Method for resourceful treatment of solution containing copper, manganese and zinc

Abstract

The invention provides a resourceful treatment method for a solution containing copper, manganese and zinc. The resourceful treatment method comprises a process of replacing copper with manganese, a process of extracting zinc and a process of extracting manganese. In the resourceful treatment method, the manganese powder is used for replacing copper in the solution containing copper, manganese and zinc, effective separation of copper, manganese and zinc can be achieved, the copper content in the product replacement liquid is reduced, and meanwhile introduction of impurity ions is avoided. Besides, the extraction process is adopted to separate zinc and manganese, the separation efficiency is high, the zinc and manganese containing solution obtained through extraction is high in purity and low in impurity content and can be directly used as a raw material of the downstream industry, waste water generated in the extraction process is easy to treat and can be reused after being treated, and therefore cost can be saved, and pollution to the environment can be reduced.

Description

Technical Field

[0001] The invention relates to hydrometallurgical technology, and in particular to a method for resource processing of copper-containing manganese-zinc solution. Background Art

[0002] In the field of hydrometallurgy, especially in the hydrometallurgy of nickel and cobalt, nickel intermediates (crude nickel hydroxide) are obtained from laterite nickel ore through high-pressure acid leaching, neutralization and precipitation, and cobalt intermediates (crude cobalt hydroxide) are obtained from copper-cobalt oxide ore through acid leaching, neutralization and precipitation. Nickel intermediates and cobalt intermediates are the main raw materials for the production of battery-grade nickel sulfate and cobalt sulfate. Nickel intermediates and cobalt intermediates prepared by neutralization and precipitation often contain metals such as copper, zinc, and manganese.

[0003] In the process of producing high-purity products from raw materials such as nickel intermediates and cobalt intermediates, acidic solutions containing elements such as copper, manganese, and zinc are generated, which have high recovery value. In the related art, the acidic solution is treated by sulfidation precipitation, but it has the disadvantages of low separation efficiency, low recovery rate of valuable metals, and difficulty in recovering the treated products. Summary of the invention

[0004] In view of this, the present invention provides a method for resource processing of copper-manganese-zinc solutions to improve separation efficiency and increase the purity of target products such as sponge copper, zinc-containing solutions, and manganese-containing solutions.

[0005] Specifically, according to a first aspect of the present invention, a method for resource recovery of a copper-containing manganese-zinc solution is provided, comprising: a manganese replacement copper step: contacting the copper-containing manganese-zinc solution with manganese powder to carry out a replacement reaction, and obtaining sponge copper and a replacement liquid after the reaction; a zinc extraction step: adding a first extraction organic phase to the replacement liquid for a first extraction treatment to obtain a zinc extraction residual solution and a first loaded organic phase, adding a first acid to the first loaded organic phase for a first back extraction treatment to obtain a zinc-containing solution; and a manganese extraction step: adding a second extraction organic phase to the zinc extraction residual solution for a second extraction treatment to obtain a manganese extraction residual solution and a second loaded organic phase, adding a second acid to the second loaded organic phase for a second back extraction treatment to obtain a manganese-containing solution.

[0006] In the resource recovery treatment method provided by the present invention, manganese powder is used to replace copper in the copper-containing manganese-zinc solution through a replacement reaction, which can not only achieve effective separation of copper from manganese and zinc, reduce the copper content in the product replacement solution, but also avoid the introduction of impurity ions. In addition, the use of an extraction process to separate zinc and manganese not only has high separation efficiency, but also the extracted zinc-containing and manganese-containing solution has high purity and low impurity content, and can be directly used as a raw material for downstream industries.

[0007] In some embodiments, the manganese-copper replacement process is carried out in two or more steps. In each step, the mass of manganese powder added to the solution is 0.86-2 times the mass of copper ions in the solution.

[0008] In some embodiments, the manganese-copper replacement process is carried out in two steps, including: (a) adding a first portion of manganese powder to a copper-containing manganese-zinc solution for a replacement reaction, and separating the solid and liquid after the reaction to obtain a first sponge copper and a first replacement liquid; (b) adding a second portion of manganese powder to the first replacement liquid for a replacement reaction, and separating the solid and liquid after the reaction to obtain a second sponge copper and a second replacement liquid.

[0009] In some embodiments, the mass of the first portion of manganese powder added to the copper-manganese-zinc solution is 0.86-2 times the mass of copper ions in the copper-manganese-zinc solution.

[0010] In some embodiments, the mass of the second portion of manganese powder added to the first replacement solution is 0.86-2 times the mass of copper ions in the first replacement solution.

[0011] In some embodiments, before the replacement reaction, the pH of the copper-manganese-zinc solution is adjusted to 1.0-2.5 using a base, which can reduce the H + The reaction with manganese powder can reduce the amount of manganese powder used and save costs.

[0012] In some embodiments, in adjusting the pH of the copper-manganese-zinc solution to 1.0-2.5 using a base, the base is selected from a combination of one or more of ammonia water, sodium hydroxide, ammonium carbonate, sodium carbonate, and sodium bicarbonate;

[0013] In some embodiments, the manganese powder has a particle size of 250-350 mesh.

[0014] In some embodiments, the manganese powder has a particle size of 300 mesh.

[0015] In some embodiments, in the zinc extraction step, the extractant contained in the first extraction organic phase is an extractant containing 2-ethylhexyl phosphate mono-2-ethylhexyl ester or an extractant containing di(2,4,4-trimethylpentyl)phosphinic acid.

[0016] In some embodiments, the saponification rate of the extractant in the first extraction organic phase is 35%-55%.

[0017] In some embodiments, the number of extraction stages in the first extraction process is 4-10 stages.

[0018] In some embodiments, the zinc extraction process further comprises: before the first stripping treatment, performing a first acid washing treatment on the first loaded organic phase.

[0019] In some embodiments, the acid used in the first acid washing treatment is 1-3 mol / L hydrochloric acid.

[0020] In some embodiments, the number of washing stages in the first acid wash treatment is 4-10 stages.

[0021] In some embodiments, in the zinc extraction step, the first acid used in the first stripping treatment is 5-8 mol / L hydrochloric acid or sulfuric acid.

[0022] In some embodiments, the number of extraction stages in the first stripping treatment is 4-10.

[0023] In some embodiments, in the manganese extraction step, the extractant contained in the second extraction organic phase is C272.

[0024] In some embodiments, the saponification rate of the extractant in the second extraction organic phase is 30%-50%.

[0025] In some embodiments, the number of extraction stages in the second extraction process is 8-17 stages.

[0026] In some embodiments, in the manganese extraction step, the second loaded organic phase is subjected to a second acid washing treatment before the second stripping treatment.

[0027] In some embodiments, the acid used in the second pickling treatment is 1-2 mol / L sulfuric acid;

[0028] In some embodiments, the second acid wash treatment has 4-10 wash stages.

[0029] In some embodiments, in the manganese extraction step, the second acid used in the second stripping treatment is 4-6 mol / L sulfuric acid.

[0030] In some embodiments, the number of extraction stages in the second stripping treatment is 5-10.

[0031] In some embodiments, the copper-manganese-zinc solution is a copper-manganese-zinc solution obtained from the cobalt intermediate P204 extraction line or a copper-manganese-zinc solution obtained from the nickel intermediate P204 extraction line, or a copper-manganese-zinc solution containing 90-155 g / L Mn 2+ 、5-20g / L Zn 2+ , 0.5-4.5g / L Cu 2+ , 1-6g / L Ca 2+ 、0.2-2.5g / L Mg 2+ , 0.01-0.3g / L Co 2+ .

[0032] In some embodiments, the pH of the copper-manganese-zinc solution is 0.3-0.9.

[0033] In some embodiments, the manganese content in the sponge copper is ≤ 4%.

[0034] In some embodiments, the zinc-containing solution comprises Zn 2+ >10g / L, Mn 2+ ≤15mg / L, Cu 2+ ≤5mg / L, Ca 2+ ≤20mg / L, Mg 2+ ≤10mg / L, Co 2+ ≤5mg / L.

[0035] In some embodiments, the manganese-containing solution comprises Mn 2+ >100g / L, Zn 2+ ≤8mg / L, Cu 2+ ≤5mg / L, Ca 2+ ≤10mg / L, Mg 2+ ≤10mg / L, Co 2+ ≤500mg / L. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other implementation plans can be obtained based on these drawings without paying creative work.

[0037] Figure 1 A schematic flow chart of a method for resource recovery of copper-manganese-zinc solutions according to some embodiments of the present application is shown.

[0038] Figure 2 A schematic flow chart of a step-by-step manganese-copper replacement process according to some embodiments of the present application is shown.

[0039] Figure 3 A schematic diagram of a process for preparing zinc chloride using a zinc extraction process according to some embodiments of the present application is shown.

[0040] Figure 4 A schematic diagram of a process for preparing manganese sulfate using a manganese extraction process according to some embodiments of the present application is shown. DETAILED DESCRIPTION

[0041] The present invention will be described clearly and completely below in conjunction with the embodiments and drawings of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments that can be obtained by those of ordinary skill in the art based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0042] Herein, wt% refers to weight percentage, and unless otherwise specified, the percentages are based on mass.

[0043] Herein, particle size refers to D50, which is the particle size corresponding to 50% of the cumulative particle size distribution number of particles measured by a laser particle size analyzer, that is, particles with a particle size less than (or equal to) this particle size account for 50%.

[0044] In this article, pure water refers to water with a purity of more than 99.9% after being treated to remove impurities, minerals, and organic matter.

[0045] As mentioned above, in the prior art, sulfide precipitation and other methods are usually used to treat acidic solutions containing elements such as copper, manganese, and zinc. However, this method has disadvantages such as low separation efficiency, low recovery rate of valuable metals, and difficulty in recovering treated products.

[0046] Based on this, the present application provides a new resource treatment method for copper-containing manganese-zinc solution. The copper-containing manganese-zinc solution treated by the resource treatment method provided in the present application can be a copper-containing manganese-zinc solution obtained on the cobalt intermediate P204 extraction line; it can also be a copper-containing manganese-zinc solution obtained on the nickel intermediate P204 extraction line; it can also be a copper-containing manganese-zinc solution containing 90-155g / L Mn 2 + 、5-20g / L Zn 2+ , 0.5-4.5g / L Cu 2+ , 1-6g / L Ca 2+ 、0.2-2.5g / L Mg 2+ , 0.01-0.3g / L Co 2+ The copper-manganese-zinc solution may also contain a small amount of other valuable metals such as Fe 3+ In some embodiments, the pH of the copper-manganese-zinc solution is 0.3-0.9, such as 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9.

[0047] Figure 1A flow chart of a resource treatment method for a copper-containing manganese-zinc solution according to some embodiments of the present application is shown. It can be seen that the resource treatment method for a copper-containing manganese-zinc solution provided in the embodiment of the present application includes: a manganese replacement copper step: contacting the copper-containing manganese-zinc solution with manganese powder for a replacement reaction, and obtaining sponge copper and a replacement liquid after the reaction; a zinc extraction step: adding a first extraction organic phase to the replacement liquid for a first extraction treatment to obtain a zinc extraction residual solution and a first loaded organic phase, adding a first acid to the first loaded organic phase for a first back extraction treatment to obtain a zinc-containing solution; and a manganese extraction step: adding a second extraction organic phase to the zinc extraction residual solution for a second extraction treatment to obtain a manganese extraction residual solution and a second loaded organic phase, adding a second acid to the second loaded organic phase for a second back extraction treatment to obtain a manganese-containing solution. Figure 1 Only the above three steps are shown in order. It can be understood that Figure 1 What is shown is only a preferred situation.

[0048] In the resource recovery treatment method provided by the present invention, manganese powder is used to replace copper in the copper-containing manganese-zinc solution through a replacement reaction, which can not only achieve effective separation of copper from manganese and zinc, reduce the copper content in the product replacement solution, but also avoid the introduction of impurity ions. In addition, the use of an extraction process to separate zinc and manganese not only has high separation efficiency, but also the extracted zinc-containing and manganese-containing solution has high purity and low impurity content, and can be directly used as a raw material for downstream industries.

[0049] In some embodiments, before the replacement reaction, the pH of the copper-manganese-zinc solution is adjusted to 1.0-2.5 using a base, such as 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, and the range of any two of these values. The pH of the solution is adjusted with a base, so that the amount of manganese powder can be reduced and the cost can be saved. The base can be selected from a combination of one or more of ammonia water, sodium hydroxide, ammonium carbonate, sodium carbonate, and sodium bicarbonate. Of course, other bases known in the art can also be used, and the present invention is not further limited to this, as long as the pH can be adjusted. In some embodiments, the base can be selected from a combination of one or more of 3-8 mol / L ammonia water, 2-8 mol / L sodium hydroxide, 3-10 mol / L ammonium carbonate, 3-12 mol / L sodium carbonate, and 3-12 mol / L sodium bicarbonate.

[0050] In the manganese replacement copper process, the particle size of the manganese powder is 250-350 mesh, for example, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350 mesh, preferably, 300 mesh. If the particle size of the manganese powder is large, the manganese powder particles are too coarse, which will make the contact area between the manganese powder and the solution too small, resulting in a long reaction time; if the particle size of the manganese powder is small, the manganese powder particles are too fine, which will make the cost of grinding the manganese powder high. Controlling the particle size of the manganese powder within the above range is conducive to further balancing the cost and reaction efficiency.

[0051] In the manganese replacement copper process, manganese replacement copper can be carried out in steps. For example, it can be carried out through two or more, such as three, four or five replacement steps. The separation efficiency of copper can be improved by step-by-step replacement, while reducing the manganese content in the product sponge copper. The present application performs manganese replacement copper in steps, and the manganese content in the obtained sponge copper is ≤4%, and can even reach ≤3%, ≤2%.

[0052] In some embodiments, in each replacement step, the mass of manganese powder added to the solution is 0.86-2 times the mass of copper ions in the solution, for example 0.86, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2. If the amount of manganese powder added in each step is small, the amount of copper replaced each time is small, and more steps are required, resulting in a cumbersome process; if the amount of manganese powder added in each step is large, the replacement efficiency of manganese is low, and the manganese content in the sponge copper is too high. Controlling the amount of manganese powder added in each step within the above range can not only improve the replacement efficiency, reduce the manganese content in the product sponge copper, but also have fewer process steps and save costs.

[0053] In some embodiments, the manganese replacement of copper in the manganese replacement process is carried out in two steps, which can not only improve the separation efficiency of copper, but also reduce the manganese content in the product sponge copper, so that the manganese content in the sponge copper reaches ≤4%, or even ≤3%, ≤2%, and the process is simple and cost-saving.

[0054] Furthermore, the two steps of manganese replacing copper include: (a) adding a first portion of manganese powder to a copper-containing manganese-zinc solution for a replacement reaction, and separating the solid and liquid after the reaction to obtain a first sponge copper and a first replacement liquid, wherein the mass of the first portion of manganese powder added to the copper-containing manganese-zinc solution is 0.86-2 times the mass of copper ions in the copper-containing manganese-zinc solution; (b) adding a second portion of manganese powder to the first replacement liquid for a replacement reaction, and separating the solid and liquid after the reaction to obtain a second sponge copper and a second replacement liquid, wherein the mass of the second portion of manganese powder added to the first replacement liquid is 0.86-2 times the mass of copper ions in the first replacement liquid.

[0055] In some specific embodiments, the manganese replacement copper process includes: 1) manganese powder replacement: at room temperature, a certain amount of copper-containing manganese-zinc solution is added to the primary replacement tank, ammonia water is added to control the pH of the solution to 1.0-2.5, and then manganese powder is added, wherein the amount of manganese powder added (g) = the mass concentration of Cu in the copper-containing manganese-zinc solution (g / L) × the amount of liquid inlet (L) × (0.86-2), after adding manganese powder, react for 1-3h, perform solid-liquid separation, and obtain sponge copper and the first replacement liquid; 2) manganese powder secondary replacement: at room temperature, a certain amount of the first replacement liquid is added to the secondary replacement tank, and then manganese powder is added to replace copper, wherein the amount of manganese powder added = the mass concentration of Cu in the first replacement liquid (g / L) × the amount of liquid inlet (L) × (0.86-2), after adding manganese powder, react for 1-3h to perform solid-liquid separation, and obtain sponge copper and the second replacement liquid. Repeat the above steps until the mass concentration of copper in the final replacement liquid is ≤100mg / L.

[0056] After the copper-containing manganese-zinc solution is treated by the manganese replacement copper process, sponge copper and replacement liquid are obtained, wherein the manganese content in the sponge copper reaches ≤4%, and can even reach ≤3% or ≤2%; wherein the main metal ion in the replacement liquid is Mn 2+ 、Zn 2+ , Ca 2+ Mg 2+ , in addition, it also contains a small amount of Fe 3+ 、Co 2+ , Cu 2+ , which can be used for the next recycling process.

[0057] In order to further recycle the zinc in the replacement liquid, the resource recovery method provided in the present application also includes a zinc extraction step, including: adding a first extraction organic phase to the replacement liquid for a first extraction treatment to obtain a zinc extraction residual liquid and a first loaded organic phase, and adding a first acid to the first loaded organic phase for a first back extraction treatment to obtain a zinc-containing solution.

[0058] During the first extraction treatment of the zinc extraction process, the extractant contained in the first extraction organic phase is an extractant containing 2-ethylhexyl phosphate mono-2-ethylhexyl ester or an extractant containing di(2,4,4-trimethylpentyl)phosphinic acid. During the extraction process, on the one hand, a suitable extractant can reduce the entry of calcium into the first loaded organic phase, thereby reducing the impurity content in the zinc-containing solution obtained after the first stripping treatment. On the other hand, the suitable extractant also has a small amount of extraction of valuable metals such as cobalt and manganese. During washing, only a small amount of acid is used to wash the over-extracted cobalt and manganese from the first loaded organic phase, and the extraction auxiliary material consumption is small, saving costs. In some examples, the extractant containing 2-ethylhexyl phosphate mono-2-ethylhexyl ester is P507 extractant, and the extractant containing di(2,4,4-trimethylpentyl)phosphinic acid is C272 extractant.

[0059] In some embodiments, the first extraction organic phase is prepared by mixing an extractant containing 2-ethylhexyl phosphate mono-2-ethylhexyl ester or an extractant containing di(2,4,4-trimethylpentyl)phosphinic acid with sulfonated kerosene in a certain volume ratio, and then saponifying the extractant containing 2-ethylhexyl phosphate mono-2-ethylhexyl ester or the extractant containing di(2,4,4-trimethylpentyl)phosphinic acid with an alkali such as ammonia water or sodium hydroxide solution, wherein the volume ratio can be 1:10-1:5, such as 1:9, 1:8, 1:7, 1:6, 1:5. In some embodiments, the saponification rate of the extractant in the first extraction organic phase is 35%-55%, such as 35%, 40%, 45%, 50%, 55%.

[0060] In some embodiments, the number of extraction stages in the first extraction treatment is 4-10, for example, 4, 5, 6, 7, 8, 9, and 10 stages.

[0061] In some embodiments, before the first stripping treatment in the zinc extraction step, the first loaded organic phase is subjected to a first acid washing treatment to obtain a first acid washing solution to remove the over-extracted metal ions such as Mn in the first loaded organic phase. 2+ , Ca 2 + . In some embodiments, the acid used in the first pickling treatment may be hydrochloric acid and / or sulfuric acid. Of course, other acids may also be used, and this application does not further limit this. In some embodiments, the above acid is 1-3 mol / L, such as 1 mol / L, 2 mol / L, 3 mol / L hydrochloric acid. In some embodiments, the number of washing stages in the first pickling treatment is 4-10, such as 4, 5, 6, 7, 8, 9, 10.

[0062] In the process of the first stripping treatment of the zinc extraction process, the first acid used is hydrochloric acid and / or sulfuric acid. Of course, other acids can also be used, and this application is not further limited to this, as long as the purpose of this application can be achieved. In some embodiments, the first acid is 5-8mol / L, for example, 5mol / L, 6mol / L, 7mol / L, 8mol / L of hydrochloric acid or sulfuric acid.

[0063] In some embodiments, the number of extraction stages in the first stripping treatment is 4-10, for example, 4, 5, 6, 7, 8, 9, and 10.

[0064] In some embodiments, the zinc extraction raffinate further comprises the first acid wash solution obtained during the first acid wash treatment. The zinc extraction raffinate may comprise part of the first acid wash solution, and the remaining first acid wash solution may be open circuited for other purposes.

[0065] Figure 3 The flowchart of preparing zinc chloride by using the zinc extraction process according to some embodiments of the present application is shown. As mentioned above, the main metal ion in the replacement solution obtained after the manganese replacement copper process is Mn 2+ 、Zn 2+ , Ca 2+ Mg 2+ , in addition, it also contains a small amount of Fe 3+ 、Co 2+ , Cu 2+ In the zinc extraction process, the C272 or P507 organic phase (first extraction organic phase) after ammonia soap is completely extracted with Fe according to a certain number of stages. 3+ 、Zn 2+ , partial extraction of Co 2+ , Cu 2+ , Mn 2+ , and obtain the zinc extraction residual solution and the first loaded organic phase, and then use a certain concentration of hydrochloric acid to wash (re-extract) the Co in the first loaded organic phase. 2+ , Cu 2+ , Mn 2+ , washed Co 2+ , Cu 2+ , Mn 2+ Finally, the zinc extraction residual solution is added, and then the Zn in the first loaded organic phase after washing is extracted with hydrochloric acid of a certain concentration. 2+ , a zinc chloride solution is obtained, which can be evaporated and crystallized to prepare zinc chloride crystals. Then, Fe in the organic phase is extracted with hydrochloric acid. 3+ , chlorinated wastewater (ferric chloride solution) is obtained, and finally, the dilute hydrochloric acid entrained in the organic phase is washed with pure water to obtain chlorine washing water and C272 or P507 blank organic phase, and the blank organic phase is returned to the saponification process for ammonia soap. The saponification wastewater and chlorine washing water generated in the zinc extraction process are returned to the acid preparation process to prepare hydrochloric acid for stripping, and the anti-iron wastewater is returned to the nickel (cobalt) intermediate leaching process as acid leaching bottom water. Of course, this process can also be used to prepare zinc sulfate, which will not be repeated here.

[0066] After the zinc extraction process, a zinc-containing solution and a zinc-extracted residual solution are obtained, wherein the zinc-containing solution contains Zn 2+ >10g / L, Mn 2+ ≤15mg / L, Cu 2+ ≤5mg / L, Ca 2+ ≤20mg / L, Mg 2+ ≤10mg / L, Co 2+≤5mg / L, it can be seen that the zinc-containing solution has a low impurity content. Such a zinc-containing solution can be directly used as a raw material for downstream industries. For example, zinc sulfate and zinc chloride solutions can be used to prepare electrolytic zinc by electrolysis, and zinc sulfate and zinc chloride crystals can be prepared by evaporation and crystallization; Among them, the main metal ions in the zinc extraction residual solution are Mn 2+ , Ca 2+ Mg 2+ , in addition, it also contains a small amount of Co 2+ , Cu 2+ 、Zn 2+ , which can be used for the next recycling process.

[0067] In order to further recycle and utilize manganese in the zinc extraction waste solution, the resource recovery treatment method provided in the present application also includes a manganese extraction step, including: adding a second extraction organic phase to the zinc extraction waste solution for a second extraction treatment to obtain a manganese extraction waste solution and a second loaded organic phase, and adding a second acid to the second loaded organic phase for a second back extraction treatment to obtain a manganese-containing solution.

[0068] In the second extraction treatment of the manganese extraction step, the extractant contained in the second extraction organic phase is C272. During the extraction process, the C272 extractant does not extract calcium. Its use in conjunction with the P507 or C272 extractant in the zinc extraction step can further reduce the entry of calcium into the second loaded organic phase, thereby reducing the impurity content in the final manganese-containing solution.

[0069] In some embodiments, the second extraction organic phase is prepared by mixing the extractant C272 with sulfonated kerosene in a certain volume ratio, and then saponifying the extractant C272 with an alkali such as ammonia water or sodium hydroxide solution, wherein the volume ratio can be 1:10-1:5, such as 1:9, 1:8, 1:7, 1:6, 1:5. In some embodiments, the saponification rate of the extractant in the second extraction organic phase is 30%-50%, such as 30%, 35%, 40%, 45%, 50%.

[0070] In some embodiments, the number of extraction stages in the second extraction treatment is 8-17 stages, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, and 17 stages.

[0071] In some embodiments, before the second stripping treatment in the manganese extraction step, the second loaded organic phase is subjected to a second acid washing treatment to obtain a second acid washing solution to remove the over-extracted metal ions such as Co in the second loaded organic phase. 2+ , Ca 2 + Mg 2+. In some embodiments, the acid used in the second pickling treatment may be hydrochloric acid and / or sulfuric acid. Of course, other acids may also be used, and this application does not further limit this, as long as the purpose of this application can be achieved. In some embodiments, the acid used in the second pickling treatment is 1-2 mol / L sulfuric acid; in some embodiments, the washing level of the second pickling treatment is 4-10, for example, 4, 5, 6, 7, 8, 9, 10.

[0072] In the second stripping process of the manganese extraction step, the second acid used is hydrochloric acid and / or sulfuric acid. Of course, other acids may also be used, and this application is not further limited to this, as long as the purpose of this application can be achieved. In some embodiments, the second acid is 4-6 mol / L, such as 4 mol / L, 5 mol / L, 6 mol / L sulfuric acid.

[0073] In some embodiments, the number of extraction stages in the second stripping treatment is 5-10, for example, 5, 6, 7, 8, 9, or 10.

[0074] In some embodiments, the manganese extract raffinate further comprises the second acid wash liquid obtained during the second acid wash treatment. The manganese extract raffinate may comprise part of the second acid wash liquid, and the remaining part of the second acid wash liquid may be used for other purposes.

[0075] Figure 4 The flowchart of preparing manganese sulfate by using the manganese extraction process according to some embodiments of the present application is shown. As mentioned above, the main metal ion in the zinc extraction residual solution obtained after the zinc extraction process is Mn 2+ , Ca 2+ Mg 2+ , in addition, it also contains a small amount of Co 2+ , Cu 2+ 、Zn 2+ In the manganese extraction process, the C272 organic phase (the second extraction organic phase) after ammonia soap is completely extracted with Zn according to a certain extraction level. 2+ , Cu 2+ , Mn 2+ , partial extraction of Co 2+ Mg 2+ , Ca 2+ , to obtain the manganese extraction residual solution and the second loaded organic phase, and then use a certain concentration of hydrochloric acid to wash (strip extract) the Co in the second loaded organic phase 2+ Mg 2+ , Ca 2+ , washed Co 2+ Mg 2+ , Ca 2+Finally, the manganese extraction residual solution is entered, and then the washing hydrochloric acid entrained in the organic phase is washed with pure water to obtain chlorine washing water. The chlorine washing water enters the washing process and is used as washing acid. Then, a certain concentration of sulfuric acid is used to extract the Mn in the second loaded organic phase. 2+ , a manganese sulfate solution is obtained, which can be evaporated and crystallized to prepare manganese sulfate crystals. Then, a certain concentration of sulfuric acid is used to extract the Zn in the second loaded organic phase. 2+ , and zinc-removal wastewater (zinc sulfate wastewater) is obtained. Finally, pure water is used to wash the dilute sulfuric acid entrained in the organic phase to obtain sulfur-washing water and C272 blank organic phase. The C272 blank organic phase is returned to the saponification process for ammonia soap. The saponification wastewater and sulfur-washing water generated in the manganese extraction process are returned to the acid preparation process to prepare sulfuric acid for stripping. The zinc-removal wastewater is returned to the leaching process as acid leaching bottom water. The manganese extraction residual liquid is treated with heavy treatment, evaporated, and recycled to prepare ammonia water and hydrochloric acid.

[0076] After the manganese extraction process, a manganese-containing solution and a manganese-extracted residual solution are obtained, wherein the manganese-containing solution contains Mn 2+ >100g / L, Zn 2+ ≤8mg / L, Cu 2+ ≤5mg / L, Ca 2+ ≤10mg / L, Mg 2+ ≤10mg / L, Co 2+ ≤500mg / L. It can be seen that the manganese-containing solution has a low impurity content, and such a manganese-containing solution can be directly used as a raw material for downstream industries. For example, the manganese sulfate solution can be evaporated and crystallized to prepare battery-grade manganese sulfate crystals; wherein, the manganese extraction residual solution is ammonium chloride wastewater, which can be recycled to prepare ammonia water and hydrochloric acid after heavy treatment and evaporation treatment.

[0077] In addition, the wastewater generated by the zinc extraction process and the manganese extraction process in the present application, such as saponification wastewater, chlorine washing water, and sulfur washing water, can be directly configured with sulfuric acid or hydrochloric acid for back extraction; the generated anti-iron wastewater and anti-zinc wastewater can be directly used as acid leaching bottom water; the manganese extraction residual liquid is ammonium chloride wastewater, which can be recycled to prepare ammonia water and hydrochloric acid after heavy treatment and evaporation treatment. It can be seen that the wastewater generated by the zinc extraction process and the manganese extraction process in the present application is easy to treat and can be reused after treatment, which can not only save costs but also reduce pollution to the environment.

[0078] The present invention is described in more detail below in conjunction with the accompanying drawings and examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention. Unless otherwise specified, all raw materials and reagents in the present invention are raw materials and reagents from the conventional market.

[0079] Example

[0080] Example 1

[0081] The copper-manganese-zinc solution used in Example 1 is obtained by dissolving the cobalt intermediate in sulfuric acid, extracting impurities with P204, and stripping the obtained copper-manganese-zinc solution. The composition is shown in Table 1:

[0082] Table 1 Composition of copper-manganese-zinc solution

[0083]

[0084] 1) pH adjustment and primary replacement of manganese powder: a certain amount of copper-containing manganese-zinc solution is added to the primary replacement tank, and then stirring is started. Ammonia water is added to the primary replacement tank to adjust the pH of the solution to 1.5, and then 300-mesh manganese powder is slowly added to replace copper, wherein the amount of manganese powder added is the mass concentration of Cu ions in the copper-containing manganese-zinc solution (g / L) × the amount of copper-containing manganese-zinc solution inlet (L) × 1.3. After the manganese powder is added, it is reacted for 2 hours, and then solid-liquid separation is performed to obtain a first sponge copper and a first replacement liquid.

[0085] Table 2 Composition of the first sponge copper

[0086] element Cu(%) Mn(%) Co(%) Zn(%) Moisture (%) The first sponge copper 80.2 1.233 0.193 0.124 18.25

[0087] Table 3 Composition of the first replacement fluid

[0088]

[0089] 2) Secondary replacement with manganese powder: Add a certain amount of the first replacement liquid to the secondary replacement tank, and then slowly add 300 mesh manganese powder to replace copper, wherein the amount of manganese powder added is the Cu ion concentration in the first replacement liquid (g / L) × the first replacement liquid inlet volume (L) × 1.3. After the manganese powder is added, it is allowed to react for 2 hours, and then solid-liquid separation is performed to obtain a second sponge copper and a second replacement liquid.

[0090] Table 4 Composition of the second sponge copper

[0091] element Cu(%) Mn(%) Co(%) Zn(%) Moisture (%) Second sponge copper 75.3 3.75 0.362 0.131 20.457

[0092] Table 5 Composition of the second replacement fluid

[0093]

[0094] 3) Zinc extraction with C272: C272 and sulfonated kerosene are prepared in a volume ratio of 3:17 to prepare a first extraction organic phase, which is saponified with ammonia water and has a saponification rate of 35% to obtain a saponified organic phase, which is used to extract zinc in the second displacement liquid in a certain number of stages, wherein the extraction number is 5, to obtain a zinc extraction residual liquid and a first loaded organic phase, the first loaded organic phase is washed with 1.5 mol / L hydrochloric acid, and then stripped with 8 mol / L hydrochloric acid, wherein the washing number is 8 and the stripping number is 8, to obtain a zinc chloride solution.

[0095] Table 6 Composition of zinc chloride solution

[0096]

[0097] Table 7 Composition of zinc extraction residual solution

[0098]

[0099] 4) Extraction of manganese with C272: The volume ratio of C272 to sulfonated kerosene is 3:17 to prepare a second extraction organic phase, which is saponified with ammonia water to obtain a saponification rate of 40% to obtain a saponified organic phase, and the manganese in the zinc extraction residual solution is extracted with the saponified organic phase according to a certain number of stages, wherein the extraction number is 10, to obtain a manganese extraction residual solution and a second loaded organic phase, the second loaded organic phase is washed with 1.5 mol / L hydrochloric acid, washed with pure water for chlorine, and then stripped with 4 mol / L sulfuric acid, wherein the hydrochloric acid washing number is 4, and the stripping number is 8, to obtain a manganese sulfate solution.

[0100] Table 8 Composition of manganese sulfate solution

[0101]

[0102] Table 9 Composition of manganese extraction residual solution

[0103]

[0104] Example 2

[0105] Example 2 is basically the same as Example 1, except that: after zinc extraction with C272, 8 mol / L sulfuric acid is used for stripping to obtain a zinc sulfate solution. The composition of the zinc sulfate solution and the zinc extraction residual solution of Example 2 is as follows:

[0106] Table 10 Composition of zinc sulfate solution

[0107]

[0108] Table 11 Composition of zinc extraction residual solution

[0109]

[0110] Example 3

[0111] Example 3 is basically the same as Example 1, except that the extractant used in the extraction of Zn is P507. The composition of the zinc chloride solution and the zinc extraction residual solution of Example 3 is as follows:

[0112] Table 12 Composition of zinc chloride solution

[0113]

[0114] Table 13 Composition of zinc extraction residual solution

[0115] element Mn g / L Zn mg / L Cu mg / L Ca mg / L Mg mg / L Co mg / L Zinc extraction residue 116.49 7.59 3.89 3729 417.68 72.59

[0116] Example 4

[0117] Example 4 is basically the same as Example 1, except that during the secondary replacement of manganese powder, the amount of manganese powder added is the Cu ion concentration in the first replacement solution (g / L) × the first replacement solution inlet volume (L) × 0.86. The composition of the second sponge copper and the second replacement solution obtained by the secondary replacement of Example 4 is as follows:

[0118] Table 14 Composition of the second sponge copper

[0119] element Cu(%) Mn(%) Co(%) Zn(%) Moisture (%) Second sponge copper 76.4 2.82 0.352 0.127 20.301

[0120] Table 15 Composition of the second replacement fluid

[0121]

[0122] Example 5

[0123] The copper-manganese-zinc solution used in Example 5 is the copper-manganese-zinc solution obtained on the nickel intermediate P204 extraction line, and its composition is shown in Table 16:

[0124] Table 16 Composition of copper-manganese-zinc solution

[0125]

[0126] 1) Manganese powder primary replacement: add a certain amount of copper-containing manganese-zinc solution to the primary replacement tank and start stirring, add ammonia water to the primary replacement tank to adjust the pH of the solution to 2.0, and then slowly add 300 mesh manganese powder to replace copper, wherein the amount of manganese powder added is the Cu ion concentration in the copper-containing manganese-zinc solution (g / L) × the amount of copper-containing manganese-zinc solution inlet (L) × 0.9. After the manganese powder is added, it is reacted for 1.5 hours, and then solid-liquid separation is performed to obtain the first sponge copper and the first replacement liquid.

[0127] Table 17 Composition of the first sponge copper

[0128] element Cu(%) Mn(%) Co(%) Zn(%) Moisture (%) The first sponge copper 79.86 1.023 0.095 0.103 18.919

[0129] Table 18 Composition of the first replacement fluid

[0130]

[0131] 2) Secondary replacement with manganese powder: Add a certain amount of the first replacement liquid to the secondary replacement tank, and then slowly add 300 mesh manganese powder to the secondary replacement tank to replace copper, wherein the amount of manganese powder added is the Cu ion concentration in the first replacement liquid (g / L) × the first replacement liquid inlet volume (L) × 1.3. After the manganese powder is added, react for 2.5 hours, and then perform solid-liquid separation to obtain a second sponge copper and a second replacement liquid.

[0132] Table 19 Composition of the second sponge copper

[0133] element Cu(%) Mn(%) Co(%) Zn(%) Moisture (%) Second sponge copper 76.9 3.86 0.132 0.098 19.01

[0134] Table 20 Composition of the second replacement fluid

[0135]

[0136] 3) Zinc extraction with C272: C272 and sulfonated kerosene are prepared in a volume ratio of 3:17 to prepare a first extraction organic phase, which is saponified with ammonia water with a saponification rate of 40% to obtain a saponified organic phase, and the zinc in the second replacement liquid is extracted with the saponified organic phase in a certain number of stages, wherein the extraction number is 6, to obtain a zinc extraction residual liquid and a first loaded organic phase, the first loaded organic phase is washed with 1.5 mol / L hydrochloric acid, washed with pure water for chlorine, and then stripped with 6 mol / L sulfuric acid, wherein the hydrochloric acid washing number is 7 and the stripping number is 8, to obtain a zinc sulfate solution.

[0137] Table 21 Composition of zinc sulfate solution

[0138]

[0139] Table 22 Composition of zinc extraction residual solution

[0140]

[0141] 4) Extraction of manganese with C272: C272 and sulfonated kerosene are prepared in a volume ratio of 3:17 to prepare a second extraction organic phase, which is saponified with ammonia water to obtain a saponification rate of 40% to obtain a saponified organic phase, and the manganese in the zinc extraction residual solution is extracted with the saponified organic phase in a certain number of stages, wherein the extraction number is 9, to obtain a manganese extraction residual solution and a second loaded organic phase, the second loaded organic phase is washed with 1.5 mol / L hydrochloric acid, washed with pure water for chlorine, and then stripped with 5 mol / L sulfuric acid, wherein the hydrochloric acid washing number is 5, and the stripping number is 8, to obtain a manganese sulfate solution.

[0142] Table 23 Composition of manganese sulfate solution

[0143]

[0144] Table 24 Composition of manganese extraction residual solution

[0145]

[0146] Example 6

[0147] Example 6 is basically the same as Example 5, except that: after zinc extraction with C272, 5 mol / L hydrochloric acid is used for back extraction to obtain a zinc chloride solution. The composition of the zinc chloride solution and the zinc extraction residual solution of Example 6 is as follows:

[0148] Table 25 Composition of zinc chloride solution

[0149]

[0150] Table 26 Composition of zinc extraction residual solution

[0151]

[0152] Example 7

[0153] Example 7 is basically the same as Example 1, except that no ammonia water is added to adjust the pH of the manganese powder before the first replacement. The composition of the first sponge copper and the first replacement liquid obtained by the first replacement in Comparative Example 1 is as follows:

[0154] Table 27 Composition of the first sponge copper

[0155]

[0156]

[0157] Table 28 Composition of the first replacement fluid

[0158]

[0159] By comparing Example 1 with Example 7, it can be seen that when no ammonia water is added to adjust the pH, the copper ion concentration in the first replacement solution increases significantly. It is speculated that this is because most of the manganese powder reacts with H in the copper-containing manganese-zinc solution. + reacts with Cu 2+ The amount of manganese powder reacted was reduced.

[0160] Example 8

[0161] Example 8 is basically the same as Example 1, except that: the manganese powder replacement is changed from two replacements to one replacement, and the amount of manganese powder added in Example 8 is the same as the total amount of manganese powder added in Example 1. The composition of the sponge copper and replacement liquid obtained by the manganese powder replacement in Example 8 is as follows:

[0162] Table 29 Composition of sponge copper

[0163] element Cu(%) Mn(%) Co(%) Zn(%) Moisture (%) Sponge Copper 74.12 6.233 0.213 0.145 19.289

[0164] Table 30 Composition of replacement fluid

[0165]

[0166] By comparing Example 1 with Example 8, it can be seen that when only one replacement is used, the manganese content in the obtained sponge copper and the Cu concentration in the replacement liquid are both high, and the replacement effect is poor.

[0167] Comparative Example 1

[0168] Comparative Example 1 is basically the same as Example 1, except that P204 extractant is used in zinc extraction. The compositions of the zinc chloride solution and zinc extraction residual solution obtained in Comparative Example 1 are as follows:

[0169] Table 31 Composition of zinc chloride solution

[0170]

[0171] Table 32 Composition of zinc extraction residual solution

[0172]

[0173] By comparing Example 1 with Comparative Example 1, it can be seen that when P204 extractant is used to extract Zn, the Ca concentration in the zinc chloride solution obtained by stripping is significantly higher, and the separation effect of zinc and calcium is poor.

[0174] Comparative Example 2

[0175] Comparative Example 2 is basically the same as Example 1, except that P204 extractant is used in the manganese extraction. The compositions of the manganese sulfate solution and the manganese extraction residual solution obtained in Comparative Example 2 are as follows:

[0176] Table 33 Composition of manganese sulfate solution

[0177]

[0178] Table 34 Composition of manganese extraction residual solution

[0179]

[0180] By comparing Example 1 with Comparative Example 2, it can be seen that when P204 is used to extract Mn, the concentrations of Zn and Ca in the manganese sulfate solution obtained by stripping are high, and the separation effect of manganese and calcium is poor, resulting in the obtained manganese sulfate solution failing to meet the battery grade standard. In addition, when sulfuric acid is used to strip manganese, calcium sulfate slag is also produced. The solubility of calcium sulfate is low, and the accumulation of calcium sulfate slag will block the extraction box pipeline.

Claims

1. A method for recycling copper-manganese-zinc solution, characterized in that: include: Manganese replacing copper step: contacting the copper-containing manganese-zinc solution with manganese powder to carry out a replacement reaction, and obtaining sponge copper and replacement liquid after the reaction; Zinc extraction step: adding a first extraction organic phase to the replacement liquid to perform a first extraction treatment to obtain a zinc extraction residual solution and a first loaded organic phase, and adding a first acid to the first loaded organic phase to perform a first back extraction treatment to obtain a zinc-containing solution; Manganese extraction step: adding a second extraction organic phase to the zinc extraction residual solution for a second extraction treatment to obtain a manganese extraction residual solution and a second loaded organic phase, and adding a second acid to the second loaded organic phase for a second back extraction treatment to obtain a manganese-containing solution.

2. The method according to claim 1, characterized in that The manganese-copper replacement process is carried out in two or more steps. In each step, the mass of manganese powder added to the solution is 0.86-2 times the mass of copper ions in the solution. Preferably, the manganese-copper replacement process is carried out in two steps, including: (a) adding a first portion of manganese powder to the copper-containing manganese-zinc solution to carry out a replacement reaction, and after the reaction, solid-liquid separation to obtain a first sponge copper and a first replacement liquid, (b) adding a second portion of manganese powder to the first replacement liquid to carry out a replacement reaction, and after the reaction, solid-liquid separation to obtain a second sponge copper and a second replacement liquid; Preferably, the mass of the first part of manganese powder added to the copper-containing manganese-zinc solution is 0.86-2 times the mass of copper ions in the copper-containing manganese-zinc solution; Preferably, the mass of the second portion of manganese powder added to the first replacement solution is 0.86-2 times the mass of the copper ions in the first replacement solution; Preferably, before the replacement reaction, the pH of the copper-manganese-zinc solution is adjusted to 1.0-2.5 using a base.

3. The method according to claim 1 or 2, characterized in that: In adjusting the pH of the copper-manganese-zinc solution to 1.0-2.5 by using a base, the base is selected from a combination of one or more of ammonia water, sodium hydroxide, ammonium carbonate, sodium carbonate, and sodium bicarbonate; Preferably, the particle size of the manganese powder is 250-350 mesh, preferably 300 mesh.

4. The method according to any one of claims 1 to 3, characterized in that In the zinc extraction step, the extractant contained in the first extraction organic phase is an extractant containing 2-ethylhexyl phosphate mono-2-ethylhexyl ester or an extractant containing di(2,4,4-trimethylpentyl)phosphinic acid; Preferably, the saponification rate of the extractant in the first extraction organic phase is 35%-55%; Preferably, the extraction stages of the first extraction process are 4-10.

5. The method according to any one of claims 1 to 4, characterized in that The zinc extraction step further includes: before the first stripping treatment, performing a first acid washing treatment on the first loaded organic phase; Preferably, the acid used in the first pickling treatment is 1-3 mol / L hydrochloric acid. Preferably, the washing stages of the first pickling treatment are 4-10 stages.

6. The method according to any one of claims 1 to 5, characterized in that In the zinc extraction step, the first acid used in the first stripping treatment is 5-8 mol / L hydrochloric acid or sulfuric acid; Optionally, the extraction stages of the first stripping treatment are 4-10.

7. The method according to any one of claims 1 to 6, characterized in that In the manganese extraction step, the extractant contained in the second extraction organic phase is an extractant containing di(2,4,4-trimethylpentyl)phosphinic acid; Preferably, the saponification rate of the extractant in the second extraction organic phase is 30%-50%; Preferably, the extraction stages of the second extraction process are 8-17 stages.

8. The method according to any one of claims 1 to 7, characterized in that In the manganese extraction step, before the second stripping treatment, the second loaded organic phase is subjected to a second acid washing treatment; Preferably, the acid used in the second pickling treatment is 1-2 mol / L sulfuric acid; Preferably, the number of washing stages of the second pickling treatment is 4-10.

9. The method according to any one of claims 1 to 8, characterized in that In the manganese extraction step, the second acid used in the second stripping treatment is 4-6 mol / L sulfuric acid. Optionally, the extraction stage number of the second stripping treatment is 5-10.

10. The method according to any one of claims 1 to 9, characterized in that The copper-manganese-zinc solution is a copper-manganese-zinc solution obtained from the cobalt intermediate P204 extraction line or a copper-manganese-zinc solution obtained from the nickel intermediate P204 extraction line, or the copper-manganese-zinc solution contains 90-155 g / L Mn 2+ 、5-20g / L Zn 2 + , 0.5-4.5g / L Cu 2+ , 1-6g / L Ca 2+ , 0.2-2.5g / LMg 2+ , 0.01-0.3g / L Co 2+ ; Preferably, the pH of the copper-manganese-zinc solution is 0.3-0.9; Preferably, the manganese content in the sponge copper is ≤4%; Preferably, the zinc-containing solution comprises Zn 2+ >10g / L, Mn 2+ ≤15mg / L, Cu 2+ ≤5mg / L, Ca 2+ ≤20mg / L, Mg 2+ ≤10mg / L, Co 2+ ≤5mg / L; Preferably, the manganese-containing solution comprises Mn 2+ >100g / L, Zn 2+ ≤8mg / L, Cu 2+ ≤5mg / L, Ca 2+ ≤10mg / L, Mg 2+ ≤10mg / L, Co 2+ ≤500mg / L.

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