CN113388741A - Method for comprehensively recovering copper and cobalt from copper oxide cobalt ore - Google Patents
Method for comprehensively recovering copper and cobalt from copper oxide cobalt ore Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 164
- 239000010941 cobalt Substances 0.000 title claims abstract description 164
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 83
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 51
- FWZLXRFUDMNGDF-UHFFFAOYSA-N [Co].[Cu]=O Chemical compound [Co].[Cu]=O FWZLXRFUDMNGDF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000605 extraction Methods 0.000 claims abstract description 162
- 238000001556 precipitation Methods 0.000 claims abstract description 117
- 238000005406 washing Methods 0.000 claims abstract description 98
- 238000002156 mixing Methods 0.000 claims abstract description 96
- 238000002386 leaching Methods 0.000 claims abstract description 95
- 239000002893 slag Substances 0.000 claims abstract description 33
- 239000012535 impurity Substances 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000011084 recovery Methods 0.000 claims abstract description 25
- 238000004062 sedimentation Methods 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- 229910052569 sulfide mineral Inorganic materials 0.000 claims abstract description 6
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004071 soot Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 82
- 239000002562 thickening agent Substances 0.000 claims description 74
- 238000006386 neutralization reaction Methods 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 32
- 239000012074 organic phase Substances 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 24
- 239000008267 milk Substances 0.000 claims description 22
- 210000004080 milk Anatomy 0.000 claims description 22
- 235000013336 milk Nutrition 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 18
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 18
- 238000004070 electrodeposition Methods 0.000 claims description 18
- 239000004571 lime Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 230000003472 neutralizing effect Effects 0.000 claims description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 10
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 8
- 229910052947 chalcocite Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000011085 pressure filtration Methods 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052683 pyrite Inorganic materials 0.000 claims description 6
- 239000011028 pyrite Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 230000008719 thickening Effects 0.000 claims description 6
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000008235 industrial water Substances 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 abstract description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 abstract description 4
- 235000010265 sodium sulphite Nutrition 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000000741 silica gel Substances 0.000 abstract description 2
- 229910002027 silica gel Inorganic materials 0.000 abstract description 2
- 229940001584 sodium metabisulfite Drugs 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
Images
Classifications
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- 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
- 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
- C22B15/0084—Treating solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a method for comprehensively recovering copper and cobalt from copper oxide cobalt ores, which comprises the steps of size mixing, leaching, concentration and washing, copper recovery, cobalt recovery from low-copper raffinate and the like. Under the conditions of high ore pulp concentration and increasing the ore pulp temperature to 60-85 ℃ by utilizing the heat release of concentrated sulfuric acid, the invention adopts the sulfide minerals, the copper sulfide slag obtained by treating the copper-containing solution by adopting a sulfide precipitation method, and smelting soot of incompletely oxidized sulfide minerals to replace sodium pyrosulfite or sodium sulfite to be used as cobalt leachingThe reducing agent is discharged, SO that the cost of the reducing agent is greatly reduced, and SO is prevented from being generated when sodium metabisulfite or sodium sulfite is used as a cobalt leaching reducing agent in an acidic environment2Causing environmental unfriendliness. More importantly, under the conditions of high ore pulp concentration and high-temperature leaching, the leaching rate of copper and cobalt is improved, the leaching of harmful impurity silicon is greatly reduced, and the adverse effect of silica gel generation on subsequent procedures such as sedimentation, extraction and the like is reduced.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a method for comprehensively recovering copper and cobalt from copper oxide cobalt ores.
Background
The extraction process of the copper-cobalt oxide ore can be generally divided into a pyrogenic process and a wet process, wherein the pyrogenic process is represented by a process for producing crude copper or copper-cobalt alloy by electric furnace reduction smelting, and the conventional principle flow of the wet process is 'leaching-purification-precipitation'. With the development of science and technology, the cobalt extraction technology at home and abroad has new development, including sulfuric acid pressure leaching, solvent extraction, bioleaching technology and the like. At present, the sulfuric acid leaching, the pressure ammonia leaching and the biotechnology can realize the recycling of copper and cobalt in the copper-cobalt oxide ore. The sulfuric acid leaching and the pressurized ammonia leaching are both realized for industrial implementation and application, but most cobalt production enterprises adopt the traditional acid leaching process, the process has long service life, mature process conditions and simple operation, and has the defects that a large amount of silicon is leached in the acid leaching process, the subsequent sedimentation and extraction are influenced, the acid leaching environment is not friendly, the cobalt recovery and impurity removal process is complicated, the cobalt recovery rate is low, the medicament consumption is large, the cost is high and the like; the pressurized ammonia leaching can recycle ammonia, but has higher investment and actual production cost.
With the increasingly decreasing global mineral resource amount and the stricter environmental protection policy, it is particularly urgent to find a method for comprehensively recovering copper and cobalt from copper oxide cobalt ore, which has the advantages of short process flow, simple operation, low production cost, strong adaptability, high recovery rate of valuable metals and environmental friendliness.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for comprehensively recovering copper and cobalt from copper oxide cobalt ores.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for comprehensively recovering copper and cobalt from copper oxide cobalt ore comprises the following specific steps:
s1, size mixing: grinding the copper oxide cobalt ore until the granularity is-74 mu m and the mass ratio is 70-80%, then adding the copper oxide cobalt ore into a size mixing tank, and adding the solution A into the size mixing tank to obtain ore pulp with the mass percentage concentration of 55-60%; adding concentrated sulfuric acid to adjust the pH value of the ore pulp to 1.0-1.5, controlling the temperature of the ore pulp to 60-85 ℃, simultaneously adding a reducing agent B, and adjusting the oxidation-reduction potential of the ore pulp to 350mv of 300-;
s2, leaching: conveying the ore pulp finally obtained in the step S1 to a No. 1 acid leaching tank with mechanical stirring, and then sequentially carrying out n-grade leaching reaction through a No. 2 acid leaching tank, a No. 3 acid leaching tank, a No. … … acid leaching tank and a No. n acid leaching tank, wherein the total reaction time is 5-7 h; after the reaction is finished, adding the solution C into the n # acid leaching tank, and adjusting the mass percentage concentration of the ore pulp in the n # acid leaching tank to 8-15%;
s3, concentration, thickening and washing: sending the ore pulp in the n # acid leaching tank to a concentration thickener for sedimentation to obtain a concentration overflow and a concentration bottom flow, carrying out countercurrent washing on the concentration bottom flow by adopting an m-level washing thickener, sending the washing overflow obtained by the 1 st-level washing thickener and the concentration overflow to a material liquid pool for mixing to obtain an extraction material liquid, adding washing water from the m-level washing thickener, mixing the washing water and the m-1 st-level bottom flow, then entering the m-level washing thickener, neutralizing the bottom flow obtained by the m-level washing thickener by adopting lime milk until the pH value is 6-9, then sending the obtained bottom flow to a slag pulp pool for storage, automatically flowing the obtained overflow of the m-level washing thickener into the m-1-level washing thickener, mixing the obtained overflow with the m-2-level washing thickener bottom flow, then entering the m-1-level washing thickener, and so on;
s4, copper recovery: arranging an extraction first-stage mixing tank, an extraction second-stage mixing tank and an extraction third-stage extraction mixing tank; pumping the extraction liquid obtained in the step S3 into an extraction first-stage mixing tank and an extraction second-stage mixing tank respectively, mixing the extraction liquid entering the extraction first-stage mixing tank with an organic phase, and performing first-stage extraction only to obtain a high-copper raffinate; mixing the extraction feed liquid entering the second-stage extraction mixing tank with an organic phase, performing second-stage extraction, and entering a third-stage extraction mixing tank for third-stage extraction to obtain a low-copper raffinate; in the extraction process, the organic phase flows to the third stage extraction flow and the second stage extraction flow, and then flows from the second stage extraction flow to the first stage extraction flow; the loaded organic phase flowing out from the first-stage extraction is subjected to reverse extraction by using an electrodeposition barren solution, the obtained reverse extraction copper-rich solution is sent into an electrodeposition system for electrodeposition to obtain cathode copper, and the reverse extraction empty loaded organic phase is returned to the extraction third-stage extraction mixing tank, and the process is circulated;
s5, recovering cobalt from the low-copper raffinate:
s5.1, neutralizing, removing acid and removing impurities: sending the low-copper raffinate obtained in the step S4 into a neutralization tank, introducing air into the neutralization tank, stirring and reacting for 30-60 min, then adding a neutralizing agent D into the neutralization tank for neutralization reaction, controlling the neutralization reaction time to be 120-180 min, and controlling the end-point pH value of neutralization reaction slag slurry to be 5.2-5.6; after the reaction is finished, carrying out dense settling to obtain a neutralization acid and impurity removal overflow and a neutralization acid and impurity removal underflow, and sending the neutralization acid and impurity removal underflow to a level 1 washing thickener in step S3 to further recover copper and cobalt in the neutralization acid and impurity removal underflow;
s5.2, first-stage cobalt precipitation: feeding the neutralized, acid-removed and impurity-removed overflow obtained in the step S5.1 into a No. 1 cobalt precipitation tank, sequentially carrying out k-level first-stage cobalt precipitation reaction through a No. 2 cobalt precipitation tank, … … and a No. k cobalt precipitation tank, and adding active magnesium oxide emulsion into the No. 1 cobalt precipitation tank; controlling the total reaction time to be 5-7h, simultaneously controlling the pH value of the k # cobalt precipitation tank to be 8.0-8.3, and obtaining a cobalt hydroxide product and a first-stage cobalt precipitation filtrate after the reaction is finished and pressure filtration;
s5.3, secondary cobalt precipitation: feeding the first-stage cobalt precipitation filtrate into a second-stage cobalt precipitation reaction tank, adding lime milk for carrying out second-stage cobalt precipitation reaction for 2-3h, and controlling the pH value of the second-stage cobalt precipitation reaction end point to be 8.4-8.6; and after the reaction is finished, filter pressing is carried out to obtain second-stage cobalt precipitation slag and second-stage cobalt precipitation filtrate, the second-stage cobalt precipitation slag returns to a neutralization tank for neutralization, acid removal and impurity removal, and the second-stage cobalt precipitation filtrate is sent to an m-th-level washing thickener to be used as washing water.
Further, the solution a is industrial water in the initial period of operation, and the high copper raffinate obtained in step S4 is used after the operation is stable.
Further, in step S1, the reducing agent B is one or more of chalcocite, pyrite, copper sulfide slag obtained by treating a copper-containing solution by a sulfide precipitation method, and smelting soot in which sulfide minerals are not completely oxidized.
Furthermore, the chalcocite and the pyrite are ground to be more than 60% of the particle size of-20 μm in mass.
In step S2, the solution C is a sulfuric acid solution having a pH of 1.8 to 2.0 at the initial stage of operation, and the supernatant of the thickener is used after the operation is stabilized.
Further, in step S2, n.gtoreq.4.
Further, in step S3, m.gtoreq.4.
Further, in step S5.2, the activated magnesium oxide milk is added intermittently, and the activated magnesium oxide milk added secondarily is prepared before each addition.
Further, in step S4, the neutralizing agent D is one or more of limestone powder slurry, lime milk, and sodium hydroxide.
Further, in step S5.2, k is equal to or greater than 3.
The invention has the beneficial effects that:
(1) according to the invention, under the conditions of high ore pulp concentration and increasing the ore pulp temperature to 60-85 ℃ by utilizing concentrated sulfuric acid heat release, the copper sulfide slag obtained by treating a copper-containing solution by adopting a sulfide precipitation method and sulfide mineral incompletely oxidized smelting soot are adopted to replace sodium pyrosulfite or sodium sulfite as a cobalt leaching reducing agent, SO that the cost of the reducing agent is greatly reduced, and SO generated when the sodium pyrosulfite or sodium sulfite is adopted as the cobalt leaching reducing agent in an acidic environment is avoided2Causing environmental unfriendliness. Of greater importanceUnder the conditions of high ore pulp concentration and high-temperature leaching, the leaching rate of copper and cobalt is improved, the leaching of harmful impurity silicon is greatly reduced, and the adverse effect of silica gel generation on subsequent procedures such as sedimentation, extraction and the like is reduced.
(2) The invention adopts the supernatant of the concentration thickener to dilute the acid leaching pulp, thereby not only improving the sedimentation effect of the acid leaching pulp, but also ensuring the copper and cobalt concentrations of the leaching liquid.
(3) In the invention, the copper concentration of the raffinate obtained by the primary extraction of part of the extraction liquid is higher, and the raffinate is returned to the pulp for size mixing before acid leaching, so that the copper content of the acid leaching liquid is ensured; part of the extraction liquid adopts raffinate with extremely low copper concentration obtained by two-stage extraction to be sent to a cobalt precipitation system for recovering cobalt, so that on one hand, the copper loss is reduced, the total recovery rate of copper is improved, and on the other hand, the copper content in a cobalt product is well controlled.
(4) In the invention, the active magnesium oxide emulsion is prepared discontinuously and added discontinuously, thus ensuring the activity of magnesium oxide, improving the utilization rate of magnesium oxide and reducing the consumption of magnesium oxide and the magnesium content of cobalt products.
(5) The method for treating the copper oxide cobalt ore has the advantages of simple operation, strong adaptability, low medicament and production cost, environmental friendliness, easy industrialization and the like, can realize high-efficiency recovery of copper and cobalt, and has huge economic, social and environmental benefits.
Drawings
FIG. 1 is a schematic flow chart of a method according to various embodiments of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
Example 1
In this example, a copper cobalt oxide ore was used in china, and the analysis results of the main elements are shown in table 1.
TABLE 1 analysis result of main element of certain copper oxide cobalt ore in China
The embodiment provides a method for comprehensively recovering copper and cobalt from copper-cobalt oxide ore, which treats the copper-cobalt oxide ore, as shown in fig. 1, and comprises the following specific processes:
s1, size mixing: finely grinding the copper-cobalt oxide ore until the granularity is-74 mu m and the proportion is 70%, then adding the copper-cobalt oxide ore into a size mixing tank, adjusting the copper-cobalt oxide ore to the pulp mass percentage concentration of 60% in the processing water of the size mixing tank, adding concentrated sulfuric acid to adjust the pH value of the pulp to 1.0, heating the pulp to 80 ℃ by the heat release of the concentrated sulfuric acid, and finally adding chalcocite to adjust the redox potential of the pulp to 350 mv. The chalcocite is ground to the granularity of-20 mu m and the mass ratio of the chalcocite is more than 60 percent.
S2, leaching: and (3) conveying the ore pulp prepared in the step (S1) to a No. 1 acid leaching tank with mechanical stirring, then sequentially passing through a No. 2 acid leaching tank, a No. 3 acid leaching tank, a No. 4 acid leaching tank, a No. 5 acid leaching tank and a No. 6 acid leaching tank to carry out 6-stage leaching reaction, wherein the total reaction time is 7 hours, after the reaction is finished, a sulfuric acid solution with the pH value of 2.0 is added into the No. 6 acid leaching tank, and the mass percentage concentration of the ore pulp in the No. 6 tank is adjusted to 15%.
S3, concentration, thickening and washing: sending the ore pulp after the reaction of the No. 6 acid leaching tank to a concentration thickener for sedimentation to obtain concentration overflow and concentration underflow, carrying out countercurrent washing on the concentration underflow by using a 4-level washing thickener, sending the washing overflow and the concentration overflow obtained by the 1-level washing thickener to a material liquid pool for mixing to obtain extraction material liquid, adding washing water from the 4-level washing thickener, mixing the washing water with the 3-level underflow, then sending the mixture to the 4-level washing thickener, neutralizing the underflow obtained by the 4-level washing thickener by using lime milk until the pH value is 9, then sending the obtained underflow to a slag pulp pool for storage, automatically flowing the overflow obtained by the 4-level washing thickener into the 3-level washing thickener, mixing the obtained overflow with the underflow of the 2-level washing thickener, then sending the obtained overflow to the 3-level thickener, and so on;
s4, copper recovery: arranging an extraction first-stage mixing tank, an extraction second-stage mixing tank and an extraction third-stage extraction mixing tank; and (4) pumping the extraction liquid obtained in the step (S3) into the extraction first-stage mixing tank and the extraction second-stage mixing tank respectively, mixing the extraction liquid entering the extraction first-stage mixing tank with the organic phase, and performing first-stage extraction only to obtain the high-copper raffinate. Mixing the extraction liquid entering the second-stage extraction mixing tank with an organic phase, and sequentially carrying out second-stage extraction and third-stage extraction to obtain a low-copper raffinate; in the extraction process, the organic phase flows to the third stage extraction flow and the second stage extraction flow, and then flows from the second stage extraction flow to the first stage extraction flow; and (3) carrying out back extraction on the loaded organic phase flowing out from the first-stage extraction by using an electrodeposition barren solution, sending the obtained back-extraction copper-rich solution into an electrodeposition system for electrodeposition to obtain cathode copper, and returning the back-extraction empty loaded organic phase to the extraction third-stage extraction mixing tank, and circulating the steps.
S5, recovering cobalt from the low-copper raffinate: the cobalt recovery of the low-copper raffinate comprises the working procedures of neutralization, acid removal, impurity removal, first-stage cobalt precipitation and second-stage cobalt precipitation, and comprises the following specific steps:
s5.1, neutralizing, removing acid and removing impurities: and (3) conveying the low-copper raffinate obtained in the step S4 to a neutralization tank, introducing air, stirring and reacting for 50min, adding limestone powder slurry into the neutralization tank, performing neutralization reaction for 60min, adding lime milk, performing neutralization reaction for 120min, controlling the pH value of the slag slurry at the end point of the neutralization reaction to be 5.4, performing concentration and sedimentation after the reaction is finished, obtaining a neutralization acid-removal impurity-removal overflow and a neutralization acid-removal impurity-removal underflow, conveying the neutralization acid-removal impurity-removal underflow to a level 1 washing thickener in the step S3, and further recovering copper and cobalt in the neutralization acid-removal impurity-removal underflow slag slurry.
S5.2, first-stage cobalt precipitation: and (3) feeding the neutralized, acid-removed and impurity-removed overflow into a No. 1 cobalt precipitation tank, adding active magnesium oxide emulsion into the No. 1 cobalt precipitation tank at intervals, then sequentially carrying out 3-stage first-stage cobalt precipitation reaction through a No. 2 cobalt precipitation tank and a No. 3 cobalt precipitation tank, controlling the total reaction time to be 7h, simultaneously controlling the pH value of the No. 3 cobalt precipitation tank to be 8.3, and carrying out filter pressing after the reaction is finished to obtain a cobalt hydroxide product and a first-stage cobalt precipitation filtrate. The active magnesium oxide emulsion is prepared discontinuously according to the time of discontinuous addition.
S5.3, secondary cobalt precipitation: and (3) conveying the first-stage cobalt precipitation filtrate to a second-stage cobalt precipitation reaction tank, adding lime milk to perform second-stage cobalt precipitation reaction for 2 hours, controlling the pH value of the second-stage cobalt precipitation reaction end point to be 8.6, performing pressure filtration after the reaction is finished to obtain second-stage cobalt precipitation slag and second-stage cobalt precipitation filtrate, returning the second-stage cobalt precipitation slag to a neutralization tank for neutralization, acid removal and impurity removal, and conveying the second-stage cobalt precipitation filtrate to a 4 th-stage washing thickener to be used as water for washing CCD.
In this example, the copper leaching rate and the recovery rate were 92.42% and 90.73%, respectively, the cobalt leaching rate and the recovery rate were 87.92% and 82.36%, respectively, and the cobalt content of the cobalt hydroxide product was 31.14%.
Example 2
In this example, a cobalt-copper oxide ore of Congo (gold) was used, and the analysis results of the main elements are shown in Table 2.
TABLE 2 analysis results of main elements of a cobalt-copper oxide ore from Congo (gold)
In this embodiment, a method for comprehensively recovering copper and cobalt from a copper-cobalt oxide ore is adopted to treat the copper-cobalt oxide ore, as shown in fig. 1, the specific process is as follows:
s1, size mixing: the copper-cobalt oxide ore is finely ground until the granularity is-74 mu m and the proportion is 75%, then the copper-cobalt oxide ore is added into a size mixing tank, the copper-cobalt oxide ore is adjusted to the mass percent concentration of 55% in the pulp by the processing water of the size mixing tank, concentrated sulfuric acid is added to adjust the pH value of the pulp to 1.2, the concentrated sulfuric acid releases heat to heat the pulp to 85 ℃, and pyrite is added to adjust the redox potential of the pulp to 330 mv. The pyrite is ground to be with the granularity of-20 mu m and the mass ratio of more than 60 percent.
S2, leaching: and (3) conveying the ore pulp prepared in the step (S1) to a No. 1 acid leaching tank with mechanical stirring, then sequentially passing through a No. 2 acid leaching tank, a No. 3 acid leaching tank, a No. 4 acid leaching tank, a No. 5 acid leaching tank and a No. 6 acid leaching tank to carry out 6-stage leaching reaction, wherein the total reaction time is 6 hours, after the reaction is finished, a sulfuric acid solution with the pH value of 1.8 is added into the No. 6 acid leaching tank, and the mass percentage concentration of the ore pulp in the No. 6 acid leaching tank is adjusted to 10%.
S3, concentration, thickening and washing: sending the ore pulp after the reaction of the No. 6 acid leaching tank to a concentration thickener for sedimentation to obtain a concentration overflow and a concentration underflow, then adopting a 5-level washing thickener for countercurrent washing, mixing the washing overflow obtained by the 1 st-level washing thickener with a concentration overflow feeding liquid pool to obtain an extraction liquid, adding washing water from the 5 th-level washing thickener, mixing the washing water with the 4 th-level underflow, then entering the 5 th-level washing thickener, neutralizing the underflow obtained by the 5 th-level washing thickener by using lime milk until the pH value is 8.5, then sending the obtained underflow to a slag pulp pool for storage, automatically flowing the obtained overflow of the 5 th-level washing thickener into the 4 th-level washing thickener, mixing the obtained overflow with the underflow of the 3 rd-level washing thickener, then entering the 4 th-level washing thickener, and so on;
s4, copper recovery: and (4) pumping the extraction liquid obtained in the step (S3) into the extraction first-stage mixing tank and the extraction second-stage mixing tank respectively, mixing the extraction liquid entering the extraction first-stage mixing tank with the organic phase, and performing first-stage extraction only to obtain the high-copper raffinate. Mixing the extraction liquid entering the second-stage extraction mixing tank with an organic phase, and sequentially carrying out second-stage extraction and third-stage extraction to obtain a low-copper raffinate; in the extraction process, the organic phase flows to the third stage extraction flow and the second stage extraction flow, and then flows from the second stage extraction flow to the first stage extraction flow; and (3) carrying out back extraction on the loaded organic phase flowing out from the first-stage extraction by using an electrodeposition barren solution, sending the obtained back-extraction copper-rich solution into an electrodeposition system for electrodeposition to obtain cathode copper, and returning the back-extraction empty loaded organic phase to the extraction third-stage extraction mixing tank, and circulating the steps.
S5, recovering cobalt from the low-copper raffinate: the cobalt recovery of the low-copper raffinate comprises the working procedures of neutralization, acid removal, impurity removal, first-stage cobalt precipitation and second-stage cobalt precipitation, and comprises the following specific steps:
s5.1, neutralizing, removing acid and removing impurities: and (3) sending the low-copper raffinate obtained in the step S4 to a neutralization tank, introducing air, stirring and reacting for 60min, adding lime milk into the neutralization tank to perform neutralization reaction for 180min, controlling the pH value of the slag slurry at the end of the neutralization reaction to be 5.6, performing dense settling after the reaction is finished to obtain a neutralization acid-removal impurity-removal overflow and a neutralization acid-removal impurity-removal underflow, sending the neutralization acid-removal impurity-removal underflow to a level 1 washing thickener in the step S3, and further recovering copper and cobalt in the neutralization acid-removal impurity-removal underflow slag slurry.
S5.2, first-stage cobalt precipitation: and (3) overflowing the neutralized and acid-removed impurities to a No. 1 cobalt precipitation tank, adding active magnesium oxide emulsion to the No. 1 cobalt precipitation tank intermittently, then carrying out 3-stage first-stage cobalt precipitation reaction through the No. 2 cobalt precipitation tank and the No. 3 cobalt precipitation tank in sequence, controlling the total reaction time to be 6h, controlling the pH value of the No. 3 cobalt precipitation tank to be 8.2, and carrying out filter pressing after the reaction is finished to obtain a cobalt hydroxide product and a first-stage cobalt precipitation filtrate.
S5.3, secondary cobalt precipitation: and (3) conveying the first-stage cobalt precipitation filtrate to a second-stage cobalt precipitation reaction tank, adding lime milk to perform second-stage cobalt precipitation reaction for 2 hours, controlling the pH value of the second-stage cobalt precipitation reaction end point to be 8.5, performing pressure filtration after the reaction is finished to obtain second-stage cobalt precipitation slag and second-stage cobalt precipitation filtrate, returning the second-stage cobalt precipitation slag to a neutralization tank for neutralization, acid removal and impurity removal, and conveying the second-stage cobalt precipitation filtrate to a 5-stage washing thickener to be used as water for washing CCD.
In this example, the leaching rate and recovery rate of copper were 96.21% and 94.87%, respectively, the leaching rate and recovery rate of cobalt were 90.42% and 84.68%, respectively, and the cobalt content of the cobalt hydroxide product was 34.61%.
Example 3
In this example, zabetan copper cobalt oxide ore was used, and the analysis results of the main elements are shown in table 3.
TABLE 3 analysis results of major elements of Zanza certain copper oxide cobalt ore
The invention provides a method for comprehensively recovering copper and cobalt from copper oxide cobalt ores, which is used for treating the copper oxide cobalt ores, and comprises the following specific processes as shown in figure 1:
s1, size mixing: the copper-cobalt oxide ore is finely ground until the granularity is 80 percent to 74 mu m, then the copper-cobalt oxide ore is added into a size mixing tank, the copper-cobalt oxide ore is adjusted to 55 percent of pulp mass percentage concentration by processing water in the size mixing tank, concentrated sulfuric acid is added to adjust the pH value of the pulp to 1.5, the concentrated sulfuric acid releases heat to heat the pulp to 65 ℃, and finally copper sulfide slag obtained by treating copper-containing solution by a sulfide precipitation method is added to adjust the redox potential of the pulp to 300 mv.
S2, leaching: and (3) conveying the ore pulp prepared in the step (S1) to a No. 1 acid leaching tank with a mechanical stirrer, then sequentially passing through a No. 2 acid leaching tank, a No. 3 acid leaching tank, a No. 4 acid leaching tank, a No. 5 acid leaching tank and a No. 6 acid leaching tank to carry out 6-stage leaching reaction, wherein the total reaction time is 6 hours, after the reaction is finished, a sulfuric acid solution with the pH value of 1.8 is added into the No. 6 acid leaching tank, and the mass percentage concentration of the ore pulp in the No. 6 acid leaching tank is adjusted to 8%.
S3, concentration, thickening and washing: sending the ore pulp after the reaction of the No. 6 acid leaching tank to a concentration thickener for sedimentation to obtain a concentration overflow and a concentration underflow, then adopting a 5-level washing thickener for countercurrent washing, mixing the washing overflow obtained by the 1 st-level washing thickener with a concentration overflow feeding liquid pool to obtain an extraction liquid, adding washing water from the 5 th-level washing thickener, mixing the washing water with the 4 th-level underflow, then entering the 5 th-level washing thickener, neutralizing the underflow obtained by the 5 th-level washing thickener by using lime milk until the pH value is 8.0, then sending the obtained underflow to a slag pulp pool for storage, automatically flowing the obtained overflow of the 5 th-level washing thickener into the 4 th-level washing thickener, mixing the obtained overflow with the underflow of the 3 rd-level washing thickener, then entering the 4 th-level thickener, and so on;
s4, copper recovery: arranging an extraction first-stage mixing tank, an extraction second-stage mixing tank and an extraction third-stage extraction mixing tank; and (4) pumping the extraction liquid obtained in the step (S3) into the extraction first-stage mixing tank and the extraction second-stage mixing tank respectively, mixing the extraction liquid entering the extraction first-stage mixing tank with the organic phase, and performing first-stage extraction only to obtain the high-copper raffinate. Mixing the extraction liquid entering the second-stage extraction mixing tank with an organic phase, and sequentially carrying out second-stage extraction and third-stage extraction to obtain a low-copper raffinate; in the extraction process, the organic phase flows to the third stage extraction flow and the second stage extraction flow, and then flows from the second stage extraction flow to the first stage extraction flow; and (3) carrying out back extraction on the loaded organic phase flowing out from the first-stage extraction by using an electrodeposition barren solution, sending the obtained back-extraction copper-rich solution into an electrodeposition system for electrodeposition to obtain cathode copper, and returning the back-extraction empty loaded organic phase to the extraction third-stage extraction mixing tank, and circulating the steps.
S5, recovering cobalt from the low-copper raffinate: the cobalt recovery of the low-copper raffinate comprises the working procedures of neutralization, acid removal, impurity removal, first-stage cobalt precipitation and second-stage cobalt precipitation, and comprises the following specific steps:
s5.1, neutralizing, removing acid and removing impurities: and (3) conveying the low-copper raffinate obtained in the step S4 to a neutralization tank, introducing air, stirring and reacting for 50min, adding limestone powder slurry into the neutralization tank, performing neutralization reaction for 60min, adding lime milk, performing neutralization reaction for 120min, controlling the pH value of the slag slurry at the end point of the neutralization reaction to be 5.6, performing concentration and sedimentation after the reaction is finished, obtaining a neutralization acid-removal impurity-removal overflow and a neutralization acid-removal impurity-removal underflow, conveying the neutralization acid-removal impurity-removal underflow to a level 1 washing thickener in the step S3, and further recovering copper and cobalt in the neutralization acid-removal impurity-removal underflow slag slurry.
S5.2, first-stage cobalt precipitation: and (3) overflowing the neutralized and acid-removed impurities to a No. 1 cobalt precipitation tank, adding active magnesium oxide emulsion to the No. 1 cobalt precipitation tank intermittently, then carrying out 3-stage first-stage cobalt precipitation reaction through the No. 2 cobalt precipitation tank and the No. 3 cobalt precipitation tank in sequence, controlling the total reaction time to be 6h, controlling the pH value of the No. 3 cobalt precipitation tank to be 8.0, and carrying out filter pressing after the reaction is finished to obtain a cobalt hydroxide product and a first-stage cobalt precipitation filtrate.
S5.3, secondary cobalt precipitation: and (3) delivering the first-stage cobalt precipitation filtrate to a second-stage cobalt precipitation reaction tank, adding lime milk to perform second-stage cobalt precipitation reaction for 3 hours, controlling the pH value of the second-stage cobalt precipitation reaction end point to be 8.5, performing pressure filtration after the reaction is finished to obtain second-stage cobalt precipitation slag and second-stage cobalt precipitation filtrate, returning the second-stage cobalt precipitation slag to a neutralization tank for neutralization, acid removal and impurity removal, and delivering the second-stage cobalt precipitation filtrate to a 5-stage washing thickener to be used as water for washing CCD.
In this example, the leaching rate and recovery rate of copper were 95.27% and 93.60%, respectively, the leaching rate and recovery rate of cobalt were 94.87% and 89.25%, respectively, and the cobalt content of the cobalt hydroxide product was 38.11%.
Example 4
In this example, copobalite of koruweiqi was used, and the analysis results of the main elements are shown in table 4.
TABLE 4 analysis results of major elements of copper-cobalt oxide ore of Luweiqi
In this embodiment, a method for comprehensively recovering copper and cobalt from a copper-cobalt oxide ore is adopted to treat the copper-cobalt oxide ore, as shown in fig. 1, the specific process is as follows:
s1, size mixing: the copper-cobalt oxide ore is finely ground until the granularity is-74 mu m and the proportion is 70%, then the copper-cobalt oxide ore is added into a size mixing tank, the copper-cobalt oxide ore is adjusted to the mass percent concentration of 55% in the pulp by the processing water of the size mixing tank, concentrated sulfuric acid is added to adjust the pH value of the pulp to 1.2, the concentrated sulfuric acid releases heat to heat the pulp to 60 ℃, and finally smelting soot which is not completely oxidized by sulfide minerals is added to adjust the redox potential of the pulp to 300 mv.
S2, leaching: and (3) conveying the ore pulp prepared in the step (S1) to a No. 1 acid leaching tank with a mechanical stirrer, then sequentially passing through a No. 2 acid leaching tank, a No. 3 acid leaching tank, a No. 4 acid leaching tank, a No. 5 acid leaching tank and a No. 6 acid leaching tank to carry out 6-stage leaching reaction, wherein the total reaction time is 5 hours, after the reaction is finished, a sulfuric acid solution with the pH value of 1.8 is added into the No. 6 acid leaching tank, and the mass percentage concentration of the ore pulp in the No. 6 acid leaching tank is adjusted to 10%.
S3, concentration, thickening and washing: sending the ore pulp after the reaction of the No. 6 acid leaching tank to a concentration thickener for sedimentation to obtain a concentration overflow and a concentration underflow, carrying out countercurrent washing on the concentration underflow by adopting a 5-level washing thickener, adding washing water from the 5-level washing thickener, mixing the washing water with the 4 th underflow, then sending the mixture into the 5 th-level washing thickener, neutralizing the underflow obtained by the 5 th-level washing thickener by adopting lime milk until the pH value is 6.0, then sending the mixture into a slag pulp library for storage, automatically flowing the overflow obtained by the 5 th-level washing thickener into the 4 th-level washing thickener, mixing the overflow with the underflow of the 3 rd-level washing thickener, then sending the mixture into the 4 th-level thickener, and so on;
s4, copper recovery: arranging an extraction first-stage mixing tank, an extraction second-stage mixing tank and an extraction third-stage extraction mixing tank; and (4) pumping the extraction liquid obtained in the step (S3) into the extraction first-stage mixing tank and the extraction second-stage mixing tank respectively, mixing the extraction liquid entering the extraction first-stage mixing tank with the organic phase, and performing first-stage extraction only to obtain the high-copper raffinate. Mixing the extraction liquid entering the second-stage extraction mixing tank with an organic phase, and sequentially carrying out second-stage extraction and third-stage extraction to obtain a low-copper raffinate; in the extraction process, the organic phase flows to the third stage extraction flow and the second stage extraction flow, and then flows from the second stage extraction flow to the first stage extraction flow; and (3) carrying out back extraction on the loaded organic phase flowing out from the first-stage extraction by using an electrodeposition barren solution, sending the obtained back-extraction copper-rich solution into an electrodeposition system for electrodeposition to obtain cathode copper, and returning the back-extraction empty loaded organic phase to the extraction third-stage extraction mixing tank, and circulating the steps.
S5, recovering cobalt from the low-copper raffinate: the cobalt recovery of the low-copper raffinate comprises the working procedures of neutralization, acid removal, impurity removal, first-stage cobalt precipitation and second-stage cobalt precipitation, and comprises the following specific steps:
s5.1, neutralizing, removing acid and removing impurities: and (3) sending the low-copper raffinate obtained in the step S4 to a neutralization tank, introducing air, stirring and reacting for 30min, adding lime milk into the neutralization tank to perform neutralization reaction for 120min, controlling the pH value of the slag slurry at the end of the neutralization reaction to be 5.2, performing dense settling after the reaction is finished to obtain a neutralization acid-removal impurity-removal overflow and a neutralization acid-removal impurity-removal underflow, sending the neutralization acid-removal impurity-removal underflow to a level 1 washing thickener in the step S3, and further recovering copper and cobalt in the neutralization acid-removal impurity-removal underflow slag slurry.
S5.2, first-stage cobalt precipitation: and (3) overflowing the neutralized and acid-removed impurities to a No. 1 cobalt precipitation tank, adding active magnesium oxide emulsion to the No. 1 cobalt precipitation tank intermittently, then carrying out 3-stage first-stage cobalt precipitation reaction through the No. 2 cobalt precipitation tank and the No. 3 cobalt precipitation tank in sequence, controlling the total reaction time to be 5h, controlling the pH value of the No. 3 cobalt precipitation tank to be 8.2, and carrying out filter pressing after the reaction is finished to obtain a cobalt hydroxide product and a first-stage cobalt precipitation filtrate.
S5.3, secondary cobalt precipitation: and (3) conveying the first-stage cobalt precipitation filtrate to a second-stage cobalt precipitation reaction tank, adding lime milk to perform second-stage cobalt precipitation reaction for 2 hours, controlling the pH value of the second-stage cobalt precipitation reaction end point to be 8.4, performing pressure filtration after the reaction is finished to obtain second-stage cobalt precipitation slag and second-stage cobalt precipitation filtrate, returning the second-stage cobalt precipitation slag to a neutralization tank for neutralization, acid removal and impurity removal, and conveying the second-stage cobalt precipitation filtrate to a 5-stage washing thickener to be used as water for washing CCD.
In the present example, the leaching rate and recovery rate of copper were 95.69% and 93.35%, respectively, the leaching rate and recovery rate of cobalt were 89.49% and 83.21%, respectively, and the cobalt content of the cobalt hydroxide product was 32.14%.
Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.
Claims (10)
1. A method for comprehensively recovering copper and cobalt from copper oxide cobalt ore is characterized by comprising the following specific steps:
s1, size mixing: grinding the copper oxide cobalt ore until the granularity is-74 mu m and the mass ratio is 70-80%, then adding the copper oxide cobalt ore into a size mixing tank, and adding the solution A into the size mixing tank to obtain ore pulp with the mass percentage concentration of 55-60%; adding concentrated sulfuric acid to adjust the pH value of the ore pulp to 1.0-1.5, controlling the temperature of the ore pulp to 60-85 ℃, simultaneously adding a reducing agent B, and adjusting the oxidation-reduction potential of the ore pulp to 350mv of 300-;
s2, leaching: conveying the ore pulp finally obtained in the step S1 to a No. 1 acid leaching tank with mechanical stirring, and then sequentially carrying out n-grade leaching reaction through a No. 2 acid leaching tank, a No. 3 acid leaching tank, a No. … … acid leaching tank and a No. n acid leaching tank, wherein the total reaction time is 5-7 h; after the reaction is finished, adding the solution C into the n # acid leaching tank, and adjusting the mass percentage concentration of the ore pulp in the n # acid leaching tank to 8-15%;
s3, concentration, thickening and washing: sending the ore pulp in the n # acid leaching tank to a concentration thickener for sedimentation to obtain a concentration overflow and a concentration bottom flow, carrying out countercurrent washing on the concentration bottom flow by adopting an m-level washing thickener, sending the washing overflow obtained by the 1 st-level washing thickener and the concentration overflow to a material liquid pool for mixing to obtain an extraction material liquid, adding washing water from the m-level washing thickener, mixing the washing water and the m-1 st-level bottom flow, then entering the m-level washing thickener, neutralizing the bottom flow obtained by the m-level washing thickener by adopting lime milk until the pH value is 6-9, then sending the obtained bottom flow to a slag pulp pool for storage, automatically flowing the obtained overflow of the m-level washing thickener into the m-1-level washing thickener, mixing the obtained overflow with the m-2-level washing thickener bottom flow, then entering the m-1-level washing thickener, and so on;
s4, copper recovery: arranging an extraction first-stage mixing tank, an extraction second-stage mixing tank and an extraction third-stage extraction mixing tank; pumping the extraction liquid obtained in the step S3 into an extraction first-stage mixing tank and an extraction second-stage mixing tank respectively, mixing the extraction liquid entering the extraction first-stage mixing tank with an organic phase, and performing first-stage extraction only to obtain a high-copper raffinate; mixing the extraction feed liquid entering the second-stage extraction mixing tank with an organic phase, performing second-stage extraction, and entering a third-stage extraction mixing tank for third-stage extraction to obtain a low-copper raffinate; in the extraction process, the organic phase flows to the third stage extraction flow and the second stage extraction flow, and then flows from the second stage extraction flow to the first stage extraction flow; the loaded organic phase flowing out from the first-stage extraction is subjected to reverse extraction by using an electrodeposition barren solution, the obtained reverse extraction copper-rich solution is sent into an electrodeposition system for electrodeposition to obtain cathode copper, and the reverse extraction empty loaded organic phase is returned to the extraction third-stage extraction mixing tank, and the process is circulated;
s5, recovering cobalt from the low-copper raffinate:
s5.1, neutralizing, removing acid and removing impurities: sending the low-copper raffinate obtained in the step S4 into a neutralization tank, introducing air into the neutralization tank, stirring and reacting for 30-60 min, then adding a neutralizing agent D into the neutralization tank for neutralization reaction, controlling the neutralization reaction time to be 120-180 min, and controlling the end-point pH value of neutralization reaction slag slurry to be 5.2-5.6; after the reaction is finished, carrying out dense settling to obtain a neutralization acid and impurity removal overflow and a neutralization acid and impurity removal underflow, and sending the neutralization acid and impurity removal underflow to a level 1 washing thickener in step S3 to further recover copper and cobalt in the neutralization acid and impurity removal underflow;
s5.2, first-stage cobalt precipitation: feeding the neutralized, acid-removed and impurity-removed overflow obtained in the step S5.1 into a No. 1 cobalt precipitation tank, sequentially carrying out k-level first-stage cobalt precipitation reaction through a No. 2 cobalt precipitation tank, … … and a No. k cobalt precipitation tank, and adding active magnesium oxide emulsion into the No. 1 cobalt precipitation tank; controlling the total reaction time to be 5-7h, simultaneously controlling the pH value of the k # cobalt precipitation tank to be 8.0-8.3, and obtaining a cobalt hydroxide product and a first-stage cobalt precipitation filtrate after the reaction is finished and pressure filtration;
s5.3, secondary cobalt precipitation: feeding the first-stage cobalt precipitation filtrate into a second-stage cobalt precipitation reaction tank, adding lime milk for carrying out second-stage cobalt precipitation reaction for 2-3h, and controlling the pH value of the second-stage cobalt precipitation reaction end point to be 8.4-8.6; and after the reaction is finished, filter pressing is carried out to obtain second-stage cobalt precipitation slag and second-stage cobalt precipitation filtrate, the second-stage cobalt precipitation slag returns to a neutralization tank for neutralization, acid removal and impurity removal, and the second-stage cobalt precipitation filtrate is sent to an m-th-level washing thickener to be used as washing water.
2. The method as claimed in claim 1, wherein the solution A is industrial water in the initial period of operation, and the high copper raffinate obtained in step S4 is used after the operation is smooth.
3. The method of claim 1, wherein in step S1, the reductant B is one or more of chalcocite, pyrite, copper sulfide slag obtained by treating a copper-containing solution by sulfidic precipitation, and smelting soot from which sulfide minerals are not completely oxidized.
4. A method according to claim 3, wherein the chalcocite or pyrite is finely ground to a particle size of-20 μm and has a mass fraction of greater than 60%.
5. The method according to claim 1, wherein in step S2, the solution C is a sulfuric acid solution having a pH of 1.8 to 2.0 at an initial operation stage, and a supernatant of a thickener is used after the operation is stabilized.
6. The method of claim 1, wherein in step S2, n.gtoreq.4.
7. The method of claim 1, wherein in step S3, m.gtoreq.4.
8. The method according to claim 1, wherein in step S5.2, the activated magnesium oxide milk is added intermittently, and the activated magnesium oxide milk added in this second time is prepared before each addition.
9. The method according to claim 1, wherein in step S4, the neutralizing agent D is one or more of limestone powder slurry, lime milk and sodium hydroxide.
10. The method according to claim 1, wherein in step S5.2, k ≧ 3.
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| CN115323170A (en) * | 2022-08-09 | 2022-11-11 | 沈阳有色冶金设计研究院有限公司 | Wet smelting method by combined treatment of flotation tailings containing copper oxide and cobalt and ore |
| CN115323170B (en) * | 2022-08-09 | 2024-01-09 | 沈阳有色冶金设计研究院有限公司 | Wet smelting method for combined treatment of flotation tailings containing copper oxide and cobalt and ore |
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