CN114058876B - Method for extracting cobalt from cobalt-iron slag - Google Patents
Method for extracting cobalt from cobalt-iron slag Download PDFInfo
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- CN114058876B CN114058876B CN202111284910.3A CN202111284910A CN114058876B CN 114058876 B CN114058876 B CN 114058876B CN 202111284910 A CN202111284910 A CN 202111284910A CN 114058876 B CN114058876 B CN 114058876B
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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Abstract
The application relates to the technical field of hydrometallurgy, and provides a method for extracting cobalt from cobalt iron slag, which comprises the following steps: firstly, taking cobalt iron slag and an ammonia sulfate solution for leaching reaction, then adding a complexing agent for complexing reaction, and after solid-liquid separation, obtaining filtrate containing a cobalt complex and low-cobalt iron slag; then carrying out acid washing reaction on the low-cobalt iron slag to obtain cobalt washing liquid; and finally, carrying out cobalt precipitation reaction on the filtrate containing the cobalt complex and the cobalt washing solution in an alkaline environment, and carrying out solid-liquid separation to obtain a cobalt hydroxide precipitate. The method has the advantages that the conditions of pH value, temperature, time and the like of a reaction system are controlled to leach cobalt, and the leached cobalt is subjected to a complex reaction to extract the cobalt in a complex form, so that the aim of reducing the cobalt content of cobalt-iron slag is fulfilled; the filtrate containing the cobalt-ammonia complex can be converted into the cobalt hydroxide precipitate by controlling the cobalt precipitation condition, and compared with an acid leaching method, the whole reaction process has the advantages of better material recovery effect and lower auxiliary material consumption.
Description
Technical Field
The application belongs to the technical field of hydrometallurgy, and particularly relates to a method for recovering cobalt from cobalt iron slag.
Background
At present, the iron removal process of cobalt liquid in hydrometallurgy is realized by adjusting the pH value of the liquid to 2.5-3 and utilizing Fe 3+ And Co 2+ HydrolysisThe purpose of purifying solution is achieved by the difference of the pH value of the generated hydroxide, and the traditional cobalt solution iron removal process comprises the following steps: the method comprises the steps of leaching a cobalt raw material by using industrial sulfuric acid to obtain a primary leachate and primary leaching slag, wherein the primary leachate contains high iron, and the primary leachate needs to be leached for the second time to remove iron in the primary leachate, and filtered to obtain a liquid after iron removal and iron slag, but iron compounds in the iron slag have a certain adsorption effect on cobalt, so that the cobalt entering the iron slag is difficult to leach by using dilute sulfuric acid, and the recovery difficulty of the cobalt is high.
In the traditional process, in the process of extracting cobalt from cobalt-containing minerals or intermediate products thereof, the secondary leaching residue obtained finally by reaction often contains high cobalt, the cobalt content is 0.3-0.1%, and the cobalt content in iron slag is high, so that valuable metals are lost.
Therefore, in order to improve the recovery rate of cobalt, it is necessary to further extract and recover this part of cobalt iron slag.
Disclosure of Invention
The application aims to provide a method for extracting cobalt from cobalt-iron slag, and aims to solve the problem that the cobalt content in the cobalt-iron slag obtained in the existing process of extracting cobalt from cobalt-containing minerals or intermediate products of the cobalt-containing minerals is relatively high.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
the application provides a method for extracting cobalt from cobalt iron slag, which comprises the following steps:
taking cobalt-iron slag and an ammonia sulfate solution for leaching reaction, then adding a complexing agent for complexing reaction, and after solid-liquid separation, obtaining a filtrate containing a cobalt complex and low-cobalt iron slag;
carrying out acid washing reaction on the low-cobalt iron slag to obtain cobalt washing liquid;
and carrying out cobalt precipitation reaction on the filtrate containing the cobalt complex and the cobalt washing solution in an alkaline environment, and carrying out solid-liquid separation to obtain a cobalt hydroxide precipitate.
The method for extracting cobalt from cobalt-iron slag comprises the steps of firstly taking the cobalt-iron slag and ammonium sulfate solution for leaching reaction, enabling part of cobalt to be dissolved from the cobalt-iron slag and then to be subjected to complexing reaction with a complexing agent to form a cobalt complex, and obtaining filtrate containing the cobalt complex and low-cobalt-iron slag containing lower cobalt after solid-liquid separation; and then carrying out acid washing on the low-cobalt iron slag to further dissolve cobalt in the low-cobalt iron slag to obtain cobalt washing liquid, wherein the cobalt washing liquid can be recovered as a product and can also be subjected to cobalt precipitation reaction with a filtrate containing a cobalt complex, and the cobalt washing liquid is used for adjusting the pH value of a reaction system so as to carry out cobalt precipitation reaction on the cobalt complex and the cobalt washing liquid in an alkaline environment to obtain a directly-recovered cobalt hydroxide precipitate. The method has the advantages of simple process and low consumption of required materials and reagents.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for extracting cobalt from cobalt iron slag provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the foregoing processes do not imply an execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not limit the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The embodiment of the application provides a method for extracting cobalt from cobalt iron slag, which comprises the following steps:
s10: taking cobalt iron slag and ammonium sulfate solution to carry out leaching reaction, then adding an ammonia water complexing agent to carry out complex reaction, and carrying out solid-liquid separation to obtain the cobalt (NH) containing 3 ) x (OH) y Ammonia water, filtrate of ammonium sulfate and low-cobalt iron slag;
s20: carrying out acid washing reaction on the low-cobalt iron slag to obtain cobalt washing liquid;
s30: and carrying out cobalt precipitation reaction on the filtrate containing the cobalt-ammonia complex and the cobalt washing solution in an alkaline environment, and carrying out solid-liquid separation to obtain a cobalt hydroxide precipitate.
According to the method for extracting cobalt from cobalt-iron slag provided by the embodiment of the application, firstly, the cobalt is dissolved from the cobalt-iron slag by adopting ammonium sulfate to obtain a solution containing cobalt sulfate, then a complexing agent is added to control the alkaline pH value of a reaction system, so that cobalt ions and the complexing agent are subjected to a complexing reaction to form a cobalt-ammonia complex, and a filtrate containing the cobalt-ammonia complex, ammonia water and ammonium sulfate and low-cobalt-iron slag containing lower cobalt are obtained after filtration; in the step, most of cobalt can be separated from the cobalt-iron slag only by adding ammonium sulfate and a complexing agent in sequence, the process is simple, and all reagents are few; secondly, acid washing is carried out on the low-cobalt iron slag by using dilute sulfuric acid, so that cobalt can be further dissolved from the low-cobalt iron slag, and the obtained cobalt washing liquid can be recycled as one of the products and can also be used for subsequently adjusting the pH value of a cobalt precipitation reaction system, thereby further improving the recovery rate of cobalt in the cobalt iron slag; thirdly, adding cobalt washing liquid into the solution containing the cobalt-ammonia complex to adjust the alkaline pH value of the reaction system to a target value, so that the cobalt-ammonia complex is completely converted into cobalt hydroxide precipitate, and the final product is extracted in the form of cobalt hydroxide. The method only needs to control the conditions of pH value, temperature, time and the like of a reaction system to leach the cobalt, and the leached cobalt is subjected to a complex reaction to separate the cobalt from the cobalt-iron slag in a cobalt-ammonia complex form, so that the aim of reducing the content of the cobalt in the cobalt-iron slag is fulfilled; meanwhile, the stability of the formed cobalt-ammonia complex is poor, the filtrate containing the cobalt-ammonia complex can be converted into the cobalt hydroxide precipitate by controlling the cobalt precipitation condition, and simultaneously, the ammonia in the solution can be recycled. In step S10, as an embodiment of the present application, a method for obtaining a filtrate containing a cobalt-ammonia complex and a low-cobalt iron slag includes the following steps: taking cobalt-iron slag and ammonium sulfate to carry out leaching reaction to obtain a solution containing cobalt sulfate; adding a complexing agent into the solution containing cobalt sulfate to adjust the pH value of the reaction system to a first target alkaline pH value for complexing reaction, and after solid-liquid separation, obtaining a filtrate containing a cobalt-ammonia complex and low-cobalt iron slag. Specifically, the complexing agent is ammonia water.
The method mainly aims at the problem that cobalt content of cobalt iron slag generated in the cobalt hydrometallurgy process is high, and the purpose of reducing the cobalt content of the cobalt iron slag is achieved by extracting cobalt through a complexation method. Because iron compounds in the cobalt iron slag have a certain adsorption effect on cobalt in the solution during iron removal, cobalt entering the iron slag is difficult to leach out by using high-concentration sulfuric acid, the recovery difficulty of the cobalt is high, and further increased reaction conditions such as acidity, reaction temperature and the like often cause leaching of iron in the cobalt iron slag (the iron slag begins to dissolve into the solution when the pH value is less than 1), so that the aim of reducing cobalt content in the slag cannot be achieved in an acidic system. While the present application utilizes Co 2+ Has a certain complexing effect with ammonia water, fe 3+ Without complexing, by controlling pH, temperature, pressure, NH 4 + The concentration of the cobalt in the cobalt iron slag reaches the aim of selectively leaching cobalt so as to reduce the cobalt content of the cobalt iron slag. Compared with an acid leaching method, the method has obvious selectivity for cobalt in the cobalt-iron slag, and meanwhile, due to the fact that the stability of the cobalt-ammonia complex is poor, the filtrate containing the cobalt-ammonia complex, ammonia water and ammonium sulfate obtained through subsequent filtration can be used for recycling the ammonia water in the solution by controlling the cobalt precipitation condition, and therefore the material and reagent consumption of the method is lower than that of the acid leaching method.
Specifically, the cobalt-iron slag can be a slag after leaching treatment of a cobalt-containing mineral or a cobalt intermediate product. Taking cobalt iron slag and ammonium sulfate according to a certain proportion, putting the cobalt iron slag and the ammonium sulfate into a high-pressure reaction kettle, and stirring to leach cobalt from the cobalt iron slag to generate cobalt sulfate; then adding ammonia water into the reaction kettle and continuously stirring to adjust the pH value of the reaction system to a first target alkaline pH value so that cobalt ions and the ammonia water are subjected to a complex reaction under an alkaline condition to generate a cobalt-ammonia complex; and finally, filtering to obtain filtrate containing ammonia water, ammonium sulfate and cobalt-ammonia complex and low-cobalt iron slag containing less cobalt. The step is mainly to leach most of cobalt from the cobalt-iron slag and carry out a complex reaction by adding ammonium sulfate and a complexing agent and controlling the conditions of pH value, temperature, pressure, time and the like of a reaction system, thereby obtaining an unstable cobalt-ammonia complex.
In some embodiments, the first target alkaline pH is 10-12. Specifically, the first target alkaline pH may be 10, 11, or 12. With the increase of the first target alkaline pH value in this embodiment, the leaching rate of cobalt from the cobalt-iron slag is faster, but the first target alkaline pH value is too low, so that other impurities can be leached while the leaching rate of cobalt is increased, which is not beneficial to the subsequent extraction of cobalt.
In some embodiments, the liquid-to-solid ratio of cobalt-iron slag to the ammonium sulfate solution is 1g (1-10) mL. Specifically, the liquid-solid ratio of the cobalt-iron slag to the ammonium sulfate solution can be, but is not limited to, 1. With the increase of the liquid-solid ratio of the cobalt iron slag to the ammonium sulfate solution in the embodiment, the leaching rate of cobalt leached from the cobalt iron slag can be improved, but the excessive ammonium sulfate solution is added, so that the leaching rate of cobalt can be improved, but the waste of materials can be caused, and therefore, the reagent can be saved while the leaching rate of cobalt can be improved by controlling the liquid-solid ratio of the cobalt iron slag to the ammonium sulfate solution within a proper range, and the cobalt extraction cost can be saved.
In some embodiments, the temperature of the leaching reaction is 100-120 ℃. Specifically, the temperature of the leaching reaction may be 100 ℃, 110 ℃ or 120 ℃. Along with the improvement of the leaching reaction temperature in the embodiment, the leaching efficiency of cobalt from cobalt iron slag can be improved, but the leaching reaction temperature is too high, other impurities are easy to leach, and the subsequent extraction of cobalt is not facilitated.
In some embodiments, the temperature of the complexation reaction is 100-120 ℃. Specifically, the temperature of the complexation reaction may be 100 ℃, 110 ℃ or 120 ℃. With the increase in the temperature of the complexation reaction in this example. The method is favorable for the cobalt ions and ammonia water to carry out complexing reaction in an alkaline environment so as to generate the cobalt-ammonia complex, but the complexing reaction temperature is too high, so that the complex product is easy to dissolve, and the extraction of the cobalt product is not facilitated, therefore, the complexing reaction temperature is controlled in a proper range, and the cobalt ions are more easily converted into the cobalt-ammonia complex.
In some embodiments, the leaching reaction time is 2-8 hours. Specifically, the leaching reaction time may be, but is not limited to, 2,3,4,5,6,7 and 8 hours. Along with the extension of the leaching reaction time in the embodiment, the leaching efficiency of cobalt from cobalt iron slag can be improved, but the leaching reaction time is too long, other impurities are easy to leach, and the subsequent extraction of cobalt is not facilitated.
In some embodiments, the complexation reaction time is 6-10 hours. Specifically, the complexation reaction time may be, but is not limited to, 6,7,8,9, and 10 hours. As the time of the complexation reaction in this example was extended. The method is favorable for the cobalt ions and ammonia water to carry out complexation reaction in an alkaline environment to generate the cobalt-ammonia complex, but the complexation reaction time is too long, so that the complex product is easy to dissolve, and the extraction of the cobalt product is not favorable, therefore, the complexation reaction time is controlled in a proper range, and the cobalt ions are easier to be completely converted into the cobalt-ammonia complex.
In step S20, the step of performing an acid washing reaction on the low-cobalt iron slag to obtain a cobalt washing solution includes: according to a certain solid-liquid ratio of the low-cobalt iron slag and the dilute sulfuric acid, the dilute sulfuric acid with a certain concentration is taken to carry out acid washing on the low-cobalt iron slag for a certain time at a certain temperature, so as to obtain cobalt washing liquid and iron slag. The cobalt washing liquid comprises a small amount of cobalt sulfate, a small amount of ammonium sulfate and sulfuric acid. The low cobalt iron slag is acid-washed by dilute sulphuric acid, so that the recovery rate of cobalt in the cobalt iron slag can be further improved, the obtained cobalt washing liquid can be used as a cobalt product to be recovered, and the obtained cobalt washing liquid can also be used for adjusting the pH value in a reaction system for precipitating cobalt by a subsequent cobalt-ammonia complex.
In some embodiments, the solid-to-liquid ratio of the low cobalt iron slag to the dilute sulfuric acid is 1g (1-5) mL. Specifically, the solid-to-liquid ratio of the low-cobalt iron slag to the dilute sulfuric acid can be, but is not limited to, 1:5. along with the increase of the solid-liquid ratio of the low-cobalt iron slag to the dilute sulfuric acid, namely the liquid phase is large and easy to stir, cobalt is easier to pickle from the low-cobalt iron slag, but the added dilute sulfuric acid is too much, so that the pickling reaction of the cobalt can be improved, but the consumption of a reagent can be increased, therefore, the solid-liquid ratio of the low-cobalt iron slag to the dilute sulfuric acid is controlled in a proper range, the pickling rate of the cobalt can be improved, the reagent can be saved, and the cobalt extraction cost is saved.
In some embodiments, the pH of the dilute sulfuric acid is 1.0-2.0. Specifically, the pH of the dilute sulfuric acid may be 1.0, 1.5, or 2.0. With the increase of the pH value of the dilute sulfuric acid in this embodiment, the elution rate of cobalt from the low-cobalt iron slag is faster, but the pH value of the dilute sulfuric acid is too high, so that the elution rate of cobalt is increased, and other impurities are also eluted, which is not beneficial to the subsequent extraction of cobalt. In some embodiments, the time of the acid wash reaction is 1-2 hours; the temperature of the acid washing reaction is 40-100 ℃. Specifically, the time of the acid washing reaction may be 1 hour, 1.5 hours, or 2 hours. The temperature of the acid wash reaction may be, but is not limited to, 40 ℃,50 ℃,60 ℃,70 ℃,80 ℃,90 ℃ and 100 ℃. Along with the time extension and the temperature rise in the embodiment, the leaching rate of cobalt from the low-cobalt iron slag can be improved, however, the leaching of other impurities is easily caused due to overlong pickling reaction time and overhigh temperature, and the difficulty of subsequent cobalt extraction is increased, so that the pickling reaction time and temperature are controlled within a proper range, and the pickling reaction is favorably carried out.
In step S30, the cobalt precipitation reaction is performed on the filtrate containing the cobalt-ammonia complex and the cobalt washing solution in an alkaline environment, and after solid-liquid separation, the method for obtaining the cobalt hydroxide precipitate includes: and adding cobalt washing liquid into the filtrate containing the cobalt-ammonia complex, controlling the adding flow rate of the cobalt washing liquid, and adjusting the pH value to a second target alkaline pH value to perform a precipitation reaction to obtain a cobalt hydroxide precipitate. Specifically, adding cobalt washing liquid into the filtrate containing the cobalt-ammonia complex at a certain rate, periodically detecting the pH value of the filtrate containing the cobalt-ammonia complex, reacting for a period of time after the pH value of the filtrate reaches a second target alkaline pH value to keep the reaction system stable, repeatedly operating until the pH value of the reaction system is stabilized in a target range for aging, fully settling the precipitate, keeping the target time, and filtering to obtain the cobalt hydroxide precipitate. The pH value of the reaction system is adjusted by controlling the adding amount of the cobalt washing liquid, so as to meet the alkaline pH value that cobalt ammonia complex and cobalt ions in the cobalt washing liquid can generate complex reaction with ammonia water.
In some embodiments, the second target alkaline pH is 9-9.5. Specifically, the second target alkaline pH may be 9, may also be 9.2, and may also be 9.5. The cobalt-ammonia complex is stable in the environment with the pH value of 10-12, and can be dissociated to generate cobalt hydroxide precipitate at the pH value of 7-10 or above 12. And controlling the second target alkalinity value within a proper range, so that the cobalt-ammonia complex is easily dissociated and generates a cobalt hydroxide precipitation product with hydroxide.
In some embodiments, the precipitation reaction time is 10-18 hours. Specifically, the time of the precipitation reaction may be 10 hours, 15 hours, or 18 hours. As the time of the precipitation reaction in the embodiment is prolonged, the cobalt ammonia complex and the cobalt ions in the cobalt washing solution can be completely converted into the cobalt hydroxide precipitate.
The contents of the main components of the cobalt-iron slag are shown in table 1, and the following description will be given with reference to specific examples.
TABLE 1
| Components | Co | Cu | Fe | Ca | Mg | Mn |
| Content (%) | 0.142 | 0.0093 | 46.03 | 0.044 | 0.016 | 0.022 |
Example 1
The embodiment provides a method for extracting cobalt from cobalt iron slag, which comprises the following steps:
s10: according to the liquid-solid ratio of 1; after the leaching reaction is finished, slowly adding ammonia water into the reaction kettle, adjusting the alkaline pH value of the reaction system to 10, and then carrying out a complexing reaction at the temperature of 120 ℃ for 6 hours at the stirring speed of 200r/min; and filtering after the complexing reaction time is up to obtain filtrate containing cobalt-ammonia complex, ammonia water and ammonium sulfate and low-cobalt iron slag.
S20: and (3) carrying out acid washing reaction on the low-cobalt iron slag by using dilute sulfuric acid with the pH value of 2 according to the solid-liquid ratio of 1.
S30: and (3) adjusting the pH value of the filtrate containing the cobalt-ammonia complex, the ammonia water and the ammonium sulfate obtained by filtering by using a cobalt washing solution, and standing and aging the reaction system for 12 hours after the pH value reaches 9-9.5, so that the cobalt in the cobalt-ammonia complex and the cobalt washing solution and the ammonia water are subjected to precipitation reaction in an alkaline environment to generate a cobalt hydroxide precipitate.
Example 2
The embodiment provides a method for extracting cobalt from cobalt iron slag, which comprises the following steps:
s10: according to the liquid-solid ratio of 1; after the leaching reaction is finished, slowly adding ammonia water into the reaction kettle, adjusting the alkaline pH value of the reaction system to 11, and then performing a complexing reaction at the temperature of 120 ℃ for 6 hours at a stirring speed of 200r/min; and filtering after the complexing reaction time is up to obtain filtrate containing cobalt-ammonia complex, ammonia water and ammonium sulfate and low-cobalt iron slag.
S20: and (3) carrying out acid washing reaction on the low-cobalt iron slag by using dilute sulfuric acid with the pH value of 2 according to the solid-liquid ratio of 1.
S30: and (3) adjusting the pH value of the filtrate containing the cobalt-ammonia complex, the ammonia water and the ammonium sulfate obtained by filtering by using a cobalt washing solution, and standing and aging the reaction system for 12 hours after the pH value reaches 9-9.5, so that the cobalt in the cobalt-ammonia complex and the cobalt washing solution is subjected to precipitation reaction with the ammonia water in an alkaline environment to generate a cobalt hydroxide precipitate.
Example 3
The embodiment provides a method for extracting cobalt from cobalt iron slag, which comprises the following steps:
s10: according to the liquid-solid ratio of 1; after the leaching reaction is finished, slowly adding ammonia water into the reaction kettle, adjusting the alkaline pH value of the reaction system to 12, and then performing a complexing reaction at the temperature of 120 ℃ for 6 hours at a stirring speed of 200r/min; and filtering after the complexing reaction time is up to obtain filtrate containing cobalt-ammonia complex, ammonia water, ammonium sulfate and low-cobalt iron slag.
S20: and (3) carrying out acid washing reaction on the low-cobalt iron slag by using dilute sulfuric acid with the pH value of 2 according to the solid-liquid ratio of 1.
S30: and (3) adjusting the pH value of the filtrate containing the cobalt-ammonia complex, the ammonia water and the ammonium sulfate obtained by filtering by using a cobalt washing solution, and standing and aging the reaction system for 12 hours after the pH value reaches 9-9.5, so that the cobalt in the cobalt-ammonia complex and the cobalt washing solution and the ammonia water are subjected to precipitation reaction in an alkaline environment to generate a cobalt hydroxide precipitate.
The extraction result of cobalt extracted from the cobalt iron slag is detected and analyzed by adopting an atomic absorption spectrometry, and the detection result is shown in table 2:
TABLE 2
| pH | Cobalt iron slag (g) | Cobalt hydroxide (g) | Cobalt-containing liquid for cobalt (g) | The tailings contain cobalt (g) | Cobalt recovery (%) |
| 10 | 998.98 | 0.45 | 0.21 | 0.073 | 45.8 |
| 11 | 998.21 | 0.58 | 0.38 | 0.043 | 67.6 |
| 12 | 998.77 | 0.38 | 1.15 | 0.085 | 37.3 |
The cobalt content of the cobalt washing solution in table 2 is the weight of the cobalt washing solution obtained by the acid washing reaction in step S20 minus the cobalt content of the remaining cobalt washing solution used for adjusting the alkaline pH value of the reaction system in step S30; the cobalt content of the post-slag is to underestimate the cobalt content of the treated slag obtained after the acid washing reaction of the iron slag; the cobalt recovery rate is the percentage of cobalt in the cobalt washing liquid and cobalt in the cobalt iron slag after cobalt and cobalt hydroxide are contained. The results of the analysis of the results of the detection of the extraction of cobalt from cobalt iron slag by the atomic absorption spectrometry shown in table 2 above were obtained as follows: along with the rise of the alkaline pH value of the reaction system, the cobalt content of the extracted cobalt hydroxide and the cobalt washing liquid is increased and then reduced, when the pH value is 11, the cobalt content of the extracted cobalt hydroxide and the cobalt washing liquid is maximum, the recovery rate of cobalt is up to 67.6 percent, which indicates that the proper alkaline pH value of the reaction system is adjusted, which is beneficial to leaching the cobalt in the cobalt iron slag, thereby improving the recovery rate of cobalt; the cobalt content of the slag is below 0.09g, which shows that the recovery rate of the cobalt recovered by the method for extracting cobalt in the embodiment of the application is high.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. The method for extracting cobalt from cobalt iron slag is characterized by comprising the following steps of:
taking cobalt iron slag and an ammonia sulfate solution for leaching reaction, adding a complexing agent for complexing reaction, and after solid-liquid separation, obtaining filtrate containing cobalt-ammonia complex, ammonia water and ammonium sulfate and low-cobalt iron slag; the cobalt in the cobalt-containing ammonia complex is divalent;
carrying out acid washing reaction on the low-cobalt iron slag by using dilute sulfuric acid with the pH value of 1.0-2.0 to obtain cobalt washing liquid;
adding the cobalt washing solution into the filtrate containing the cobalt ammonia complex, ammonia water and ammonium sulfate, controlling the addition amount of the cobalt washing solution to adjust the pH value to a second target alkaline pH value to perform a precipitation reaction, and performing solid-liquid separation to obtain a cobalt hydroxide precipitate;
wherein the second target alkaline pH is 9-9.5;
the solid-to-liquid ratio of the low-cobalt iron slag to the dilute sulfuric acid is 1g (1-5) mL.
2. The method for extracting cobalt from cobalt-iron slag as claimed in claim 1, wherein said method for obtaining cobalt complex containing filtrate and low cobalt-iron slag comprises the steps of:
carrying out leaching reaction on the cobalt-iron slag and the ammonium sulfate to obtain a solution containing cobalt sulfate;
and adding an ammonia water complexing agent into the solution containing the cobalt sulfate to adjust the pH value of the reaction system to a first target alkaline pH value for complexing reaction, and performing solid-liquid separation to obtain a filtrate containing the cobalt-ammonia complex and low-cobalt iron slag.
3. The method of extracting cobalt from cobalt iron slag according to claim 2, wherein said first target alkaline pH is 10-12.
4. The method for extracting cobalt from cobalt-iron slag according to any one of claims 1 to 3, wherein the liquid-solid ratio of the cobalt-iron slag to the ammonia sulfate solution is 1g (1-10) mL.
5. The method for extracting cobalt from cobalt-iron slag as claimed in claim 4, wherein the temperature of said leaching reaction is 100-120 ℃; and/or
The temperature of the complexing reaction is 100-120 ℃; and/or
The leaching reaction time is 2-8 hours; and/or
The complexing reaction time is 6-10 hours.
6. The method for extracting cobalt from cobalt-iron slag as claimed in claim 1, wherein said dilute sulfuric acid has a pH of 2.0-3.0; and/or
The time of the acid washing reaction is 1-2 hours; and/or
The temperature of the acid washing reaction is 40-100 ℃.
7. The method for extracting cobalt from cobalt-iron slag as claimed in claim 6, wherein the precipitation reaction time is 10-18 hours.
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