bottom of the autoclave to be heated, and the temperature of the slurry is controlled by the steam addition amount to be 110 to 120 degrees Celsius, and the leaching time is 100 minutes.
- the overall recovery rate of copper is 86%.
- Embodiment 3 is a diagrammatic representation of Embodiment 3
- the combined rate of encapsulated complex copper oxide ore is less than 10%, the copper grade is 1.0%, the distribution of copper in free copper oxide is 39%, hematite, limonite and biotite contain 1.6-2.0% copper. Mine, limonite, black The distribution of copper in mica is 40%, and quartz and kaolinite are the main gangue minerals.
- the fineness of grinding is -0.074mm, and the mass percentage is 90%.
- the slurry after grinding enters the mixing tank to adjust the slurry.
- the concentration of pulp is 40%, and it is dried per ton.
- the amount of minerals is first added with 600 g of sodium sulfide, 1000 g of inhibitor water glass is added, and the mixture is stirred for 4 minutes to 6 minutes.
- the collector is 200 g of isoamyl xanthate, 200 g of hydroxamic acid, 300 g of oxidized paraffin soap, and stirred for 4 minutes. ⁇ 6 minutes, after a rough selection and a second sweep, the flotation coarse concentrate and flotation tailings are finally produced.
- the leaching slurry is pressurized and discharged from the top of the kettle, mixed with the low-grade copper-containing tailings, and the leaching is continued for 60 minutes.
- the leaching is completed, and the solid-liquid separation is performed.
- the leaching solution is obtained by extracting electrowinning.
- the overall recovery rate of copper is 80%.
Abstract
Description
Claims (5)
- 一种包裹型复杂氧化铜矿回收利用的方法,其特征在于按以下步骤进行:(1)对于结合率小于10%,游离氧化铜矿中铜的分布率小于40%,褐铁矿、赤铁矿、黑云母中包裹铜的分布率40%~50%的包裹型复杂氧化铜矿石,首先进行碎矿和磨矿,磨矿细度为-0.074mm质量百分含量占75%~90%,磨矿后的矿浆进入搅拌桶调浆,矿浆质量百分浓度35%~40%,按照每吨干矿量加入硫化钠600克~800克,加入抑制剂水玻璃1000克~1500克,搅拌4分钟~6分钟,捕收剂黄药200克~400克,羟肟酸200克~300克,脂肪酸类捕收剂300克~500克,搅拌4分钟~6分钟,经过一次粗选、二次扫选,产出浮选粗精矿和浮选尾矿;(2)将步骤(1)的浮选尾矿用磁感应强度为1.0T~1.6T的强磁场磁选机回收包裹铜的铁质和黑云母矿物获得磁选精矿,同时获得低品位含铜磁选尾矿;(3)将步骤(1)的浮选粗精矿和步骤(2)的磁选精矿合并获得含铜粗精矿,含铜粗精矿在液固比为2~3:1的条件下在加压釜中进行硫酸浸出,浸出矿浆pH值控制在1.0~1.5,矿浆温度摄氏100度~130度,浸出时间90分钟~120分钟;(4)将步骤(3)的浸出矿浆从加压釜顶部放出,与低品位含铜尾矿混合搅拌浸出60分钟~90分钟,浸出结束,固液分离,浸出液采用萃取电积获得电积铜。
- 根据权利要求1所述的包裹型复杂氧化铜矿回收利用的方法,其特征在于,所述的赤铁矿、褐铁矿、黑云母包裹体含铜1.6~2.8%。
- 根据权利要求1所述的包裹型复杂氧化铜矿回收利用的方法,其特征在于,所述的包裹型氧化铜矿石含铜品位为1.0%~2.0%。
- 根据权利要求1所述的包裹型复杂氧化铜矿回收利用的方法,其特征在于,所述的黄药为异戊基和丁基黄药。
- 根据权利要求1所述的包裹型复杂氧化铜矿回收利用的方法,其特征在于,加压釜中的矿浆加热通过在加压釜底部通入高温高压蒸汽来实现。
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