CN117165780A - Method for recovering copper and cobalt from copper-cobalt-containing material - Google Patents
Method for recovering copper and cobalt from copper-cobalt-containing material Download PDFInfo
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- CN117165780A CN117165780A CN202311075812.8A CN202311075812A CN117165780A CN 117165780 A CN117165780 A CN 117165780A CN 202311075812 A CN202311075812 A CN 202311075812A CN 117165780 A CN117165780 A CN 117165780A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000010949 copper Substances 0.000 title claims abstract description 102
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 102
- 239000010941 cobalt Substances 0.000 title claims abstract description 93
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 93
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 32
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 title claims description 25
- 238000002386 leaching Methods 0.000 claims abstract description 207
- 238000000605 extraction Methods 0.000 claims abstract description 31
- 238000001556 precipitation Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 238000004070 electrodeposition Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 230000003472 neutralizing effect Effects 0.000 claims description 11
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 7
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical group [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 3
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical group [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims description 3
- 235000010261 calcium sulphite Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 10
- 150000001869 cobalt compounds Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- FWZLXRFUDMNGDF-UHFFFAOYSA-N [Co].[Cu]=O Chemical compound [Co].[Cu]=O FWZLXRFUDMNGDF-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NHPHQYDQKATMFU-UHFFFAOYSA-N [Cu]=S.[Co] Chemical compound [Cu]=S.[Co] NHPHQYDQKATMFU-UHFFFAOYSA-N 0.000 description 1
- INSXADAKBSCPPL-UHFFFAOYSA-L [OH-].[OH-].[Co].[Co++] Chemical compound [OH-].[OH-].[Co].[Co++] INSXADAKBSCPPL-UHFFFAOYSA-L 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of wet treatment of copper-containing materials, and relates to a method for recovering copper and cobalt from copper-containing cobalt-containing materials, which comprises the following steps: s1, carrying out one-stage normal pressure leaching treatment on copper and cobalt materials to obtain one-stage leaching liquid and one-stage leaching slag; s2, carrying out secondary pressure leaching treatment on the primary leaching slag to obtain secondary leaching liquid and secondary leaching slag, wherein the secondary leaching liquid comprises residual acid which is not reacted by the secondary pressure leaching treatment; s3, returning the second-stage leaching solution to the step S1 for first-stage normal pressure leaching, and sequentially carrying out neutralization, extraction, back extraction and electrodeposition treatment on the first-stage leaching solution in the step S3 to obtain electrodeposited copper; s4, carrying out cobalt precipitation reaction on the copper raffinate after the extraction treatment to obtain a cobalt product. In the method, after the second stage pressure leaching in the step S2, the liquid returns to the step S1 and is subjected to the first stage normal pressure leaching, and then the metallic copper, the metallic cobalt and the copper and cobalt elements in part of copper and cobalt compounds in the copper and cobalt raw materials are obviously extracted.
Description
Technical Field
The invention belongs to the technical field of wet treatment of copper-containing materials, and particularly relates to a method for recovering copper and cobalt from copper-cobalt-containing materials.
Background
The smelting process of the copper-cobalt-containing material is divided into two modes of pyrometallurgy and wet smelting. The pyrometallurgy process has high energy consumption, large equipment investment and limited metal recovery rate, and a large amount of produced smelting slag still contains a certain amount of Co, cu, fe, si, mg, ca, al and other valuable components, so that cobalt and copper elements entering the smelting slag can not be effectively recovered, thereby causing waste of resources such as copper, cobalt and the like.
Patent document CN116219165a discloses a method for extracting copper, manganese and cobalt from copper, manganese and cobalt-containing materials, wherein the method aims at treating copper and cobalt material components with specific content, and cannot adapt to materials with large fluctuation of raw material components. Especially for materials with lower copper and cobalt contents, the soaking effect is limited. The pH of the solution after cobalt precipitation mentioned in the patent document is controlled to be 7.5-8.5 in the cobalt precipitation process stage, the acidity of the solution is low, and the promotion effect on the acid leaching process is extremely limited.
Disclosure of Invention
Aiming at the problems, the invention adopts the following technical scheme: a process for recovering copper and cobalt from a copper-cobalt-containing material, the process comprising the steps of:
s1, carrying out one-stage normal pressure leaching treatment on copper and cobalt materials to obtain one-stage leaching liquid and one-stage leaching slag;
s2, carrying out secondary pressure leaching treatment on the primary leaching slag to obtain secondary leaching liquid and secondary leaching slag, wherein the secondary leaching liquid comprises residual acid which is not reacted by the secondary pressure leaching treatment;
s3, returning the second-stage leaching solution to the step S1 for first-stage normal pressure leaching, and sequentially carrying out neutralization, extraction, back extraction and electrodeposition treatment on the first-stage leaching solution in the step S3 to obtain electrodeposited copper;
s4, carrying out cobalt precipitation reaction on the copper raffinate after the extraction treatment to obtain a cobalt product.
Further, in the step S1, the one-stage atmospheric leaching treatment conditions are as follows: the leaching temperature is 25-90 ℃, the leaching time is 1-5 h, the pH of the leaching solution is 2.0-4.0, and the liquid-solid ratio is 1.5:1-8:1.
Further, in step S2, the two-stage pressure leaching treatment conditions are: the leaching temperature is 180-240 ℃, the leaching time is 1-5 h, the leaching pressure is 0.1-0.8 MPa, the pH of the leaching solution is 0.3-1.0, and the liquid-solid ratio is 1.5:1-8:1.
Further, step S1 includes: mixing a copper cobalt material, a sulfuric acid solution and an oxidant, and performing primary normal pressure leaching treatment to obtain primary leaching solution; the mass concentration of the sulfuric acid solution is 25% -60% according to the material ratio of the sulfuric acid solution to the copper cobalt being 1.5:1-8:1; the oxidant is at least one of sulfur dioxide, flue gas containing sulfur dioxide, sodium thiosulfate, calcium sulfite, sodium metabisulfite, potassium sulfite or ammonium sulfite.
Further, step S2 includes: mixing the first-stage leaching residue with sulfuric acid solution and water, and performing second-stage pressure leaching treatment to obtain a second-stage leaching solution.
Further, step S3 includes: returning the second-stage leaching solution to the step S1 for first-stage normal pressure leaching, wherein the comprehensive leaching rate of copper in the first-stage leaching solution in the step S3 is more than or equal to 95%, and the leaching rate of cobalt is more than or equal to 90%; adding a neutralizing agent into the first-stage leaching solution in the step S3 to perform a neutralization precipitation reaction, controlling the pH value to be 3.5-5.5, and the temperature to be 40-80 ℃ to remove iron and aluminum in the leaching solution, so that the iron concentration in the leaching solution from which the iron and the aluminum are removed is not higher than 5ppm, and the aluminum concentration is not higher than 10ppm; adding an extractant into the leaching solution from which iron and aluminum are removed, and carrying out extraction and back extraction treatment to obtain a back extraction solution; and adding the strip liquor into an electrodeposition system for electrodeposition to obtain electrodeposited copper.
Further, step S4 includes: adding a neutralizing agent into the copper raffinate obtained by the extraction in the step S3 to carry out cobalt precipitation reaction, wherein the copper content in the copper raffinate is less than 50mg/L, the pH value is controlled to be 7.0-8.5, the obtained cobalt product is cobalt hydroxide, and the cobalt concentration in the cobalt precipitation solution is less than 6mg/L.
Further, mixing the two-stage leaching residue after the two-stage pressure leaching treatment in the step S2, the iron-aluminum residue after the neutralization treatment in the step S3 for removing iron and aluminum, and the cobalt-precipitation post-solution after the cobalt-precipitation reaction in the step S4, and adding a neutralizer for treatment to generate tailings.
Further, the neutralizer is NaOH, mgO, caCO 3 Or Ca (OH) 2 At least one of (a) and (b); the extractant consists of amine extractant and neutral oxygen-containing extractant.
Further, the residual acid which is not reacted after the second-stage pressure leaching treatment is sulfuric acid, and the pH value of the second-stage leaching solution is 0.3-1.0.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method for recovering copper and cobalt from the copper-cobalt-containing material, the pH value of the second-stage leaching solution in the step S2 is only 0.3-1.0, the acidity is still high, and after the second-stage leaching solution returns to the step S1 for one-stage normal pressure leaching, the metallic copper, metallic cobalt and copper and cobalt elements in partial copper and cobalt compounds in the copper and cobalt raw material can be obviously extracted; meanwhile, the open-circuit solution after the return liquid is leached again under normal pressure has higher copper and cobalt content than the solution after the leaching in the step S2; in addition, the residual acid in the secondary leaching process can be recovered, so that the secondary leaching liquid can be recycled, the consumption of new acid is reduced, and the comprehensive acid consumption of the process is reduced;
(2) The method for recycling copper and cobalt from the copper-cobalt-containing material has strong raw material adaptability, and is applicable to copper-cobalt associated raw ores, copper-cobalt concentrate, copper-cobalt ore smelting slag and mixed ores with large copper and cobalt content fluctuation and complex impurity components; the inclusion is good, and the method is applicable to copper cobalt sulfide ores and copper cobalt oxide ores; especially for the associated materials with lower copper and cobalt content, the comprehensive recovery of copper and cobalt can be realized, and a better recovery effect is obtained;
(3) By the method for recycling copper and cobalt from the copper-cobalt-containing material, various valuable metal products are recycled, such as valuable metal copper and valuable metal cobalt are recycled, the comprehensive leaching rate of copper is more than or equal to 95%, the comprehensive leaching rate of cobalt is more than or equal to 90%, the cobalt content of cobalt hydroxide is more than or equal to 40%, the water content is less than or equal to 55%, and the recycling value is superior to that of the prior art.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for recovering copper and cobalt from a copper and cobalt-containing material.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A method for recovering copper and cobalt from a copper and cobalt-containing material, as shown in fig. 1, comprising the steps of:
s1, carrying out one-stage normal pressure leaching treatment on copper and cobalt materials to obtain one-stage leaching liquid and one-stage leaching slag; s2, carrying out secondary pressure leaching treatment on the primary leaching slag to obtain secondary leaching liquid and secondary leaching slag, wherein the secondary leaching liquid comprises residual acid which is not reacted by the secondary pressure leaching treatment; s3, returning the second-stage leaching solution to the step S1 for the first-stage normal pressure leaching treatment, and sequentially carrying out neutralization, extraction, back extraction and electrodeposition treatment on the first-stage leaching solution in the step S3 to obtain electrodeposited copper; s4, carrying out cobalt precipitation reaction on the copper raffinate after the extraction treatment to obtain a cobalt product.
In the embodiment of the present invention, step S1 includes: and mixing the copper cobalt material, the sulfuric acid solution and the oxidant, and performing one-stage normal pressure leaching treatment to obtain one-stage leaching solution. Wherein the oxidant is at least one of sulfur dioxide, flue gas containing sulfur dioxide, sodium thiosulfate, calcium sulfite, sodium metabisulfite, potassium sulfite or ammonium sulfite; when the catalyst is sulfur dioxide gas or flue gas containing sulfur dioxide, the sulfur dioxide needs to be mixed with one or more of oxygen, air or oxygen-enriched gas, the volume concentration of the sulfur dioxide is 0.2-3% of the total volume of the oxygen-containing gas and the sulfur dioxide gas, and the mixed gas inlet amount is 0.2-1Nm 3 /m 3 Pulp min; when the catalyst is a sulfur-containing reagent such as sodium sulfite or sodium metabisulfite, the addition amount of the catalyst is 0.5-5% of the mass of the copper-cobalt oxide ore raw ore.
In the embodiment of the present invention, in step S1, a section of atmospheric leaching treatment conditions is set as follows: the leaching temperature is 25-90 ℃, the leaching time is 1-5 h, the pH of the leaching solution is 2.0-4.0, and the liquid-solid ratio is 1.5:1-8:1.
In the embodiment of the present invention, step S2 includes: mixing the first-stage leaching residue with sulfuric acid solution and water, and performing second-stage pressure leaching treatment to obtain a second-stage leaching solution. The second-stage leaching solution comprises residual acid which is not reacted after the second-stage pressure leaching treatment, and the pH value of the second-stage leaching solution is 0.3-1.0.
In the embodiment of the present invention, in step S2, the two-stage pressure leaching treatment conditions are set as follows: the leaching temperature is 180-240 ℃, the leaching time is 1-5 h, the leaching pressure is 0.1-0.8 MPa, the pH of the leaching solution is 0.3-1.0, and the liquid-solid ratio is 1.5:1-8:1.
In the embodiment of the invention, a first-stage normal pressure leaching process and a second-stage pressure leaching process are adopted, and the first-stage normal pressure leaching process can remove non-mineral substances in copper-cobalt-containing materials, such as carbonate, calcium and the like; meanwhile, the metal phase in the raw material can be removed, and the subsequent metal phase is prevented from entering the autoclave to have explosion danger. In the prior art, copper and cobalt are recovered from copper-cobalt-containing materials, a section of normal pressure leaching process is adopted, the leaching rate of copper and cobalt in the normal pressure leaching stage is lower, and particularly, the leaching effect on raw materials with lower copper and cobalt content is poorer; the leaching rate of cobalt and copper can be further improved under the condition of pressure and oxygen introduction in the second stage pressure leaching process and the condition of intensified leaching. In addition, the leached liquid in the second-stage pressure leaching process still has certain acidity, the leached liquid is recycled to recover residual acid (sulfuric acid solution) therein, and a certain amount of acid is provided for the first-stage normal pressure leaching process of the copper cobalt slag, so that the new addition amount of the sulfuric acid solution in the first-stage normal pressure leaching process is reduced, the comprehensive acid consumption of the process is reduced, and the production cost is reduced. Meanwhile, the leached liquid is completely recycled, and the subsequent neutralization treatment of waste acid is omitted. In addition, the liquid returning liquid after the two-stage pressure leaching is subjected to normal pressure leaching again, copper and cobalt elements in the raw materials are further enriched in the liquid phase, the concentration of copper and cobalt in the leached liquid can be further improved, subsequent copper extraction and cobalt precipitation are facilitated, and meanwhile, the comprehensive copper and cobalt recovery rate of the whole process is improved.
In the embodiment of the present invention, step S3 includes: returning the second-stage leaching solution to the step S1 for carrying out the leaching solution subjected to the first-stage normal pressure leaching, adding a neutralizing agent for carrying out a neutralization precipitation reaction, controlling the pH value to be 3.5-5.5, and removing iron and aluminum in the leaching solution to ensure that the iron concentration in the leaching solution from which the iron and the aluminum are removed is not higher than 5ppm and the aluminum concentration is not higher than 10ppm; then adding an extractant into the leaching solution from which the iron and the aluminum are removed, and carrying out extraction and back extraction treatment to obtain a back extraction solution; and adding the strip liquor into an electrodeposition system for electrodeposition to obtain electrodeposited copper. The comprehensive leaching rate of copper in the first-stage leaching solution in the step S3 is more than or equal to 95 percent, and the leaching rate of cobalt is more than or equal to 90 percent.
In the embodiment of the invention, in the step S3, the organic phase used in the copper extraction process comprises a copper extractant and a diluent solvent, the copper extractant consists of an amine extractant and a neutral oxygen-containing extractant, an alcohol reagent is used as a phase regulator, and aviation kerosene, 260# solvent oil (sulfonated kerosene) or Escaid100 is used as the diluent solvent. After extraction, washing a copper-rich organic phase by using a water phase, back-extracting by using a copper electrodeposit anolyte, and allowing the back-extracted electro-rich liquid, namely back-extracted liquid, to enter an electrodeposit system for electrodepositing to obtain electrodeposited copper; and the raffinate is subjected to subsequent cobalt precipitation reaction. The copper extractant is used for extraction and back extraction, so that the copper extraction efficiency is improved, copper can be enriched, and only a small amount of copper can enter raffinate.
In the embodiment of the present invention, step S4 includes: adding a neutralizing agent into the copper raffinate obtained by the extraction in the step S3 to carry out cobalt precipitation reaction, wherein the copper content in the copper raffinate is less than 50mg/L, the pH value is controlled to be 7.0-8.5, the obtained cobalt product is cobalt hydroxide, and the cobalt concentration in the cobalt precipitation solution is less than 6mg/L.
In addition, mixing the two-stage leaching slag obtained after the two-stage pressure leaching treatment in the step S2, the iron-aluminum slag obtained after the neutralization treatment in the step S3 for removing iron and aluminum, and the cobalt-precipitation post-solution obtained after the cobalt-precipitation reaction in the step S4, and adding a neutralizer for treatment to generate tailings.
In the step S3 or the step S4 or the treatment process of generating tailings, the neutralizing agent is NaOH, mgO, caCO 3 Or Ca (OH) 2 At least one of them.
The core of the invention is that the first stage leaching slag generated in the first stage normal pressure leaching process is subjected to the second stage pressure leaching treatment, copper and cobalt valuable metals in the materials can be further extracted by the second stage pressure leaching treatment, meanwhile, unreacted sulfuric acid in the second stage pressure leaching process can be further recovered and recycled to the first stage normal pressure leaching process, and the recovered residual acid and the next batch of copper-cobalt-containing materials are continuously subjected to the first stage normal pressure leaching treatment in the production process, so that the sulfuric acid consumption in the whole process flow is reduced, and the production cost is reduced to a certain extent. In addition, the sulfuric acid in the whole process flow does not need to be added with a subsequent acid neutralization treatment device, so that the post-treatment cost is reduced. After the secondary pressure leaching, the liquid returning liquid is leached again under normal pressure, the copper and cobalt concentration in the liquid phase can be further improved, the subsequent copper extraction and cobalt precipitation reactions are obtained, and the comprehensive recovery rate of copper and cobalt is improved.
The invention will be further described with reference to the following examples:
the copper and cobalt containing raw materials used in the examples are shown in table 1 below.
TABLE 1 copper and cobalt containing raw material composition
| Element(s) | Co | Cu | Fe | Al | Ca | Mg | Si | S | |
| Copper cobalt slag | Content/% | 1.59 | 6.10 | 31.22 | 0.87 | 0.67 | 0.44 | 10.48 | 1.65 |
Example 1
Weighing 100g of copper-cobalt ore smelting slag (the components of which are shown in table 1), adding 15g of concentrated sulfuric acid and 500g of water, and introducing an oxidant SO 2 Carrying out one-stage normal pressure leaching with air mixed gas, wherein the leaching temperature is 50 ℃, the leaching time is 3 hours, the pH value of a leaching system is controlled to be 3.1-3.3, and the liquid-solid ratio is 5:1, filtering to obtain filtrate and filter residue. Mixing filter residues with 25g of sulfuric acid and 275g of water, performing two-stage pressure leaching, wherein the leaching temperature is 220 ℃, the oxygen partial pressure is 0.5MPa, the leaching time is 2h, the pH value of a leaching system is controlled to be 0.5-0.6, and the liquid-solid ratio is 6:1, filtering to obtain a second-stage leaching solution and leaching residues. After the second leaching, the copper leaching rate is 91%, and the cobalt comprehensive leaching rate is 95.3%.
Returning the leaching solution of the second stage to the first stage for leaching under normal pressure, adding 100g of copper-cobalt ore smelting slag, proper amount of water and sulfuric acid, and controlling the pH value of a leaching system to be 3.1-3.3, wherein the liquid-solid ratio is 5:1, leaching at 50 ℃, filtering to obtain a first-stage leaching solution and a first-stage leaching residue leaching solution, wherein the comprehensive leaching rate of copper is 96%, and the comprehensive leaching rate of cobalt is 97.5%.
Neutralizing and precipitating the first-stage leaching solution, extracting, back extracting and electrodepositing to obtain electrodeposited copper; wherein the neutralizing agent is CaCO 3 Controlling the pH value to be 4.6 in the process of the neutralization precipitation reaction, and carrying out the neutralization precipitation reaction at the temperature of 70 ℃ to ensure that the iron concentration in the leaching solution for removing iron and aluminum is not higher than 5ppm and the aluminum concentration is not higher than 10ppm; the extractant is Lix984N; adding a calcium carbonate neutralizer into the extracted copper raffinate to carry out cobalt precipitation reaction, wherein the copper content in the copper raffinate is 45mg/L, the pH value is controlled to be 7.8, the obtained cobalt product is cobalt hydroxide, the cobalt concentration in the cobalt precipitation solution is 5mg/L, the cobalt hydroxide cobalt content is 40%, and the water content is 53%.
Examples 2 to 3 differ from example 1 in that the process parameters are different and the process steps are the same; the leaching rates of copper and cobalt and the product index of cobalt hydroxide are shown in table 1.
Example 4 differs from example 1 in that the raw material composition is different and the process steps are the same; the leaching rates of copper and cobalt and the product index of cobalt hydroxide are shown in table 1.
Comparative example 1 differs from example 1 in that only one stage of atmospheric leaching was performed, and no two stage of pressure leaching was performed. The leaching rate index of copper and cobalt is shown in table 1.
Comparative example 2 differs from example 1 in that only the first-stage atmospheric leaching and the second-stage pressure leaching are performed, and the second-stage leachate is not returned to step S1 to perform the first-stage atmospheric leaching. The leaching rate index of copper and cobalt is shown in table 1.
TABLE 2 data relating to examples 1-4 and comparative examples 1-2
As can be seen from the combination of the copper-cobalt leaching rates of the example 1 and the comparative example 2, after the secondary pressure leaching, the concentration of copper and cobalt in the liquid phase can be further improved after the secondary pressure leaching is carried out again by normal pressure leaching (the comprehensive leaching rates of copper and cobalt in the example 1 are respectively 96.08% and 97.51%, and the comprehensive leaching rates of copper and cobalt in the comparative example 2 are respectively 91.39% and 93.33%); as can be seen from the combination of example 1 and comparative example 1, the two-stage pressure leaching process can further improve the leaching rate of cobalt and copper under the conditions of pressure and oxygen introduction under the condition of intensified leaching (the comprehensive leaching rates of copper and cobalt in example 1 are respectively 96.08% and 97.51%, and the comprehensive leaching rates of copper and cobalt in comparative example 1 are respectively 58.27% and 42.01%).
Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A process for recovering copper and cobalt from a copper-cobalt-containing material, said process comprising the steps of:
s1, carrying out one-stage normal pressure leaching treatment on copper and cobalt materials to obtain one-stage leaching liquid and one-stage leaching slag;
s2, carrying out secondary pressure leaching treatment on the primary leaching slag to obtain secondary leaching liquid and secondary leaching slag, wherein the secondary leaching liquid comprises residual acid which is not reacted by the secondary pressure leaching treatment;
s3, returning the second-stage leaching solution to the step S1 for the first-stage normal pressure leaching treatment, and sequentially carrying out neutralization, extraction, back extraction and electrodeposition treatment on the first-stage leaching solution in the step S3 to obtain electrodeposited copper;
s4, carrying out cobalt precipitation reaction on the copper raffinate after the extraction treatment to obtain a cobalt product.
2. The method according to claim 1, wherein in step S1, the one-stage atmospheric leaching treatment conditions are: the leaching temperature is 25-90 ℃, the leaching time is 1-5 h, the pH of the leaching solution is 2.0-4.0, and the liquid-solid ratio is 1.5:1-8:1.
3. The method according to claim 1, characterized in that in step S2, the two-stage pressure leaching treatment conditions are: the leaching temperature is 180-240 ℃, the leaching time is 1-5 h, the leaching pressure is 0.1-0.8 MPa, the pH of the leaching solution is 0.3-1.0, and the liquid-solid ratio is 1.5:1-8:1.
4. The method according to claim 2, wherein step S1 comprises:
mixing a copper cobalt material, a sulfuric acid solution and an oxidant, and performing primary normal pressure leaching treatment to obtain primary leaching solution;
the mass concentration of the sulfuric acid solution is 25% -60% according to the material ratio of the sulfuric acid solution to the copper cobalt being 1.5:1-8:1;
the oxidant is at least one of sulfur dioxide, flue gas containing sulfur dioxide, sodium thiosulfate, calcium sulfite, sodium metabisulfite, potassium sulfite or ammonium sulfite.
5. A method according to claim 3, wherein step S2 comprises:
mixing the first-stage leaching residue with sulfuric acid solution and water, and performing second-stage pressure leaching treatment to obtain a second-stage leaching solution.
6. The method according to claim 1, wherein step S3 comprises:
returning the second-stage leaching solution to the step S1 for the first-stage normal pressure leaching treatment, wherein the comprehensive leaching rate of copper in the first-stage leaching solution in the step S3 is more than or equal to 95 percent, and the leaching rate of cobalt is more than or equal to 90 percent;
adding a neutralizing agent into the first-stage leaching solution in the step S3 to perform a neutralization precipitation reaction, controlling the pH value to be 3.5-5.5, and the temperature to be 40-80 ℃ to remove iron and aluminum in the leaching solution, so that the iron concentration in the leaching solution from which the iron and the aluminum are removed is not higher than 5ppm, and the aluminum concentration is not higher than 10ppm;
adding an extractant into the leaching solution from which iron and aluminum are removed, and performing extraction and back extraction treatment to obtain back extraction solution;
and adding the strip liquor into an electrodeposition system for electrodeposition to obtain electrodeposited copper.
7. The method of claim 6, wherein step S4 comprises:
adding a neutralizing agent into the copper raffinate obtained by the extraction in the step S3 to carry out cobalt precipitation reaction, wherein the copper content in the copper raffinate is less than 50mg/L, the pH value is controlled to be 7.0-8.5, the obtained cobalt product is cobalt hydroxide, and the cobalt concentration in the cobalt precipitation solution is less than 6mg/L.
8. The method of claim 7, wherein the two-stage leaching residue after the two-stage pressure leaching treatment of the step S2, the iron-aluminum residue after the neutralization treatment of the step S3 to remove iron and aluminum, and the cobalt-precipitation post-solution after the cobalt-precipitation reaction of the step S4 are mixed, and the mixture is treated with a neutralizing agent to generate tailings.
9. The method of any one of claims 6-8, wherein the neutralizing agent is NaOH, mgO, caCO 3 Or Ca (OH) 2 At least one of (a) and (b); the extractant consists of amine extractant and neutral oxygen-containing extractant.
10. The method according to any one of claims 1 to 8, wherein the residual acid which is not reacted in the second stage pressure leaching treatment is sulfuric acid, and the pH of the second stage leachate is from 0.3 to 1.0.
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