JPH0681051A - Production of metal by reduction reaction of metal halide - Google Patents

Abstract

PURPOSE:To refine a reducing agent and to obtain the metal contg. decreased impurities by inserting metals absorbing the impurities contained in the reducing agent into a reaction system. CONSTITUTION:The metals 8 absorbing the impurities contained in the reducing agent are previously arranged in a laminar form on the rooster 2 in the bottom in a reaction vessel 1 at the time of assembling the reaction vessel. The liquid reducing agent to be used for reaction prior to the start of the post reaction is poured into the reaction vessel 1 and is brought into contact with the metals 8 arranged on the rooster 2. The liquid metal halide is thereafter dropped from the upper part of the reaction vessel 1 to start the reduction reaction. The formed metal is deposited and grown on the metals 8 arranged on the rooster 2, by which the formed metal ingot is obtd. Examples of the metals 8 absorbing the impurities include metal titanium, metal zirconium or the alloys thereof.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a metal by a reduction reaction of a metal halide. More specifically, the present invention relates to a method for producing a metal containing few impurities by purifying the reducing agent by inserting a metal that absorbs impurities contained in the reducing agent into the reaction system.

[0002]

2. Description of the Related Art Titanium metal is a typical example of a metal produced by a reduction reaction of a metal halide. When metallic titanium is industrially produced by a reduction reaction of titanium halide, the so-called chlor method is mainly adopted. In this method, magnesium as a reducing agent is injected in a molten state into a reaction vessel 1 in which an inert gas is sealed, and then titanium tetrachloride is dropped from the upper portion of the reaction vessel 1 to start a reduction reaction, and the produced titanium metal titanium is produced. Is generally deposited and grown on the rustle 2 at the bottom of the reaction vessel 1 and collected as a metallic titanium mass.

[0003]

In the case of producing metallic titanium by the above method, impurities such as iron, aluminum, oxygen and nitrogen contained in magnesium used as a reducing agent are produced at the initial stage of the reduction reaction and molten magnesium is produced. It is contained in the titanium metal on the bottom side of the metal titanium lumps that have settled down and deposited and grown on the rustle 2 at the bottom of the inside of the reaction vessel 1 and aggregated.

As a result, since the bottom side of the obtained metallic titanium ingot contains a large amount of impurities, unreacted magnesium and magnesium chloride contained in this metallic titanium ingot are removed by vacuum separation and purification, followed by cutting, crushing and crushing. When the metal titanium with a specific particle size (hereinafter referred to as “sponge titanium”) is subjected to sieving, the bottom part of this mass cannot be used as a material for wrought materials or aircraft parts, so cutting During the treatment, the bottom side portion was previously cut and removed by a cutting press, and only the non-defective portion was cut, pulverized, and sieved to produce a product, thus lowering the product yield.

The present invention is intended to solve the above problems and to provide a method for producing a metal by a reduction reaction of a metal halide capable of improving the quality of a produced metal lump and improving the product yield. There is.

[0006]

In order to achieve the above object, the inventors of the present invention have conducted extensive studies and as a result, if a specific metal is arranged in layers on the rostrur 2 at the bottom of the reaction vessel 1 in advance. The inventors have found that the metal absorbs impurities contained in the reducing agent inserted thereafter and refines the reducing agent in the reaction vessel 1, and has completed the present invention.

That is, according to the present invention, in the method for producing a metal by a reduction reaction of a metal halide, a metal for absorbing impurities contained in a reducing agent is previously arranged in layers on the roster 2 at the bottom of the reaction vessel 1. I am trying.

More specifically, when assembling the reaction vessel, a metal for absorbing impurities contained in the reducing agent is arranged in layers on the rostr 2 at the bottom of the inside of the reaction vessel 1 and before starting the reaction thereafter. The liquid reducing agent used in the reaction is the reaction vessel 1
It is injected into the inside and brought into contact with the metal arranged on the rustle 2. After that, a liquid metal halide is dropped from the upper part of the reaction vessel 1 to start the reduction reaction, and the produced metal is deposited and grown on the metal arranged on the roster 2 to obtain a produced metal mass.

In the present invention, examples of the metal that absorbs the impurities contained in the reducing agent include metallic titanium, metallic zirconium and alloys thereof.

These metals do not need to be of high purity, and if the content of the metal is 50% or more, it is sufficient to absorb the impurities contained in the reducing agent, and thus they are produced by the conventional method. It is possible to repeatedly use crushed parts of the bottom of the titanium metal lump containing a large amount of impurities, stainless steel reaction vessels and high iron-containing produced metals that are produced by the reaction during the reduction reaction. Since it is possible, it does not increase the manufacturing cost. Also, scraps of processed products such as alloy wire rods can be used.

The shape may be any as long as it can be arranged in a layered manner on the roster 2, but in order to sufficiently absorb the impurities contained in the reducing agent, the surface area of the metal in contact with the reducing agent should be secured. If it is sponge-like, the particle size is preferably 300 mm or less, and otherwise the specific surface area is preferably 0.5 cm ² / g or more.

Further, the amount of the metal to be placed on the roster 2 may be any amount necessary for placing it on the rostrur 2 in a layered manner, and if the amount is large, the production efficiency of the target produced metal is greatly increased. Therefore, it is preferably in the range of 0.5 to 10% of the target weight of the produced metal.

In the present invention, the reducing agent is purified by contacting the reducing agent with a metal that absorbs impurities contained in the reducing agent in the reaction system. However, contact between the two is performed in advance outside the reaction system. The method of supplying the reducing agent thus purified into the reaction vessel is also effective for producing a metal containing few impurities by the reduction reaction of the metal halide.

[0014]

The metal that absorbs the impurities contained in the reducing agent, which is arranged in layers in advance on the rostr 2 at the bottom of the reaction vessel 1, is
Contact with a liquid reducing agent injected into the reaction vessel 1 to absorb impurities such as iron, aluminum, oxygen, nitrogen contained in the reducing agent, and reduction with less impurities for the reduction reaction occurring in the reaction vessel 1. Supply the agent. For this reason, the produced metal settles in the reducing agent in a state in which the reducing agent hardly contains impurities, and is deposited on the metal that absorbs the impurities contained in the reducing agent that are arranged in layers on the rostr 2 in advance. It accumulates and grows in blocks. Therefore, the existence of a portion containing a large amount of impurities at the bottom of the obtained produced metal ingot is greatly reduced.

Further, the metal that absorbs the impurities contained in the reducing agent, which are arranged in layers on the roster 2 in advance, easily fixes the fine metal generated in the initial stage of the reduction reaction.
This fine metal is not mixed in the halide of the reducing agent that is by-produced by the reaction and is removed to the outside of the system in a timely manner.

[0016]

EXAMPLES Examples of the present invention will be described for the production of metallic titanium. Example In the reduction reaction apparatus shown in FIG. 1, when the reduction reaction apparatus was assembled, the particle size was about 50 to 100 mm and the pure Ti content was about 90 wt.
% Spongy metallic titanium 8 was laid in layers in an amount of 3% of the weight of the target metallic titanium produced. After assembling the reduction reactor, the inside of the reaction vessel 1 is replaced with Ar gas, and molten Mg is injected into the reaction vessel 1 from the Mg inlet 5 while the heating furnace 7 is operating.

Next, from the TiCl ₄ dropping pipe 4, TiCl ₄
Is added dropwise, and metallic titanium and by-product MgCl ₂ are produced in the reduction reaction container 1. The by-product MgCl ₂ is removed from the system through the MgCl ₂ vent pipe 3 at a suitable time, and after the reduction reaction is completed, unreacted Mg and M in the reduction reaction container 1 are removed.
A metallic titanium mass containing gCl ₂ is obtained.

Unreacted Mg contained in this metallic titanium mass
After removing MgCl ₂ and MgCl ₂ by vacuum separation and purification, they are taken out from the reaction vessel 1. Then, from this metal titanium lump, first, the portion containing a large amount of impurities at the bottom of the lump is cut and removed by a cutting press, and the remaining portion is cut into small blocks, which are then processed using a crusher and a sieving machine. , 0.8
The results of investigation of the impurity content and Brinell hardness of titanium sponge obtained as a size of 3 to 12.7 mm are the average values of 10 batches produced by the method, and the average of 10 batches of titanium sponge produced by the conventional method. Table 1 in comparison with the values
Shown in. Iron, aluminum, oxygen, nitrogen and Brinell hardness in titanium sponge produced by the method of the present invention,
Both are lower than those manufactured by the conventional method, and the quality is improved.

[0019]

Table 1 Conventional method Inventive method Fe (wt.%) 0.025 0.020 Al (wt.%) 0.004 0.002 O (wt.%) 0.030 0.025 N (wt.% ) 0.004 0.002 Hardness (HB) 93 89

Further, the removal amount of the portion containing a large amount of impurities at the bottom of the metallic titanium ingot was reduced to about 1/3 of the conventional method.

[0021]

EFFECTS OF THE INVENTION By using the method for producing a metal by the reduction reaction of a metal halide of the present invention, it is possible to obtain a produced metal lump of good quality and improve the yield and quality of the product as compared with the conventional method. I can.

Further, as a raw material for molten salt electrolysis for regenerating the halide of a reducing agent produced as a by-product during the reduction reaction and recycling this as a reducing agent, a halide containing no finely formed metal is used. As a result, the electrolysis efficiency in the molten salt electrolysis can be improved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a reduction reaction apparatus for producing metallic titanium according to the present invention.

[Explanation of symbols]

1 Reaction Vessel 2 Rostor 3 MgCl ₂ Drain Pipe 4 TiCl ₄ Drip Pipe 5 Mg Inlet 7 Heating Furnace 8 Sponge Metal Titanium

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[Procedure amendment]

[Submission date] September 9, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a metal by a reduction reaction of a metal halide. More specifically, the present invention relates to a method for producing a metal containing few impurities by purifying the reducing agent by inserting a metal that absorbs impurities contained in the reducing agent into the reaction system.

[0002]

2. Description of the Related Art Titanium metal is a typical example of a metal produced by a reduction reaction of a metal halide. When metallic titanium is industrially produced by a reduction reaction of titanium halide, the so-called chlor method is mainly adopted. In this method, magnesium as a reducing agent is injected in a molten state into a reaction vessel 1 in which an inert gas is sealed, and then titanium tetrachloride is dropped from the upper portion of the reaction vessel 1 to start a reduction reaction, and the produced titanium metal titanium is produced. Is generally deposited and grown on the rustle 2 at the bottom of the reaction vessel 1 and collected as a metallic titanium mass.

[0003]

In the case of producing metallic titanium by the above method, impurities such as iron, aluminum, oxygen and nitrogen contained in magnesium used as a reducing agent are produced at the initial stage of the reduction reaction and molten magnesium is produced. It is contained in the titanium metal on the bottom side of the metal titanium lumps that have settled down and deposited and grown on the rustle 2 at the bottom of the inside of the reaction vessel 1 and aggregated.

As a result, since the bottom side of the obtained metallic titanium ingot contains a large amount of impurities, unreacted magnesium and magnesium chloride contained in this metallic titanium ingot are removed by vacuum separation and purification, followed by cutting, crushing and crushing. When the metal titanium with a specific particle size (hereinafter referred to as “sponge titanium”) is subjected to sieving, the bottom part of this mass cannot be used as a material for wrought materials or aircraft parts, so cutting During the treatment, the bottom side portion was previously cut and removed by a cutting press, and only the non-defective portion was cut, pulverized, and sieved to produce a product, thus lowering the product yield.

The present invention is intended to solve the above problems and to provide a method for producing a metal by a reduction reaction of a metal halide capable of improving the quality of a produced metal lump and improving the product yield. There is.

[0006]

In order to achieve the above object, the inventors of the present invention have conducted extensive studies and as a result, if a specific metal is arranged in layers on the rostrur 2 at the bottom of the reaction vessel 1 in advance. The inventors have found that the metal absorbs impurities contained in the reducing agent inserted thereafter and refines the reducing agent in the reaction vessel 1, and has completed the present invention.

That is, according to the present invention, in the method for producing a metal by a reduction reaction of a metal halide, a metal for absorbing impurities contained in a reducing agent is previously arranged in layers on the roster 2 at the bottom of the reaction vessel 1. I am trying.

More specifically, when assembling the reaction vessel, a metal for absorbing impurities contained in the reducing agent is arranged in layers on the rostr 2 at the bottom of the inside of the reaction vessel 1 and before starting the reaction thereafter. The liquid reducing agent used in the reaction is the reaction vessel 1
It is injected into the inside and brought into contact with the metal arranged on the rustle 2. After that, a liquid metal halide is dropped from the upper part of the reaction vessel 1 to start the reduction reaction, and the produced metal is deposited and grown on the metal arranged on the roster 2 to obtain a produced metal mass.

In the present invention, examples of the metal that absorbs the impurities contained in the reducing agent include metallic titanium, metallic zirconium and alloys thereof.

These metals do not need to be of high purity, and if the content of the metal is 50% or more, it is sufficient to absorb the impurities contained in the reducing agent, and thus they are produced by the conventional method. It is possible to repeatedly use crushed parts of the bottom of the titanium metal lump containing a large amount of impurities, stainless steel reaction vessels and high iron-containing produced metals that are produced by the reaction during the reduction reaction. Since it is possible, it does not increase the manufacturing cost. Also, scraps of processed products such as alloy wire rods can be used.

The shape may be any as long as it can be arranged in a layered manner on the roster 2, but in order to sufficiently absorb the impurities contained in the reducing agent, the surface area of the metal in contact with the reducing agent should be secured. If it is sponge-like, the particle size is preferably 300 mm or less, and otherwise the specific surface area is preferably 0.5 cm ² / g or more.

Further, the amount of the metal to be placed on the roster 2 may be any amount necessary for placing it on the rostrur 2 in a layered manner, and if the amount is large, the production efficiency of the target produced metal is greatly increased. Therefore, it is preferably in the range of 0.5 to 10% of the target weight of the produced metal.

In the present invention, the reducing agent is purified by contacting the reducing agent with a metal that absorbs impurities contained in the reducing agent in the reaction system. However, contact between the two is performed in advance outside the reaction system. The method of supplying the reducing agent thus purified into the reaction vessel is also effective for producing a metal containing few impurities by the reduction reaction of the metal halide.

[0014]

The metal that absorbs the impurities contained in the reducing agent, which is arranged in layers in advance on the rostr 2 at the bottom of the reaction vessel 1, is
Contact with a liquid reducing agent injected into the reaction vessel 1 to absorb impurities such as iron, aluminum, oxygen, nitrogen contained in the reducing agent, and reduction with less impurities for the reduction reaction occurring in the reaction vessel 1. Supply the agent. For this reason, the produced metal settles in the reducing agent in a state in which the reducing agent hardly contains impurities, and is deposited on the metal that absorbs the impurities contained in the reducing agent that are arranged in layers on the rostr 2 in advance. It accumulates and grows in blocks. Therefore, the existence of a portion containing a large amount of impurities at the bottom of the obtained produced metal ingot is greatly reduced.

Further, the metal that absorbs the impurities contained in the reducing agent, which are arranged in layers on the roster 2 in advance, easily fixes the fine metal generated in the initial stage of the reduction reaction.
This fine metal is not mixed in the halide of the reducing agent that is by-produced by the reaction and is removed to the outside of the system in a timely manner.

[0016]

EXAMPLES Examples of the present invention will be described for the production of metallic titanium. Example In the reduction reaction apparatus shown in FIG. 1, when the reduction reaction apparatus was assembled, the particle size was about 50 to 100 mm and the pure Ti content was about 90 wt.
% Spongy metallic titanium 8 was laid in layers in an amount of 3% of the weight of the target metallic titanium produced. After assembling the reduction reactor, the inside of the reaction vessel 1 is replaced with Ar gas, and molten Mg is injected into the reaction vessel 1 from the Mg inlet 5 while the heating furnace 7 is operating.

Next, from the TiCl ₄ dropping pipe 4, TiCl ₄
Is added dropwise, and metallic titanium and by-product MgCl ₂ are produced in the reduction reaction container 1. The by-product MgCl ₂ is removed from the system through the MgCl ₂ vent pipe 3 at a suitable time, and after the reduction reaction is completed, unreacted Mg and M in the reduction reaction container 1 are removed.
A metallic titanium mass containing gCl ₂ is obtained.

Unreacted Mg contained in this metallic titanium mass
After removing MgCl ₂ and MgCl ₂ by vacuum separation and purification, they are taken out from the reaction vessel 1. Then, from this metal titanium lump, first, the portion containing a large amount of impurities at the bottom of the lump is cut and removed by a cutting press, and the remaining portion is cut into small blocks, which are then processed using a crusher and a sieving machine. , 0.8
The results of investigation of the impurity content and Brinell hardness of titanium sponge obtained as a size of 3 to 12.7 mm are the average values of 10 batches produced by the method, and the average of 10 batches of titanium sponge produced by the conventional method. Table 1 in comparison with the values
Shown in. Iron, aluminum, oxygen, nitrogen and Brinell hardness in titanium sponge produced by the method of the present invention,
Both are lower than those manufactured by the conventional method, and the quality is improved.

[0019]

Table 1 Conventional method Inventive method Fe (wt.%) 0.025 0.020 Al (wt.%) 0.004 0.002 O (wt.%) 0.030 0.025 N (wt.% ) 0.004 0.002 Hardness (HB) 93 89

Further, the removal amount of the portion containing a large amount of impurities at the bottom of the metallic titanium ingot was reduced to about 1/3 of the conventional method.

[0021]

EFFECTS OF THE INVENTION By using the method for producing a metal by the reduction reaction of a metal halide of the present invention, it is possible to obtain a produced metal lump of good quality and improve the yield and quality of the product as compared with the conventional method. I can.

Further, as a raw material for molten salt electrolysis for regenerating the halide of a reducing agent produced as a by-product during the reduction reaction and recycling this as a reducing agent, a halide containing no finely formed metal is used. As a result, the electrolysis efficiency in the molten salt electrolysis can be improved.

Claims (1)

[Claims] 1. A method for producing a metal by a reduction reaction of a metal halide, characterized in that a metal for absorbing impurities contained in a reducing agent is arranged in layers on a rostrut at the bottom of the reaction vessel. A method for producing a metal by a reduction reaction of a metal fluoride.