JP5497723B2 - Copper concentrate processing method - Google Patents

Description

  The present invention relates to a method for treating copper concentrate.

Copper ore produced in copper mines is mainly sulfide ore. Roughly categorizing sulfide ores, relatively high copper grade secondary sulfide ores, mainly composed of minerals such as chalcocite (Cu ₂ S) and copper indigo (CuS), and the first generation mainly composed of chalcopyrite (CuFeS ₂ ) Divided into sulfide ores. In recent years, copper ores collected at copper mines are mainly the latter. As a result, impurities such as iron increase and the copper quality tends to decrease. This causes factors such as a decrease in copper quality and an increase in iron content of copper concentrates produced for copper smelting in the mine.

  In general, through the smelting of copper concentrate, the copper content is recovered as product copper and the iron content is recovered as slag. The recent reduction in the quality of copper concentrate causes an increase in production costs in the copper smelting process. Furthermore, in the domestic copper smelting industry, the supply and demand of slag caused by copper smelting has suffered, and exports are unprofitable, putting pressure on business profits. If the copper grade of copper concentrate further declines in the future, the iron content in copper concentrate will increase and business profits may be deteriorated due to slag.

One means for solving these problems is the application of a copper concentrate pretreatment method. In the pretreatment method, copper concentrate particles mainly composed of chalcopyrite (CuFeS ₂ ) are reacted with sulfur (S) at a predetermined temperature, and refined composed of copper indigo (CuS) and pyrite (FeS ₂ ). It is a process of sulfidizing into mineral particles. This sulfidation conversion reaction is known as a pretreatment method for wet smelting in the sense that it forms chalcopyrite (CuFeS ₂ ), which is difficult to be leached, in a relatively easy leaching form, but from pretreatment to hydrometallurgy. This is a process that is not widely used from the viewpoint of total cost.

As another means for solving the above-mentioned problems, the physical separation of copper indigo (CuS) and pyrite (FeS ₂ ) after sulfur conversion reaction with sulfur, and dry smelting as a high copper grade concentrate mainly composed of copper indigo (CuS) (For example, refer to Patent Document 1). In Patent Document 1, in the selection of copper indigo (CuS) and pyrite (FeS ₂ ), an electrostatic method, a gravitational method, a magnetic method, a wind method, a particle size method, a hydrocyclone method, a flotation process or It is disclosed to perform by these combinations.

International Publication No. 2008/074805

However, Patent Document 1 does not describe a specific method for selecting copper indigo (CuS) and pyrite (FeS ₂ ). Further, there is no mention of Cu loss to tailings enriched with iron removed after sorting.

  The Cu grade of slag enriched with iron generated from a copper smelter is about 0.6 mass% to 0.8 mass%, and the Cu loss from copper concentrate to slag is about 1.5 mass%. Since Cu loss from the copper concentrate deteriorates the profit of the copper smelter, in the method of performing dry smelting after the physical sorting, it is preferable that the Cu loss in the physical sorting can be reduced below the Cu loss to the slag. That is, it is preferable that the Cu grade and the Cu recovery rate of the tailings obtained by concentrating iron recovered after the physical sorting are not more than slag.

  In view of the above-described problems, an object of the present invention is to provide a copper concentrate treatment method that can efficiently and economically remove Fe-rich tailings from copper concentrate while suppressing Cu loss.

Method of processing copper concentrate according to the present invention, to copper concentrate containing chalcopyrite (CuFeS _2), sulfur, in a molar ratio of 1.0 to 1.2 relative to the copper of the copper concentrate in It was added, and the sulfide conversion process for sulfurizing the copper concentrates, sulphide conversion particles obtained by the sulfurization conversion step, and McCaw step of the 50% particle diameter is McCaw to be 15Myuemu～50myuemu, the milling ore It is characterized by including a separation step of separating the fine particles obtained by the process into a flotation concentrate having a high Cu grade and a flotation tailing having a low Cu grade by performing a flotation process. According to the copper concentrate processing method of the present invention, it is possible to efficiently and economically remove the Fe-concentrated tailings from the copper concentrate while suppressing Cu loss.

  The sulfidation conversion step may be performed at 300 ° C to 450 ° C. In the grinding process, a wet pulverizer or a dry pulverizer may be used. In the flotation process, a xanthate collection agent may be used as a collection agent. In the flotation process, the collection agent addition amount may be in the range of 100 to 2000 ppm with respect to the concentrate to be subjected to the flotation process.

  In the said flotation process, you may maintain the pH of the solution containing the concentrate used for a flotation process in the range of 9-13. In the flotation process, methyl isobutyl carbinol or pine oil may be used as a foaming agent. In the flotation process, an air supply type flotation machine, an air suction type flotation machine, a mechanical stirring type flotation machine, or a combination thereof may be used. Flotation treatment may be performed again on the high-quality floating concentrate obtained in the separation step.

  ADVANTAGE OF THE INVENTION According to this invention, the processing method of the copper concentrate which can remove an Fe concentration tailing from copper concentrate efficiently and economically can be provided, suppressing Cu loss.

It is process drawing which shows an example of the processing method of the copper concentrate which concerns on this embodiment. It is a sulfide conversion particle obtained by mapping of copper indigo (CuS) and pyrite (FeS ₂ ) identified by EPMA. It is an XRD analysis result of the copper concentrate before a sulfidation conversion process. It is a XRD analysis result of the conversion particle | grains after a sulfidation conversion process. It is a particle size distribution measurement result of the grinding particle after grinding process ball mill 5min. It is a particle size distribution measurement result of the grinding particle after grinding process ball mill 15min. It is a particle size distribution measurement result of the grinding particle after grinding process ball mill 30min. It is a particle size distribution measurement result of the grinding particle after the grinding process ball mill 60min. It is a particle size distribution measurement result of the grinding particle after the grinding process ball mill 90min. It is a result of the flotation concentrate Cu quality and Cu recovery rate in a flotation process.

  Hereinafter, an embodiment for carrying out the present invention will be described.

(Embodiment)
This embodiment reduces the amount of iron contained in the copper concentrate by removing the Fe-concentrated tailings while suppressing Cu loss by milling the copper concentrate particles that have undergone sulfidation conversion and subjecting them to a flotation process. In addition, it provides a process that can improve the profitability of the business by reducing the amount of slag generated.

The target processed product according to the present embodiment is a copper concentrate generally used for dry copper smelting, and is a copper concentrate containing chalcopyrite (CuFeS ₂ ), and even a slight amount of chalcopyrite (CuFeS ₂ ) is present in the copper concentrate. do it. In order to confirm the presence of chalcopyrite (CuFeS ₂ ), the copper concentrate may be sampled and then analyzed by XRD. Moreover, as an example of the quality of the copper concentrate containing chalcopyrite (CuFeS ₂ ), copper is contained in an amount of 20 mass% to 34 mass%, and iron is contained in an amount of 20 mass% to 35 mass%. Since such a copper concentrate contains a lot of iron, a large amount of slag is generated in the smelting process.

FIG. 1 is a process diagram showing an example of a copper concentrate processing method according to this embodiment. With reference to FIG. 1, first, a sulfidation conversion step is performed on copper concentrate. For example, sulfur (S) is added at a molar ratio of 1.0 to 1.2 with respect to copper (Cu) in the copper concentrate. As an example, sulfur is added in the form of elemental sulfur and mixed well. The mixed processed material is subjected to heat treatment at a predetermined temperature and a predetermined time in an inert atmosphere. This heat treatment can be performed using, for example, a rotary kiln. For example, nitrogen gas can be used as the inert atmosphere. Moreover, it is preferable that heat processing time shall be 30 minutes-60 minutes. This is because the remaining amount of unreacted chalcopyrite (CuFeS ₂ ) can be reduced.

It is preferable that the heat processing temperature in a sulfidation conversion process is 300 to 450 degreeC. For example, when the sulfide conversion step is performed at 275 ° C. below 300 ° C., the remaining amount of chalcopyrite (CuFeS ₂ ), which is a compound contained in the copper concentrate before the sulfide conversion step, increases, so It is not suitable for this process of separating Cu and Fe as pyrite (FeS ₂ ). Also, when treated at temperatures above 450 ° C., unstable state of covellite (CuS), a possibility that by including Han ore _(Cu 5 FeS ₄₎ is produced, it is difficult to separate the Cu and Fe There is. Therefore, the heat treatment temperature is preferably 300 ° C to 450 ° C. Moreover, from the viewpoint of separation of copper indigo (CuS) and pyrite (FeS ₂ ), the heat treatment temperature is more preferably 400 ° C. to 450 ° C.

As a result of the heat treatment, sulfide conversion particles composed of copper indigo (CuS) and pyrite (FeS ₂ ) are obtained. The sulfide conversion particles, pyrite (FeS ₂₎ is present as an inner shell, pyrite and (FeS ₂₎ covellite (CuS) is configured to cover a shell. FIG. 2 shows sulfide conversion particles obtained by mapping copper indigo (CuS) and pyrite (FeS ₂ ) identified by an electron beam microanalyzer (EPMA). Referring to FIG. 2, light gray pyrite (FeS ₂ ) is covered with dark gray copper indigo (CuS).

Therefore, referring to FIG. 1 again, a grinding process is performed on the sulfide conversion particles that have undergone the sulfide conversion process. In the milling process, a wet pulverizer or a dry pulverizer can be used. As a pulverizer, for example, a ball mill, a jet mill, an attrition mill, a tube mill, or the like can be used, and any kind can be used. By carrying out the milling process, the sulfide-change particles can be separated into copper indigo (CuS) and pyrite (FeS ₂ ).

Next, the flotation process is performed on the milling particles obtained by the milling process (separation process). In the flotation process, an air supply type flotation machine, an air suction type flotation machine, a mechanical stirring type flotation machine, or a combination thereof can be used. By carrying out the flotation process, the grinding particles are separated into a flotation concentrate that floats and a flotation tailing that sinks. By using butyl xanthate (BX) that preferentially collects copper indigo (CuS) as a collector and Ca (OH) ₂ as a pH adjuster, copper indigo (CuS) is given priority by the collector. The flotation concentrate contains a relatively large amount of copper indigo (CuS). Moreover, the floatation of pyrite (FeS ₂ ) is suppressed by setting the pH of the solution to the alkali side, and the flotation tailings contain a relatively large amount of pyrite (FeS ₂ ). That is, the flotation concentrate contains a relatively high amount of high-quality Cu minerals, and the flotation tailing contains a relatively high amount of high-quality Fe minerals. Therefore, the flotation concentrate with high Cu quality and the flotation tailing with low Cu quality can be recovered by the flotation process.

  In addition, the pH adjuster and the collection agent in the flotation process are not limited to this. As the collection agent, for example, a xanthate collection agent such as isopropyl xanthate (IPX) or ethyl xanthate (EX) can be used. The amount of butyl xanthate added is not particularly limited, but is preferably 100 g to 2000 g with respect to 1 t of concentrate to be subjected to the flotation process. For example, NaOH may be used as the pH adjuster. Moreover, although the pH of the solution containing the concentrate used as the object of a flotation process is not specifically limited, It is preferable that it is 9-13. Therefore, it is preferable that the addition amount of the pH adjusting agent is determined so as to maintain the pH of the solution to be subjected to the flotation process at 9 to 13. Moreover, the foaming agent in the flotation process is not particularly limited. As an example of the foaming agent, methyl isobutyl carbinol (MIBC), pine oil, or the like can be used.

When selecting copper indigo (CuS) and pyrite (FeS ₂ ) in the sulfide conversion particles in the above-mentioned milling and flotation, it is necessary to separate both minerals by grinding the sulfide conversion particles. As a result of diligent tests and investigations by the present inventors, it was found that the particle size at which copper indigo blue (CuS) and pyrite (FeS ₂ ) are separated into simple substances is 50% of the grinding particles is 10 μm or less. . However, in the flotation process, particles having a particle size of 10 μm or less generally have poor buoyancy, and the Cu recovery rate of the flotation concentrate is reduced. Moreover, Cu loss to a flotation tailing increases with this. From this, in order to reduce Cu loss to the flotation tailings, simple substance separation is inadequate, but by grinding the sulfide conversion particles so that the 50% particle diameter is 15 μm to 50 μm, Cu loss can be reduced by preventing the deterioration of the floatability of particles in the treatment and recovering the Fe enriched flotation tailings with low Cu quality. By using the obtained flotation concentrate as a copper smelting concentrate, the copper smelting with a low Cu loss from the copper concentrate and a small amount of slag generation can be performed.

  The conditions of the flotation process can be arbitrarily changed according to the Cu quality of the selected concentrate, the Cu recovery rate in the flotation process, the processing cost, and the like. Moreover, what is necessary is just to implement a flotation process in multiple steps, when aiming at the further improvement of Cu quality of a flotation concentrate. Or after dividing into a flotation concentrate and a flotation tailing, the flotation concentrate may be re-milled to the required particle size and the flotation process may be performed again.

  Examples based on the above embodiment will be described below.

In the sulfide conversion step, copper concentrate containing chalcopyrite (CuFeS ₂ ) (Cu grade = 33 mass%, Fe grade = 24 mass%, 50% particle size = 58 μm) and elemental sulfur in a molar ratio Cu: The mixture was mixed at S = 1.0: 1.2 and heat-treated at 425 ° C. for 60 minutes in a nitrogen atmosphere to convert chalcopyrite (CuFeS ₂ ) into copper indigo (CuS) and pyrite (FeS ₂ ). In addition, the analysis result by XRD of FIG. 3 confirmed that chalcopyrite (CuFeS ₂ ) was present in the copper concentrate. As can be seen from the analysis result by XRD in FIG. 4, copper indigo (CuS) and pyrite (FeS ₂ ) are generated in the sulfide-changed particles obtained after the sulfide conversion step. The vertical axis in FIG. 3 represents intensity (Counts).

  Next, the sulfide conversion particles (Cu quality = 31 mass%, Fe quality = 21 mass%) were milled by changing the grinding time with a wet ball mill, and the flotation process was carried out. The weight ratio, Cu recovery rate, Cu quality, Fe recovery rate, and Fe quality of the obtained flotation concentrate and flotation tailing were investigated. The grinding time of the ball mill at this time is 5, 15, 30, 60, and 90 min, and FIGS. 5, 6, 7, 8, and 9 show the particle size distribution of each grinding particle. The 50% particle size is 42, 19, 16, 8, 6 μm in order from the mining time of 5 min. A 50% particle diameter of 42 μm is taken as Example 1, a 50% particle diameter of 19 μm is taken as Example 2, and a 50% particle diameter of 16 μm is taken as Example 3. Further, the 50% particle size of 8 μm is set as Comparative Example 1, the 50% particle size of 6 μm is set as Comparative Example 2, and the case where grinding is not performed is set as Comparative Example 3.

In the above flotation process, 150 g of ore concentrate and a collector butyl xanthate corresponding to 500 ppm are added to a solution adjusted to pH 12.5 using Ca (OH) ₂ as a pH adjuster, for 30 minutes. After conditioning, 20 μl (microliter) of MIBC as a foaming agent was added to the above solution, and air bubbles were generated in an agitaire type flotation machine. After the start of the treatment, the particles adhering to the bubbles and rising were collected and used as a flotation concentrate. Then, 100 ppm of BX was added, the flotation concentrate was collected each time, and finally BX was added to 1000 ppm. Table 1 shows the results of the flotation tailings at each grinding time when BX was added up to 1000 ppm. FIG. 10 shows the results of the Cu quality and the Cu recovery rate of the flotation concentrate up to each BX addition amount with BX added from 500 ppm to 1000 ppm.

  As shown in FIG. 10, the flotation concentrate with higher Cu quality than the sulfide conversion particles was recovered at any grinding particle size. In addition, the Cu grade of the flotation concentrate is improved by reducing the grinding particle size. This is because the copper particle (CuS) that is separated as a single substance increases as the grain size of the ore is reduced. However, as shown in Table 1, when the 50% particle size of the milling particles was less than 15 μm, the Cu grade of the flotation tailing was high and higher than the slag generated by copper smelting. In addition, the Cu recovery rate of the flotation tailings was higher than that in the condition where the 50% particle size of the milling particles was 15 to 50 μm. It can be seen that when the 50% particle size of the milling particles is less than 15 μm, the Cu loss to the flotation tailings increases. On the other hand, flotation tailings with 50% particle size of 15-50 μm of milling particles have low Cu quality and Cu recovery rate, and the Cu recovery rate is less than 1%. From the above, it can be seen that the Fe concentrated tailings can be efficiently and economically removed from the copper concentrate while suppressing Cu loss.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and changes can be made within the scope of the gist of the present invention described in the claims. It can be changed.

Claims (9)

Sulfur conversion in which sulfur is added to a copper concentrate containing chalcopyrite (CuFeS ₂ ) in a molar ratio of 1.0 to 1.2 with respect to the copper in the copper concentrate, and the copper concentrate is sulfided. Process,
A grinding step of grinding the sulfide-converted particles obtained by the sulfide conversion step so that the 50% particle diameter is 15 μm to 50 μm;
A separation step of separating the fine particles obtained by the grinding step into a flotation concentrate having a high Cu grade and a flotation tailing having a low Cu grade by performing a flotation process. A processing method for copper concentrate.   The method for treating copper concentrate according to claim 1, wherein the sulfidation conversion step is performed at 300 ° C. to 450 ° C.   2. The copper concentrate processing method according to claim 1, wherein a wet pulverizer or a dry pulverizer is used in the grinding step.   The processing method of the copper concentrate in any one of Claims 1-3 using a xanthate type | system | group collection agent as a collection agent in the said floatation process.   The copper concentrate according to any one of claims 1 to 4, wherein in the flotation process, the amount of the collection agent added is in a range of 100 to 2000 ppm with respect to the concentrate to be subjected to the flotation process. Processing method.   In the said flotation process, the pH of the solution containing the concentrate used for a flotation process is maintained in the range of 9-13, The processing method of the copper concentrate in any one of Claims 1-5 characterized by the above-mentioned.   In the said flotation process, methyl isobutyl carbinol or a pine oil is used as a foaming agent, The processing method of the copper concentrate in any one of Claims 1-6 characterized by the above-mentioned.   The copper according to any one of claims 1 to 7, wherein in the flotation process, an air supply type flotation machine, an air suction type flotation machine, a mechanical stirring type flotation machine, or a combination thereof is used. Concentrate processing method.   The method for processing a copper concentrate according to any one of claims 1 to 8, wherein the floating concentrate having a high Cu quality obtained in the separation step is subjected to a flotation process again.

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