CN115323170B - Wet smelting method for combined treatment of flotation tailings containing copper oxide and cobalt and ore - Google Patents
Wet smelting method for combined treatment of flotation tailings containing copper oxide and cobalt and ore Download PDFInfo
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- CN115323170B CN115323170B CN202210947005.XA CN202210947005A CN115323170B CN 115323170 B CN115323170 B CN 115323170B CN 202210947005 A CN202210947005 A CN 202210947005A CN 115323170 B CN115323170 B CN 115323170B
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 44
- 239000010941 cobalt Substances 0.000 title claims abstract description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000005188 flotation Methods 0.000 title claims abstract description 35
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 23
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 23
- 238000003723 Smelting Methods 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 111
- 229910052802 copper Inorganic materials 0.000 claims abstract description 109
- 238000000605 extraction Methods 0.000 claims abstract description 76
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000002386 leaching Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 238000004070 electrodeposition Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- 239000002562 thickening agent Substances 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 239000008267 milk Substances 0.000 claims description 6
- 210000004080 milk Anatomy 0.000 claims description 6
- 235000013336 milk Nutrition 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000005363 electrowinning Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- FWZLXRFUDMNGDF-UHFFFAOYSA-N [Co].[Cu]=O Chemical compound [Co].[Cu]=O FWZLXRFUDMNGDF-UHFFFAOYSA-N 0.000 claims description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000009854 hydrometallurgy Methods 0.000 claims 3
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- 238000013019 agitation Methods 0.000 description 5
- -1 hydrogen cobalt oxide Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
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
- 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
- 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—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
- 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
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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
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to the technical field of ore wet smelting, in particular to a method for carrying out combined treatment on flotation tailings containing copper oxide and cobalt and ores, which comprises the steps of leaching the ores containing copper oxide and cobalt; leaching the flotation tailings; extracting; back extraction; electro-deposition; and (5) cobalt deposition. The extraction of the copper oxide and cobalt ore is two-stage high copper extraction and one-stage back extraction, and the extraction of the flotation tailings is two-stage low copper extraction. The method provided by the invention can not only recycle valuable metals in the high-consumption acid flotation tailings and effectively utilize the residual acid, but also reduce the production cost of the cobalt precipitation process; simultaneously inhibiting the water expansion of the wet smelting system; and the process flow is simplified and simplified, and is relatively flexible.
Description
Technical Field
The invention relates to the technical field of ore wet smelting, and particularly provides a method for carrying out combined treatment on flotation tailings containing copper oxide and cobalt and ore.
Background
At present, the flotation tailings and ores containing the copper and cobalt oxides are subjected to single or mixed leaching treatment, the leached liquid is divided into high-copper liquid and low-copper liquid according to the copper content of liquid-solid separation stock solution and washing liquid, the high-copper liquid and the low-copper liquid are respectively extracted to obtain high-copper raffinate and low-copper raffinate, the high-copper raffinate is returned to a leaching system or a liquid-solid separation and washing system for use, and the low-copper raffinate is sent to a cobalt precipitation workshop for impurity removal and cobalt extraction. The flotation tailings with high copper content and low acid consumption can be independently subjected to agitation leaching treatment, and the independent treatment with higher acid consumption increases the cost and is not suitable for exploitation.
In the actual production process of the prior main popular process flow, the acid water is recycled, the copper-containing low-copper feed liquid is higher in copper content and acid content, after the acid is released by extracting copper, the copper content in raffinate is 0.2-0.5g/l, and the acid content is 14-20g/l, and the raffinate is sent to a cobalt precipitation workshop to produce crude hydrogen cobalt oxide.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for carrying out combined treatment on flotation tailings containing copper oxide and cobalt and ores for wet smelting.
The invention is realized in such a way that a method for carrying out combined treatment on flotation tailings containing copper oxide and cobalt and ore for wet smelting is provided, which comprises the following steps:
1) Leaching copper oxide-containing and cobalt ore:
101 Crushing, grinding and grading: crushing and grinding copper oxide-and cobalt-containing ore to obtain ore pulp with certain fineness;
102 Dewatering until the ore pulp reaches a certain concentration;
103 Stirring and leaching: firstly, acidifying and diluting ore pulp, and then pumping the ore pulp into a plurality of serial stirring leaching tanks added with concentrated sulfuric acid and reducing agent for stirring and leaching at normal temperature for a certain time;
104 Solid-liquid separation: carrying out solid-liquid separation on leached ore pulp through a concentrator, enabling overflowed high-copper feed liquid to flow to a high-copper feed liquid pool for clarification, and then pumping the high-copper feed liquid into an extraction workshop; the underflow of the thickener is pumped into a washing thickener by a slag slurry pump to carry out multistage series countercurrent washing, the washing liquid of each stage is returned to the previous stage, the last stage is returned to the ore pulp before liquid-solid separation, the underflow of the last washing thickener is sent into a No. 1 environment-friendly slag warehouse, and the liquid of the No. 1 environment-friendly slag warehouse is returned to the ore pulp after dehydration in step 102);
2) Leaching of flotation tailings:
201 Screening and pulping): adding second-stage high-copper raffinate into flotation tailings for pulping after screening;
202 Stirring and leaching: pumping the flotation tailings pulp into a plurality of serial stirring leaching tanks for adding concentrated sulfuric acid for stirring leaching;
203 Liquid-solid separation: carrying out solid-liquid separation on leached flotation tailing pulp through a thickener, conveying overflowed low-copper feed liquid into a low-copper feed liquid pool for clarification, and then pumping into an extraction workshop; the underflow of the thickener is pumped into a No. 2 environment-friendly slag warehouse by a slag slurry pump, and the return liquid of the No. 2 environment-friendly slag warehouse is sent into the thickener for mixing and acid adjustment and overflows to a low-copper feed liquid pool;
3) Extraction and back extraction:
301 High copper extraction: after the high copper feed liquid enters an extraction workshop, carrying out primary high copper extraction to obtain primary high copper raffinate, and carrying out secondary high copper extraction on the primary high copper raffinate to obtain secondary high copper raffinate;
302 Low copper extraction: after the low copper feed liquid enters an extraction workshop, carrying out primary low copper extraction to obtain primary low copper raffinate, and carrying out secondary low copper extraction on the primary low copper raffinate to obtain secondary low copper raffinate; the loaded organic phase obtained by the second-stage low-copper extraction returns to the first-stage low-copper extraction process, and the loaded organic phase obtained by the first-stage low-copper extraction automatically flows to the second-stage high-copper extraction process;
303 Back extraction: the loaded organic phases obtained by the two-stage low-copper extraction and the two-stage high-copper extraction in series are converged, and the electric lean solution is adopted for back extraction to obtain copper-containing electric rich solution and a regenerated organic phase;
4) Electrodeposition: electro-deposition is carried out on the electro-rich liquid from the back extraction to generate cathode copper and electro-lean liquid, and the electro-lean liquid is returned to the back extraction step;
5) Cobalt precipitation: removing impurities from the second-stage low-copper raffinate, and then carrying out cobalt precipitation to obtain a crude hydrogen-producing cobalt oxide product and treated liquid.
Preferably, in the step 101), the crushed lump size of the copper oxide-containing and cobalt-containing ores is 0-250mm, and the fineness of the grinding ore is 70% of the content of less than 200 meshes;
in step 102), dehydrating until the concentration of ore pulp reaches 65%;
in the step 103), the number of the stirring leaching tanks is 4, the stirring leaching time at normal temperature is 4 hours, and the pH is controlled to be 1.5-2.0.
Further preferably, in step 202), the number of the agitation leaching tanks is 3, the time of agitation leaching is 1h, and the pH is controlled to be 1.8-2.0.
It is further preferred that in step 301) and step 302) the extractant is 5540, the diluent is 260# solvent oil, and the organic phase of the extraction process is 75% solvent oil and 25% extractant are mixed.
Further preferably, in the step 4), the electrolytic deposition is performed by using an insoluble anode and a stainless steel permanent cathode, and the liquid supply mode in the electrolytic deposition tank is a lower-inlet upper-outlet circulation mode, and the current density is 230-300A/m 2 The cell voltage is 1.8-2.2V, and the cathode period is 6d; the electrodeposited electrolean solution becomes a stripping pre-solution in the stripping process.
Further preferably, in the step 5), the cobalt precipitation process comprises adding lime milk to remove iron, adding magnesium oxide to precipitate cobalt, and then adding lime milk to remove magnesium; the crude cobalt hydroxide obtained needs to be flash dried.
It is further preferable that a water return tank is provided, the water overflowed in the dewatering process in the step 102) enters the water return tank, the water return tank is connected with a new water pipe, and the water required for grinding and classifying in the step 101) comes from the water return tank, the treated liquid in the step 5) is respectively returned to the water return tank, the countercurrent washing process in the step 104), the process that the underflow of countercurrent washing enters the 1# environment-friendly slag warehouse, and the process that the underflow in the liquid-solid separation enters the 2# environment-friendly slag warehouse.
It is further preferred that a flocculant is added during both the liquid-solid separation process of step 104) and the countercurrent washing process.
Compared with the prior art, the invention has the advantages that:
1. by making a reasonable process flow, valuable metals in the high-consumption acid flotation tailings can be recovered, residual acid can be effectively utilized, and the production cost of the cobalt precipitation process can be reduced;
2. inhibiting water expansion of the hydrometallurgical system;
3. the process flow is simplified and relatively flexible.
Drawings
The invention will be described in further detail with reference to the accompanying drawings and embodiments:
FIG. 1 is a schematic flow chart of the method.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1, the invention provides a method for wet smelting by combined treatment of flotation tailings containing copper oxide and cobalt and ore, which comprises the following steps:
1) Leaching copper oxide-containing and cobalt ore:
101 Crushing, grinding and grading: crushing and grinding copper oxide-and cobalt-containing ore to obtain ore pulp with certain fineness; the broken block size of the copper oxide-containing and cobalt ore is 0-250mm, and the fineness of the grinding ore is 70% of the content of less than 200 meshes;
in the step, the main ore deposit ore adopts a process flow of one-stage open circuit crushing and pre-screening, and the crushing process comprises coarse crushing, semi-autogenous grinding and ball milling.
102 Dewatering until the concentration of ore pulp reaches 65%; in order to reduce liquid expansion, the material before entering the stirring leaching is recycled with acid water to the greatest extent, and a section of deep cone high-efficiency concentrator is adopted for dewatering the overflow of the cyclone;
103 Stirring and leaching: firstly, acidifying and diluting ore pulp, adjusting the concentration of the ore pulp to 25%, and then pumping the ore pulp into 4 stirring leaching tanks which are connected in series and added with concentrated sulfuric acid and a reducing agent for stirring and leaching for 4 hours at normal temperature, wherein the pH value is controlled to be 1.5-2.0; sodium metabisulfite is selected as a reducing agent;
104 Solid-liquid separation: carrying out solid-liquid separation on leached ore pulp through a concentrator, enabling overflowed high-copper feed liquid to flow to a high-copper feed liquid pool for clarification, and then pumping the high-copper feed liquid into an extraction workshop; the underflow of the thickener is pumped into a washing thickener by a slag slurry pump to carry out multistage series countercurrent washing, the washing liquid of each stage is returned to the previous stage, the last stage is returned to the ore pulp before liquid-solid separation, the underflow of the last washing thickener is sent into a No. 1 environment-friendly slag warehouse, and the liquid of the No. 1 environment-friendly slag warehouse is returned to the ore pulp after dehydration in step 102);
2) Leaching of flotation tailings:
201 Screening and pulping): adding second-stage high-copper raffinate into flotation tailings for pulping after screening;
202 Stirring and leaching: pumping the flotation tailings pulp into 3 agitation leaching tanks which are connected in series and are added with concentrated sulfuric acid for agitation leaching; the stirring leaching time is 1h, and the pH is controlled between 1.8 and 2.0.
203 Liquid-solid separation: carrying out solid-liquid separation on leached flotation tailing pulp through a thickener, conveying overflowed low-copper feed liquid into a low-copper feed liquid pool for clarification, and then pumping into an extraction workshop; the underflow of the thickener is pumped into a No. 2 environment-friendly slag warehouse by a slag slurry pump, and the return liquid of the No. 2 environment-friendly slag warehouse is sent into the thickener for mixing and acid adjustment and overflows to a low-copper feed liquid pool;
3) Extraction and back extraction:
301 High copper extraction: after the high copper feed liquid enters an extraction workshop, carrying out primary high copper extraction to obtain primary high copper raffinate, and carrying out secondary high copper extraction on the primary high copper raffinate to obtain secondary high copper raffinate;
302 Low copper extraction: after the low copper feed liquid enters an extraction workshop, carrying out primary low copper extraction to obtain primary low copper raffinate, and carrying out secondary low copper extraction on the primary low copper raffinate to obtain secondary low copper raffinate; the loaded organic phase obtained by the second-stage low-copper extraction returns to the first-stage low-copper extraction process, and the loaded organic phase obtained by the first-stage low-copper extraction automatically flows to the second-stage high-copper extraction process;
in steps 301) and 302), the extractant was 5540, the diluent was 260# solvent oil, and the organic phase of the extraction process was 75% solvent oil and 25% extractant were mixed.
303 Back extraction: the loaded organic phases obtained by the two-stage low-copper extraction and the two-stage high-copper extraction in series are converged, and the electric lean solution is adopted for back extraction to obtain copper-containing electric rich solution and a regenerated organic phase;
4) Electrodeposition: electro-deposition is carried out on the electro-rich liquid from the back extraction to generate cathode copper and electro-lean liquid, and the electro-lean liquid is returned to the back extraction step;
the electrowinning adopts insoluble anode and stainless steel permanent cathode to operate, the liquid supply mode in electrowinning tank adopts the circulation mode of lower inlet and upper outlet, and the current density is 230-300A/m 2 The cell voltage is 1.8-2.2V, and the cathode period is 6d; the electrodeposited electrolean solution becomes a stripping pre-solution in the stripping process.
5) Cobalt precipitation: removing impurities from the second-stage low-copper raffinate, and then carrying out cobalt precipitation to obtain a crude hydrogen-producing cobalt oxide product and treated liquid.
The cobalt precipitation process comprises the steps of adding lime milk to remove iron, adding magnesium oxide to precipitate cobalt, and then adding lime milk to remove magnesium; the crude cobalt hydroxide obtained needs to be flash dried.
In order to realize the circulation of liquid, as an improvement of the technical scheme, the water overflowed in the dehydration process in the step 102) enters a water return tank, the water return tank is connected with a new water pipe, and the water required by grinding and classification in the step 101) comes from the water return tank, the treated liquid in the step 5) is respectively returned to the water return tank, the countercurrent washing process in the step 104), the process that the underflow of countercurrent washing enters a No. 1 environment-friendly slag warehouse, and the process that the underflow in the liquid-solid separation in the step 203) enters a No. 2 environment-friendly slag warehouse.
It is further preferred that a flocculant is added during both the liquid-solid separation process of step 104) and the countercurrent washing process. So as to quicken ore sedimentation and shorten separation time.
The invention processes acid consumption flotation tailings by reasonably formulating the process flow and utilizing valuable metals, free acid and the like in the high-copper raffinate, thereby enriching the concentration of copper and cobalt metals and Cu 2+ Concentration of 2-4g/l, co 2+ The concentration is 2g/l, the acid content in the solution is reduced, the stirring end point pH is 1.5-2, and the feed liquid pH is 2-3. Extracting low-copper feed liquid and Cu 2+ The concentration is less than or equal to 0.08g/l, co 2+ The concentration is 2g/l, the acid content is less than or equal to 10g/l, and the cobalt oxide is sent to a cobalt precipitation workshop to produce crude hydrogen cobalt oxide.
Compared with the independent treatment, the combined method is adopted to treat the flotation tailings, and according to the metal and material price of 5 months in 2022, the cost of copper per ton can be reduced by 10000-15000 yuan, the cost of cobalt per ton can be reduced by 20000-30000 yuan, and even the independent treatment of the tailings is not feasible.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. The method for carrying out combined treatment on flotation tailings containing copper oxide and cobalt and ore for wet smelting is characterized by comprising the following steps:
1) Leaching copper oxide-containing and cobalt ore:
101 Crushing, grinding and grading: crushing and grinding copper oxide-and cobalt-containing ore to obtain ore pulp with certain fineness;
102 Dewatering until the ore pulp reaches a certain concentration;
103 Stirring and leaching: firstly, acidifying and diluting ore pulp, and then pumping the ore pulp into a plurality of serial stirring leaching tanks added with concentrated sulfuric acid and reducing agent for stirring and leaching at normal temperature for a certain time;
104 Solid-liquid separation: carrying out solid-liquid separation on leached ore pulp through a concentrator, enabling overflowed high-copper feed liquid to flow to a high-copper feed liquid pool for clarification, and then pumping the high-copper feed liquid into an extraction workshop; the underflow of the thickener is pumped into a washing thickener by a slag slurry pump to carry out multistage series countercurrent washing, the washing liquid of each stage is returned to the previous stage, the last stage is returned to the ore pulp before liquid-solid separation, the underflow of the last washing thickener is sent into a No. 1 environment-friendly slag warehouse, and the liquid of the No. 1 environment-friendly slag warehouse is returned to the ore pulp after dehydration in step 102);
2) Leaching of flotation tailings:
201 Screening and pulping): adding second-stage high-copper raffinate into flotation tailings for pulping after screening;
202 Stirring and leaching: pumping the flotation tailings pulp into a plurality of serial stirring leaching tanks for adding concentrated sulfuric acid for stirring leaching;
203 Liquid-solid separation: carrying out solid-liquid separation on leached flotation tailing pulp through a thickener, conveying overflowed low-copper feed liquid into a low-copper feed liquid pool for clarification, and then pumping into an extraction workshop; the underflow of the thickener is pumped into a No. 2 environment-friendly slag warehouse by a slag slurry pump, and the return liquid of the No. 2 environment-friendly slag warehouse is sent into the thickener for mixing and acid adjustment and overflows to a low-copper feed liquid pool;
3) Extraction and back extraction:
301 High copper extraction: after the high copper feed liquid enters an extraction workshop, carrying out primary high copper extraction to obtain primary high copper raffinate, and carrying out secondary high copper extraction on the primary high copper raffinate to obtain secondary high copper raffinate;
302 Low copper extraction: after the low copper feed liquid enters an extraction workshop, carrying out primary low copper extraction to obtain primary low copper raffinate, and carrying out secondary low copper extraction on the primary low copper raffinate to obtain secondary low copper raffinate; the loaded organic phase obtained by the second-stage low-copper extraction returns to the first-stage low-copper extraction process, and the loaded organic phase obtained by the first-stage low-copper extraction automatically flows to the second-stage high-copper extraction process;
303 Back extraction: the loaded organic phases obtained by the two-stage low-copper extraction and the two-stage high-copper extraction in series are converged, and the electric lean solution is adopted for back extraction to obtain copper-containing electric rich solution and a regenerated organic phase;
4) Electrodeposition: electro-deposition is carried out on the electro-rich liquid from the back extraction to generate cathode copper and electro-lean liquid, and the electro-lean liquid is returned to the back extraction step;
5) Cobalt precipitation: removing impurities from the second-stage low-copper raffinate, and then carrying out cobalt precipitation to obtain a crude hydrogen-producing cobalt oxide product and treated liquid.
2. The method for combined treatment and wet smelting of copper oxide and cobalt containing flotation tailings and ore according to claim 1, wherein in step 101), the broken lump size of copper oxide and cobalt containing ore is 0-250mm, and the fineness of the ore is 70% of the content of less than 200 meshes;
in step 102), dehydrating until the concentration of ore pulp reaches 65%;
in the step 103), the number of the stirring leaching tanks is 4, the stirring leaching time at normal temperature is 4 hours, and the pH is controlled to be 1.5-2.0.
3. The method for combined treatment and hydrometallurgical treatment of copper oxide and cobalt containing flotation tailings and ores according to claim 1, wherein in step 202), the number of the stirring leaching tanks is 3, the stirring leaching time is 1h, and the pH is controlled to be 1.8-2.0.
4. The method for combined treatment of copper oxide and cobalt containing flotation tailings and ore hydrometallurgical process according to claim 1, wherein in step 301) and step 302), the extractant is 5540, the diluent is 260# solvent oil, and the organic phase of the extraction process is 75% solvent oil and 25% extractant is mixed.
5. The method for combined treatment of copper oxide and cobalt containing flotation tailings and ore hydrometallurgy according to claim 1, wherein in the step 4), the electrowinning is operated by adopting an insoluble anode and a stainless steel permanent cathode, the liquid supply mode in the electrowinning tank is adopted, the lower inlet and upper outlet circulation mode is adopted, and the current density is 230-300A/m 2 The cell voltage is 1.8-2.2V, and the cathode period is 6d; the electrodeposited electrolean solution becomes a stripping pre-solution in the stripping process.
6. The method for combined treatment of wet smelting of flotation tailings and ore containing copper oxide and cobalt according to claim 1, wherein in step 5), the cobalt precipitation process comprises adding lime milk to remove iron, adding magnesium oxide to precipitate cobalt, and then adding lime milk to remove magnesium; the crude cobalt hydroxide obtained needs to be flash dried.
7. The method for combined treatment of wet smelting of copper oxide and cobalt containing flotation tailings and ore according to claim 1, wherein a water return tank is provided, water overflowed in the dewatering process in step 102) enters the water return tank, the water return tank is connected with a new water pipe, water required for grinding and classification in step 101) comes from the water return tank, treated liquid in step 5) is respectively returned to the water return tank, the countercurrent washing process in step 104), the countercurrent washing underflow enters a No. 1 environment-friendly slag warehouse, and the underflow enters a No. 2 environment-friendly slag warehouse in step 203) of liquid-solid separation.
8. The method for combined treatment of copper oxide and cobalt containing flotation tailings and ore hydrometallurgical process according to claim 1, wherein a flocculant is added during both the liquid-solid separation process and the counter current washing process of step 104).
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| WO1994024334A1 (en) * | 1993-04-19 | 1994-10-27 | Magma Copper Company | Process for making copper metal powder, copper oxides and copper foil |
| RU2336344C1 (en) * | 2007-04-16 | 2008-10-20 | Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) | Method of production of cathode copper out of sulphide oxidised copper ores |
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