Method for preparing manganese electrowinning solution from laterite nickel ore and use

Abstract

The present application discloses a method for preparing a manganese electrowinning solution from laterite nickel ore, comprising the following steps: adding an acid to a manganese slag underflow of laterite nickel ore for pretreatment, followed by filter pressing to obtain pretreated manganese slag; slurrying the pretreated manganese slag to obtain a manganese slurry; adding an acid to the manganese slurry for manganese leaching, followed by filter pressing to obtain a manganese leachate and leaching residue; adding a neutralizing agent to the manganese leachate for neutralization, followed by filter pressing to obtain a neutralized manganese solution and neutralization residue; adding a heavy metal impurity removal agent to the neutralized manganese solution for impurity removal, followed by filter pressing to obtain a manganese solution and filter residue; adding an additive to the manganese solution for manganese electrowinning to obtain a manganese plate and a post-electrowinning manganese solution; and reusing the post-electrowinning manganese solution as a slurrying liquid in the slurrying process. This patent proposes, for the first time, a low-cost industrialized process for manganese recovery and utilization from laterite nickel ore, solving the problems of manganese resource waste in a laterite nickel ore metallurgical process and pollution caused by manganese slag landfilling.

Description

Method for preparing manganese electrowinning solution from laterite nickel ore and application TECHNICAL FIELD

[0001] The present application relates to the technical field of manganese resource recovery, in particular to a method for preparing manganese electrowinning solution from laterite nickel ore and application. BACKGROUND

[0002] With the sharp decrease of sulfide nickel ore reserves, laterite nickel ore has become a mineral resource that countries pay attention to and focus on mining. Whether it is through pyrometallurgical process to prepare nickel-iron or icynite or wet process to prepare MHP, a large amount of manganese resources in laterite nickel ore are treated and filled. Among them, limonite type laterite nickel ore is commonly used in the field of hydrometallurgy, and the manganese grade of this type of ore is 0.4%-0.8%, accounting for 40%-70% of nickel. High-pressure leaching to prepare MHP intermediate product is a typical industrialization process for treating this type of ore. In the high-pressure leaching section, more than 90% of manganese can be leached, but about 20% of it enters MHP when it is precipitated, and the rest of the manganese is precipitated and treated as waste slag. About 0.3-0.6 tons of manganese slag will be produced for every 1 ton (calculated by nickel) of MHP.

[0003] Manganese is widely used in alloying, steel, battery, catalyst and other fields. Manganese ore is rhodochrosite and pyrolusite, but rapid mining and use has caused the reserves and grade of manganese ore to decrease continuously. In addition, currently, after being crushed and treated, the industry generally uses a reduction roasting combined with acid leaching process to extract manganese from manganese ore, and this process is complicated, energy-consuming and polluting.

[0004] Therefore, recovering manganese from laterite nickel ore and other metallurgical waste slag can not only alleviate the problem of manganese resource shortage caused by rapid mining of manganese ore, but also solve the pollution problem caused by filling of waste manganese slag.

[0005] SUMMARY

[0006] Therefore, the present application provides a method for preparing manganese electrowinning solution from laterite nickel ore and application, which is used to solve the problem of how to use laterite nickel ore manganese slag to prepare manganese electrowinning solution to solve the waste of manganese resources in the metallurgical process of laterite nickel ore and the pollution problem caused by filling of manganese slag.

[0007] To achieve the above technical purposes, the present application adopts the following technical solutions:

[0008] In a first aspect, the present application provides a method for preparing manganese electrowinning solution from laterite nickel ore, comprising the following steps:

[0009] S1. Adding acid to the underflow of laterite nickel ore manganese slag for pretreatment, and then pressure filtering to obtain filtrate and pretreated manganese slag, and collecting the filtrate for waste liquid treatment;

[0010] S2. The pretreated manganese residue is slurried to obtain a manganese slurry;

[0011] S3. An acid is added to the manganese slurry for manganese leaching, and then pressure filtration is performed to obtain a manganese leaching solution and a leaching residue, and the leaching residue is collected for tail residue treatment;

[0012] S4. A neutralizing agent is added to the manganese leaching solution for neutralization, and then pressure filtration is performed to obtain a manganese neutralization solution and a neutralization residue, and the neutralization residue is collected for tail residue treatment;

[0013] S5. A heavy metal impurity removal agent is added to the manganese neutralization solution for impurity removal, and then pressure filtration is performed to obtain a manganese solution and a filter residue;

[0014] S6. An additive is added to the manganese solution for manganese electrodeposition to obtain a manganese plate and a manganese post-electrodeposition solution, and the manganese post-electroposition solution is reused as a slurry solution in the slurring process of step S2.

[0015] Preferably, in step S1, the mass ratio of the manganese residue underflow to the acid is 1:0.001-0.05; the reaction temperature of the pretreatment is 25-90°C, and the reaction time is 1-120 min.

[0016] Preferably, in step S2, the solid-liquid ratio of the slurry is 1:2-10.

[0017] Preferably, in step S3, the acid includes one or more of sulfuric acid, hydrochloric acid, and nitric acid; the manganese leaching temperature is 25-90°C, and the manganese leaching time is 0.01-10 h.

[0018] Preferably, in step S3, a reducing agent is also added, and the reducing agent includes but is not limited to one or more of sulfur dioxide, hydrogen peroxide, sodium pyrosulfite, sodium sulfide, pyrite, iron powder, and coal powder.

[0019] Preferably, in step S4, the neutralizing agent includes but is not limited to one or more of inorganic alkali, limestone, lime milk, manganese carbonate, and ammonium sulfate; in step S4, the pH value of the mixed solution after the neutralizing agent is added to the manganese leaching solution is 0.5-6.5, the neutralization temperature is 25-90°C, and the neutralization time is 0.01-5 h.

[0020] Preferably, in step S4, the neutralization step is one to three steps.

[0021] Preferably, in step S5, the heavy metal impurity removal step is one to three steps.

[0022] Preferably, in step S5, the heavy metal impurity removal agent includes but is not limited to one or more of manganese sulfide, sodium sulfide, barium sulfide, ammonium sulfide, ethylene thiourea, and sodium dimethyldithiocarbamate; the impurity removal temperature is 25-90°C, and the impurity removal time is 0.1-10 h.

[0023] Preferably, in step S6, the additive comprises one or more of SeO2, SO2.

[0024] Preferably, in step S6, the manganese electrodeposition post-liquid comprises one or more of manganese cathode liquid, manganese anode liquid.

[0025] The beneficial effects of the present application are as follows: the present application proposes a low-cost industrialization process for recycling manganese from laterite nickel ore, greatly reducing the resource waste problem and environmental pollution caused by the large amount of manganese resources buried during the extraction of nickel and cobalt from laterite nickel ore, and preparing manganese electrodeposition liquid, the recovery rate of manganese can reach more than 90%, and the purity of manganese plate can reach 99.9%, which alleviates the problem of tight manganese ore resources and has a certain promoting effect on the cost reduction and efficiency increase of new energy related enterprises facing overcapacity. BRIEF DESCRIPTION OF DRAWINGS

[0026] Fig. 1 is a process flow diagram of the present application. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application will be further described in detail below in combination with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0028] Please refer to Fig. 1, the present application provides a method for preparing manganese electrodeposition liquid from laterite nickel ore, comprising the following steps:

[0029] S1. Add acid to the laterite nickel ore manganese slag underflow for pretreatment, and then filter to obtain filtrate and pretreated manganese slag, collect the filtrate for waste liquid treatment;

[0030] S2. Slurry the pretreated manganese slag to obtain manganese slurry;

[0031] S3. Add acid to the manganese slurry for manganese leaching, and then filter to obtain manganese leaching liquid and leaching residue, collect the leaching residue for tail residue treatment;

[0032] S4. Add a neutralizing agent to the manganese leaching liquid for neutralization, and then filter to obtain manganese neutralization liquid and neutralization residue, collect the neutralization residue for tail residue treatment;

[0033] S5. Add a heavy metal impurity removal agent to the manganese neutralization liquid for impurity removal, and then filter to obtain manganese liquid and filter residue;

[0034] S6. Add an additive to the manganese liquid for manganese electrodeposition to obtain a manganese plate and a manganese electrodeposition post-liquid, and the manganese electrodeposition post-liquid is reused as a slurry liquid to the slurry process of step S2.

[0035] Preferably, in step S1, the mass ratio of manganese residue underflow to acid is 1:0.001-0.05; the reaction temperature of pre-treatment is 25-90℃, and the reaction time is 1-120min.

[0036] Preferably, in step S2, the solid-liquid ratio of slurry is 1:2-10.

[0037] Preferably, in step S3, the acid includes one or more of sulfuric acid, hydrochloric acid, and nitric acid; the temperature of manganese leaching is 25-90℃, and the time of manganese leaching is 0.01-10h.

[0038] Preferably, in step S3, a reducing agent is also added, which includes but is not limited to one or more of sulfur dioxide, hydrogen peroxide, sodium pyrosulfite, sodium sulfide, pyrite, iron powder, and coal powder.

[0039] Preferably, in step S4, the neutralizing agent includes but is not limited to one or more of inorganic base, limestone, lime milk, manganese carbonate, and ammonium sulfate; in step S4, the pH value of the mixed solution after adding the neutralizing agent to the manganese leaching solution is 0.5-6.5, the neutralization temperature is 25-90℃, and the neutralization time is 0.01-5h. The inorganic base includes one or more of sodium hydroxide, potassium hydroxide, and ammonia water.

[0040] Preferably, in step S4, the neutralization step is one to three steps. In some embodiments, step S4 is repeated twice before step S5, and the specific operation is as follows: S4.1, a first neutralizing agent is added to the manganese leaching solution for one-time neutralization, and then pressure filtration is performed to obtain a first manganese neutralization liquid and a first neutralization residue; the first neutralization residue is collected for tail residue treatment; S4.2, a second neutralizing agent is added to the first manganese neutralization liquid for two-time neutralization, and then pressure filtration is performed to obtain a second manganese neutralization liquid and a second neutralization residue; the second neutralization residue is collected for tail residue treatment. The first neutralizing agent includes but is not limited to one or more of hydroxides such as sodium hydroxide, limestone, lime milk, manganese carbonate, ammonia water, and ammonium sulfate; in step S4, the pH value of the mixed solution after adding the first neutralizing agent to the manganese leaching solution is 0.5-6.5, the one-time neutralization temperature is 25-90℃, and the one-time neutralization time is 0.01-5h; the second neutralizing agent includes but is not limited to one or more of hydroxides such as sodium hydroxide, limestone, lime milk, manganese carbonate, ammonia water, and ammonium sulfate.

[0041] Preferably, in step S5, the heavy metal removal step is one to three steps. It is worth noting that one or more steps of removal are selected according to the concentration of heavy metals and the properties of different heavy metal removal agents. If the concentration of heavy metals is low, one-step removal is used; if the concentration of heavy metals is high, multi-step removal (two or three steps) is used, which is beneficial to reduce the cost of manganese recovery and obtain manganese liquid with higher purity.

[0042] Preferably, in step S5, the pH value of the mixed solution after adding the second neutralizing agent in the first manganese neutralized solution is 1.5-6.5, the temperature of the secondary neutralization is 25-90℃, and the time of the secondary neutralization is 0.01-5h.

[0043] Preferably, in step S5, the heavy metal impurity removing agent includes but is not limited to one or more of manganese sulfide, sodium sulfide, barium sulfide, ammonium sulfide, ethylene, and sodium sulfide; the temperature of the impurity removal is 25-90℃, and the time of the impurity removal is 0.1-10h.

[0044] Preferably, in step S6, the additive includes one or more of SeO2 and SO2.

[0045] Preferably, in step S6, the manganese electrode post-electrodeposition solution includes one or more of manganese cathode solution and manganese anode solution.

[0046] The manganese electrode post-electrodeposition solution obtained by the manganese electrode is the manganese cathode solution or the manganese anode solution discharged after one cycle of electrodeposition, wherein the manganese electrode post-electrodeposition solution is the manganese cathode solution when the cathode is bagged, and the manganese electrode post-electrodeposition solution is the manganese anode solution when the anode is bagged.

[0047] In this application, the wastewater treatment is carried out by a wastewater treatment system, and the tailings treatment is carried out by a tailings treatment system.

[0048] Hereinafter, the present scheme will be further described through specific examples.

[0049] Example 1

[0050] A method for preparing a manganese electrode solution from laterite nickel ore, comprising the following steps:

[0051] S1. Adding concentrated sulfuric acid to the underflow of the manganese residue of the laterite nickel ore concentrated by the thickener to pretreat the manganese residue, wherein the mass ratio of the manganese residue underflow to the concentrated sulfuric acid is 1:0.02, the reaction temperature of the pretreatment is 25℃, the reaction time is 10min, and after the reaction is completed, pressure filtration is carried out to obtain a filtrate and pretreated manganese residue, and the filtrate is collected and treated in a wastewater treatment system;

[0052] S2. Adding manganese electrode post-electrodeposition solution as a slurry liquid to the pretreated manganese residue for slurry, and the solid-liquid ratio of the slurry is 1:2.5 to obtain a manganese slurry;

[0053] S3. Adding concentrated sulfuric acid and 30% hydrogen peroxide to the manganese slurry for manganese reduction leaching, wherein the solid-liquid ratio of the pretreated manganese residue to the concentrated sulfuric acid is 1:0.6, the solid-liquid ratio of the pretreated manganese residue to the hydrogen peroxide is 1:0.17, the leaching temperature is 60℃, the leaching time is 1h, and after the reaction is completed, pressure filtration is carried out to obtain a manganese leaching solution and a leaching residue; the leaching residue is washed at the same time during pressure filtration, and the leaching residue is collected and treated in a tailings system;

[0054] S4. limestone is added to the manganese leaching solution for primary neutralization, the pH of the primary neutralized solution is adjusted to 2, the reaction temperature of the primary neutralization is 55°C, the reaction time is 0.5h, then pressure filtration is performed to obtain a first manganese neutralized solution and a first neutralized residue; the first neutralized residue is collected for tail residue treatment; lime milk is added to the first manganese neutralized solution for secondary neutralization, the pH of the secondary neutralized solution is adjusted to 6.2, the reaction temperature of the secondary neutralization is 50°C, the reaction time is 0.5h, then pressure filtration is performed to obtain a second manganese neutralized solution and a second neutralized residue; the second neutralized residue is collected for tail residue treatment;

[0055] S5. sodium dimethyldithiocarbamate is added to the second manganese neutralized solution to remove heavy metal impurities, the reaction temperature of the impurity removal is 45°C, the reaction time is 3h, then pressure filtration is performed and the solution is left to stand for 16h to obtain a manganese solution after removal of heavy metals and a filter residue;

[0056] S6. SeO2 is added to the manganese solution after removal of heavy metals to perform manganese electrodeposition, to obtain a manganese plate and a manganese electrodeposition solution; the manganese electrodeposition solution is reused as a slurrying solution in the slurrying procedure of step S2.

[0057] Example 2

[0058] A method for preparing a manganese electrodeposition solution from laterite nickel ore, other contents are the same as in Example 1, and the only difference from Example 1 is that ammonia water is added to the first manganese neutralized solution for secondary neutralization, and other steps and conditions are the same as in Example 1.

[0059] Example 3

[0060] A method for preparing a manganese electrodeposition solution from laterite nickel ore, other contents are the same as in Example 2, and the only difference from Example 2 is that the removal of heavy metals is divided into two steps, the first step uses barium sulfide to remove more than 90% of the heavy metals, and the second step uses sodium dimethyldithiocarbamate to remove heavy metals in depth, and other steps and conditions are the same as in Example 1.

[0061] Example 4

[0062] A method for preparing a manganese electrodeposition solution from laterite nickel ore, other contents are the same as in Example 1, and the only difference from Example 1 is that SO2 is added to the manganese solution after removal of heavy metals for manganese electrodeposition, and other steps and conditions are the same as in Example 1.

[0063] Comparative Example 1

[0064] A method for preparing a manganese electrodeposition solution from laterite nickel ore, other contents are the same as in Example 1, and the only difference is that no reducing agent is added in step S2.

[0065] Comparative Example 2

[0066] A method for preparing manganese electrowinning solution from laterite nickel ore, other contents are the same as example 1, the difference is that in step S4, the pH of the once neutralized solution is adjusted to 6.8.

[0067] Test and evaluation

[0068] The recovery rate of manganese and the purity of manganese plate obtained by testing each example and comparative example are tested, and the test results are shown in Table 1.

[0069] Table 1 test results

[0070] Comparative example 3 and example 1 found that if the concentration of heavy metals in the neutralized manganese solution is high, the two-step heavy metal impurity removal using different heavy metal impurity removal agents can appropriately improve the recovery rate of manganese and the purity of manganese plate. In comparative example 1, no reducing agent is added, and the recovery rate of manganese decreases significantly. In comparative example 2, the pH of the neutralization is too high, and the recovery rate of manganese decreases. The above results show that the low-cost industrialization process for recovering and utilizing manganese from laterite nickel ore proposed in the present application not only greatly reduces the resource waste problem and environmental pollution caused by a large amount of manganese resources being buried during the extraction of nickel and cobalt from laterite nickel ore, but also alleviates the problem of manganese resource shortage. Moreover, the recovered manganese is used in the field of manganese electrowinning, the recovery rate of manganese can reach more than 90%, and the purity of manganese plate can reach 99.9%. The above results have a certain promoting effect on the cost reduction and efficiency improvement of new energy related enterprises facing overcapacity.

[0071] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto. Any changes or replacements within the technical scope disclosed in the present application can be easily thought by those skilled in the art, and should be covered within the protection scope of the present application.

Claims

1. A process for the preparation of manganese electrowinning solution from lateritic nickel ore, characterized in that, The method comprises the following steps: S1. Adding acid to the underflow of laterite nickel ore manganese slag for pretreatment, and then pressure filtration to obtain filtrate and pretreated manganese slag, and collecting the filtrate for waste liquid treatment; S2. Slurrying the pretreated manganese slag to obtain manganese slurry; S3. Adding acid to the manganese slurry for manganese leaching, and then pressure filtration to obtain manganese leaching solution and leaching residue, and collecting the leaching residue for tail residue treatment; S4. Adding a neutralizing agent to the manganese leaching solution for neutralization, and then pressure filtration to obtain manganese neutralization solution and neutralization residue, and collecting the neutralization residue for tail residue treatment; S5. Adding a heavy metal impurity removal agent to the manganese neutralization solution for impurity removal, and then pressure filtration to obtain manganese solution and filter residue; S6. Adding an additive to the manganese solution for manganese electrodeposition to obtain manganese plate and manganese post-electrodeposition solution, and recycling the manganese post-electroposition solution as a slurry liquid to the slurry process of step S2.

2. The process for the preparation of manganese electrowinning solution from laterite nickel ore according to claim 1, characterized in that, In step S1, the mass ratio of the manganese slag underflow to the acid is 1:0.001-0.05; the reaction temperature of the pretreatment is 25-90℃, and the reaction time is 1-120 min.

3. The process for the preparation of manganese electrowinning solution from laterite nickel ore according to claim 1, characterized in that, In step S2, the solid-liquid ratio of the slurry is 1:2-10.

4. The method for producing manganese electrowinning solution from laterite nickel ore according to claim 1, characterized by, In step S3, the acid comprises one or more of sulfuric acid, hydrochloric acid and nitric acid; the temperature of the manganese leaching is 25-90℃, and the manganese leaching time is 0.01-10 h.

5. The process for the preparation of manganese electrowinning solution from nickel laterite ore according to claim 1, characterized in that, In step S3, a reducing agent is further added.

6. The process for the preparation of manganese electrowinning solution from nickel laterite ore according to claim 1, characterized in that, In step S4, the pH value of the mixed solution after adding the neutralizing agent to the manganese leaching solution is 0.5-6.5, the neutralization temperature is 25-90℃, and the neutralization time is 0.01-5 h.

7. The process for the preparation of manganese electrowinning solution from nickel laterite ore according to claim 1, characterized in that, In step S4, the neutralization step is one to three steps.

8. The process for the preparation of manganese electrowinning solution from laterite nickel ore according to claim 1, characterized in that, In step S5, the heavy metal impurity removal step is one to three steps.

9. The process for the preparation of manganese electrowinning solution from nickel laterite ore according to claim 1, characterized in that, In step S5, the temperature of the impurity removal is 25-90℃, and the impurity removal time is 0.1-10 h.

10. The process for the preparation of manganese electrowinning solution from nickel laterite ore according to claim 1, characterized in that, In step S6, the manganese post-electrodeposition solution comprises one or more of manganese cathode solution and manganese anode solution.

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