KR102444771B1 - Preparation method of niobium metal or niobium alloy using the magnesium vapor - Google Patents

Abstract

The present invention relates to a method for producing niobium metal or a niobium alloy using magnesium vapor, and more particularly, to a method of reducing niobium oxide or niobium complex oxide by contacting it with magnesium vapor, wherein the reducing step is at a first temperature A first step of reducing while raising the temperature to a second temperature in; and a second step of reducing at the second temperature, wherein the first temperature is 700°C to 875°C, and the second temperature is 900°C to 975°C, niobium metal or niobium alloy using magnesium vapor. It relates to a manufacturing method.

Description

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a method for producing niobium or a niobium alloy using magnesium vapor.

Most of the niobium (Nb) is contained together with tantalum in the ores, and the collected ore is crushed and concentrated through flotation and strong magnetic beneficiation, and then other mineral components are removed through chemical treatment to remove niobium pentoxide (Nb ₂ O ₅ ). ) and a mixture of tantalum pentoxide (Ta ₂ O ₅ ) is obtained, and it is separated and recovered in the form of niobium pentoxide (Nb ₂ O ₅ ). Metal niobium (Nb) is obtained by reducing such niobium oxide or niobium complex oxide such as niobium pentoxide.

The main use of niobium (Nb) is to be added as an alloying agent in steel production, about 80% or more is produced in the form of ferroniobium (FeNb). Ferroniobium (FeNb) is an alloy of iron and niobium and contains about 60 to 70% of niobium, and is usually obtained by reducing iron oxide and niobium oxide or a complex oxide of niobium complex oxide to aluminum at high temperature.

In addition, niobium (Nb) forms an Nb-Ni alloy with a composition ratio of about 65%-35% with nickel, so Inconel alloys widely used in industry (especially, Inconel 718 series: contains about 3 to 4% of niobium) ) is used to prepare the master alloy for manufacturing

As a method of manufacturing such a niobium alloy (Nb alloy), niobium metal scrap and other metal scrap such as iron and nickel are directly melted in an oxygen-free vacuum atmosphere, and nickel (Ni), iron (Fe), etc. for niobium oxide and alloy There are known methods for reducing metal oxide of metal oxide by using a reducing agent, but among them, it is difficult to secure niobium scrap, so the latter reduction process that can use substantially inexpensive niobium oxide or niobium composite oxide is being commercialized.

However, since niobium oxide is a non-reducing oxide such as oxides containing tantalum (Ta), niobium (Nb), titanium (Ti), zirconium (Zr), vanadium (V), hafnium (Hf), and the like, reduction from hydrogen is not possible. It is difficult to reduce using metals such as aluminum (Al), magnesium (Mg), and calcium (Ca) as a reducing agent. However, more measures are needed to improve this.

As a method of manufacturing a niobium-nickel alloy using an aluminum (Al) reducing agent, a niobium-nickel alloy by uniformly mixing niobium oxide and nickel oxide with aluminum (Al) powder and then explosively reducing it with an igniter. and Al ₂ O ₃ Al-Thermite method of separating the niobium-nickel alloy from the Al ₂ O ₃ slag after manufacturing has been known.

The above method has an advantage in that it is possible to increase the production efficiency due to the high reducibility of the aluminum (Al) reducing agent, while the relatively expensive aluminum (Al) powder is used as the reducing agent, and the aluminum (Al) component is added to the niobium alloy. There are disadvantages such as contamination by more than several% and the metal oxides used as raw materials in Al ₂ O ₃ slag are mixed and consumed, so that the recovery rate of the niobium alloy is low at about 50 to 70% level.

On the other hand, when magnesium (Mg) is used as a reducing agent, the melting point of magnesium (Mg) is relatively low at 650 ° C. It has an advantage over the case of using an aluminum (Al) reducing agent in that it can recover niobium and niobium oxide or niobium composite oxide in a higher yield.

As a related art, Korean Patent Laid-Open No. 10-2001-92260 discloses a method for reducing tantalum or niobium using magnesium (Mg), and in detail, niobium pentoxide (Nb ₂ O ₅ ) and pentoxide After dropping or stacking a metal oxide such as tantalum (Ta ₂ O ₅ ), magnesium is separately supplied as a vapor vaporized at a high temperature from the outside, and the magnesium vapor reacts with the metal oxide to reduce the metal oxide to produce a metal powder. has been manufactured

However, in this method, excess magnesium is supplied in order to perform complete reduction, and thus excess magnesium remaining after the reaction is removed through chemical treatment, so there is a problem in that magnesium is consumed unnecessarily.

In order to solve this problem, Korean Patent No. 10-1476308 discloses an apparatus for reducing metal oxide by contacting a metal oxide with magnesium vapor and a method for reducing metal oxide using the same, in detail, A reduction apparatus for a metal oxide capable of providing a magnesium reducing agent only as much as the reaction amount with which magnesium reacts by deriving a reaction amount, thereby preventing the problem of excessive magnesium consumption during the reaction, and a reduction method using the same have been disclosed.

On the other hand, the vaporization activity of magnesium (Mg) vapor rapidly increases as the temperature rises, and as a result, it does not participate in the reaction and exits the reaction vessel or is condensed in the cooling unit, etc. Due to this, a larger amount of magnesium must be used, and it is difficult for the reduction reaction to be stably maintained for a long time and it takes more time for the reduction to be completed. No method for reducing magnesium loss to increase reaction participation has been disclosed.

Accordingly, the present inventors, as a method of manufacturing niobium metal or niobium alloy using magnesium vapor, control the heat treatment conditions in the reducing step to prevent loss of magnesium vapor during the reaction, thereby preventing loss of magnesium vapor from participating in the reduction reaction. By reducing the amount of magnesium, niobium metal or niobium alloy can be effectively manufactured in a smaller amount and in a shorter time, and ultimately, a method for increasing manufacturing efficiency has been found and the present invention has been completed.

Republic of Korea Patent Publication No. 10-2001-92260 Republic of Korea Patent Registration No. 10-1476308

An object of one aspect is to provide a method for preparing niobium metal or niobium alloy by reducing niobium oxide or niobium complex oxide with magnesium vapor.

In order to achieve the above object,

in one aspect

A method for producing niobium metal or a niobium alloy by reducing niobium oxide or niobium complex oxide with magnesium vapor, the method comprising:

reducing the niobium oxide or niobium complex oxide by contacting it with magnesium vapor;

The reducing step is

A first step of reducing while raising the temperature from the first temperature to the second temperature; and

a second step of reducing at the second temperature;

The first temperature is 700°C to 875°C, and the second temperature is 900°C to 975°C, a method for producing niobium metal or a niobium alloy using magnesium vapor is provided.

The first step may be reduced while raising the temperature from the first temperature to the second temperature for 15 to 30 hours.

The first step may be reduced while raising the temperature from the first temperature to the second temperature at a temperature increase rate of 1 ℃ / h to 10 ℃ / h.

The first temperature may be a temperature of 825 °C to 875 °C.

The reducing at the second temperature may be performed for 1 to 10 hours.

The method for producing the niobium metal or niobium alloy,

It may further include; removing impurities including magnesium oxide (MgO) from the product obtained by the reducing step.

The impurities may be removed by an acid treatment process.

In addition, the niobium composite oxide is nickel (Ni), iron (Fe), tantalum (Ta), niobium (Nb), titanium (Ti), zirconium (Zr), vanadium (V), hafnium (Hf), scandium (Sc) ) and one or more metals selected from yttrium (Y) may be further included.

The niobium composite oxide may be prepared by mixing and sintering niobium oxide and a metal oxide other than niobium.

The sintering may be performed at a temperature of 1000°C to 1500°C.

In the method for producing niobium metal or niobium alloy using magnesium vapor provided in one aspect, the temperature is gradually increased when niobium oxide or niobium complex oxide is reduced by magnesium vapor, whereby magnesium vapor during the reduction reaction is generated on the inner wall of a reaction vessel, etc. Condensation or discharge to the outside of the reaction vessel can be solved.

Accordingly, the loss of magnesium can be reduced, and the reduction rate of niobium oxide or niobium composite oxide can be increased to increase the recovery rate of niobium metal, and the reduction reaction can be completed in a shorter time, thereby improving production efficiency.

In addition, it is possible to prevent the risk of explosion in which magnesium condensed on the inner wall of the reaction vessel reacts rapidly when it comes into contact with air at room temperature.

In addition, it can be manufactured at a low temperature and low cost compared to the conventional method using an aluminum (Al) reducing agent, and the manufacturing efficiency of niobium metal or niobium alloy can be improved.

1 is a diagram schematically showing a time-temperature graph in the reduction step of a method for manufacturing niobium metal or niobium alloy using magnesium vapor according to one aspect;
Figure 2 is a schematic diagram showing the result of performing a method for producing niobium according to an aspect using an exemplary reducing device,
3 is a diagram schematically illustrating the problem of the reduction process using the conventional magnesium vapor,
4 is a view schematically showing a time-temperature graph in the reduction step during the manufacturing step of the niobium alloy according to Example 1,
5 is a view schematically showing a time-temperature graph in the reduction step during the manufacturing step of the niobium alloy according to Example 2;
6 is a view schematically showing a time-temperature graph in the reduction step during the manufacturing step of the niobium alloy according to Example 3;
7 is a diagram schematically illustrating a time-temperature graph in a reduction step during a manufacturing step of a niobium alloy according to Comparative Example 1. Referring to FIG.

Hereinafter, embodiments of the present invention will be described in detail.

The following examples are only provided to more completely explain the present invention to those with average knowledge in the art, and the scope of the present invention is not limited to the examples described below, but various modifications can be

Furthermore, "including" a certain element throughout the specification means that other elements may be further included, rather than excluding other elements, unless otherwise stated.

in one aspect

A method for producing niobium metal or a niobium alloy by reducing niobium oxide or niobium complex oxide with magnesium vapor, the method comprising:

reducing the niobium oxide or niobium complex oxide by contacting it with magnesium vapor;

The reducing step is

A first step of reducing while raising the temperature from the first temperature to the second temperature; and

a second step of reducing at the second temperature;

The first temperature is 700°C to 875°C, and the second temperature is 900°C to 975°C, a method for producing niobium metal or a niobium alloy using magnesium vapor is provided.

Hereinafter, a method of manufacturing a niobium metal or a niobium alloy using magnesium vapor provided according to an aspect will be described in detail for each step with reference to the drawings.

1 is a diagram schematically showing a time-temperature graph in a reduction reaction of a method for producing niobium metal or a niobium alloy using magnesium vapor provided according to an aspect, and FIG. 2 is an exemplary production in which the method can be performed. It is a schematic diagram showing the device.

The niobium oxide may be reduced to niobium by being contacted with the magnesium vapor, and the niobium composite oxide may be reduced to a niobium alloy (Nb-Metal) by being contacted with the magnesium vapor.

The method for producing niobium metal or niobium alloy using magnesium vapor provided according to an aspect is a method for preparing niobium metal or niobium alloy by reducing niobium oxide or niobium complex oxide with magnesium vapor, wherein niobium oxide or niobium complex oxide and reducing by contact with steam.

In this case, the niobium oxide used is NbO, Nb ₂ O ₃ , NbO ₂ or Nb ₂ O ₅ It may include one or more of oxides having various oxygen numbers such as, and preferably, Nb ₂ O ₅ in the most stable state. For example, as shown in Scheme 1 below, niobium may be prepared by reducing the Nb ₂ O ₅ using magnesium (Mg) vapor.

<Scheme 1>

Nb ₂ O ₅ + 5Mg = 2Nb + 5MgO

In addition, the niobium composite oxide may include niobium and a metal other than niobium, and as a metal other than niobium, nickel (Ni), iron (Fe), tantalum (Ta), niobium (Nb), titanium (Ti) , zirconium (Zr), vanadium (V), hafnium (Hf), scandium (Sc) and yttrium (Y) a method of manufacturing an alloy comprising at least one metal selected from the group consisting of niobium and Includes a metal other than niobium, and the metal other than niobium is nickel (Ni), iron (Fe), tantalum (Ta), niobium (Nb), titanium (Ti), zirconium (Zr), vanadium (V), hafnium It may include at least one metal selected from (Hf), scandium (Sc), and yttrium (Y).

The niobium composite oxide may be prepared by mixing and sintering niobium oxide and a metal oxide other than niobium.

The niobium oxide and the metal oxide other than the niobium may be in a powder form.

The mixing may be mixed using a mortar or the like, and may be mixed by a method of mechanical milling, but is not limited thereto, and may be performed by various methods of mixing the powder.

In addition, the sintering may be performed in an atmospheric atmosphere, may be performed at a temperature of 800 °C to 1500 °C, preferably at a temperature of 1000 °C to 1400 °C, preferably 8 hours to 12 hours It is possible to induce inter-particle diffusion of the niobium oxide and the metal oxide other than the niobium.

The reducing step of the method for manufacturing niobium metal or niobium alloy provided according to an aspect may be performed using the reducing device shown in FIG. 2 .

Referring to Figure 2, the reduction device is a reaction vessel; a niobium oxide raw material crucible provided inside the reaction vessel and loaded with niobium oxide; a magnesium melting crucible spaced apart from the niobium oxide raw material crucible and charged with a magnesium raw material; and an inert gas supply unit provided on an upper surface of the room application container; It may include a vacuum composition unit provided on the upper surface of the reaction vessel.

In the step of reducing the niobium oxide or niobium complex oxide by contacting it with magnesium (Mg) vapor, the temperature inside the reaction vessel of the reduction device of FIG. It may be carried out as a method of generating magnesium vapor from, but is not limited thereto, and magnesium vapor itself may be used.

The niobium oxide may be reduced to niobium (Nb) by being contacted with the magnesium vapor, and the niobium complex oxide may be reduced to a niobium alloy by being contacted with the magnesium vapor.

In order to completely reduce the niobium oxide or niobium complex oxide by the magnesium vapor, the amount of magnesium charged into the reaction vessel is an amount capable of reducing 100% of the niobium oxide or niobium complex oxide. it is preferable

For example, when niobium pentoxide (Nb ₂ O ₅ ) is used as niobium oxide to prepare niobium metal, the magnesium is the niobium pentoxide (Nb 2 ) in an amount sufficient to reduce the niobium pentoxide (Nb ₂ O ₅ ) by 100% _. O ₅ ) An amount of 5 moles or more per 1 mole may be charged, 5 moles to 20 moles may be charged, 10 to 20 moles may be charged, and 12 moles to 18 moles may be charged.

In addition, in order to reduce 100% of the composite metal oxide prepared by mixing 100 g of niobium pentoxide (Nb ₂ O ₅ ) and 79 g of nickel oxide (NiO) used to prepare a 53% Nb-47% Ni alloy, 70 g or more of magnesium is It may be desirable to use

Meanwhile, before heating the inside of the reaction vessel, a step of depressurizing the inside of the reaction vessel and then injecting an inert gas may be further performed. This may be to remove oxygen in the reaction vessel so that magnesium vapor generated after heating is better utilized for reduction of niobium oxide or niobium complex oxide.

The decompression may be performed through a vacuum composition unit including a vacuum processing means such as a vacuum pump provided on one surface of the upper portion of the reaction vessel, and the inert gas may be injected through an inert gas supply unit connected to the reaction vessel. In addition, the reduced pressure and the injection of the inert gas may be performed through the same configuration.

For example, after removing air in the reaction vessel by connecting a vacuum pump to the inert gas supply unit, the inert gas may be injected through the inert gas supply unit. However, the configuration of the inert gas supply unit and the vacuum composition unit is not limited thereto, and their configuration may be appropriately changed according to the manufacturing conditions of the reducing device.

The reduced pressure may be performed to form a pressure of 10 ^-1 to 10 ^-3 torr, and the inert gas is one selected from argon (Ar), nitrogen (N ₂ ), helium (He), and a mixture thereof. may be used, and the pressure inside the reaction vessel may be appropriately introduced within the range of 1 to 2 atmospheres, but is not limited thereto, and the pressure level and the inert gas used may vary depending on the conditions of use.

At this time, the reason that the pressure of the inert gas exceeds 1 atm is to block the inflow of external air as the pressure rises due to an increase in temperature during heating for the reduction of the metal oxide later. Through this, it is possible to prevent air from flowing into the reaction vessel during the reduction reaction. In addition, the pressure inside the heating furnace can be maintained at an appropriate atmospheric pressure by venting the inert gas inside the reaction vessel several times.

Referring to Figure 1, the reducing step includes a first step of reducing while raising the temperature from a first temperature to a second temperature.

In this case, the first temperature is a temperature at which the reduction reaction of the niobium oxide or the niobium complex oxide is initiated by the magnesium vapor, and may be 650° C. or higher, and preferably 700° C. to 875° C., which is a temperature at which magnesium vapor is effectively generated. It can be from 775°C to 875°C, from 800°C to 875°C, from 825°C to 875°C, from 700°C to 850°C, from 775°C to 850°C, 800 It may be from ℃ to 850 ℃, it may be from 825 ℃ to 850 ℃.

If the first temperature is less than 700 ℃, the generation of magnesium vapor is insufficient, there may be a problem that the time consumed for the reduction reaction is somewhat cut off. The amount of magnesium vapor that does not participate in the reduction reaction may be increased.

The first step may be a step for solving a problem in which magnesium vapor is condensed on the inner wall of the reaction vessel during the reduction reaction or is lost by being discharged to the outside of the reaction vessel.

3 is a schematic view to explain the problems of the reduction process using the conventional magnesium vapor. As shown in FIG. 3 in the conventional case, the magnesium vapor during the reduction reaction is partially condensed on the inner wall of the reaction vessel. In this way, magnesium condensed on the inner wall of the reaction vessel reacts rapidly with air even at room temperature, and there is a risk of explosion, so there is a problem that the magnesium condensed on the inner wall of the reaction vessel needs to be partially oxidized and stabilized before opening the reaction vessel.

On the other hand, in the method for producing niobium metal or niobium alloy using magnesium vapor, which is provided according to an aspect, by performing a first step of reducing while raising the temperature from the first temperature to the second temperature, magnesium is condensed on the inner wall of the reaction vessel or to the outside. It can be prevented from being discharged, so it is possible to solve the problem of loss of magnesium vapor without participating in the reduction of niobium oxide or niobium complex oxide. have.

If the first step is not performed, when the temperature is raised to the target temperature for reduction, magnesium vapor in the reaction vessel may be condensed on the inner wall of the reaction vessel or may be lost by escaping to the outside of the reaction vessel. Accordingly, it is possible to ultimately reduce the reduction rate of the niobium oxide or the niobium composite oxide.

Before performing the reduction reaction at the second temperature (or target temperature), the method for producing niobium metal or niobium alloy using magnesium vapor provided in one aspect is 50° C. to 300° C., preferably 100° C. than the second temperature to 250 ° C., preferably 100 ° C. to 150 ° C. By reducing while increasing the temperature from the lower first temperature to the second temperature (or target temperature), the reduction rate of niobium oxide or niobium complex oxide by increasing the participation in the reduction reaction of the magnesium vapor may be increased, and may be a method of increasing the recovery rate of the produced niobium metal.

In this case, the second temperature is a temperature at which the reduction reaction of the niobium oxide or the niobium composite oxide by the magnesium proceeds more rapidly, and may preferably be 900°C to 975°C, and more preferably 900°C to 950°C. .

If the second temperature is less than 900° C., the reduction of the niobium oxide or the niobium composite oxide may not be properly performed, or a problem may occur that it takes too much time for the reduction of the niobium oxide or the niobium composite oxide, When the second temperature exceeds 975° C., the generation rate and vaporization activity of the magnesium vapor are greatly increased, so that the contact rate with the magnesium vapor and niobium oxide is lowered, thereby making it difficult to proceed with the normal reduction reaction.

The first step may be reduced while raising the temperature from the first temperature to the second temperature for 15 hours to 30 hours, and may be reduced while raising the temperature for 20 hours to 25 hours.

If the first step is performed for less than 15 hours, a problem in that the niobium oxide cannot be completely reduced may occur, and when the first step is performed for a time exceeding 30 hours, the niobium oxide There may be a problem in that it takes too much time for the reduction of the oxide or the niobium complex oxide.

In addition, the first step may be reduced while raising the temperature from the first temperature to the second temperature at a temperature increase rate of 1 °C/h to 10 °C/h, and at a temperature increase rate of 2 °C/h to 8 °C/h , It can be reduced while heating, preferably at a temperature increase rate of 2 °C / h to 5 °C / h.

If the first step is performed at a temperature increase rate of less than 1°C/h, there may be a problem that it takes too much time for the reduction of the niobium oxide or the niobium composite oxide, and the first step is 10 If it is carried out at a temperature increase rate exceeding ℃/h, there may be a problem that the niobium oxide cannot be completely reduced.

In the method for manufacturing niobium metal or niobium alloy using magnesium vapor provided according to an aspect, the reducing step further includes a second step of reducing at the second temperature.

The second step may be performed for 1 to 10 hours, and may be performed for 2 to 8 hours. It can be carried out for 3 to 7 hours.

In the method for producing niobium metal or niobium alloy using magnesium vapor provided according to an aspect, the reducing step may be performed for 15 hours to 30 hours, and preferably for 20 to 27 hours, 22 to 25 can be done over time.

For example, the first step may be performed for 25 hours and the second step may be performed for 5 hours for a total of 30 hours, the first step may be performed for 20 hours and the second step may be performed for 5 hours for 25 hours can be done while

The method for producing niobium metal or niobium alloy using magnesium vapor provided according to an aspect may further include removing impurities including magnesium oxide (MgO) from the product obtained by the reducing step.

The impurities may further include magnesium (Mg), and the impurities may be removed by an acid treatment process.

The acid treatment process may be performed by immersing the product obtained in the reducing step in an acid solution.

For example, impurities including magnesium oxide (MgO) may be removed by immersing the product obtained in the reducing step in 1 to 10% hydrochloric acid aqueous solution.

The method for manufacturing niobium metal or niobium alloy using magnesium vapor provided according to an aspect may further include washing and drying after removing the impurities by the acid treatment.

The washing may be performed using ethanol, and the drying may be performed by a vacuum drying method, but is not limited thereto, and other conventional methods used for washing and drying an acid solution may be performed.

Hereinafter, the present invention will be described in detail through Examples and Experimental Examples.

However, the following examples and experimental examples are merely illustrative, and the present invention is not limited by the following examples.

<Example 1> Preparation of Nb-Ni alloy

Step 1: After uniformly mixing 79 g of nickel oxide (NiO) with 100 g of niobium pentoxide (Nb ₂ O ₅ ) in a turbula mixer, it was sintered at 1300° C. in the air for 10 hours to form a composite metal oxide.

Step 2: The prepared composite metal oxide was charged into the central vessel of the reaction chamber as shown in FIG. 2, and magnesium (Mg) powder as a reducing agent was charged into the central vessel of the reaction vessel so as to be separated from the composite metal oxide.

At this time, the magnesium (Mg) powder was excessively charged to about 200 g, which is about three times the theoretical weight of 70 g for 100% reduction of the composite metal oxide.

Step 3: After forming the inside of the reaction vessel in a vacuum of 10 ^-2 torr, and filling argon (Ar) gas at 1 atm pressure, as shown in FIG. 4 , the temperature was raised to 800° C. at a rate of 10° C./min, Reducing while raising the temperature for 25 hours in a temperature range of 800 °C to 950 °C, and furnace cooling after reducing at 950 °C for 5 hours to prepare a 53%Nb-47%Ni alloy.

<Example 2>

The same method as in Example 1 was performed except that step 3 of Example 1 was performed in the following manner.

Step 3: After forming the inside of the reaction vessel in a vacuum of 10 ^-2 torr, and filling argon (Ar) gas at 1 atmosphere, as shown in FIG. 5 , the temperature was raised to 850° C. at a rate of 10° C./min. , was reduced while raising the temperature for 25 hours in a temperature range of 850 ° C. to 950 ° C., followed by reduction at 950 ° C. for 5 hours, followed by furnace cooling, to prepare a 53%Nb-47%Ni alloy.

<Example 3>

The same method as in Example 1 was performed except that step 3 of Example 1 was performed in the following manner.

Step 3: After forming the inside of the reaction vessel in a vacuum of 10 ^-2 torr, and filling argon (Ar) gas at 1 atmosphere, as shown in FIG. 6 , the temperature is raised to 850° C. at a rate of 10° C./min. , was reduced while raising the temperature for 20 hours in a temperature range of 850 ° C. to 950 ° C., and then furnace cooled after reducing at 950 ° C. for 5 hours to prepare a 53%Nb-47%Ni alloy.

<Comparative Example 1> Preparation of Nb-Ni

The same method as in Example 1 was performed except that step 3 of Example 1 was performed in the following manner.

Step 3: After forming the inside of the reaction vessel in a vacuum of 10 ⁻² torr, argon (Ar) gas was filled at 1 atmosphere, and then, as in FIG. 7, the temperature was raised to 950° C. at a rate of 10° C./min. After reducing at ℃ for 30 hours and then furnace cooling, 53%Nb-47%Ni alloy was prepared.

<Experimental Example 1>

In the method of manufacturing a niobium alloy according to an aspect, the following experiment was performed to confirm whether the magnesium vapor satisfactorily participated in the reduction reaction.

The amount of magnesium required for 100% reduction of the composite metal oxide (composite metal oxide in which 100 g of niobium pentoxide (Nb ₂ O ₅ ) and 79 g of nickel oxide (NiO) is mixed and sintered) used as a raw material is 70 g, and the composite metal The theoretical weight of the product (Nb-Ni alloy + MgO) produced when the oxide is 100% reduced is 249 g in total, which is a 139% increase compared to the weight (179 g) of the composite metal oxide used as a raw material.

In Examples 1 to 3 and Comparative Example 1, in which raw metal oxide powder and magnesium were charged into the reaction vessel under the above conditions, and the heat treatment conditions during reduction were changed as shown in FIGS. 4 to 7, the product after the reduction reaction was By measuring the weight, the increase in the weight of the product relative to the weight of the composite metal oxide used as a raw material is shown in Table 1 below, and compared with the theoretical weight increase (139%) of the product achieved when it is reduced by 100%, magnesium vapor was used to check whether or not it participated well in the reduction reaction.

Weight increase after reduction reaction (%) Example 1 144.8 Example 2 141.6 Example 3 141.0 Comparative Example 1 132

As shown in Table 1, in Example 1, in the case of Comparative Example 1, which was immediately heated to 950° C. and maintained for 30 hours, the weight increase after reduction was 132%, which is somewhat insufficient compared to the theoretical value (139%). It can be seen that, despite the fact that 200 g of magnesium powder was used and a significantly larger amount than the value (70 g) required for 100% reduction of the composite metal oxide used as a raw material was used, all of the composite metal oxide could not be reduced, It can be expected that this is because some of the magnesium vapor generated by the vaporization of the magnesium powder is not used in the composite metal oxide and is lost.

On the other hand, in the case of Example 1, the total reduction time was adjusted to 30 hours as in Comparative Example 1 by heating at a low rate of heating from 800°C to 950°C for 25 hours, and maintaining at 950°C for 5 hours, and the weight increase after reduction was about 145 % was increased from the theoretical value (139%), and through this, it can be expected that all of the composite metal oxides were well reduced to form a niobium-nickel alloy. In addition, it can be expected that the increase in measured weight is greater than the increase in theoretical weight because some excess magnesium (Mg) is additionally adsorbed.

In addition, in the case of Example 2, the temperature was raised at a low speed from 850 ° C. to 950 ° C. for 25 hours and maintained at 950 ° C. for 5 hours to adjust the total reduction time to 30 hours as in Comparative Example 1, and the weight increase after reduction was about It was increased to 142% from the theoretical value (139%), and through this, it can be expected that all of the composite metal oxides were well reduced to form a niobium-nickel alloy.

In addition, in the case of Example 3, the total reduction time was shortened to 25 hours by heating at a low speed from 850°C to 950°C for 20 hours and maintaining it at 950°C for 5 hours. value (139%) was increased, and through this, it can be expected that all of the composite metal oxides were well reduced to form a niobium-nickel alloy.

Through this, when the niobium alloy is manufactured using the reduction reaction of the magnesium vapor, the activity of the magnesium vapor is controlled by further including the step of reducing the temperature by increasing the temperature at a low speed at a lower speed than performing the reduction at a single temperature. It can be seen that the recovery rate of the niobium alloy can be increased through not losing steam and can be sufficiently used for the reduction reaction.

Claims (10)

A method for producing niobium metal or a niobium alloy by reducing niobium oxide or niobium complex oxide with magnesium vapor, the method comprising:
reducing the niobium oxide or niobium complex oxide by contacting it with magnesium vapor;
The reducing step is
A first step of reducing the temperature while raising the temperature from the first temperature to the second temperature at a temperature increase rate of 1 ℃ / h to 10 ℃ / h; and
a second step of reducing at the second temperature for 1 to 10 hours;
The first temperature is 700 ℃ to 875 ℃, the second temperature is 900 ℃ to 975 ℃, a method of producing a niobium metal or niobium alloy using magnesium vapor.
According to claim 1,
The first step is to reduce the temperature while raising the temperature from the first temperature to the second temperature for 15 hours to 30 hours, a method of producing a niobium metal or niobium alloy using magnesium vapor.
delete According to claim 1,
The first temperature is a temperature of 825 ℃ to 875 ℃, a method of manufacturing a niobium metal or niobium alloy using magnesium vapor.
delete According to claim 1,
The method for producing the niobium metal or niobium alloy,
Removing impurities including magnesium oxide (MgO) from the product obtained by the reducing step; further comprising, a method for producing a niobium metal or a niobium alloy using magnesium vapor.
7. The method of claim 6,
The method for producing a niobium metal or niobium alloy using magnesium vapor, wherein the impurities are removed by an acid treatment process.
According to claim 1,
The niobium composite oxide is
from nickel (Ni), iron (Fe), tantalum (Ta), niobium (Nb), titanium (Ti), zirconium (Zr), vanadium (V), hafnium (Hf), scandium (Sc) and yttrium (Y). A method for producing a niobium metal or a niobium alloy using magnesium vapor, comprising at least one selected metal.
According to claim 1,
The niobium composite oxide is
A method for producing niobium metal or a niobium alloy using magnesium vapor, which is produced by mixing and sintering niobium oxide and a metal oxide other than niobium.
10. The method of claim 9,
The sintering is performed at a temperature of 1000 ° C to 1500 ° C, a method for producing a niobium metal or niobium alloy using magnesium vapor.

Images