CN112680603A - Method for leaching cobalt by using low-cost medicament instead of sodium metabisulfite - Google Patents
Method for leaching cobalt by using low-cost medicament instead of sodium metabisulfite Download PDFInfo
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- CN112680603A CN112680603A CN202011500664.6A CN202011500664A CN112680603A CN 112680603 A CN112680603 A CN 112680603A CN 202011500664 A CN202011500664 A CN 202011500664A CN 112680603 A CN112680603 A CN 112680603A
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Abstract
The invention relates to a method for leaching cobalt by replacing sodium metabisulfite with a low-cost medicament, which comprises the steps of early-stage ore grinding, medium-stage pulp conditioning, agitation leaching, later-stage extraction and electrodeposition to obtain cathode copper and cobalt precipitation to obtain cobalt hydroxide, adding sulfuric acid and a reducing agent ferrous sulfate into the ore pulp of copper-cobalt oxide ore by agitation leaching, and replacing sodium metabisulfite with ferrous sulfate to reduce the cost for producing cobalt and improve the field operation environment.
Description
Technical Field
The invention relates to the technical field of wet metallurgy, in particular to a method for leaching cobalt by using a low-cost medicament to replace sodium metabisulfite.
Background
Cobalt is a rare metal, is widely applied to the fields of alloy manufacture, aerospace and the like, and is an important strategic substance. The cobalt oxide powder material in the form of an important cobalt product has a wide market application prospect in the traditional industrial field and the high-tech fields such as electronics, telecommunication and the like. By the end of 2016, the world has found that the resource amount of cobalt is 2500 ten thousand tons, and the reserve amount is 720 ten thousand tons, wherein the sum of the reserves of Congo (gold), Australia and Cuba 3 accounts for 69.4% of the world, and particularly, the reserve amount of the cobalt of Congo (gold) is up to 340 ten thousand tons, which is the first in the world. The reserves of Chinese cobalt resources are only 8 ten thousand tons, which account for 1.1 percent of the reserves of the whole world.
The extraction process of the copper-cobalt oxide ore can be generally divided into a fire process and a wet process: the pyrogenic process is to produce raw copper or copper-cobalt alloy by reduction smelting in an electric furnace; the wet process comprises the steps of early-stage ore grinding, medium-stage size mixing, stirring leaching and extraction, and later-stage electrodeposition to obtain cathode copper and cobalt precipitation to obtain cobalt hydroxide, namely the cathode copper is produced by adopting a leaching-extraction-electrodeposition process flow, and cobalt-containing raffinate after copper extraction is subjected to impurity removal-cobalt precipitation process to produce cobalt salt or a cobalt compound, wherein sulfuric acid and a reducing agent are adopted in the leaching process, and the known reducing agent is sodium metabisulfite or SO2Gas can all achieveGood leaching effect, but the dosage of the medicament is large, SO the production cost is high, and both have SO during leaching2The gas is released or overflows to make the field working environment worse.
Through retrieval, the current distinctive cobalt leaching method comprises the following steps: chinese patent CN110184455A discloses a leaching method of refractory cobalt ore, which comprises the steps of crushing a biomass reducing agent, adding a sulfuric acid solution for hydrolysis to prepare a hydrolysis material, dissolving the hydrolysis material in water, then adding the refractory cobalt ore for leaching to obtain a leaching material, and carrying out solid-liquid separation on the leaching material to obtain a cobalt-containing leaching solution; chinese patent CN108315553B discloses a "leaching method of copper cobalt sulfide ore", which is to grind raw ore to obtain copper cobalt sulfide ore with predetermined fineness, mix and size-blend the copper cobalt sulfide ore and sulfuric acid solution, add sodium chlorate into the pulp, stir and leach, filter to obtain cobalt leachate; chinese patent CN103480495B discloses a method for recovering valuable metals such as copper and cobalt from copper-cobalt ore acid leaching and smelting slag by combining with flotation and smelting, which is to perform flotation under conventional alkaline conditions, wherein only most of copper-cobalt sulfide ore and a small part of free copper-cobalt oxide ore can be recovered, and copper hydroxide and copper carbonate existing in the form of precipitate in the slag washing process are difficult to recover. But the problem that the dosage of the medicament is large, the production cost is high and SO is generated during leaching is not detected2The prior art has the problem that the field working environment becomes severe due to gas release or overflow.
The method for leaching cobalt by replacing sodium metabisulfite with a low-cost medicament is urgent and has great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for leaching cobalt by using a low-cost medicament instead of sodium metabisulfite, which can reduce the production cost of cobalt and improve the field operation environment.
The task of the invention is completed by the following technical scheme:
a process for extracting Co from the copper-Co oxide ore pulp includes such steps as early grinding, medium-stage mixing, stirring for leaching, later extraction-electrodeposition to obtain cathode copper and depositing Co to obtain Co hydroxide, and adding sulfuric acid and ferrous sulfate as reducer to the ore pulp.
Leaching the cobalt of the ore, wherein the theoretical ferrous sulfate consumption is 7.2kg and the theoretical Fe2+The consumption is 2.6 kg; the iron ion content of the leaching solution is 2.6g/L, the concentration of the leaching ore pulp is 25 percent, and the theoretical stirring leaching contains 7.8kg/t of Fe2+And the amount is 3 times of the theoretical required amount, and after the system is operated, the ferrous sulfate can not be supplemented in the agitation leaching process.
SO-substituted ferric sulfate in high-copper raffinate2Reduced to ferrous sulfate, with the chemical reaction equation 2CoO (OH) +3H2SO4+2FeSO4＝2CoSO4+Fe2(SO4)3+4H2OSO2+2H2O+Fe2(SO4)3＝2FeSO4+2H2SO4
The percentages referred to in the description are percentages by mass, CCD refers to the washing system.
The invention has the following advantages or effects:
(1) the copper-cobalt oxide ore acid leaching slag is pulped without grinding, and is directly added with a medicament for treatment and then sent to a flotation working section.
(2) Controlling the ore pulp potential at the reaction end point to be 330 mV-400 mV, the copper leaching rate to be more than 92% and the cobalt leaching rate to be more than 90%.
(3) And the copper hydroxide, the copper carbonate and part of the refractory ore combined with the copper oxide existing in the leaching residue in the form of precipitate are re-dissolved into the raffinate to be recovered.
(4) Compared with the adoption of sodium metabisulfite, the method saves $ 2000-3000 per ton of cobalt and improves the field operation environment.
(5) The method does not change the basic steps of the original process, and only selects a low-cost reducing agent ferrous sulfate and adds an iron reduction system closed container.
(6) Description of the drawings
FIG. 1 is a process flow diagram of a method for leaching cobalt by using a low-cost medicament instead of sodium metabisulfite according to the invention.
The description is described in further detail below with reference to the accompanying drawings.
Detailed Description
As shown in figure 1, the method for leaching cobalt by replacing sodium metabisulfite with low-cost medicament of the invention comprises the steps of early-stage ore grinding, medium-stage size mixing, agitation leaching, late-stage extraction-electrodeposition to obtain cathode copper and cobalt precipitation to obtain cobalt hydroxide, and the agitation leaching of ore pulp of copper-cobalt oxide ore is added with sulfuric acid and reducing agent ferrous sulfate, so that the cost for producing cobalt is reduced and the field operation environment is improved by replacing sodium metabisulfite with ferrous sulfate.
The process of the invention may further be:
the specific process steps and conditions are as follows:
A. grinding and pulp mixing, namely performing conventional grinding and pulp mixing on the copper-cobalt oxide ore;
B. stirring and leaching, namely adjusting the pH of ore pulp to 1.5-1.8 by using sulfuric acid, adding a specific reducing agent ferrous sulfate, wherein the dosage of ferrous ions is 1.2-1.5 times of the content of cobalt ions, and controlling the reduction oxidation potential to 330-400 mV to obtain leached ore pulp;
C. carrying out dense washing, namely carrying out dense washing on the leached ore pulp to obtain high-copper stock solution and low-copper stock solution;
D. extracting and electrodepositing, namely performing secondary extraction on the high-copper feed liquid and the low-copper feed liquid respectively to obtain copper-containing pregnant solution capable of being electrodeposited into cathode copper, high-copper raffinate and low-copper raffinate;
E. reducing, pumping the high copper raffinate into an iron reduction system and introducing SO2Reducing ferric sulfate of the high-copper raffinate into ferrous sulfate, and returning the ferrous sulfate to the stirring leaching;
F. removing impurities and precipitating cobalt, namely removing iron and precipitating copper from the low-copper raffinate, and then removing impurities and precipitating cobalt from the solution after removing iron and precipitating copper to obtain a cobalt hydroxide product.
The iron reduction system is a closed capacity reducer capable of preventing SO2The spill-over worsens the field work environment.
And the copper-rich liquid obtained by the secondary extraction of the low-copper feed liquid is returned to the secondary extraction of the high-copper feed liquid for circulation.
And the underflow slag of the low-copper feed liquid and the low-copper feed liquid is treated and discharged.
The following further describes embodiments of the present invention with reference to specific examples and comparative examples.
Example 1
Congo (gold) certain copper-cobalt oxide ore contains Cu6.32% and Co0.38%.
The copper and cobalt are leached by adding sodium pyrosulfite into sulfuric acid, the pH value of ore pulp is controlled to be 1.5-1.6, and the potential is controlled to be 330-400 mV. The leaching rates of copper and cobalt are respectively 94.32 percent and 90.45 percent, the consumption of copper acid per ton is 2.29t, and the consumption of sodium metabisulfite per ton is 3.74 t.
At present, ferrous sulfate is used for replacing sodium metabisulfite, an iron reduction system is added, SO2 from a sulfur acid-making plant is introduced to reduce ferric sulfate into ferrous sulfate, the ferrous sulfate is returned to a leaching system to be used as a reducing agent to leach cobalt, the leaching rates of copper and cobalt are 93.82% and 90.30% respectively, the consumption of copper acid per ton is 2.11t, and the consumption of iron cobalt sulfate per ton is 1.25 t. The cobalt saves 3.74t of sodium metabisulfite per ton and adds 1.25t of ferrous sulfate (the construction cost of the iron reduction system and the operating cost $ 45/ton of cobalt). The unit price of sodium metabisulfite is 780 dollars per ton, and the unit price of ferrous sulfate is 100 dollars per ton, so that the production cost of cobalt per ton is saved by 2747 dollars.
Example 2
The domestic copper-cobalt oxide ore contains Cu3.35% and Co0.62%.
The original method is to leach the ore pulp by adding sodium pyrosulfite into sulfuric acid, wherein the pH value of the ore pulp is controlled to be 1.5-1.6 and the potential is controlled to be 330-380 mV in the leaching process. The leaching rates of copper and cobalt are respectively 93.40% and 90.45%, the acid consumption per ton of copper is 2.83t, and the consumption per ton of cobalt sodium pyrosulfite is 3.25 t.
At present, ferrous sulfate is used for replacing sodium metabisulfite for leaching, an iron reduction system is added, SO2 from a sulfur acid-making plant is introduced to reduce ferric sulfate into ferrous sulfate, the ferrous sulfate is returned to the leaching system to be used as a reducing agent for leaching cobalt, the leaching rates of copper and cobalt are respectively 92.96% and 89.21%, the consumption of copper acid per ton is 2.63t, and the consumption of ferrous sulfate is 1.75 t. 3.25t of sodium metabisulfite is saved per ton of cobalt. An increase of 1.75t of ferrous sulphate (construction costs of the iron reduction system and operating costs $ 57/ton cobalt). The unit price of sodium metabisulfite is 780 dollars/ton, and the unit price of ferrous sulfate is 100 dollars/ton, so that the production cost of cobalt per ton is saved by 2303 dollars.
The above embodiments are only preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Claims (5)
1. A process for extracting cobalt by using low-cost chemical instead of sodium pyrosulfite includes such steps as early-stage grinding, medium-stage mixing, stirring for leaching, later-stage extraction-electrodeposition to obtain cathode copper and depositing cobalt to obtain cobalt hydroxide, and features that the sulfuric acid and ferrous sulfate as reducer are added to the ore pulp of copper-cobalt oxide ore for stirring and leaching, and the ferrous sulfate is used instead of sodium pyrosulfite to lower the cost of cobalt production and improve the field operation environment.
2. The method of claim 1, wherein the specific process steps and conditions are as follows:
A. grinding and pulp mixing, namely performing conventional grinding and pulp mixing on the copper-cobalt oxide ore;
B. stirring and leaching, namely adjusting the pH of ore pulp to 1.5-1.8 by using sulfuric acid, adding a specific reducing agent ferrous sulfate, wherein the dosage of ferrous ions is 1.2-1.5 times of the content of cobalt ions, and controlling the reduction oxidation potential to 330-400 mV to obtain leached ore pulp;
C. carrying out dense washing, namely carrying out dense washing on the leached ore pulp to obtain high-copper stock solution and low-copper stock solution;
D. extracting and electrodepositing, namely performing secondary extraction on the high-copper feed liquid and the low-copper feed liquid respectively to obtain copper-containing pregnant solution capable of being electrodeposited into cathode copper, high-copper raffinate and low-copper raffinate;
E. reducing, pumping the high copper raffinate into an iron reduction system and introducing SO2Reducing ferric sulfate of the high-copper raffinate into ferrous sulfate, and returning the ferrous sulfate to the stirring leaching;
F. removing impurities and precipitating cobalt, namely removing iron and precipitating copper from the low-copper raffinate, and then removing impurities and precipitating cobalt from the solution after removing iron and precipitating copper to obtain a cobalt hydroxide product.
3. According to claimThe method of claim 2, wherein the iron reduction system is a closed volume reducer that prevents SO2The spill-over worsens the field work environment.
4. The method as set forth in claim 2, characterized in that the copper-rich liquor of said second extraction of low-copper liquor is recycled to the second extraction of high-copper liquor.
5. The method as claimed in claim 2 or 4, wherein the underflow slag treatment discharge of the low copper feed solution is performed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115786727A (en) * | 2022-12-16 | 2023-03-14 | 广东省科学院资源利用与稀土开发研究所 | Method for synchronously and intensively leaching low-grade copper oxide cobalt ore |
| CN116219197A (en) * | 2022-12-20 | 2023-06-06 | 江西佳纳能源科技有限公司 | Leaching method of intermediate product of cobalt or nickel |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115786727A (en) * | 2022-12-16 | 2023-03-14 | 广东省科学院资源利用与稀土开发研究所 | Method for synchronously and intensively leaching low-grade copper oxide cobalt ore |
| CN116219197A (en) * | 2022-12-20 | 2023-06-06 | 江西佳纳能源科技有限公司 | Leaching method of intermediate product of cobalt or nickel |
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