Method for preparing manganese electrodeposition liquid from laterite-nickel ore based on continuous resin process

Abstract

The invention discloses a method for preparing manganese electrodeposition liquid from laterite-nickel ore based on a continuous resin process, which comprises the following steps: adsorbing manganese in MHP filtrate prepared from laterite-nickel ore by using a multi-stage continuous resin process to obtain manganese adsorption resin; the manganese adsorption resin is desorbed through the manganese electrodeposition post-solution, and a manganese desorption solution is obtained; the pH value of the manganese desorption solution is adjusted to remove iron and aluminum, and manganese liquid with iron and aluminum removed is obtained; heavy metal impurity removing agents such as MnS, BaS and sodium dimethyl dithiocarbamate are added into the manganese liquid subjected to iron and aluminum removal for impurity removal, and manganese electrodeposition liquid is obtained; carrying out manganese electrodeposition by using the manganese electrodeposition liquid to obtain an electrodeposition manganese plate and manganese electrodeposition post-liquid; and the manganese electrodeposition post-solution is used as a desorption solution to be circulated to the next round of desorption process of the resin. According to the method, the manganese electrodeposition post-liquid is circulated to the resin desorption process, so that the process from manganese recovery to utilization is simplified, the cost of manganese resource recovery and application is reduced, and the industrialization problem of manganese recovery and utilization of new energy enterprises at present is solved.

Description

Technical Field

[0001] The present application relates to the technical field of hydrometallurgy, and in particular to a method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process. Background Art

[0002] As we all know, in the current era of new energy, various companies mainly prepare nickel-cobalt intermediate MHP from laterite nickel ore through hydrometallurgical processes, and then purify it into battery-grade nickel-cobalt (manganese) crystals, and finally recreate new energy materials. Among them, manganese is relatively difficult to hydrolyze compared to nickel and cobalt. Therefore, about 80% of the manganese in laterite nickel ore exists in the filtrate after the preparation of MHP from laterite nickel ore. At present, the manganese in the filtrate is precipitated as an impurity and landfilled in the form of tailings, which causes a large waste of manganese resources.

[0003] Manganese is widely used in the preparation of various alloys, steel, catalysts, battery materials and other fields, but the existing technology does not propose an effective method for recovering manganese resources in the filtrate of MHP prepared from laterite nickel ore. Therefore, it is a very urgent issue to develop a low-cost industrial process for recovering manganese from laterite nickel ore.

[0004] This application has developed a method for preparing manganese electrolytic solution from the filtrate after preparing MHP from laterite nickel ore based on a continuous resin process, and the solution after manganese electrolytic solution is recycled to the resin analysis process. This not only significantly simplifies the process of manganese recovery and utilization, but also greatly reduces the cost of manganese resource recovery and its application, and solves the current industrialization problem of manganese recovery and utilization in new energy enterprises. Summary of the invention

[0005] In view of this, the present application provides a method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process, which is used to solve the problem of how to recycle manganese in the MHP filtrate prepared from laterite nickel ore.

[0006] In order to achieve the above technical objectives, this application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process, comprising the following steps:

[0008] S1. Adsorbing manganese in the filtrate after preparing MHP from laterite nickel ore using a multi-stage continuous resin process to obtain a manganese adsorption resin;

[0009] S2. The manganese adsorption resin is analyzed with an analytical solution to obtain a manganese analytical solution;

[0010] S3. Adjust the pH value of the manganese analysis solution to remove iron and aluminum. After the reaction is completed, filter press to obtain a manganese solution after removing iron and aluminum;

[0011] S4. Add a heavy metal impurity remover to the manganese solution after iron and aluminum removal to remove impurities. After the reaction is completed, filter press and let stand to obtain a manganese electrolytic solution;

[0012] S5. Use the manganese electrolytic solution to perform manganese electrolytic deposition to obtain an electrolytic manganese plate and a manganese electrolytic solution; and circulate the manganese electrolytic solution as an analytical solution to the analytical process of step S2.

[0013] Preferably, step S1 specifically comprises: using one or more of HP606, HP4080, D854, D851, LSC-495, LSC-930, and CH27 resins as multi-stage continuous resins, and passing the filtrate after preparing MHP from laterite nickel ore through a column for adsorption at a flow rate of 0.5 BV / h-10 BV / h.

[0014] Preferably, in step S2, the acidity of the analytical solution is 20-300 g / L, and the flow rate of the analytical solution entering the column for analysis is 0.5 BV / h-8 BV / h.

[0015] Preferably, in step S3, the step of removing iron and aluminum includes: adjusting the pH value of the manganese analysis solution to 5-6.5.

[0016] Preferably, in step S4, the heavy metal impurity remover includes but is not limited to one or more of MnS, BaS, and sodium thiamethoxam, the filter press is left standing for 6-24 hours, and the impurity removal process is one-step or multiple-step impurity removal.

[0017] Preferably, in step S5, the process parameters for manganese electrowinning are: ammonium sulfate concentration 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 with ammonia water, the cathode current density is 300-430 A / m2, the electrowinning temperature is 35-42°C, and the electrode distance is 60-80 mm.

[0018] Preferably, in step S5, the cycle of manganese electrowinning is: 12-36h.

[0019] Preferably, when the manganese electrodeposition solution is circulated to the analysis step as an analysis solution, acid is added to the manganese electrodeposition solution.

[0020] Preferably, in step S1, the number of stages of the multi-stage continuous resin is 1-50.

[0021] In a second aspect, the present application provides a method for use in recovering valuable metals.

[0022] The beneficial effects of the present application are as follows: The present application develops a method for preparing manganese electrolytic solution from the filtrate after preparing MHP from laterite nickel ore based on a continuous resin process, and the liquid after manganese electrolytic solution is recycled to the resin analysis process, which not only significantly simplifies the process of manganese recovery and utilization, but also greatly reduces the cost of manganese resource recovery and its application, and solves the current industrialization problem of manganese recovery and utilization in new energy enterprises. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a process flow chart of this application. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solution and advantages of the present application more clear, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application and are not used to limit the present application.

[0025] like Figure 1 As shown, the present application provides a method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process, comprising the following steps:

[0026] S1. Adsorbing manganese in the filtrate after preparing MHP from laterite nickel ore using a multi-stage continuous resin process to obtain a manganese adsorption resin;

[0027] S2. The manganese adsorption resin is analyzed with an analytical solution to obtain a manganese analytical solution;

[0028] S3. Adjust the pH value of the manganese analysis solution to remove iron and aluminum. After the reaction is completed, filter press to obtain a manganese solution after removing iron and aluminum;

[0029] S4. Add a heavy metal impurity remover to the manganese solution after iron and aluminum removal to remove impurities. After the reaction is completed, filter press and let stand to obtain a manganese electrolytic solution;

[0030] S5. Use manganese electrolytic solution to carry out manganese electrolytic deposition to obtain manganese electrolytic plates and manganese electrolytic solution, and circulate the manganese electrolytic solution as an analytical solution to the analytical process of step S2.

[0031] The present application obtains manganese electrolytic solution through resin adsorption-analysis-impurity removal process and then performs manganese electrolysis, and circulates the recovered manganese electrolytic solution to the analytical process. The above method can effectively recover manganese in the filtrate of MHP prepared from laterite nickel ore. Step S1 adsorbs and enriches manganese by adsorption, step S2 converts manganese and other elements into solution state in adsorbed state by analytical process, the purpose of steps S3 and S4 is to remove impurities, and the purpose of step S5 is to recover manganese through manganese electrolysis, and recycle the manganese and acid in the obtained manganese electrolytic solution.

[0032] In some embodiments, step S1 specifically comprises: using one or more of HP606, HP4080, D854, D851, LSC-495, LSC-930, and CH27 resins as multi-stage continuous resins, and passing the filtrate after preparing MHP from laterite nickel ore through a column at a flow rate of 0.5 BV / h-10 BV / h for adsorption.

[0033] In some embodiments, in step S2, the acidity of the analytical solution is 20-300 g / L, and the flow rate of the analytical solution entering the column for analysis is 0.5 BV / h-8 BV / h.

[0034] The acidity of the analytical solution is within the specified range of this application, which is beneficial for technicians to adjust the acidity of the analytical solution according to the specific continuous resin device and its adsorption, analytical process or manganese electrolytic process parameters to obtain a manganese electrolytic solution that meets the electrolytic requirements.

[0035] In some embodiments, in step S3, the step of removing iron and aluminum includes: adjusting the pH value of the manganese analysis solution to 5-6.5.

[0036] In some embodiments, before adjusting the pH value of the manganese analysis solution to 5-6.5, the pH value of the manganese analysis solution is first adjusted to 2-3.

[0037] In some embodiments, in step S4, the heavy metal impurity remover includes one or more of MnS, BaS, and sodium thiamethoxam, and the filter press is left standing for 6-24 hours.

[0038] In some embodiments, in step S5, the process parameters of manganese electrowinning are: ammonium sulfate concentration 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 with ammonia water, and the cathode current density is 300-430 A / m 2 , the electrodeposition temperature is 35-42℃, and the electrode distance is 60-80mm.

[0039] Under the manganese electrowinning process defined in the present application, the manganese electrowinning efficiency and production efficiency can be improved, and high-quality manganese electrowinning plates can be obtained.

[0040] In some embodiments, in step S5, the cycle of manganese electrowinning is: 12-36 hours.

[0041] In some embodiments, when the manganese electrodeposition solution is circulated to the analysis process as an analysis solution, it also includes adding acid to the manganese electrodeposition solution.

[0042] In some embodiments, the number of the multi-stage continuous resin stages is 1-50 stages.

[0043] In some embodiments, in step S4, the impurity removal process is a one-step impurity removal or a multi-step impurity removal.

[0044] The manganese electrolytic solution is circulated to the analytical solution (acid solution). On the one hand, the acid in the manganese electrolytic solution can be added to the analytical solution for utilization, thereby reducing the amount of acid used for analysis. On the other hand, the manganese that has not been completely electrolytically formed in the manganese electrolytic solution can be used as a raw material for re-circulation electrolysis to improve the recovery rate of manganese.

[0045] The present application provides an application of a method in recovering valuable metals.

[0046] The method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process provided in the present application is not limited to recovering manganese from MHP filtrate prepared from laterite nickel ore. The method can be comprehensively used for the recovery of valuable metals in other materials, including but not limited to battery materials, manganese ore, and wastewater, and the valuable metals include but are not limited to nickel and cobalt.

[0047] The present solution is further described below through specific embodiments.

[0048] Example 1

[0049] A method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process comprises the following steps:

[0050] S1. Using 8-stage series D851 resin columns, the filtrate after preparing MHP from laterite nickel ore (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) was passed through the column at a flow rate of 2 BV / h for manganese adsorption resin. When Mn in the adsorption tail liquid was greater than 5 mg / L, the filtrate was stopped.

[0051] S2. Use 225g / L sulfuric acid solution as the analytical solution, and analyze the manganese adsorption resin at a flow rate of 1.5BV / h through the column to obtain a manganese analytical solution, and analyze until the resin basically recovers to the color before adsorption. The components of the obtained manganese analytical solution are: Ni: 0.064g / L, Co: 0.129g / L, Fe: 0.003g / L, Al: 0.004g / L, Mn: 47.56g / L, Ca: 0.005g / L, Mg: 0.004g / L.

[0052] S3. The pH value of the manganese analysis solution is adjusted to 2 with limestone, and then the pH value of the manganese analysis solution is further adjusted to 6.2 with ammonia water. After the reaction is completed, the manganese solution after iron and aluminum are removed is obtained by filter pressing. The components of the manganese solution after iron and aluminum are removed are: Ni: 0.056g / L, Co: 0.118g / L, Fe, Al: 0g / L, Mn: 45.52g / L, Ca: 0.58g / L, Mg: 0.004g / L.

[0053] S4. 1.2 g / L BaS heavy metal impurity remover is added to the manganese solution after iron and aluminum removal for impurity removal. After the reaction is completed, filter press and let stand for 16 hours to obtain manganese electrolytic solution. The components of the manganese electrolytic solution are: 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.

[0054] S5. Use the manganese electrolytic solution to perform manganese electrolytic production to obtain an electrolytic manganese plate and a manganese electrolytic solution, and then circulate the manganese electrolytic solution as an analytical solution to the next round of resin analytical process described in step S2. The manganese electrolytic process parameters are: ammonium sulfate concentration of 100 g / L, selenium dioxide concentration of 0.035 g / L, pH adjusted to 7 with ammonia water, cathode current density of 390 A / m 2 , the electrolytic temperature is 40℃, the inter-electrode distance is 70mm, and the electrolytic cycle is 24h. The purity of the electrolytic manganese plate obtained is 99.84%, and the liquid composition after manganese electrolytic is: Ni: 0.0003g / L, Co: 0.0002g / L, Fe, Al: 0g / L, Mn: 16.50g / L, Ca: 0.59g / L, Mg: 0.004g / L.

[0055] Example 2

[0056] A method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process, the other contents are the same as those in Example 1, and the only difference from Example 1 is that in step S1, the number of series stages of the resin column is changed to 8, and the flow rate of the filtrate after preparing MHP from laterite nickel ore through the column can be increased to 3BV / h. Tests show that the composition of the obtained manganese analytical solution is Ni: 0.071g / L, Co: 0.141g / L, Fe: 0.003g / L, Al: 0.004g / L, Mn: 46.26g / L, Ca: 0.004g / L, Mg: 0.003g / L. The manganese analytical solution can obtain a manganese electrolytic solution that meets the electrolytic requirements by using the same process method as in Example 1.

[0057] Example 3

[0058] A method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process, the other contents are the same as those of Example 1, and the only difference from Example 1 is that in step S4, after removing impurities with BaS heavy metal impurity remover, 0.2g / L sodium fumer is used for deep impurity removal, and the obtained manganese electrolytic solution has the following components: Ni, Co: 0g / L, Mn: 44.80g / L, Ca: 0.59g / L, Mg: 0.004g / L. After manganese electrolytic deposition, the purity of the electrolytic manganese plate is 99.92%, indicating that deep impurity removal is crucial to improving the purity of the manganese plate.

[0059] Example 4

[0060] A method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process, the other contents are the same as those of Example 1, and the difference from Example 2 is that: in step S5, the electrolytic cycle is shortened to 16h, and the test finds that the composition of the manganese electrolytic 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 electrolytic solution increases, the acidity of the manganese electrolytic solution is adjusted to 170g / L and circulated as an analytical solution to the next round of resin analysis process described in S2, and a manganese analytical solution with a manganese concentration of 45g / L is also obtained. Subsequently, impurities are removed to obtain a manganese electrolytic solution for electrolytic deposition, and the purity of the electrolytic manganese plate is measured to be 99.85%, indicating that the acidity of the analytical solution is closely related to the manganese electrolytic cycle. At the same time, the process provided in this application can be adjusted in a timely manner according to the needs in the actual production process, so as to facilitate implementation.

[0061] Comparative Example 1

[0062] A method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process, the other contents are the same as those of Example 1, except that step S3 is not included. The purity of the obtained electrolytic manganese plate is measured to be lower than 99.70%, which does not meet the standard of the manganese metal industry. It is shown that step S3 not only increases the pH of the manganese analytical solution and paves the way for the subsequent removal of heavy metals and their manganese electrolytic deposition, but also plays a decisive role in the purity of the manganese plate.

[0063] In the prior art, when mining and utilizing laterite nickel ore, alkaline substances are used to precipitate manganese in the filtrate after precipitation of MHP into slag for landfill treatment. 2+ It is easily oxidized in the chemical reaction to form high-valent manganese oxides. Therefore, if manganese is extracted from the manganese slag, reduction leaching is required, and then multi-step impurity removal is performed. Obviously, the method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process provided in the present application can eliminate the currently used manganese precipitation process, and at the same time, manganese can be recovered at low cost and applied to the field of manganese electrolytic solution. Therefore, the method provided in the present application is based on a continuous resin process, which creatively recycles the manganese electrolytic solution to the resin analysis process, which not only significantly simplifies the process of manganese recovery and utilization, but also greatly reduces the cost of manganese resource recovery and its application, and solves the industrialization problem of manganese recovery and application in current new energy enterprises as a precedent.

[0064] It is worth noting that the method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process provided in the present application is not limited to recovering manganese from the MHP filtrate prepared from laterite nickel ore. The method can be comprehensively used for the recovery of valuable metals in other materials, including but not limited to battery materials, manganese ore, and wastewater, and valuable metals include but are not limited to nickel and cobalt.

[0065] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed in the present application should be covered within the protection scope of the present application.

Claims

1. A method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process, characterized in that: The following steps are involved: S1. Adsorbing manganese in the filtrate after preparing MHP from laterite nickel ore using a multi-stage continuous resin process to obtain a manganese adsorption resin; S2. The manganese adsorption resin is analyzed with an analytical solution to obtain a manganese analytical solution; S3. Adjust the pH value of the manganese solution to remove iron and aluminum, and filter press after the reaction to obtain a manganese solution after removing iron and aluminum; S4. Add a heavy metal impurity remover to the manganese solution after the iron and aluminum removal to remove impurities. After the reaction, filter press and let stand to obtain a manganese electrolytic solution; S5. Use the manganese electrolytic solution to perform manganese electrolytic deposition to obtain an electrolytic manganese plate and a manganese electrolytic solution, and circulate the manganese electrolytic solution as an analytical solution to the analytical process described in step S2.

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

3. The method for preparing manganese electrolytic solution from laterite nickel ore based on continuous resin process according to claim 1, characterized in that: In step S2, the acidity of the analytical solution is 20-300 g / L, and the flow rate of the analytical solution entering the column for analysis is 0.5 BV / h-8 BV / h.

4. The method for preparing manganese electrolytic solution from laterite nickel ore based on a continuous resin process according to claim 1, characterized in that: In step S3, the step of removing iron and aluminum includes: adjusting the pH value of the manganese analysis solution to 5-6.

5.

5. The method for preparing manganese electrolytic solution from laterite nickel ore based on continuous resin process according to claim 1, characterized in that: In step S4, the filter press is left to stand for 6-24 hours, and the impurity removal process is a one-step or multi-step impurity removal process.

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

7. The method for preparing manganese electrolytic solution from laterite nickel ore based on continuous resin process according to claim 1, characterized in that: In step S5, the cycle of manganese electrowinning is: 12-36h.

8. The method for preparing manganese electrolytic solution from laterite nickel ore based on continuous resin process according to claim 1, characterized in that: When the manganese electrolytic solution is circulated to the analysis step as an analysis solution, it also includes adding acid to the manganese electrolytic solution.

9. The method for preparing manganese electrolytic solution from laterite nickel ore based on continuous resin process according to claim 1, characterized in that: 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 to 9 in recovering valuable metals.

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