Process for removing manganese from cobalt precipitation tail liquid
By using calcium oxide or kiln dust as a neutralizer in the cobalt precipitation tail liquor, combined with sodium persulfate oxidant and ultrasonic-assisted reaction, the problem of low manganese removal rate in the cobalt precipitation tail liquor was solved, and efficient and low-cost manganese removal effect was achieved, ensuring the stability of the copper-cobalt smelting process and product quality.
Patent Information
- Application Number
- CN202510565456.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-30
- Publication Date
- 2025-09-12
AI Technical Summary
In the existing technology, during the copper-cobalt combined hydrometallurgical smelting process, the removal rate of impurity manganese in the cobalt precipitation tail liquid is not high, resulting in a continuous increase in the Mn²⁺ concentration in the system, affecting the quality of copper extraction, copper electrowinning processes and the crude cobalt hydroxide product of the cobalt system.
Calcium oxide or kiln dust is used as a neutralizing agent, combined with sodium persulfate as an oxidizing agent, and ultrasonic-assisted reaction is used to adjust the amount of neutralizing agent added and the reaction time. The cobalt precipitation tail liquid is filtered, concentrated, neutralized and filtered to generate ferric hydroxide, aluminum hydroxide and manganese hydroxide precipitates, and the iron, aluminum and manganese impurities in the tail liquid are removed.
It significantly improves the removal rate of manganese, reduces the cost of manganese removal, extends the service life of the anode, ensures the purity of the cathode copper, reduces the ratio of manganese entrained into the organic phase, and stabilizes the chelating ability of the extractant and copper.
Smart Images
Figure CN120624818A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of manganese removal from cobalt precipitation tail liquid, and in particular relates to a process for removing manganese from cobalt precipitation tail liquid. Background Art
[0002] In the process of copper-cobalt combined hydrometallurgy, the treatment of cobalt precipitation tailings has always been a major problem faced by the industry: with the continuous development and utilization of mineral resources, the grade of valuable metal cobalt in the ore has gradually decreased, while the content of impurity manganese has increased. In the production of some mining companies in the existing technology, during the operation of the copper raffinate treatment system, the cobalt concentration of the low-copper raffinate is relatively low, and the impurity manganese content has seriously threatened the operation of the copper extraction and copper electrowinning processes and the quality of the crude cobalt hydroxide product of the cobalt system.
[0003] In the existing technology, there are also a series of targeted treatment processes to address the problem of manganese impurities. The most commonly used one is to use part of the copper raffinate to open the circuit when extracting cobalt from the raffinate, neutralize it with lime to remove impurities, and precipitate the cobalt with magnesium oxide. The cobalt precipitate tail liquid is then returned to the production system for recycling. However, the removal effect of the manganese impurity using (SO2 + air) as an oxidant combined with lime neutralization and impurity removal may fluctuate greatly. During the oxidation neutralization and impurity removal process, the manganese removal rate may not be high. After the two stages of cobalt precipitation, a large amount of Mn²⁺ may still remain in the cobalt precipitation tail liquid and re-enter the production system, causing the Mn²⁺ concentration in the system to continue to rise. Therefore, a process that can remove manganese from the tail liquid at low cost and high efficiency is particularly important. Summary of the Invention
[0004] In response to the problems raised in the existing background technology, the present invention provides a process for removing manganese from cobalt precipitation tail liquid.
[0005] The technical solutions adopted in the present invention are as follows.
[0006] A process for removing manganese from cobalt precipitation tail liquid, which collects the cobalt precipitation tail liquid produced by the workshop and uses a cobalt precipitation thickener to filter and concentrate the collected tail liquid; The treated tail liquid is pumped into a manganese removal stirring tank, and a neutralizing agent is added to the manganese removal stirring tank for neutralization reaction; After the neutralization reaction, the neutralized material in the manganese removal stirring tank is discharged into a plate and frame filter press for filter pressing treatment. After the filter pressing treatment, the manganese slag is discharged, and the waste liquid after manganese removal is discharged into the circulating water pool.
[0007] Preferably, when the tail liquid and the neutralizer are undergoing the neutralization reaction, an oxidant is also added to the manganese removal stirring tank.
[0008] Furthermore, the neutralizing agent is calcium oxide.
[0009] Furthermore, the oxidant is sodium persulfate.
[0010] Furthermore, the neutralization reaction in the manganese removal stirred tank specifically includes the following steps: S1, react for 0.4-0.6h to remove iron and aluminum impurities in the tail liquid; S2. React for another 1.5-2.5 hours to remove manganese in the tail liquid.
[0011] Furthermore, when removing iron and aluminum impurities in the tail liquid in step S1, the equation is as follows: Neutralizer reacts with water to produce , making the solution alkaline:
[0012] Iron ion precipitation:
[0013] Aluminum ion precipitation:
[0014] When the neutralizer reacts with water, the pH value of the solution is 7.5-8.
[0015] Furthermore, in step S2, when removing manganese from the tail liquid, the equation is as follows: Continue to add neutralizer to increase the pH of the solution:
[0016] Oxidation by oxidants:
[0017]
[0018] When the neutralizer is added, the pH value of the solution is 8.5-9.5.
[0019] Furthermore, when the manganese slag is discharged after the filter press treatment, the manganese slag is also recovered and treated. The treatment steps are: mixing the manganese slag with sulfuric acid solution, heating it to 80-90° C. and then leaching it for 1-3 hours.
[0020] Furthermore, the mass ratio of the manganese slag to the sulfuric acid solution is 1:5.
[0021] Preferably, during the neutralization reaction, ultrasound is used to assist the neutralization reaction, with an ultrasound frequency of 20-40 kHz and a power density of 50-100 W / m³.
[0022] Compared with the prior art, the present invention has the following beneficial effects: The present invention significantly improves the manganese removal rate by adjusting the amount of neutralizer added and the reaction time, and combining technical means such as ultrasonic-assisted reaction. At the same time, the present invention uses low-cost calcium oxide or kiln dust as the neutralizer, and through the appropriate addition amount, avoids excessive use of the neutralizer, effectively reducing the cost of manganese removal. At the same time, the present invention adds an oxidant during the neutralization reaction, reducing the probability of manganese entrained in the extraction being oxidized to a high-valent state during the electrodeposition process, which is beneficial to extending the service life of the anode and ensuring the purity of the cathode copper. At the same time, the ratio of manganese entrained into the organic phase during extraction is reduced, reducing or avoiding the oxidation reaction of manganese on the organic phase, and ensuring the chelating ability of the extractant and copper reaction to be relatively stable for a long time. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] In order to more clearly illustrate the technical solutions in the embodiments or exemplary embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments or exemplary descriptions. Obviously, the drawings described below are only some embodiments of the present application and should not be regarded as limiting the scope. For ordinary technicians in this field, other drawings can be obtained according to the drawings without paying creative work.
[0024] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION
[0025] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Generally, the components of the embodiments of the present application described and shown in the drawings here can be arranged and designed in various different configurations.
[0026] Therefore, the following detailed description of the embodiments of the present application provided in the accompanying drawings is not intended to limit the scope of the present application for protection, but merely represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present application.
[0027] Example 1: Reference Figure 1 , a process for removing manganese from cobalt precipitation tailings, the steps are as follows: Tail liquid collection and pretreatment: 1000L of cobalt precipitation tail liquid is collected in the cobalt workshop, and the tail liquid is filtered and concentrated using a cobalt precipitation thickener to remove some large particle impurities and concentrate the tail liquid volume to 800L to improve subsequent processing efficiency.
[0028] Preparation for neutralization reaction: Pump 800L of treated tail liquid into the manganese removal stirring tank; then weigh 16kg of calcium oxide as a neutralizing agent and prepare 5kg of sodium persulfate as an oxidizing agent.
[0029] Neutralization reaction: Turn on the stirring device of the manganese removal stirring tank, set the stirring speed to 300r / min, and at the same time turn on the ultrasonic equipment with a frequency of 20kHz and a power density of 50W / m³ to assist the reaction; First, add calcium oxide and react for 0.5 hours. At this time, calcium oxide reacts with water to form calcium hydroxide, which rapidly raises the pH value of the solution to 7.8. Iron ions and aluminum ions form iron hydroxide and aluminum hydroxide precipitates respectively, thereby removing iron and aluminum impurities in the tail liquid. The reaction equation is as follows: Calcium oxide reacts with water:
[0030] Iron ion precipitation:
[0031] Aluminum ion precipitation:
[0032] Then, sodium persulfate was added and the reaction was continued for 2 hours to further increase the pH value of the solution to 9. Sodium persulfate oxidized the divalent manganese ions to tetravalent manganese ions, which then reacted with calcium hydroxide to form manganese hydroxide precipitates, achieving the removal of manganese. The reaction equation is as follows: Continue adding calcium oxide to increase the pH of the solution:
[0033] Oxidation by oxidants:
[0034] Filtration and waste liquid treatment: After the neutralization reaction is completed, the neutralized material in the manganese removal stirring tank is discharged into the plate and frame filter press for filtration treatment; after filtration, 15kg of manganese slag is obtained, and the manganese slag is discharged. The waste liquid after manganese removal is 780L and is discharged into the circulating water pool for temporary storage. After passing the subsequent test, it can be reused in other production links.
[0035] The waste liquid was tested using an ion detector. After manganese removal, the manganese ion concentration in the waste liquid dropped to 0.2 g / L, and the manganese removal rate reached 87.5%.
[0036] Manganese slag recovery and treatment: 15 kg of the obtained manganese slag is mixed with 75 kg of sulfuric acid solution, poured into a reactor, heated to 85 ° C, and leached for 2 hours; during the leaching process, part of the manganese element in the manganese slag is converted into manganese sulfate and enters the solution. Subsequently, manganese can be further recovered through extraction, electrolysis or other wet smelting processes to achieve resource recycling.
[0037] Example 2: Reference Figure 1 , a process for removing manganese from cobalt precipitation tailings, the steps are as follows: Tail liquid collection and pretreatment: 1500L of cobalt precipitation tail liquid is collected in the cobalt workshop, and the tail liquid is filtered and concentrated using a cobalt precipitation thickener to remove some large particle impurities and concentrate the tail liquid volume to 1200L to improve subsequent processing efficiency.
[0038] Preparation for neutralization reaction: Pump the treated 1200L tail liquid into the manganese removal stirring tank; then weigh 24kg of calcium oxide as a neutralizing agent and prepare 7.5kg of sodium persulfate as an oxidizing agent.
[0039] Neutralization reaction: Turn on the stirring device of the manganese removal stirring tank, set the stirring speed to 350r / min, and at the same time turn on the ultrasonic equipment with a frequency of 30kHz and a power density of 75W / m³ to assist the reaction; First, add calcium oxide and react for 0.4 hours. At this time, calcium oxide reacts with water to form calcium hydroxide, causing the pH value of the solution to rise rapidly to 7.5. Iron ions and aluminum ions form iron hydroxide and aluminum hydroxide precipitation respectively, thereby removing iron and aluminum impurities in the tail liquid. The reaction equation is as follows: Calcium oxide reacts with water:
[0040] Iron ion precipitation:
[0041] Aluminum ion precipitation:
[0042] Then, sodium persulfate was added and the reaction continued for 2.5 hours to further increase the pH value of the solution to 9.5. Sodium persulfate oxidized the divalent manganese ions to tetravalent manganese ions, which then reacted with calcium hydroxide to form manganese hydroxide precipitates, achieving the removal of manganese. The reaction equation is as follows: Continue adding calcium oxide to increase the pH of the solution:
[0043] Oxidation by oxidants:
[0044] Filtration and waste liquid treatment: After the neutralization reaction is completed, the neutralized material in the manganese removal stirring tank is discharged into the plate and frame filter press for filtration treatment; after filtration, 22 kg of manganese slag is obtained, and the manganese slag is discharged. The waste liquid after manganese removal is 1170 L, which is discharged into the circulating water pool for temporary storage. After passing the subsequent test, it can be reused in other production links.
[0045] The waste liquid was tested using an ion detector. After manganese removal, the manganese ion concentration in the waste liquid dropped to 0.18 g / L, and the manganese removal rate reached 88.9%.
[0046] Manganese slag recovery and treatment: Mix the obtained 22kg manganese slag with 110kg sulfuric acid solution, pour the mixture into a reactor, heat to 90℃, and leach for 1h. During the leaching process, part of the manganese element in the manganese slag is converted into manganese sulfate and enters the solution. Subsequently, manganese can be further recovered through extraction, electrolysis or other wet smelting processes to achieve resource recycling.
[0047] Example 3: Reference Figure 1 , a process for removing manganese from cobalt precipitation tailings, the steps are as follows: Tail liquid collection and pretreatment: 800L of cobalt precipitation tail liquid is collected in the cobalt workshop, and the tail liquid is filtered and concentrated using a cobalt precipitation thickener to remove some large particle impurities and concentrate the tail liquid volume to 650L to improve subsequent processing efficiency.
[0048] Preparation for neutralization reaction: Pump the treated 650L tail liquid into the manganese removal stirring tank; then weigh 13kg of calcium oxide as a neutralizing agent and prepare 4kg of sodium persulfate as an oxidizing agent.
[0049] Neutralization reaction: Turn on the stirring device of the manganese removal stirring tank, set the stirring speed to 250r / min, and at the same time turn on the ultrasonic equipment with a frequency of 40kHz and a power density of 100W / m³ to assist the reaction; First, add calcium oxide and react for 0.6 hours. At this time, calcium oxide reacts with water to form calcium hydroxide, which rapidly raises the pH value of the solution to 8. Iron ions and aluminum ions form iron hydroxide and aluminum hydroxide precipitates respectively, thereby removing iron and aluminum impurities in the tail liquid. The reaction equation is as follows: Calcium oxide reacts with water:
[0050] Iron ion precipitation:
[0051] Aluminum ion precipitation:
[0052] Then, sodium persulfate was added and the reaction was continued for 1.5 hours to further increase the pH value of the solution to 8.5. Sodium persulfate oxidized the divalent manganese ions to tetravalent manganese ions, which then reacted with calcium hydroxide to form manganese hydroxide precipitates, achieving the removal of manganese. The reaction equation is as follows: Continue adding calcium oxide to increase the pH of the solution:
[0053] Oxidation by oxidants:
[0054] Filtration and waste liquid treatment: After the neutralization reaction is completed, the neutralized material in the manganese removal stirring tank is discharged into the plate and frame filter press for filtration treatment; after filtration, 12 kg of manganese slag is obtained, and the manganese slag is discharged. The waste liquid after manganese removal is 630 L, which is discharged into the circulating water pool for temporary storage. After passing the subsequent test, it can be reused in other production links.
[0055] The waste liquid was tested using an ion detector. After manganese removal, the manganese ion concentration in the waste liquid dropped to 0.22 g / L, and the manganese removal rate reached 86.1%.
[0056] Manganese slag recovery and treatment: 12 kg of the obtained manganese slag is mixed with 60 kg of sulfuric acid solution, poured into a reactor, heated to 80°C, and leached for 3 hours. During the leaching process, part of the manganese element in the manganese slag is converted into manganese sulfate and enters the solution. Subsequently, manganese can be further recovered through extraction, electrolysis or other wet smelting processes to achieve resource recycling.
[0057] Comparative Example 1: A process for removing manganese from cobalt precipitation tail liquid is basically the same as Example 1, except that the amount of calcium oxide added is 13.6 kg.
[0058] Comparative Example 2: A process for removing manganese from cobalt precipitation tail liquid is basically the same as that of Example 1, except that the amount of calcium oxide added is 14.8 kg.
[0059] Comparative Example 3: A process for removing manganese from cobalt precipitation tail liquid is basically the same as Example 1, except that the amount of calcium oxide added is 17.2 kg.
[0060] Combining Comparative Examples 1-3 and Example 1, a manganese removal test was conducted, and after the test, the waste liquid pH and manganese removal rate were statistically calculated. The calculation results are shown in the following table: Table 1
[0061] Combined with the data in Table 1, it can be seen that as the amount of calcium oxide increases, the manganese removal rate increases.
[0062] It should be noted that in order to ensure production costs, the oxidation amount can be twice the theoretical amount, which can ensure the manganese removal rate while effectively controlling costs.
[0063] Comparative Example 4: A process for removing manganese from cobalt precipitation tailings is basically the same as that of Example 1, except that kiln dust is used as the neutralizing agent.
[0064] Combining Comparative Examples 1-4 and Example 1, the neutralization efficiency of calcium oxide and kiln dust was tested, and the test data are shown in the following table; Table 2
[0065] Combined with the data in Table 2, it can be seen that when kiln dust is used as a manganese removal neutralizer, when the amount of kiln dust added is 1.57 times the amount of calcium oxide used, the manganese removal efficiency of the two is similar.
[0066] In summary, the present invention significantly improves the manganese removal rate by adjusting the amount of neutralizer added and the reaction time, and combining technical means such as ultrasonic-assisted reaction. At the same time, the present invention uses low-cost calcium oxide or kiln dust as a neutralizer, and through the appropriate amount of addition, avoids excessive use of the neutralizer, effectively reducing the cost of manganese removal; at the same time, the present invention adds an oxidant during the neutralization reaction, reducing the probability of manganese entrained in the extraction being oxidized to a high-valent state during the electrodeposition process, which is beneficial to extending the service life of the anode and ensuring the purity of the cathode copper; at the same time, the ratio of manganese entrained into the organic phase during extraction is reduced, reducing or avoiding the oxidation reaction of manganese on the organic phase, so that the chelating ability of the extractant and copper reaction can be relatively stable for a long time.
[0067] The above-described embodiments merely represent preferred embodiments of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous modifications, improvements, and substitutions without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention.
Claims
1. A process for removing manganese from cobalt precipitation tail liquid, characterized in that: Collect the cobalt precipitation tail liquid produced in the workshop and use the cobalt precipitation thickener to filter and concentrate the collected tail liquid; The treated tail liquid is pumped into a manganese removal stirring tank, and a neutralizing agent is added to the manganese removal stirring tank for neutralization reaction; After the neutralization reaction, the neutralized material in the manganese removal stirring tank is discharged into a plate and frame filter press for filter pressing treatment. After the filter pressing treatment, the manganese slag is discharged, and the waste liquid after manganese removal is discharged into the circulating water pool.
2. A process for removing manganese from cobalt precipitation tail liquid according to claim 1, characterized in that: When the tail liquid and the neutralizer are undergoing neutralization reaction, an oxidant is also added to the manganese removal stirring tank.
3. A process for removing manganese from cobalt precipitation tail liquid according to claim 2, characterized in that: The neutralizing agent is calcium oxide.
4. A process for removing manganese from cobalt precipitation tail liquid according to claim 2, characterized in that: The oxidant is sodium persulfate.
5. A process for removing manganese from cobalt precipitation tail liquid according to claim 4, characterized in that: The neutralization reaction in the manganese removal stirred tank specifically includes the following steps: S1, react for 0.4-0.6h to remove iron and aluminum impurities in the tail liquid; S2. React for another 1.5-2.5 hours to remove manganese in the tail liquid.
6. A process for removing manganese from cobalt precipitation tail liquid according to claim 5, characterized in that: When removing iron and aluminum impurities in the tail liquid in step S1, the equation is as follows: Neutralizer reacts with water to produce , making the solution alkaline: Iron ion precipitation: Aluminum ion precipitation: When the neutralizer reacts with water, the pH value of the solution is 7.5-8.
7. A process for removing manganese from cobalt precipitation tail liquid according to claim 6, characterized in that: When removing manganese from the tail liquid in step S2, the equation is as follows: Continue to add neutralizer to increase the pH of the solution: Oxidation by oxidants: When the neutralizer is added, the pH value of the solution is 8.5-9.
5.
8. A process for removing manganese from cobalt precipitation tail liquid according to claim 1, characterized in that: When the manganese slag is discharged after the filter press treatment, the manganese slag is also recovered and treated. The treatment steps are: mixing the manganese slag with sulfuric acid solution, heating it to 80-90° C. and then leaching it for 1-3 hours.
9. A process for removing manganese from cobalt precipitation tail liquid according to claim 8, characterized in that: The mass ratio of the manganese slag to the sulfuric acid solution is 1:
5.
10. The process for removing manganese from cobalt precipitation tail liquid according to claim 1, characterized in that: During the neutralization reaction, ultrasonic waves are used to assist the neutralization reaction. The ultrasonic frequency is 20-40kHz and the power density is 50-100W / m³.