Method for preparing manganese electrowinning solution from laterite nickel ore on basis of continuous resin process

Abstract

The present application discloses a method for preparing a manganese electrowinning solution from laterite nickel ore on the basis of a continuous resin process. The method comprises the following steps: using a multi-stage continuous resin process to adsorb manganese in an MHP filtrate prepared from laterite nickel ore to obtain a manganese-adsorbed resin; desorbing the manganese-adsorbed resin using a post-electrowinning manganese solution to obtain a manganese desorption solution; adjusting the pH value of the manganese desorption solution to remove iron and aluminum, so as to obtain an iron- and aluminum-removed manganese solution; adding a heavy metal impurity removing agent such as MnS, BaS, and sodium dimethyldithiocarbamate to the iron- and aluminum-removed manganese solution for impurity removal, to obtain a manganese electrowinning solution; performing manganese electrowinning using the manganese electrowinning solution to obtain an electrowon manganese plate and a post-electrowinning manganese solution; and recycling the post-electrowinning manganese solution as a desorption solution to the next round of resin desorption process. By recycling the post-manganese electrowinning solution to the resin desorption process, the present application not only simplifies the process from manganese recovery to utilization, but also reduces the costs of manganese resource recycling and application, thereby solving the industrialization problem of manganese recycling and utilization in existing new energy enterprises.

Description

A method for preparing manganese electrowinning solution from laterite nickel ore based on continuous resin process TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrometallurgy, and particularly relates to a method for preparing manganese electrowinning solution from laterite nickel ore based on continuous resin process. BACKGROUND

[0002] It is known that in the current new energy era, various enterprises mainly prepare nickel-cobalt intermediate products MHP from laterite nickel ore through a hydrometallurgical process, then purify the MHP into battery-grade nickel-cobalt (manganese) crystals, and finally produce new energy materials. Among them, manganese is more difficult to hydrolyze than nickel-cobalt, so about 80% of the manganese in the laterite nickel ore exists in the filtrate after the preparation of MHP from the laterite nickel ore. At present, the manganese in the filtrate is precipitated as an impurity and is landfilled in the form of tailings, which causes a large waste of manganese resources.

[0003] Manganese is widely used in various fields such as alloy, steel, catalyst, battery material, etc., but the existing technology does not propose an effective recovery method for the manganese resources in the MHP filtrate prepared from laterite nickel ore. Therefore, it is a very urgent task to develop a low-cost industrial process for recovering manganese from laterite nickel ore.

[0004] The present application develops a method for preparing manganese electrowinning solution from the filtrate after the preparation of MHP from laterite nickel ore based on a continuous resin process, and circulates the manganese electrowinning solution to the resin elution process. This not only significantly simplifies the process of manganese recovery and utilization, but also greatly reduces the cost of manganese resource recovery and application, and solves the industrialization problem of manganese recovery and utilization in current new energy enterprises.

[0005] SUMMARY

[0006] Therefore, the present application provides a method for preparing manganese electrowinning solution from laterite nickel ore based on a continuous resin process, which is used to solve the problem of how to recover and utilize manganese in the MHP filtrate prepared from laterite nickel ore.

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

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

[0009] S1. Using a multi-stage continuous resin process to adsorb manganese in the filtrate after the preparation of MHP from laterite nickel ore, to obtain manganese adsorption resin;

[0010] S2. Eluting the manganese adsorption resin with an elution solution to obtain a manganese elution solution;

[0011] S3. Adjusting the pH value of the manganese elution solution, removing iron and aluminum, and then filtering under pressure to obtain the manganese solution after removing iron and aluminum;

[0012] S4. Adding a heavy metal impurity removing agent to the manganese solution after removing iron and aluminum, removing impurities, and then filtering under pressure and standing to obtain the manganese electrowinning solution;

[0013] S5. Using the manganese electrowinning solution to perform manganese electrowinning to obtain the manganese plate and the manganese electrowinning solution; and recycling the manganese electrowinning solution as the elution solution to the elution process of step S2.

[0014] Preferably, step S1 specifically comprises: using one or more of HP606, HP4080, D854, D851, LSC-495, LSC-930, and CH27 resin as the multi-stage continuous resin, and passing the prepared MHP filtrate of the laterite nickel ore through the column at a flow rate of 0.5 BV / h-10 BV / h.

[0015] Preferably, in step S2, the acidity of the elution solution is 20-300 g / L, and the flow rate of the elution solution entering the column for elution is 0.5 BV / h-8 BV / h.

[0016] Preferably, in step S3, the step of removing iron and aluminum comprises: adjusting the pH value of the manganese elution solution to 5-6.5.

[0017] Preferably, in step S4, the heavy metal impurity removing agent comprises but is not limited to one or more of MnS, BaS, and sodium formate, the time for filtering under pressure and standing is 6-24 h, and the impurity removing process is one-step or multi-step impurity removing.

[0018] Preferably, in step S5, the process parameters of manganese electrowinning are as follows: the concentration of ammonium sulfate is 70-125 g / L, the concentration of the additive selenium dioxide is 0.025-0.045 g / L, the pH value is adjusted to 6.7-7.3 by using ammonia water, the cathode current density is 300-430 A / m2, the electrowinning temperature is 35-42℃, and the pole distance is 60-80 mm.

[0019] Preferably, in step S5, the cycle of manganese electrowinning is 12-36 h.

[0020] Preferably, when the manganese electrowinning solution is recycled as the elution solution to the elution process, the method further comprises adding acid to the manganese electrowinning solution.

[0021] Preferably, in step S1, the number of stages of the multi-stage continuous resin is 1-50.

[0022] In a second aspect, the application provides a method for recovering valuable metals.

[0023] The beneficial effects of the present application are as follows: the present application develops a method for preparing manganese electrowinning solution from the filtrate after preparing MHP from laterite nickel ore based on a continuous resin process. The manganese electrowinning solution is recycled to the resin elution process, which not only significantly simplifies the process of manganese recovery and utilization, but also greatly reduces the cost of manganese resource recovery and application, and solves the industrialization problem of manganese recovery and utilization of current new energy enterprises. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is a process flow diagram of the present application. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical scheme and advantages of the present application clearer and more apparent, 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 not to limit the present application.

[0026] As shown in Figure 1, the present application provides a method for preparing manganese electrowinning solution from laterite nickel ore based on a continuous resin process, which comprises the following steps:

[0027] S1. Using a multi-stage continuous resin process to adsorb manganese in the filtrate after preparing MHP from laterite nickel ore, to obtain manganese adsorption resin;

[0028] S2. Eluting the manganese adsorption resin with an elution solution to obtain a manganese elution solution;

[0029] S3. Adjusting the pH value of the manganese elution solution to remove iron and aluminum, and after the reaction is completed, pressure filtration is performed to obtain manganese solution after iron and aluminum removal;

[0030] S4. Adding a heavy metal impurity removal agent to the manganese solution after iron and aluminum removal to remove impurities, and after the reaction is completed, pressure filtration and standing are performed to obtain manganese electrowinning solution;

[0031] S5. Using the manganese electrowinning solution for manganese electrowinning to obtain an electrowinning manganese plate and manganese electrowinning solution, and recycling the manganese electrowinning solution as an elution solution to the elution process of step S2.

[0032] The present application obtains manganese electrowinning solution through resin adsorption-elution-impurity removal process, and then performs manganese electrowinning, and recycles the recovered manganese electrowinning solution to the elution process. The above method can effectively recover manganese in the MHP filtrate prepared from laterite nickel ore. Step S1 enriches manganese by adsorption, step S2 converts elements such as manganese from adsorbed state to solution state by elution, the purpose of steps S3 and S4 is to remove impurities, and the purpose of step S5 is to recover manganese by manganese electrowinning, and to recycle the manganese and acid in the obtained manganese electrowinning solution again.

[0033] In some embodiments, step S1 specifically comprises: using one or more of HP606, HP4080, D854, D851, LSC-495, LSC-930, CH27 resin as a multi-stage continuous resin, and passing the MHP post-filtrate of the laterite nickel ore through the column at a flow rate of 0.5-10 BV / h.

[0034] In some embodiments, in step S2, the acidity of the elution solution is 20-300 g / L, and the flow rate of the elution solution into the column is 0.5-8 BV / h.

[0035] The acidity of the elution solution is within the scope of the present application, which is beneficial for the skilled person to adjust the acidity of the elution solution according to the specific continuous resin device and its adsorption, elution process or manganese electrowinning process parameters, so as to obtain manganese electrowinning solution meeting the electrowinning requirements.

[0036] In some embodiments, in step S3, the step of removing iron and aluminum comprises: adjusting the pH value of the manganese elution solution to 5-6.5.

[0037] In some embodiments, before adjusting the pH value of the manganese elution solution to 5-6.5, the pH value of the manganese elution solution is first adjusted to 2-3.

[0038] In some embodiments, in step S4, the heavy metal impurity removal agent comprises one or more of MnS, BaS, and sodium formate, and the pressure filtration standing time is 6-24 h.

[0039] In some embodiments, in step S5, the process parameters of manganese electrowinning are: the concentration of ammonium sulfate is 70-125 g / L, the concentration of the additive selenium dioxide is 0.025-0.045 g / L, the pH value is adjusted to 6.7-7.3 by using ammonia water, the cathode current density is 300-430 A / m 2 , the electrowinning temperature is 35-42°C, and the pole distance is 60-80 mm.

[0040] Under the manganese electrowinning process defined in the present application, the efficiency of manganese electrowinning and production efficiency can be improved, and high-quality manganese plates can be obtained.

[0041] In some embodiments, in step S5, the cycle of manganese electrowinning is 12-36 h.

[0042] In some embodiments, when the manganese electrowinning solution is recycled to the elution process as an elution solution, acid is added to the manganese electrowinning solution.

[0043] In some embodiments, the number of stages of the multi-stage continuous resin is 1-50 stages.

[0044] In some embodiments, in step S4, the impurity removal process is one-step impurity removal or multi-step impurity removal.

[0045] The manganese electrodeposition post-solution is circulated to the elution solution (acid-containing solution), which can supplement the acid in the manganese electrodeposition post-solution to the elution solution for utilization, reduces the acid amount used for elution, and can further recycle the manganese not completely electrodeposited in the manganese electrodeposition post-solution as raw material for recycling electrodeposition, so as to improve the manganese recovery rate.

[0046] The application provides a method for recovering valuable metals.

[0047] The method for preparing the manganese electrodeposition solution from the laterite nickel ore based on the continuous resin process provided by the application is not limited to the recovery of manganese from the MHP filtrate prepared from the laterite nickel ore, and can be used for the recovery of valuable metals from other materials, including but not limited to battery materials, manganese ores and wastewater, and the valuable metals include but are not limited to nickel and cobalt.

[0048] The application will be further described below through specific examples.

[0049] Example 1

[0050] A method for preparing a manganese electrodeposition solution from a laterite nickel ore based on a continuous resin process, comprising the following steps:

[0051] S1. The filtrate (Ni: 0.002 g / L, Co: 0.004 g / L, Fe: 0.0002 g / L, Al: 0.0003 g / L, Mn: 1.45 g / L, Ca: 0.57 g / L, Mg: 5.32 g / L) prepared from the laterite nickel ore after MHP is passed through a column at a flow rate of 2 BV / h to adsorb manganese on the resin, and the filtration is stopped when the Mn in the tail liquid is greater than 5 mg / L.

[0052] S2. The manganese adsorption resin is eluted with 225 g / L sulfuric acid solution as the elution solution at a flow rate of 1.5 BV / h to obtain a manganese elution solution, and the elution is stopped until the resin is basically restored to the color before adsorption. The composition of the obtained manganese elution solution is: Ni: 0.064 g / L, Co: 0.129 g / L, Fe: 0.003 g / L, Al: 0.004 g / L, Mn: 47.56 g / L, Ca: 0.005 g / L, Mg: 0.004 g / L.

[0053] S3. The pH value of the manganese elution solution is adjusted to 2 by using limestone, and then the pH value of the manganese elution solution is further adjusted to 6.2 by using ammonia water. After the reaction is completed, the manganese solution after iron and aluminum removal is obtained by pressure filtration, and the composition of the manganese solution after iron and aluminum removal is: Ni: 0.056 g / L, Co: 0.118 g / L, Fe, Al: 0 g / L, Mn: 45.52 g / L, Ca: 0.58 g / L, Mg: 0.004 g / L.

[0054] S4. 1.2 g / L BaS heavy metal impurity remover was added to the manganese solution after iron and aluminum removal to remove impurities. After the reaction, the manganese electrodeposition liquid was obtained by pressure filtration and standing for 16 h. The composition of the manganese electrodeposition liquid was: Ni, Co: 0.001 g / L, Fe, Al: 0 g / L, Mn: 44.89 g / L, Ca: 0.59 g / L, Mg: 0.004 g / L.

[0055] S5. The manganese electrodeposition liquid was used for manganese electrodeposition to obtain an electrodeposited manganese plate and a manganese electrodeposition post-liquid. The manganese electrodeposition post-liquid was then recycled as an elution liquid to the next round of elution process of the resin in step S2. The manganese electrodeposition process parameters were: ammonium sulfate concentration was 100 g / L, selenium dioxide concentration was 0.035 g / L, ammonia water was used to adjust the pH to 7, the cathode current density was 390 A / m 2 , the electrodeposition temperature was 40°C, the pole distance was 70 mm, and the electrodeposition period was 24 h. The purity of the obtained electrodeposited manganese plate was 99.84%, and the composition of the manganese electrodeposition post-liquid was: Ni: 0.0003 g / L, Co: 0.0002 g / L, Fe, Al: 0 g / L, Mn: 16.50 g / L, Ca: 0.59 g / L, Mg: 0.004 g / L.

[0056] Example 2

[0057] A method for preparing a manganese electrodeposition liquid from laterite nickel ore based on a continuous resin process, other contents are the same as example 1, the difference with example 1 is only in step S1, the series number of the resin column is changed to 8, and the flow rate of the filtrate after preparing MHP from laterite nickel ore can be increased to 3 BV / h. It is found that the composition of the obtained manganese elution liquid is Ni: 0.071 g / L, Co: 0.141 g / L, Fe: 0.003 g / L, Al: 0.004 g / L, Mn: 46.26 g / L, Ca: 0.004 g / L, Mg: 0.003 g / L. The manganese elution liquid can be used to obtain a manganese electrodeposition liquid meeting the electrodeposition requirements by using the same process method as example 1.

[0058] Example 3

[0059] A method for preparing a manganese electrodeposition liquid from laterite nickel ore based on a continuous resin process, other contents are the same as example 1, the difference with example 1 is only in step S4, after removing impurities with BaS heavy metal impurity remover, 0.2 g / L of thiozole sodium is used for deep impurity removal. The composition of the obtained manganese electrodeposition liquid is: Ni, Co: 0 g / L, Mn: 44.80 g / L, Ca: 0.59 g / L, Mg: 0.004 g / L. After manganese electrodeposition test, the purity of the electrodeposited manganese plate is 99.92%, which shows that deep impurity removal is crucial to improve the purity of the manganese plate.

[0060] Example 4

[0061] A method for preparing manganese electrowinning solution from laterite nickel ore based on continuous resin process, other contents are the same as example 1, the difference from example 2 is that in step S5, the electrowinning period is reduced to 16h, it is found by test that the composition of the manganese electrowinning solution is: Ni, Co: 0g / L, Mn: 27.61g / L, Ca: 0.59g / L, Mg: 0.004g / L. Since the manganese concentration in the manganese electrowinning solution increases, the acidity of the manganese electrowinning solution is adjusted to 170g / L as the elution solution and circulated to the resin elution process described in S2 of the next round, and the manganese elution solution with a manganese concentration of 45g / L is also obtained, and then impurities are removed to obtain the manganese electrowinning solution for electrowinning, and the purity of the manganese plate is measured to be 99.85%, which indicates that the acidity of the elution solution is closely related to the manganese electrowinning period. At the same time, the process provided by the application can be adjusted in time according to the needs in the actual production process, which is convenient to implement.

[0062] Comparative example 1

[0063] A method for preparing manganese electrowinning solution from laterite nickel ore based on continuous resin process, other contents are the same as example 1, the difference is that step S3 is not included. The purity of the obtained manganese plate is less than 99.70%, which does not meet the standard of the manganese metal industry. It is shown that, in addition to the role of increasing the pH of the manganese elution solution and laying the foundation for subsequent heavy metal removal and manganese electrowinning, step S3 also plays a decisive role in the purity of the manganese plate.

[0064] In the prior art, when exploiting and utilizing laterite nickel ore, the manganese in the filtrate after MHP precipitation is precipitated as slag by using alkaline substances for landfill treatment. Since Mn 2+ In chemical reactions, it is easy to be oxidized to form high-valence manganese oxides, so if manganese is extracted from the manganese slag, reduction leaching needs to be performed, and then multi-step impurity removal needs to be performed. Obviously, the method for preparing manganese electrowinning solution from laterite nickel ore based on continuous resin process provided by the application can reduce the current manganese precipitation process, and at the same time, manganese can be recovered and applied in the field of manganese electrowinning at low cost. Therefore, the continuous resin process provided by the application creatively circulates the manganese electrowinning solution to the resin elution process, which not only significantly simplifies the process of manganese recovery and utilization, but also greatly reduces the cost of manganese resource recovery and application, and solves the industrialization problem of manganese recovery and application in the current new energy enterprise as an example.

[0065] It is worth noting that the method for preparing manganese electrowinning solution from laterite nickel ore based on continuous resin process provided by the application is not limited to the recovery of manganese from the MHP filtrate prepared from laterite nickel ore, and the method can be used for the recovery of valuable metals in other materials, including but not limited to battery materials, manganese ore, wastewater, and valuable metals including but not limited to nickel and cobalt.

[0066] The above merely provides the preferred embodiments of the present application, and the protection scope of the present application is not limited thereto, and any changes or substitutions easily conceived by those skilled in the art within the technical scope disclosed by the present application shall be covered within the protection scope of the present application.

Claims

1. A process for the preparation of manganese electrowinning solution from lateritic nickel ores based on a continuous resin process, characterized by, The method comprises the following steps: S1. Adsorbing manganese in filtrate after preparation of MHP from laterite nickel ore by using multi-stage continuous resin process to obtain manganese adsorption resin; S2. Eluting the manganese adsorption resin with elution liquid to obtain manganese elution liquid; S3. Adjusting pH value of the manganese elution liquid to remove iron and aluminum, and after reaction, pressure filtration is performed to obtain manganese liquid after removal of iron and aluminum; S4. Adding heavy metal impurity removing agent to the manganese liquid after removal of iron and aluminum to remove impurities, and after reaction, pressure filtration and standing are performed to obtain manganese electrodeposition liquid; S5. Electrodeposition is performed by using the manganese electrodeposition liquid to obtain electrodeposited manganese plate and manganese electrodeposition post-liquid, and the manganese electrodeposition post-liquid is recycled as elution liquid to the elution process in step S2.

2. The process for the preparation of manganese electrowinning solution from laterite nickel ore based on continuous resin process as claimed in claim 1 wherein, Step S1 specifically comprises: using one or more of HP606, HP4080, D854, D851, LSC-495, LSC-930 and CH27 resin as multi-stage continuous resin, and flowing filtrate after preparation of MHP from laterite nickel ore through the column at a flow rate of 0.5-10 BV / h for adsorption.

3. The process for the preparation of manganese electrowinning solution from laterite nickel ore based on continuous resin process as claimed in claim 1 wherein, In step S2, the acidity of the elution liquid is 20-300 g / L, and the flow rate of the elution liquid for column elution is 0.5-8 BV / h.

4. The process for the preparation of manganese electrowinning solution from laterite nickel ore based on continuous resin process as claimed in claim 1 wherein, In step S3, the step of removing iron and aluminum comprises: adjusting pH value of the manganese elution liquid to 5-6.

5.

5. The process for the preparation of manganese electrowinning solution from laterite nickel ore based on continuous resin process as claimed in claim 1 wherein, In step S4, the standing time after pressure filtration is 6-24 h, and the impurity removing process is one-step or multi-step impurity removing.

6. The process for the preparation of manganese electrowinning solution from laterite nickel ore based on continuous resin process as claimed in claim 1 wherein, The process parameters of the manganese electrodeposition in step S5 are as follows: the concentration of ammonium sulfate is 70-125 g / L, the concentration of additive selenium dioxide is 0.025-0.045 g / L, the pH is adjusted to 6.7-7.3 by ammonia water, the cathode current density is 300-430 A / m 2 , the electrodeposition temperature is 35-42 ℃, and the pole distance is 60-80 mm.

7. The process for the preparation of manganese electrowinning solution from laterite nickel ore based on continuous resin process as claimed in claim 1 wherein, In step S5, the cycle of manganese electrodeposition is 12-36 h.

8. The process for the preparation of manganese electrowinning solution from laterite nickel ore based on continuous resin process as claimed in claim 1 wherein, When the manganese electrodeposition post-liquid is recycled as elution liquid to the elution process, acid is further added to the manganese electrodeposition post-liquid.

9. The process for the preparation of manganese electrowinning solution from laterite nickel ore based on continuous resin process as claimed in claim 1 wherein, In step S1, the number of stages of the multi-stage continuous resin is 1-50.

10. Use of the method according to any one of claims 1-9 in recovery of valuable metals.

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