KR101218043B1 - Separation and refining method of pure material in alloy using centrifugation and manufactured pure material using the same - Google Patents

Abstract

The present invention comprises the steps of preparing a molten alloy by melting an alloy including a first component, air cooling the molten metal to a temperature at which the first component forms a primary, and when the first component forms a primary, the molten metal It relates to a method for separating the pure material in the alloy and the alloy refining method using centrifugation comprising the step of centrifugation, and each step of collecting the first component and the remaining components through the centrifugation.

Description

Separation and refining method of pure material in alloy using centrifugation and pure material manufactured using same

The present invention relates to a pure material separation method and an alloy refining method in the alloy using centrifugation to separate the material forming the primary in the alloy by centrifugation and a pure material produced using the same.

Since alloys are generally metal compounds containing two or more elements, it is difficult to separate one material from the alloy. As a conventional method used to separate an alloy, a method of dissolving only a certain element in an alloy using a chemical solvent that reacts with a certain element, or a method of burning out a certain element of an alloy element and taking the remaining material is used. It also became. However, these methods have a problem that the process is complicated, a metal other than the desired material should be discarded, and the separation efficiency is low.

As another method, a method of centrifugation using a specific gravity difference between materials constituting the alloy has been used. In this regard, Korean Patent No. 0182230 (hereinafter referred to as “Prior Art 1”) describes an apparatus and a method for separating and purifying pure metals and gradient alloys using centrifugal force. The prior art 1 relates to a method of melting an alloy in a heating furnace, followed by centrifugation for about 1 hour, and then separating it by the specific gravity difference of each metal forming an alloy by applying centrifugal force to the molten alloy. In the prior art 1, the centrifugal separation is performed in one separator tube according to the specific gravity difference of each metal constituting the alloy. In this part, low specific gravity metals are collected. Therefore, not only is it necessary to separate one material from the alloy, but it is also difficult to completely separate only one pure material from the alloy.

In addition, Japanese Patent No. 2636162 (hereinafter referred to as "Prior Art 2") describes a method of deironing an aluminum alloy material. Prior art 2 melts an aluminum alloy material having a high iron content and centrifugs it to separate components containing high specific gravity iron on the outer wall of the centrifuge, and the remaining components from which iron is separated are moved from the inside of the centrifuge to the outside through the bottom. The present invention relates to a method of lowering the iron component in the aluminum alloy material discharged. The prior art 2 is to perform the iron removal in the aluminum alloy by using the specific gravity difference of the metal elements constituting the alloy, it can not be used for separation between metals with similar specific gravity, and because only one pure material is separated in the non-solidified state, high purity Difficult to obtain separately.

It is an object of the present invention to provide a method for separating pure substances in an alloy using centrifugal separation that can separate pure substances forming primary crystals with high purity even when the difference in specific gravity between elements constituting the alloy is small. In addition, by separating the pure material in the alloy, it is possible to recycle the alloy scrap, to provide a pure material in the alloy separation method using a centrifugal separation that can separate the pure material in the metal in a short time using a simple process. In addition, to provide an alloy refining method that can further improve the purity of the components obtained after the alloy separation than the purity of the components added to the alloy prior to alloy production.

In accordance with an embodiment of the present invention for realizing the above object, the method for separating pure substances in an alloy using a centrifugal separation comprises: melting an alloy including a first component to prepare a molten metal, and the first component forms a primary tablet Air-cooling the molten metal to a temperature to which the first component forms a primary phase, and centrifuging the molten metal, and collecting the first component and the remaining components through the centrifugation, respectively. have.

The said 1st component can be characterized by being a substance which forms primary crystal in needle shape or plate shape, without forming an intermetallic compound.

The first component may be at least one selected from silicon, iron, titanium, and copper.

The alloy may be characterized in that the remaining components other than the first component is at least one selected from aluminum, magnesium, iron, and copper.

The alloy may be characterized in that the aluminum-silicon alloy.

The temperature at which the first component forms the primary tablet may be characterized in that it is between the temperature along the liquidus line and the temperature along the solidus line in the state diagram of the alloy.

In the step of centrifugation, the gravity acceleration (g) value according to the number of revolutions for the centrifugation may be characterized in that 35g ~ 1250g.

In the centrifugation step, the first component may be separated in the form of a foam.

The centrifuged first component may be further washed with an acid solution to remove other components fused to the first component.

In the step of washing the first component with an acid solution, the first component may be separated into flakes.

In the centrifugation step, the centrifugation time may be characterized in that less than 10 minutes.

The centrifugation may be characterized in that the first component is separated from the other components, and the first component and the other components are collected in separate spaces.

Alloy refining method using a centrifugal separation according to an embodiment of the present invention for realizing the above object is to melt the alloy containing a first component to produce a molten metal, the temperature at which the first component forms a primary The step of air-cooling the molten metal, and if the first component forms a primary may comprise the step of centrifuging the molten metal, and collecting the first component and the remaining components through the centrifugation.

The purity of the first component after the centrifugation may be higher than that of the first component before the centrifugation.

It can be characterized by a pure material consisting of a first component prepared by the alloy refining method using a centrifugal separation in accordance with an embodiment of the present invention for realizing the above object.

Alloy refining method using a centrifugal separation according to an embodiment of the present invention for realizing the above object is to melt the alloy containing a first component to produce a molten metal, the temperature at which the first component forms a primary The step of air-cooling the molten metal, and if the first component forms a primary may comprise the step of centrifuging the molten metal, and collecting the first component and the remaining components through the centrifugation.

The purity of the first component after the centrifugation may be higher than that of the first component before the centrifugation.

According to the method for separating pure materials in an alloy using centrifugal separation according to the present invention configured as described above, there is an effect of separating pure materials in an alloy even when the specific gravity difference between elements constituting the alloy is small. In addition, since the pure material forming the primary in the alloy is separated by high purity by centrifugal separation, it is possible to recover and recycle the material in the alloy discarded as scrap metal, there is an effect that can separate the high purity pure material in a short time by a simple process. In addition, there is an effect that can further improve the purity of the components obtained after the alloy separation than the purity of the components added in the alloy prior to alloy production.

1 is a flowchart illustrating a method of separating pure materials in an alloy and a method for refining an alloy using centrifugal separation according to an embodiment of the present invention.
2 is a state diagram of an aluminum-silicon alloy.
Figure 3 is a photograph of the primary silicon foam taken after the centrifugation is completed according to an embodiment of the present invention.
4 is a photograph of a portion composed of components except the primary silicon foam of FIG. 3.
FIG. 5 is a photograph of silicon flakes obtained after washing the primary silicone foam of FIG. 3 with an acid. FIG.
6 is a graph showing the silicon separation yield according to the acceleration of gravity by the centrifugal rotation speed in accordance with an embodiment of the present invention.
FIG. 7 is an optical micrograph showing an internal crystal of the primary silicon foam of FIG. 3.
8 is an EDS mapping photograph before and after acid leaching primary silicon foam.
FIG. 9 is a graph illustrating the results of X-ray diffraction (XRD) component analysis of the silicon flake of FIG. 5.
FIG. 10 is a graph showing the final yield of silicon flakes of FIG. 5 according to gravity acceleration by centrifugal rotation speed.

Hereinafter, a method for separating pure substances in an alloy and an alloy refining method using centrifugal separation according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. In the present specification, the same or similar reference numerals are given to different embodiments in the same or similar configurations.

1 is a flowchart illustrating a method of separating pure materials in an alloy and a method for refining an alloy using centrifugal separation according to an embodiment of the present invention. Referring to the drawings, first, an alloy containing the first component is melted to prepare an alloy molten metal (S10). In this case, the alloy may include various components in addition to the first component. The alloy is charged into an induction furnace or the like and heated above the melting point to produce a molten liquid.

The 1st component of the components which comprise an alloy is a substance which forms primary crystals in needle shape or plate shape, without forming an intermetallic compound in the process of cooling a molten metal. Specifically, the first component may be silicon, iron, titanium, copper, and at least one selected from these components. In addition, the remaining components except the first component of the components constituting the alloy may be aluminum, magnesium, iron, copper, may be at least one selected from these components.

The molten alloy of the alloy thus produced is air cooled to a temperature at which the first component contained in the alloy forms primary crystals (S20). The temperature at which the first component forms the primary is the temperature at which the first component contained in the alloy forms the primary is between the temperature at which the liquidus line and the temperature at the solidus line are in the state diagram of the alloy. Since the temperature at which the first component forms the primary tablet varies in state depending on the type of the alloy, the temperature for air-cooling the molten metal may also vary according to the type of the alloy.

When the molten metal is cooled by air to form a primary, centrifugal force is applied to the molten metal to centrifuge the components constituting the molten metal (S30). Gravity acceleration g value according to the number of revolutions of the centrifuge for centrifugation may be 35 ~ 1250. When the gravity acceleration is less than 35g, the centrifugal force separating the first component forming the primary tablet from other components may be weak, and thus the yield of separating the first component may be reduced. In addition, when the gravity acceleration exceeds 1250g, the centrifugal force acts excessively, and the first component and the other components, which form the primary, move together, which may cause a problem in that separation efficiency is lowered.

When centrifuging the molten metal, the first component entering the primary forming temperature section solidifies as a solid before the other components, forming crystals with the primary. Therefore, a space for collecting the first component and a space for collecting the remaining components except the first component may be separately configured to separate the remaining components except the first component. Specifically, when the molten metal is put into a predetermined space and a centrifugal force is applied, the first component solidified as a solid remains inside the centrifuge, and the first component separated from the first component by centrifugal force exits the liquid to the outside of the centrifuge. Other components can be collected. In this way, the first component and the other components except for the same are collected in separate forms, respectively (S40).

Centrifugation by applying centrifugal force to the molten metal may be within 10 minutes. When the centrifugation time exceeds 10 minutes, the first component may be fused to the other components to escape to the outside of the centrifuge, so that the centrifugation time may be within 10 minutes.

When the melt is centrifuged to separate the first component from the other components, the first component collected as a solid is separated in the form of a foam. Since the first component is a substance that forms crystals in the form of needles or plates when forming the primary tablet, and when the first component is separated from the solid by solidification by centrifugation, it is in the form of such a crystal in the form of a foam having a space between the crystals. Can be solidified. The other components separated from the first component are solidified during centrifugation and after centrifugation to be collected in the form of a solid mass in a separate space.

The surface of the first component taken in the form of a foam may remain other components that are fused with the first component and are not completely separated. Therefore, in order to further improve the purity of the first component obtained in the form of a foam, it is possible to wash the first component obtained in the form of a foam using an acid solution. By this acid washing, other components that have been fused to the first component may be dissolved and removed. The acid wash may be any method as long as it can selectively dissolve only the other components except the first component, such as a method of leaching in an acid solution. The acid solution may be any acid solution of any kind as long as it can dissolve other components except the first component such as hydrochloric acid, sulfuric acid, nitric acid, or a mixture of one or more of these acids. As shown in FIG. 5, after washing the first component in foam form with acid, the first component may be separated and collected in a flake form. In this case, the first component obtained in the form of flakes may have a purity of 99.9% or more.

≪ Example 1 >

Hereinafter, Embodiment 1 of the present invention will be described in detail with reference to FIGS. 2 to 10. The alloy of Example 1 is an aluminum-silicon alloy, and in detail, an aluminum -50 wt% silicon hypereutectic alloy is used. The alloy is heated in an induction furnace to prepare a molten metal, which is then centrifuged. At this time, the centrifugation time was within about 1 minute. In this alloy, the molten metal is air-cooled, and the component that forms the primary crystal is silicon, wherein the silicon particles crystallize into needles to form the primary crystal. As shown in the photo of Fig. 3, the primary silicon foam is collected when the centrifugation is completed. Components including aluminum and other components except the primary silicon foam are obtained in the form of solid lumps, the shape of which is illustrated in FIG. 4. In addition, the silicon flakes obtained after washing the primary silicone foam of FIG. 3 with an acid are as shown in the photograph of FIG. 5. In this Example 1, the gravitational acceleration according to the centrifugal rotation speed was set to about 32g, 40g, 57g, 72g, and the experiments were carried out according to the respective rotational speeds.

Referring to the state diagram of the aluminum-silicon alloy of FIG. 2, both aluminum and silicon exist as liquids at temperatures above the liquidus line, and when the aluminum-silicon alloy is dissolved and then cooled, the silicon first forms a solid crystal and solidifies at 577 ° C. or less. It can be seen that aluminum solidifies. Therefore, in the case of the aluminum-silicon alloy, the molten metal can be air cooled to a temperature within 577 ° C to 1414 ° C. In Example 1, aluminum--50 wt% silicon hypereutectic alloy was used. In this case, the solid phase rate of primary silicon was 24% based on the state diagram. Thus, when silicon was completely separated from the alloy, 24% of the silicon was obtained. It can be said that the ground is completely recovered. Referring to FIG. 6, when the gravity acceleration is 32 g according to the centrifugal rotation speed, the separation yield of silicon is about 75%. From these results, it can be seen that in the acceleration of gravity of 32 g, aluminum remains on the surface of the primary silicon or inside the microcracks of the primary silicon without being effectively separated. However, as the gravitational acceleration increases to about 40g, 57g, and 72g, the silicon separation yield is lowered to about 43%, 37%, and 35%, approaching the solid phase rate of primary silicon, which is close to 24%. The gravitational acceleration g value should be more than 32g to increase the silicon separation efficiency.

The result of observing the internal crystal form of the primary silicon foam obtained in Example 1 through an optical microscope is shown in FIG. 7. 7 (a) is a photograph when the gravity acceleration is about 32g, (b) is a photograph when the gravity acceleration is about 40g. In Fig. 7, the needle of black acicular crystal is silicon, and the blue part surrounding the silicon crystal is aluminum. Figure 7 (a) is a photograph when the gravity acceleration is about 32g, (b) is a photograph when the gravity acceleration is about 40g. As shown in FIG. 7, when the gravity acceleration is 32g, a large amount of aluminum is present around the silicon crystal, and thus the silicon separation yield is not good. When the gravity acceleration is about 40g, the gravity acceleration is about 32g, It can be seen that a large amount of aluminum component was separated around the silicon crystal. However, the primary silicon foam was acid leached with aqua regia because some aluminum components remained adhered to the silicon crystals.

8 is an EDS mapping photograph before and after acid leaching primary silicon foam. (A) is a photograph of the primary silicon foam before acid leaching, (b) is a photograph of the primary silicon foam after acid leaching. Referring to the results of FIG. 8, before acid leaching the primary silicon foam, silicon and aluminum are mixed, but after acid leaching, the aluminum component almost disappears and only the silicon component remains. After acid leaching, the silicone foam is taken in the form of silicone flakes.

Figure 9 shows the results of XRD (X-ray Diffraction) component analysis of the obtained silicon flakes after acid leaching, it can be seen that a clear silicon peak appears after acid leaching. 10 is a graph showing the final yield of primary silicon flakes after acid leaching. The final yield of primary silicon flakes is expressed as a percentage after dividing the weight of the final primary silicon flakes obtained by the initial charge weight. As a result, when the gravity acceleration is about 32g, the yield of 37% was found to be higher than the theoretical silicon solidity rate of 24% according to the state diagram, but as the acceleration of gravity increases, the value of the solid state calculated according to the state diagram approaches. Can be. When the gravity acceleration is about 72g, it can be seen that the final silicon yield is about 25%, which is almost identical to the calculated silicon solidity 24% according to the state diagram.

The purity of the final silicon flakes completed up to the acid leaching treatment is shown in Table 1 below.

gravitational acceleration (g)
Elements (ppm)
Purity
(wt%)

Purity except Al (wt%)
Al Ca Cr Cu Fe Mg Mn Mo Ni Ti V Zn 40 1822 9 0 34 18 One 0 124 8 One <.0000 One 99.798226 99.980383 57 2698 23 One 20 23 3 0 9 7 One <.0000 One 99.721418 99.991177 72 1191 4 One 7 20 0 0 0 2 One <.0000 One 99.877283 99.996386

In Table 1, Purity is the purity measured before acid leaching primary silicon foam, and Purity except Al is the result of measuring the purity of silicon flakes obtained after acid leaching primary silicon products. As shown in Table 1, when the gravity acceleration according to the rotational speed of the centrifugation in this Example 1 is about 40g, the purity of the final silicon flakes finally obtained is more than 99.98%, and the final product is the primary silicon as the gravity acceleration increases. It can be seen that the purity of the flakes is also improved. In the case of gravitational acceleration of about 72g according to the centrifugal rotation speed, the purity of primary silicon flakes, which is the final product, is 99.996386%, which is 99.99% or more. In addition, in the final silicon flakes, the final product, except for silicon, aluminum was the most abundant, but as the acceleration of gravity increased, the amount of aluminum was decreased, and the amount of aluminum at this time was also 1000-3000 ppm. Can be.

<Example 2>

The alloy of Example 2 is an aluminum-silicon alloy, and in detail, an aluminum -50 wt% silicon hypereutectic alloy is used. The alloy is heated in an induction furnace to prepare a molten metal, which is then centrifuged. At this time, the centrifugation time was within about 1 minute. In this alloy, the molten metal is air-cooled, and the component that forms the primary crystal is silicon, wherein the silicon particles crystallize into needles to form the primary crystal. As in Example 1, the primary silicon foam is collected when the centrifugation is completed. The collected primary silicone foam can be washed with acid and finally silicon flakes can be obtained. In Example 2, the gravity acceleration according to the centrifugal rotation speed was set to about 72g.

The purity of the silicon added during centrifugation of the alloy, that is, during alloy preparation, was measured, and the purity of the finally obtained silicon flakes after centrifugation of the alloy was measured and compared.

Component (ppm)
silicon
water
(wt%)
Ba Cr Cu Fe Mg Ni Ti Zn Before centrifugation One 15 23 54 3 6 40 <.0002 99.9854863 After centrifugation One <.0000 23 <.0000 <.0000 7 <.0002 <.0000 99.9953579

Referring to Table 2, the purity of the silicon added to the alloy before centrifuging the alloy was 99.9854863, but after centrifuging and refining the alloy, the purity of the obtained silicon flakes was 99.9953579 and the final product had a purity of 99.99. It can be seen that the increase to more than%. These results indicate that the components forming the primary tablet in the alloy by centrifuging the alloy are refined with high purity.

As described above, the method for separating pure substances in the alloy using centrifugation has the effect of separating the pure substances in the alloy even when the specific gravity difference between the elements constituting the alloy is small, and also by centrifuging the pure substances forming the crystal in the alloy. Since it is separated into high purity, there is an effect that can recover and recycle the material in the alloy discarded as scrap. In addition, there is an effect that can be separated from the pure material of high purity in a short time by a simple process. In addition, it can be seen that the use of centrifugation can effect the refining of components in the alloy with high purity.

The pure material separation method and alloy refining method in the alloy using the centrifugation as described above is not limited to the configuration and operation of the embodiments described above. The embodiments may be configured so that all or some of the embodiments may be selectively combined so that various modifications may be made.

Claims (15)

Melting the alloy containing the first component to prepare a molten metal;
Air cooling the molten metal to a temperature at which the first component forms a primary tablet;
Centrifuging the molten metal when the first component forms a primary tablet;
Through the centrifugation, separating the components other than the first component to the outside of the centrifuge, and collecting the first component of higher purity than before centrifugation inside the centrifuge; And
And washing the first component in the form of a centrifuged foam with an acid solution to remove other components fused to the surface of the first component.
The first component is a material in which primary crystals are formed in a needle or plate shape without forming an intermetallic compound, and is any one selected from silicon, iron, titanium, and copper.
delete delete The method according to claim 1,
Wherein the alloy, the remaining components other than the first component is characterized in that at least one selected from aluminum, magnesium, iron, copper, centrifugation separation method using pure substances in the alloy.
The method according to claim 1,
The alloy is characterized in that the aluminum-silicon alloy, the pure material separation method in the alloy using centrifugation.
The method according to claim 1,
The temperature at which the first component forms the primary,
In the state diagram of the alloy is characterized in that between the temperature followed by the liquidus line and the temperature along the solidus line, using a centrifugal separation method.
The method according to claim 1,
In the centrifugation step,
Gravity acceleration (g) value according to the number of revolutions for the centrifugation is characterized in that 35g ~ 1250g, separation method of pure material in the alloy using centrifugation.
delete delete The method according to claim 1,
In the step of washing the acid solution of the first component,
The first component is characterized in that the separation in the form of a flake (flake), the pure material separation method in the alloy using centrifugation.
The method according to claim 1,
In the centrifugation step,
The centrifugation time is within 10 minutes, characterized in that the separation of pure material in the alloy using centrifugation.
delete delete Melting the alloy containing the first component to prepare a molten metal;
Air cooling the molten metal to a temperature at which the first component forms a primary tablet;
Centrifuging the molten metal when the first component forms a primary tablet;
Through the centrifugation, separating the components other than the first component to the outside of the centrifuge, and collecting the first component of higher purity than before centrifugation inside the centrifuge; And
And washing the first component in the form of a centrifuged foam with an acid solution to remove other components fused to the surface of the first component.
The first component is a material in which primary crystals are formed in a needle or plate shape without forming an intermetallic compound, and is any one selected from silicon, iron, titanium, and copper,
Component except for the first component is one or more selected from aluminum, magnesium, iron and copper, alloy refining method using centrifugation.
delete

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