KR102300837B1 - Method for deoxidation of off-grade titanium sponge using magnesium - Google Patents

Abstract

The present invention provides a deoxidation method of an off-grade titanium sponge using magnesium, which manufactures a metal or metal compound of on-grade titanium (Ti) with reduced oxygen in titanium by performing deoxidation using magnesium (Mg) in a hydrogen (H_2) atmosphere after hydrogenating an off-grade titanium (Ti) sponge. The deoxidation method of an off-grade titanium sponge using magnesium comprises a step of preparing titanium hydride (TiHx) by reacting the off-grade titanium sponge in a hydrogen (H_2) gas atmosphere; a step of mixing the titanium hydride (TiHx) with magnesium and molten salt; and a step of deoxidizing the titanium hydride, magnesium and molten salt mixture in a hydrogen (H_2) gas or a mixed gas of argon (Ar) and hydrogen (H_2) to produce a metal or metal compound of on-grade titanium (Ti).

Description

METHOD FOR DEOXIDATION OF OFF-GRADE TITANIUM SPONGE USING MAGNESIUM

The present invention relates to an off-grade titanium sponge that is hydrogenated and then _{deoxidized using magnesium (Mg) in a hydrogen (H 2} ) atmosphere to reduce oxygen in the titanium (on-grade Ti). It relates to a deoxidation method of an off-grade titanium sponge using magnesium for manufacturing a metal or a metal compound.

In general, titanium-based alloy materials have corrosion resistance, heat resistance, and high strength characteristics, and are applied to military products such as bulletproof, fighter jets, submarines, and engines, and are also applied to civil products such as automobiles, medical care, and power generation facilities.

Among them, off-grade titanium sponge, which is produced at about 10-20% of production when producing titanium, is an out-of-class product and is used as a deoxidizer in the iron making process due to contamination by iron (Fe) and oxygen (O). has been

Therefore, research has been conducted by researchers who want to convert it into an on-grade Ti product by removing oxygen from the off-grade Ti sponge, which is produced about 10-20% of the titanium production, but still It was not enough to be mass-produced as a product.

Republic of Korea Patent Publication No. 10-2019-0074742 (patent publication date: June 28, 2019) provides an improved deoxidation device for manufacturing titanium powder capable of mass-producing high-purity titanium powder with low oxygen content.

The deoxidation apparatus for manufacturing titanium powder of the Korean Patent Application Laid-Open includes a deoxidation chamber in which titanium powder is deoxidized, a vapor input unit connected to a lower portion of the deoxidation chamber and injecting steam into the deoxidation chamber, and the deoxidation chamber. It includes a flow control unit for flowing the titanium powder, and a dispersion unit located in the lower portion of the deoxidation chamber.

Here, the steam input to the steam input unit contains calcium gas, but through several studies, the present applicant hydrogenated the off-grade titanium sponge and then deoxidized it using magnesium (Mg) in a _{hydrogen (H 2 ) atmosphere.} A deoxidation method of off-grade titanium sponge using magnesium to reduce oxygen in titanium was developed.

At this time, the present applicant obtained the process technology for stably manufacturing on-grade titanium under a mixed gas condition using argon and hydrogen by the deoxidation method of the off-grade titanium sponge using magnesium, thereby completing the present invention.

Republic of Korea Patent Publication No. 10-2019-0074742 (Patent publication date: June 28, 2019)

Accordingly, an object of the present invention is to provide a process technology for safely producing on-grade titanium metal or metal compound under a mixed gas condition using argon and hydrogen by deoxidation of off-grade titanium sponge.

In addition, an object of the present invention is to provide a raw material for an electronic device made of on-grade titanium metal or a metal compound.

The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to solve the above problems, according to an aspect of the present invention,

A deoxidation method for producing a metal or metal compound of on-grade Ti by removing oxygen from an off-grade Ti sponge,

preparing titanium hydride (TiH _x ) by reacting the off-grade titanium sponge in a hydrogen (H _{2 ) gas atmosphere;}

mixing the titanium hydride (TiH _x ) with magnesium and molten salt; and

The titanium hydride, magnesium, and molten salt mixture is _{deoxidized in hydrogen (H 2} ) gas, or a mixed gas of argon (Ar) and hydrogen (H ₂ ) to metal or metal of on-grade Ti comprising; preparing a compound;

A method of deoxidation of an off-grade titanium sponge using magnesium is provided.

According to one embodiment of the present invention, the oxygen concentration of the off-grade titanium (off-grade Ti) is greater than 0.18 mass%,

The oxygen concentration of the on-grade titanium may be 0.18 mass% or less.

According to an embodiment of the present invention, the metal of the on-grade titanium (on-grade Ti) is a titanium metal,

The metal compound of on-grade titanium may be titanium hydride (TiH _x ).

According to an embodiment of the present invention, the metal of the on-grade titanium (on-grade Ti) is a titanium metal,

The metal compound of on-grade titanium is titanium hydride (TiH _x ),

The oxygen concentration in the titanium may be 0.18 mass% or less.

According to one embodiment of the present invention, the off-grade titanium (off-grade Ti) sponge is prepared by reacting in a _{hydrogen (H 2 ) gas atmosphere.}

_{x of} the titanium hydride (TiH x ) may be 1.924 to 2.

According to an embodiment of the present invention, the molten salt may be at least one selected from the group consisting of magnesium chloride, potassium chloride, calcium chloride, and lithium chloride.

According to an embodiment of the present invention, the _{content ratio of the titanium hydride (TiH x} ), magnesium, and molten salt may be 1:0.5:1 to 1:2:4 by weight.

According to an embodiment of the present invention, the _{mixing ratio of the hydrogen (H 2} ) and the mixed gas of argon (Ar) is H ₂ : Ar in a molar ratio. = 5: 95 to 100: 0.

According to an embodiment of the present invention, the deoxidation

The deoxidation temperature may be 933 K to 993 K.

According to an embodiment of the present invention, the deoxidation

The concentration of the hydrogen (H ₂ ) gas may be 5 mol % to 20 mol %.

According to an embodiment of the present invention, the deoxidation method of the off-grade titanium sponge using the magnesium is

The method may further include an acid leaching step of acid leaching the metal or metal compound of on-grade Ti using a hydrochloric acid solution to remove residual molten salt and magnesium oxide formed in the deoxidation reaction.

According to an embodiment of the present invention, the single acid compound is one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, acetic acid, and hydrofluoric acid,

The mixed acid compound may be two or more selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, acetic acid, and hydrofluoric acid.

According to an embodiment of the present invention, the concentration of the hydrochloric acid solution may be 5% to 20%.

According to an embodiment of the present invention, the leaching temperature in the acid leaching step may be 0 °C to 25 °C.

According to an embodiment of the present invention, the deoxidation method of the off-grade titanium sponge using the magnesium is

A drying process may be further included after the acid leaching step.

In addition, according to another aspect of the present invention,

Provided is a raw material for an electronic device made of a metal or a metal compound of on-grade Ti formed by the deoxidation method of the off-grade titanium sponge using the magnesium.

According to the present invention, after hydrogenation of an off-grade Ti sponge, _{deoxidation using magnesium (Mg) in a hydrogen (H 2} ) atmosphere is performed to reduce oxygen in titanium (on-grade Ti) ) of metal or metal compound, so the manufacturing cost is low and economical.

In addition, since the on-grade titanium metal or metal compound is safely manufactured under a mixed gas condition using argon and hydrogen by the deoxidation method of the off-grade titanium sponge of the present invention, process safety is excellent.

In addition, since the raw material for electronic devices made of the on-grade titanium metal or metal compound of the present invention can be variously applied to military goods and civil goods, there is an advantage in a wide range of applications.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a flow chart of an off-grade Ti sponge deoxidation process using magnesium in a hydrogen atmosphere according to an embodiment of the present invention.
2 is a diagram of the oxygen and hydrogen chemical potentials of Ti-HO at 973 K according to an embodiment of the present invention.
3 is a schematic diagram of an off-grade titanium sponge deoxidation device using magnesium in a hydrogen atmosphere according to an embodiment of the present invention.
4 is an XRD analysis result of a sample before deoxidation after hydrogenation of an off-grade Ti sponge according to an embodiment of the present invention.
5 is a TG-DTA analysis result of _{titanium hydride (TiH x} ) prepared with an on-grade Ti sponge according to an embodiment of the present invention in an argon atmosphere.
6 is an XRD analysis result of the _{recovered product after deoxidation of titanium hydride (TiH x} ) prepared with off-grade Ti sponge according to an embodiment of the present invention.

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings.

Advantages and features of the present invention, and a method of achieving the same, will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings.

However, the present invention is not limited by the embodiments disclosed below, but will be implemented in a variety of different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims.

In addition, in the description of the present invention, if it is determined that related known technologies may obscure the gist of the present invention, detailed description thereof will be omitted.

Hereinafter, the present invention will be described in detail.

Deoxidation method of off-grade titanium sponge

The present invention relates to an off-grade titanium sponge that is hydrogenated and then _{deoxidized using magnesium (Mg) in a hydrogen (H 2} ) atmosphere to reduce oxygen in the titanium (on-grade Ti). Provided is a deoxidation method of an off-grade titanium sponge using magnesium for manufacturing a metal or a metal compound.

The deoxidation method of the off-grade titanium sponge using magnesium of the present invention is

A deoxidation method for producing a metal or metal compound of on-grade Ti by removing oxygen from an off-grade Ti sponge,

preparing titanium hydride (TiH _x ) by reacting the off-grade titanium sponge in a hydrogen (H _{2 ) gas atmosphere;}

mixing the titanium hydride (TiH _x ) with magnesium and molten salt; and

The titanium hydride, magnesium, and molten salt mixture is _{deoxidized in hydrogen (H 2} ) gas, or a mixed gas of argon (Ar) and hydrogen (H ₂ ) to metal or metal of on-grade Ti and preparing the compound.

The present invention relates to an off-grade titanium sponge that is hydrogenated and then _{deoxidized using magnesium (Mg) in a hydrogen (H 2} ) atmosphere to reduce oxygen in the titanium (on-grade Ti). A deoxidation method of an off-grade titanium sponge using magnesium to prepare a metal or a metal compound and use the metal or metal compound of the on-grade Ti as a raw material for electronic devices is provided.

Here, the oxygen concentration of the off-grade titanium (off-grade Ti) is more than 0.18 mass%,

The oxygen concentration of the on-grade titanium may be 0.18 mass% or less.

Here, the oxygen concentration of the on-grade titanium may be measured using an N/O/H analyzer.

And, the metal of the on-grade titanium (on-grade Ti) is a titanium metal,

The metal compound of on-grade titanium may be titanium hydride (TiH _x ).

In addition, the metal of the on-grade titanium (on-grade Ti) is a titanium metal,

The metal compound of on-grade titanium is titanium hydride (TiH _x ),

The oxygen concentration in the titanium may be 0.18 mass% or less.

At this time, the off-grade titanium (off-grade Ti) sponge was prepared by reacting it in a _{hydrogen (H 2 ) gas atmosphere.}

_{x of} the titanium hydride (TiH x ) may be 1.924 to 2.

In addition, the molten salt may be at least one selected from the group consisting of magnesium chloride, potassium chloride, calcium chloride, and lithium chloride.

Here, the content ratio of the titanium hydride (TiH _x ), magnesium, and molten salt may be 1:0.5:1 to 1:2:4 by weight.

When the content ratio of the titanium hydride (TiH _x ), magnesium, and molten salt is out of 1: 0.5 to 1: 2: 4 by weight, excess oxygen remains in the on-grade titanium metal or metal compound to escape the on-grade quality. can

In this case, the _{content ratio of the titanium hydride (TiH x} ), magnesium, and molten salt may be preferably 1: 0.7: 1.2 to 1: 1.8: 3.8 by weight, and more preferably 1: 0.9: 1.5 to It may be 1:1.5:3.5.

In addition, the _{mixing ratio of the hydrogen (H 2} ) and the mixed gas of argon (Ar) is H ₂ : Ar in a molar ratio = 5: 95 to 100: 0.

Here, the mixing ratio of the hydrogen (H ₂ ) and the mixed gas of argon (Ar) is H ₂ : Ar in a molar ratio = 5: When less than 95 (based on hydrogen), excess oxygen remains in the on-grade titanium metal or metal compound, and the on-grade quality may be deviated _{, and the mixing ratio of the hydrogen (H 2} ) and argon (Ar) gas mixture In this molar ratio H ₂ : Ar = 100: If it is more than 0 (based on hydrogen), there may be a problem that the economic feasibility is lowered.

At this time, the _{mixing ratio of the hydrogen (H 2} ) and the mixed gas of argon (Ar) is preferably H ₂ : Ar in a molar ratio. = 10: 90 to 90: 10.

And, of the deoxidation reaction

The deoxidation temperature may be 933 K to 993 K.

Here, the deoxidation reaction

The concentration of the hydrogen (H ₂ ) gas may be 5 mol % to 20 mol %.

Here, when the _{concentration of the hydrogen (H 2} ) gas is out of 5 mol % to 20 mol %, excess oxygen remains in the on-grade titanium metal or metal compound, and thus the on-grade quality may be deviated.

In this case, the _{concentration of the hydrogen (H 2} ) gas may be preferably 10 mol % to 20 mol %.

And, the deoxidation method of the off-grade titanium sponge using the magnesium is

Acid leaching step of acid leaching the metal or metal compound of on-grade Ti using hydrochloric acid solution to remove residual molten salt and magnesium oxide formed in the deoxidation reaction by acid leaching in the residual molten salt and deoxidation reaction may further include.

In this case, the concentration of the hydrochloric acid solution may be 5% to 20%.

When the concentration of the hydrochloric acid solution is less than 5%, magnesium oxide is not removed, the oxygen content of the on-grade titanium metal or metal compound may increase, and when the concentration of the hydrochloric acid solution is more than 20%, a problem of cost increase may occur.

In addition, the leaching temperature of the acid leaching step may be 0 °C to 25 °C.

According to an embodiment of the present invention, the deoxidation method of the off-grade titanium sponge using the magnesium is

A drying process may be further included after the acid leaching step.

1 is a flow chart of an off-grade Ti sponge deoxidation process using magnesium in a hydrogen atmosphere according to an embodiment of the present invention.

1, first, by reacting a titanium-off grade (off-grade Ti) sponge and hydrogen gas (H ₂₎ preparing a titanium hydride (TiH ₂₎ (100). The sample obtained after the hydrogenation reaction of the off-grade titanium sponge is mixed with Mg and molten salt, and then it is mixed with a high temperature argon (Ar) and hydrogen (H ₂ ) gas atmosphere or hydrogen (H ₂ ) gas atmosphere Deoxidized in (110).

After the deoxidation reaction, the obtained mixture is recovered by leaching with hydrochloric acid (HCl) to remove residual molten salt and magnesium oxide (MgO) generated by the deoxidation reaction, followed by drying ( 120 ).

2 is a diagram of the oxygen and hydrogen chemical potentials of the Ti—H—O system at 973 K according to an embodiment of the present invention.

A plane in the chemical potential diagram of FIG. 2 means that when the oxygen and hydrogen chemical potentials in the reaction system at 973 K are in the corresponding region, the compound in the region can be obtained as the most stable phase.

As can be seen in Figure 2, when the partial pressure of hydrogen in the reaction system at 973 K is less than 0.0055 atm, there is no hydrogen solution in Ti, and at this time, the equilibrium oxygen partial pressure by the equilibrium of Mg and MgO indicated by the red dotted line is Ti-0.5 mass%O ( Oxygen 0.5 mass% solid solution state in Ti) and Ti-0.6 mass% O corresponds to near the boundary line.

That is, it can be seen that the dissolved oxygen concentration in Ti can be reduced only to about 5000 - 6000 ppm during Ti deoxidation by Mg at 973 K in the state in which hydrogen is not dissolved in Ti and in the standard state.

Therefore, Ti with an oxygen concentration of 1800 ppm corresponding to ASTM standard Grade 1 cannot be manufactured.

However, as can be seen in FIG. 2 , when the partial pressure of hydrogen in the reaction system at 973 K is 0.0055 atm or more, it can be seen that the equilibrium oxygen partial pressure increases even if the dissolved oxygen in Ti has the same concentration.

For example, when there is no hydrogen solid solution in Ti, the oxygen partial pressure at 973 K is -20000 ppm up to 52.1 (log p _O2 ), but in the presence of hydrogen solid solution, the oxygen partial pressure at 973 K is - 50.6 (log p _{O2 )} ), it can be seen that the dissolved oxygen concentration is 20000 ppm. That is, when hydrogen in Ti is dissolved, it can be seen that the driving force of the deoxidation reaction by Mg is increased because oxygen in Ti is destabilized.

Therefore, based on such thermodynamic considerations, when hydrogen in Ti is dissolved, it can be seen that the equilibrium oxygen partial pressure due to the equilibrium of Mg and MgO indicated by the red dotted line in FIG. 2 is within the region where the dissolved oxygen concentration in Ti is 1660 ppm. have.

That is, when hydrogen in Ti is dissolved at 973 K, or when hydrogen activity is high, the concentration of dissolved oxygen in Ti can be reduced to 1660 ppm during deoxidation by Mg.

Therefore, in the case of the hydrogenation reaction, which is the first step of the process diagram shown in FIG. 1, the bulk-type off-grade titanium sponge becomes fine particles by the hydrogenation reaction of the off-grade titanium sponge, thereby improving the speed of the deoxidation reaction and solid solution hydrogen in the off-grade titanium sponge. There are two purposes to enable deoxidation by Mg even in a mixed gas atmosphere of Ar + H _{2 including H 2} atmosphere according to the effect of

3 is a schematic diagram of an off-grade titanium sponge deoxidation device using magnesium in a hydrogen atmosphere according to an embodiment of the present invention.

Referring to FIG. 3, _{after mixing molten salt of TiH x} raw material, Mg, magnesium chloride and potassium chloride in an iron crucible, it is charged into the SUS reactor, and the atmosphere gas in the reactor is replaced with a target gas, which is a mixed gas of argon and hydrogen. It proceeds by raising the temperature to the deoxidation temperature.

At this time, the deoxidation process was performed using an electric furnace installed in the glove box, and sample preparation and recovery are performed in the glove box.

After the deoxidation process is completed, the iron crucible is leached into a hydrochloric acid solution without stirring to recover the deoxidized Ti sample from the iron crucible.

After that, the sample recovered from the iron crucible is again leached while stirring the hydrochloric acid solution.

After leaching, the recovered sample is washed with distilled water and acetone and dried in the air.

Raw material for electronic devices manufactured with off-grade titanium metal or metal compound

The present invention provides a raw material for an electronic device made of a metal or a metal compound of on-grade Ti formed by the deoxidation method of the off-grade titanium sponge using magnesium.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

<Preparation example> Titanium hydride (TiH ₂ ) powder preparation

_{Off-grade titanium hydride (TiH 2} ) powder, which is a raw material for the deoxidation process, was obtained from MTIG Co., Ltd.

And, the off-grade titanium hydride (TiH ₂ ) powder, which is a raw material for the deoxidation process, was prepared by re- _{hydrogenating the titanium hydride (TiH 2} ) powder obtained from MTIG in the laboratory of the Korea Institute of Geoscience and Mineral Resources.

<Example>

<Examples 1 to 14> Deoxidation process and acid leaching of off-grade titanium sponge

Among the titanium hydride (TiH ₂ ) powder obtained from MTIG Co., Ltd., a powder having a particle size of 100 to 300 μm was _{reacted in an Ar + 5-10% H 2} atmosphere gas of 673 K for 12 hours to react titanium hydride (TiH _x ) was prepared.

Then, in the iron crucible of FIG. 3, the titanium hydride (TiH _x ) raw material, magnesium as a reducing metal, and a mixed molten salt of magnesium chloride (MgCl2) and potassium chloride (KCl) are mixed in the composition shown in Table 1 below. After charging this into the reactor, the atmosphere gas in the reactor was replaced with a mixed gas of argon and hydrogen gas, and then the temperature was raised to a deoxidation temperature of 933 K to 993 K, followed by deoxidation for 12 hours.

At this time, the deoxidation process was performed using an electric furnace installed in the glove box, and sample preparation and recovery were performed in the glove box.

After the deoxidation was completed, the iron crucible was leached in a 10% hydrochloric acid solution at room temperature for 1 hour without stirring to recover the deoxidized Ti sample from the iron crucible.

After that, the sample recovered from the iron crucible was again leached with stirring in a 10% hydrochloric acid solution at room temperature for 1 hour.

After the leaching was completed, the recovered sample was washed with distilled water and acetone, and dried in the atmosphere at room temperature for at least 1 hour.

number TiH ₂ weight (g) Molten salt weight (g) Mg weight (g) Hydrogen concentration in mixed gas (mol%) Deoxidation temperature (K) MgCl ₂ KCl Example 1 One 0.75 0.25 0.50 10 933 Example 2 One 0.75 0.25 1.00 10 933 Example 3 One 0.75 0.25 1.50 10 933 Example 4 One 0.75 0.25 2.00 10 933 Example 5 One 1.50 0.50 1.00 10 933 Example 6 One 2.25 0.75 1.00 10 933 Example 7 One 3.00 1.00 1.00 10 933 Example 8 One 3.75 1.25 1.00 10 933 Example 9 One 0.75 0.25 1.00 10 953 Example 10 One 0.75 0.25 1.00 10 973 Example 11 One 0.75 0.25 1.00 10 993 Example 12 One 0.75 0.25 0.50 0 933 Example 13 One 0.75 0.25 0.50 5 933 Example 14 One 0.75 0.25 0.50 20 933

<Experimental example>

<Experimental Example 1> Titanium hydride (TiH) ₂ ) XRD analysis

_{In order to analyze the crystal structure of titanium hydride (TiH 2} ), which is the deoxidation process power source sample, _{off-grade titanium hydride (TiH 2} ) prepared in Preparation Example and off-grade titanium from the Korea Institute of Geoscience and Mineral Resources lab The hydride (TiH ₂ ) was XRD analyzed.

4 is an XRD analysis result of the sample before deoxidation after hydrogenation of the off-grade Ti sponge prepared in the above preparation example.

Referring to FIG. 4 , in the case of a sample manufactured by MTI _{EG, it was found that the main compound was TiH 1.924,} but some Ti remained without hydrogenation.

Therefore, in order to improve the deoxidation power by Mg by increasing the concentration of dissolved hydrogen in Ti, that is, by increasing the hydrogen activity in Ti, and when Ti remains, the leaching conditions are restricted during post-treatment using an acid solution after the deoxidation reaction. For this reason, the off-grade titanium hydride (TiH ₂ ) powder manufactured by MTIG Co., Ltd. was re-hydrogenated in the laboratory of the Korea Institute of Geoscience and Mineral Resources.

When the sample prepared by MTIG Co., Ltd. was _{hydrogenated at 673 K in an Ar + 5 - 10 % H 2} atmosphere for 12 hours, the minor Ti peak disappeared, and it was found that hydrogen in the sample was maximally dissolved. _{At this time, in the case of the TiH x} raw material using the hard sponge, as a result of performing the hydrogenation treatment once again, it was analyzed that Fe in the hard sponge was present in the form of a _{FeTiH 0.02 compound.}

<Experimental Example 2> On-grade titanium hydride (TiH ₂ ) TG-DTA analysis

An on-grade titanium hydride (TiH ₂₎ (weeks) number of on-grade titanium empty AIJI hydride (TiH ₂₎ prepared in the preparation example to thermal analysis were TG-TDA.

5 is a TG-DTA analysis result of _{titanium hydride (TiH x} ) prepared by the on-grade titanium sponge prepared in the above preparation example in an argon atmosphere.

Gibbs free energy of formation at 1000 K value of TiH ₂ is - stable a TiH ₂ to 1000 K in the standard conditions as 6.559 kJ / mol.

However, as can be seen from the results of FIG. 5, as a result of TG-DTA analysis in an argon (Ar) gas atmosphere, a dehydrogenation phenomenon in which hydrogen dissolved in the raw material gradually escapes from about 773 K occurs. could check

The dehydrogenation is determined to occur because the partial pressure of hydrogen in the atmospheric gas is low when argon (Ar) gas is used.

Therefore, it was confirmed that the use of hydrogen gas during the deoxidation reaction was necessary in order to maintain a high hydrogen activity in the Ti raw material during the deoxidation reaction.

<Experimental Example 3> Deoxidation reaction result using magnesium in hydrogen atmosphere

By carrying out the deoxidation reaction of the off-grade titanium sponge of Examples 1 to 14, as shown in Table 2 below, the concentration of oxygen in the titanium is 0.144 mass% to 0.156 mass% of on-grade titanium (on-grade Ti) A metal or a metal compound was obtained.

Here, the oxygen concentration of the on-grade titanium was measured using an N/O/H analyzer.

As in the case of Example 2 and Examples 5 to 8, when the magnesium content was the same, the concentration of oxygen in titanium decreased as the total amount of molten salt decreased.

number TiH ₂ weight (g) Molten salt weight (g) Mg weight (g) Hydrogen concentration in mixed gas (mol%) Deoxidation temperature (K) Oxygen concentration in Ti (mass%) MgCl ₂ KCl Example 1 One 0.75 0.25 0.50 10 933 0.216 Example 2 One 0.75 0.25 1.00 10 933 0.144 Example 3 One 0.75 0.25 1.50 10 933 0.156 Example 4 One 0.75 0.25 2.00 10 933 0.203 Example 5 One 1.50 0.50 1.00 10 933 0.212 Example 6 One 2.25 0.75 1.00 10 933 0.223 Example 7 One 3.00 1.00 1.00 10 933 0.198 Example 8 One 3.75 1.25 1.00 10 933 0.231 Example 9 One 0.75 0.25 1.00 10 953 0.154 Example 10 One 0.75 0.25 1.00 10 973 0.160 Example 11 One 0.75 0.25 1.00 10 993 0.175 Example 12 One 0.75 0.25 0.50 0 933 0.225 Example 13 One 0.75 0.25 0.50 5 933 0.201 Example 14 One 0.75 0.25 0.50 20 933 0.142

As in Examples 9 to 11, when the deoxidation temperature is increased, it can be seen that the oxygen concentration in the titanium hydride recovered after the deoxidation reaction increases, and as shown in Table 2, the concentration of oxygen in the titanium is 0.142 mass% To 0.231 mass% of on-grade titanium metal or metal compound was obtained.

The reason that the oxygen concentration in the titanium hydride recovered after the deoxidation reaction increases when the deoxidation temperature increases is because hydrogen escapes from the titanium hydride raw material to the reaction system as the deoxidation temperature increases, so the activity of hydrogen in the titanium hydride raw material decreases. In addition, since the specific gravity of titanium metal increases, oxygen contamination increases during wet treatment after deoxidation.

As in Examples 14 and 2, it can be seen that as the hydrogen concentration in the atmospheric gas at 933 K increases, the oxygen concentration in the titanium hydride recovered after the deoxidation reaction decreases, and as shown in Table 2, the concentration of oxygen in the titanium is 0.142 mass% to 0.144 mass% of on-grade titanium metal or metal compound was obtained.

This is because, as the concentration of hydrogen in the atmosphere gas increases, the hydrogen from the titanium hydride raw material at a constant temperature is suppressed from escaping into the reaction system.

6 is an XRD analysis result of the _{recovered product after deoxidation of titanium hydride (TiH x} ) prepared with the off-grade titanium sponge.

Here, it was confirmed that the recovered product after the deoxidation reaction of the titanium hydride (TiH _{x ) was a mixture of TiH x and Ti as a result of XRD analysis.}

So far, specific embodiments of the deoxidation method of the off-grade titanium sponge using magnesium according to the present invention have been described, but it is obvious that various implementation modifications are possible within the limits that do not depart from the scope of the present invention.

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the following claims as well as the claims and equivalents.

That is, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims; All changes or modifications derived from the concept of equivalents thereof should be construed as being included in the scope of the present invention.

Claims (14)

A deoxidation method for manufacturing a metal or a metal compound of on-grade Ti by removing oxygen from an off-grade Ti sponge,
preparing titanium hydride (TiHx) by reacting the off-grade titanium sponge in a hydrogen (H _{2 ) gas atmosphere;}
mixing the titanium hydride (TiHx) with magnesium and molten salt; and
The titanium hydride, magnesium and molten salt mixture is _{deoxidized in hydrogen (H 2} ) gas, or a mixed gas of argon (Ar) and hydrogen (H ₂ ) to obtain a metal or metal compound of on-grade titanium. manufacturing; including;
The molten salt is at least one selected from the group consisting of magnesium chloride, potassium chloride, calcium chloride, and lithium chloride,
The content ratio of the titanium hydride (TiHx), magnesium and molten salt is 1: 0.5: 1 to 1: 2: 4 by weight, characterized in that
Deoxidation method of off-grade titanium sponge using magnesium.
The method of claim 1,
The oxygen concentration of the off-grade titanium (off-grade Ti) is greater than 0.18 mass%,
The oxygen concentration of the on-grade titanium (on-grade Ti) is characterized in that less than 0.18 mass%
Deoxidation method of off-grade titanium sponge using magnesium.
The method of claim 1,
The metal of the on-grade titanium (on-grade Ti) is a titanium metal,
The metal compound of on-grade titanium is titanium hydride (TiH _x ), characterized in that
Deoxidation method of off-grade titanium sponge using magnesium.
The method of claim 1,
The metal of the on-grade titanium (on-grade Ti) is a titanium metal,
The metal compound of on-grade titanium is titanium hydride (TiH _x ),
The oxygen concentration in the titanium is characterized in that 0.18 mass% or less
Deoxidation method of off-grade titanium sponge using magnesium.
The method of claim 1,
The off-grade titanium (off-grade Ti) sponge was prepared by reacting it in a _{hydrogen (H 2 ) gas atmosphere.
x of} the titanium hydride (TiH x ) is characterized in that 1.924 to 2
Deoxidation method of off-grade titanium sponge using magnesium.
delete delete The method of claim 1,
The mixing ratio of the hydrogen (H ₂ ) and the mixed gas of argon (Ar) is H ₂ : Ar in a molar ratio = 5: 95 to 100: characterized in that 0
Deoxidation method of off-grade titanium sponge using magnesium.
The method of claim 1,
of the deoxidation reaction
The hydrogen (H ₂ ) gas has a concentration of 5 mol % to 20 mol %. Deoxidation method of an off-grade titanium sponge using magnesium.
The method of claim 1,
The deoxidation method of the off-grade titanium sponge using the magnesium
The method further comprises an acid leaching step of acid leaching the metal or metal compound of on-grade Ti using a hydrochloric acid solution to remove residual molten salt and magnesium oxide formed in the deoxidation reaction.
Deoxidation method of off-grade titanium sponge using magnesium.
11. The method of claim 10,
The concentration of the hydrochloric acid solution is characterized in that 5% to 20%
Deoxidation method of off-grade titanium sponge using magnesium.
11. The method of claim 10,
The leaching temperature of the acid leaching step is 0 ℃ to 25 ℃
Deoxidation method of off-grade titanium sponge using magnesium.
11. The method of claim 10,
The deoxidation method of the off-grade titanium sponge using the magnesium
After the acid leaching step, it characterized in that it further comprises a drying process.
Deoxidation method of off-grade titanium sponge using magnesium.
Electromagnetic products made of metal or metal compound of on-grade Ti formed by the deoxidation method of the off-grade titanium sponge using magnesium according to any one of claims 1 to 5 and 8 to 13 raw material for crafting.

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