Patent Application
20210262060
The present invention relates to a method for separating copper from nickel and cobalt from a sulfide containing copper, nickel and cobalt.
Generally, nickel matte (a sulfide containing nickel and cobalt) used in a nickel smelting plant contains a small amount of copper, and not only nickel and cobalt but copper is also simultaneously leached during refining by leaching treatment (e.g., Patent Document 1). Therefore, a smelting method using nickel matte needs to have a copper removal process of removing leached copper. Therefore, when nickel matte is used in a large quantity to increase the production amount of nickel, it is required to increase loading on the copper removal process at the same time.
There is also a method in which copper contained in nickel matte, i.e., a raw material, is left as copper sulfide in a residue by leaching nickel and cobalt in the form of ion exchange in an autoclave, using a copper oxalate solution as a solvent. However, since this method necessitates the treatment of copper in the solvent as well, in addition to copper in the raw material, copper loading on the entire process increases and the process becomes complicated.
Similarly, when a low-grade nickel matte having a high copper grade is used, leaching copper also increases the loading on the copper removal process. As described above, increasing the loading on the copper removal process results in practical problems such as operation balance and a cost increase.
When taking into account these problems, there is a need for a simple method for separating copper by selectively leaching nickel and cobalt in order to suppress the loading on the copper removal process using nickel matte.
Patent Document 1: Japanese Unexamined Patent Application, Publication No. H2-197533
In view of such circumstances, the present invention is proposed and it is an object of the present invention to provide a method for efficiently separating copper from nickel and cobalt from a sulfide containing copper together with nickel and cobalt.
The present inventors have conducted extensive studies to solve the above-described problems. As a result, the inventors have found that, by pulverizing a sulfide containing copper, nickel and cobalt to a predetermined size and subjecting the sulfide to a leaching treatment under a condition of a specific redox potential (ORP) using an acid solution, nickel and cobalt can be selectively leached, and at the same time, copper can be left as a solid residue in the form of copper sulfide and separated, thereby completing the present invention.
A first aspect of the present invention relates to a method for separating copper from nickel and cobalt, in which a sulfide containing copper, nickel and cobalt is pulverized to a predetermined size, and the pulverized sulfide is subjected to a leaching treatment by stirring the pulverized sulfide in an acid solution under a condition in which a redox potential (reference electrode: silver/silver chloride electrode) is less than 100 mV.
A second aspect of the present invention relates to the method for separating copper from nickel and cobalt as described in the first aspect, in which the leaching treatment produces a leachate in which nickel and cobalt are leached, and a leach residue containing copper sulfide.
A third invention of the present invention relates to the method for separating copper from nickel and cobalt as described in the first or second aspect, in which the sulfide is pulverized so as to have a particle size of 150 μm or less as a D90 value.
A fourth aspect of the present invention relates to the method for separating copper from nickel and cobalt as described in any one of the first to third aspects, in which the leaching treatment is performed at an acid solution temperature in a range of 60° C. or more and less than 100° C.
A fifth aspect of the present invention relates to the method for separating copper from nickel and cobalt as described in any one of the first to fourth aspects, in which a hydrochloric acid solution or a sulfuric acid solution is used as the acid solution.
A sixth aspect of the present invention relates to the method for separating copper from nickel and cobalt as described in any one of the first to fifth aspects, in which the sulfide is nickel matte.
According to the present invention, it is possible to efficiently separate copper from nickel and cobalt from a sulfide containing copper together with nickel and cobalt.
Below, specific embodiments of the present invention (hereinafter, referred to as a “present embodiment”) are described in detail, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a scope in which the gist of the present invention is not changed. Note that, in this specification, the notation “X to Y” (X and Y are arbitrary numerical values) means “X or more and Y or less”.
The separation method according to the present embodiment is a method of separating copper from nickel and cobalt from a sulfide containing copper, nickel and cobalt (hereinafter, simply referred to as “sulfide”). Examples of the sulfide containing copper together with nickel and cobalt include nickel matte.
Specifically, this separation method is characterized in that the leaching treatment is conducted by pulverizing a sulfide containing copper, nickel and cobalt to a predetermined size, and stirring the pulverized sulfide using an acid solution under a condition in which a redox potential (ORP) (silver/silver chloride electrode is referenced) is less than 100 mV. By this leaching treatment, a leachate in which nickel and cobalt are leached and a solid residue in which copper is in a form of copper sulfide are produced, and copper is separated from nickel and cobalt.
According to such a method, nickel and cobalt can be selectively leached from a sulfide of a raw material, such as nickel matte, and separated from copper in the raw material, so that loading on a copper removal process can be effectively suppressed.
In the leaching treatment, prior to addition of acid solution, the sulfide containing copper, nickel and cobalt is pulverized so as to have a particle size of a predetermined size.
The particle size of the sulfide to be subjected to the leaching treatment is preferably 150 μm or less, more preferably 100 μm or less, and most preferably 40 μm or less, as a particle size (D90) value at 90% in terms of volume determined from the particle size distribution. Particle size of a sulfide (D90 value), for example, can be measured by a particle size distribution measuring apparatus or the like using a laser diffraction scattering method. Note that the lower limit value of the particle size of a sulfide is not particularly limited as long as the particle size value is a value exceeding 0 μm, and may be, for example, 5 μm or more from the viewpoint of handling and the like, and is more preferably 10 μm or more.
A method of pulverizing a sulfide is not particularly limited, and may be performed by various known methods such as dry pulverization by a jet mill, a braun mill, a ball mill, or the like, or wet pulverization by a ball mill, a bead mill, a wet jet mill, or the like.
A sulfide is pulverized and then the sulfide is subjected to a leaching treatment using an acid solution. At this time, the present embodiment is characterized in that an acid solution containing a sulfide is stirred in a condition in which the oxidation-reduction potential (ORP) of the acid solution is less than 100 mV as measured using a silver/silver chloride electrode as a reference electrode. In this way, by conducting the leaching treatment under the condition in which the oxidation-reduction potential of the acid solution is less than 100 mV, nickel and cobalt contained in the sulfide can be selectively leached, while copper can remain in the form of copper sulfide.
In other words, by performing the leaching treatment under the above-described conditions, a leachate in which nickel and cobalt are selectively leached and a leach residue (solid residue) containing copper sulfide are generated.
The acid solution is not particularly limited, and for example, a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, or the like can be used. Among them, a hydrochloric acid solution or a sulfuric acid solution is preferably used.
Generally, when the leaching treatment is performed with respect to a sulfide containing copper, nickel and cobalt using an acid solution (e.g., a hydrochloric acid solution), the following reactions (1) to (5) occur.
NiS+2HCl→NiCl2+H2S (1)
CoS+2HCl→CoCl2+H2S (2)
Ni+2HCl→NiCl2H2 (3)
Co+2HCl→CoCl2+H2 (4)
CuS+2HCl→CuCl2+H2S (5)
The present inventors have found that the reaction of the above reaction formula (5) can be significantly suppressed by setting the oxidation-reduction potential of the acidic solution containing the sulfide to be leached to a specific range in the leaching treatment, specifically, to less than 100 mV.
The condition of the redox potential (ORP) (silver/silver chloride electrode is referenced) in the leaching treatment is set to less than 100 mV as described above. Further, more preferably, the redox potential is set to less than −50 mV. In the leaching treatment, more preferably, by setting the redox potential of the solution to a condition of less than −50 mV, the reaction of the above formula (5) can be more effectively suppressed, and the copper concentration contained in the obtained leachate can be reduced to less than 0.1 g/L. Thus, copper can be more efficiently fixed in the leach residue and separability of copper from nickel and cobalt can be further improved.
There is no particular limitation on the method of controlling the redox potential. For example, when the redox potential is increased, the redox potential can be controlled by temporarily increasing the addition amount of the sulfide to be leached or adding an oxidant, for example, by blowing air.
The addition concentration of acid solution is required to be added so as to be 1 equivalent or more, preferably 1.5 equivalents or more, and more preferably 2 equivalents or more, with respect to nickel and cobalt contained in the sulfide to be treated. Further, the lower limit value of addition concentration of acid solution is preferably 3.0 equivalents or less, and more preferably 2.5 equivalents or less. Note that, when the addition concentration of acid solution exceeds 3.0 equivalents, a large amount of neutralization agent is required in a step after the leaching treatment, resulting in a decrease in economic efficiency.
The concentration of slurry generated by adding an acid solution to the sulfide is, for example, preferably 20 g/L or more, and more preferably 30 g/L or more.
The temperature of acid solution, i.e., the reaction temperature of leaching treatment, is preferably set to 60° C. or more and less 100° C., and more preferably to 75° C. or more and 98° C. or less. In particular, considering the reaction rate, it is preferable to set the temperature to about 95° C.
With respect to the treatment time of leaching treatment, it is preferable to appropriately set the treatment time depending on the addition concentration of acid solution, but it is preferable to set the treatment time, for example, to 2 hours or more and 6 hours or less, and more preferably to 4 hours or more and 6 hours or less. Although depending on the addition concentration of acid solution, if the treatment time is too short, the leaching ratio of nickel and cobalt is not increased, and there is a possibility that separation from copper becomes insufficient. On the other hand, although longer treatment time improves the leaching ratio of nickel and cobalt, the leaching ratio of copper in the sulfide is also gradually increased, and there is possibility that copper is contained in the leachate.
In the leaching treatment, an acid solution is added to a sulfide to be treated (e.g., a nickel matte or the like), and then the sulfide and the acid solution are stirred under the condition in which the redox potential is less than 100 mV. A method of stirring is not particularly limited, and may be performed using, for example, a stirring device provided with a stirring blade or the like. By carrying out leaching while stirring in this manner, the leaching ratio of nickel and cobalt can be increased.
Note that, in the leaching treatment, the redox potential of solution is constantly monitored and a time point at which the redox potential is confirmed to exceed 100 mV or more and it becomes impossible to maintain the redox potential to less than 100 mV is determined as a time point at which the reaction is terminated. Then, the reaction is suppressed by cooling and a solid-liquid separation treatment is conducted to separate a leachate containing nickel and cobalt and a leach residue containing copper sulfide. Note that the solid-liquid separation process can be performed by a known method.
Hereinafter, the present invention is described more specifically by illustrating the Examples of the present invention, but the present invention is not limited to the following Examples in any event.
Nickel matte, which is a sulfide containing copper, nickel and cobalt, was pulverized using a planetary ball mill, and three types of nickel matte samples having different particle sizes (un-pulverized sample, pulverized sample (A), and pulverized sample (B)) were prepared. Then, 6 g of each nickel matte sample was collected and 20.4 ml of a 11.64 N hydrochloric acid solution, which corresponds to 2 equivalents of nickel and cobalt in the nickel matte, was diluted to 300 ml with purified water. The liquid temperature of the solution was increased to 95° C., and then each of the nickel matte samples was added and stirred for 1 hour to 6 hours.
After stirring for a certain time period, filtration was performed for solid-liquid separation, and the content of each component in the leachate was determined by analyzing the obtained filtrate by an ICP-analyzer. Table 1 below shows the analytical values of the nickel matte, Table 2 below shows measured particle size distribution values of the nickel matte samples, and Tables 3 and 4 below show leaching conditions and results thereof. The redox potential (ORP) during the leaching treatment was relative to a silver/silver chloride electrode as a reference electrode. Note that the particle size distributions of the nickel matte samples were measured using a measuring device manufactured by Microtrac.
From Tables 3 and 4 and
However, it was found in the test of pulverized sample (B) that when the reaction was continued over 3 hours as leaching treatment time, the leaching ratio of copper increased. This is considered to be attributable to the fact that the redox potential gradually increased with the progress of the reaction.
Next, 6 g of nickel matte of pulverized sample (A) shown in Table 2 was collected and used. Hydrochloric acid corresponding to 1.5 equivalents to 2.2 equivalents of nickel and cobalt in the nickel matte was diluted to 300 ml with purified water, the temperature of the solution was increased to 95° C., and then the nickel matte sample was added and stirred for 0.5 hours to 6 hours.
After stirring for a certain time period, filtration was performed for solid-liquid separation, and the content of each component in the leachate was determined by analyzing the obtained filtrate by an ICP-analyzer. The leaching conditions and the results are shown in Table 5 and Table 6 below. Further,
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-121733 | Jun 2018 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/024805 | 6/21/2019 | WO | 00 |
