KR20170097463A - Method for manufacturing tantalum chloride - Google Patents

Abstract

The present invention relates to a method of producing tantalum chloride. Specifically, the present invention provides a method of producing tantalum chloride, comprising the steps of: preparing scrap containing tantalum; washing the scrap; crushing the scrap; thermally treating the scrap to vaporize metal impurities so as to obtain a tantalum ingot; bringing the surface of the tantalum ingot in contact with gaseous hydrogen chloride (HCl) to generate gaseous tantalum chloride; and condensing, or condensing and solidifying the gaseous tantalum chloride to obtain tantalum chloride.

Description

[0001] METHOD FOR MANUFACTURING TANTALUM CHLORIDE [0002]

The present invention relates to a method for producing tantalum chloride.

Tantalum is widely used in industries such as electric, electronic, aviation, medical, optical, and military fields because it has excellent corrosion resistance, strength, dielectric constant and processability (electric conductivity). Especially, it is used for high capacity capacitors, semiconductors, medical materials, Superalloys, and gas turbines for power generation.

However, tantalum ore is one of the representative conflict minerals in Central African conflict areas such as the Congo. In 2010, the United States created new regulations on disputed minerals, which strengthened the use of disputed minerals, resulting in difficulties in receiving and supplying natural resources. Therefore, when recycling tantalum-containing scrap, it is possible to solve the problem of regulation of use of disputed minerals, and it is possible to simultaneously improve environmental pollution and waste of resources.

However, there are only domestic demanders for tantalum in Korea, and there is no company to recycle or commercialize tantalum natural ore, so stable supply of tantalum for sustainable development of related industries is unstable.

Therefore, the development of recycling technology for tantalum is very important, and if technology for producing alloy materials by recycling domestic scrap is developed, stable supply and demand of resources needed for domestic high-tech industries will be stabilized and profitability of the industry will be improved by creating added value. I can do it.

However, in the past, tantalum turning scrap from industrial sites is being recycled in a simple form, such as removing impurities from the naked eye and selling it to foreign recycling companies.

An embodiment of the present invention is to provide a method for manufacturing tantalum chloride capable of industrial recycling of tantalum by recovering high purity tantalum from tantalum scrap and preparing tantalum chloride from the tantalum scrap.

One embodiment of the present invention is a method of manufacturing a tantalum scrap comprising: preparing scrap comprising tantalum; Washing the scrap; Crushing the scrap; Heat treating the scrap to vaporize metal impurities and obtain a tantalum ingot; Contacting gaseous hydrogen chloride (HCl) on the surface of the tantalum ingot to produce gaseous tantalum chloride; And condensing said gaseous tantalum chloride; Or condensation and solidification to obtain tantalum chloride; and a process for producing tantalum chloride.

The scrap containing tantalum may contain at least one of Cr, Fe, and Ti as metal impurities.

Wherein the scrap comprising tantalum comprises at least 0.01% by weight of Cr and at most 1% by weight of Cr; Not less than 0.01% by weight of Fe, and not more than 1% by weight of Fe; And 0.01% or more by weight of Ti, and 1% or less by weight of Ti as metal impurities.

The scrap containing tantalum may be a scrap generated in the course of turning the tantalum.

Heat treating the scrap to vaporize metal impurities and obtain a tantalum ingot; and the heat treatment temperature may be 3200 ° C or higher and 3500 ° C or lower.

Heat treating the scrap to vaporize metal impurities and obtain a tantalum ingot may be performed at a vacuum of 10 ^-5 torr or more and 10 ^-3 torr.

The step of heat treating the scrap to vaporize the metal impurities and obtain the tantalum ingot may be carried out repeatedly three times or more and five times or less.

The step of washing the scrap may be performed by immersing the scrap in a volatile organic solvent and subjecting the scrap to ultrasonic treatment.

The volatile organic solvent may include methanol, ethanol, ethyl ether, acetone, or a combination thereof.

Washing the scrap; Thereafter, the scrap may be washed with an acid.

In the step of crushing the scrap, the scrap may be crushed to a particle size of 1 cm or more and 5 cm or less.

Contacting the surface of the tantalum ingot with gaseous hydrogen chloride (HCl) to produce gaseous tantalum chloride, may be carried out by the reaction of the following reaction formula (1).

[Reaction Scheme 1]

2Ta (s) + 10HCl (g ) → 2TaCl 5 (g) + 5H 2 (g)

The step of contacting gaseous hydrogen chloride (HCl) with the surface of the tantalum ingot to produce gaseous tantalum chloride may be performed at a temperature of 239.4 ° C or higher and 500 ° C or lower.

Condensing said gaseous tantalum chloride; Or condensation and coagulation to obtain tantalum chloride may be carried out at a temperature of 65 占 폚 or higher, and 239.4 占 폚 or lower.

According to another aspect of the present invention, there is provided a method for preparing tantalum chloride, comprising: contacting gaseous hydrogen chloride (HCl) on a surface of a tantalum ingot to produce gaseous tantalum chloride; Previously, it may further comprise vaporizing an aqueous solution of hydrogen chloride (HCl).

In the step of vaporizing the hydrogen chloride (HCl) aqueous solution, the content of hydrogen chloride relative to 100 wt% of the total weight of the hydrogen chloride aqueous solution may be 20 wt% or more and 35 wt% or less.

The step of vaporizing the hydrogen chloride (HCl) aqueous solution may be carried out at a temperature of 239.4 占 폚 or higher, and 500 占 폚 or lower.

The method of manufacturing tantalum chloride according to an embodiment of the present invention may further include recovering unreacted hydrogen chloride (HCl).

An embodiment of the present invention provides a method of manufacturing tantalum chloride capable of industrial recycling of tantalum by recovering high purity tantalum from tantalum scrap and producing tantalum chloride from the tantalum scrap.

1 is a schematic block diagram of a tantalum recovery method according to an embodiment of the present invention.
2 is a photograph of tantalum turning scrap used in an embodiment of the present invention.
3 is a photograph of a tantalum ingot recovered in accordance with an embodiment of the present invention.
4 is a schematic diagram of a tantalum chlorination apparatus used in an embodiment of the present invention.
5 is X-ray diffraction (XRD) result data of tantalum chloride (TaCl ₅ ) produced according to one embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

The terms first, second and third, etc. are used to describe various portions, components, regions, layers and / or sections, but are not limited thereto. These terms are only used to distinguish any moiety, element, region, layer or section from another moiety, moiety, region, layer or section. Thus, a first portion, component, region, layer or section described below may be referred to as a second portion, component, region, layer or section without departing from the scope of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms as used herein include plural forms as long as the phrases do not expressly express the opposite meaning thereto. Means that a particular feature, region, integer, step, operation, element and / or component is specified and that the presence or absence of other features, regions, integers, steps, operations, elements, and / It does not exclude addition.

Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Commonly used predefined terms are further interpreted as having a meaning consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or very formal meanings unless defined otherwise.

FIG. 1 is a schematic diagram of a method for producing tantalum chloride according to an embodiment of the present invention. The schematic constitution diagram of the method for producing tantalum chloride of FIG. 1 is merely for illustrating the present invention, and the present invention is not limited thereto. Therefore, the method of producing tantalum chloride can be variously modified.

Hereinafter, a method for producing tantalum chloride according to an embodiment of the present invention will be described with reference to FIG.

An embodiment of the present invention comprises: (S10) preparing a scrap comprising tantalum; Washing the scrap (S20); Crushing the scrap (S30); Heat treating the scrap to vaporize metal impurities and obtain a tantalum ingot (S40); Contacting the surface of the tantalum ingot with gaseous hydrogen chloride (HCl) to produce gaseous tantalum chloride (S50); And condensing said gaseous tantalum chloride; Or condensation and solidification to obtain tantalum chloride (S60).

According to the method of manufacturing tantalum chloride according to one embodiment of the present invention, high purity tantalum metal is recovered from tantalum scrap and tantalum chloride is produced using the recovered tantalum metal, thereby improving industrial recycling of tantalum.

Hereinafter, each step will be described in detail.

First, in step S10, scrap containing tantalum is prepared. Scrap can be scrap from tantalum turning. The scrap may contain at least one of Cr, Fe, and Ti as metal impurities. Specifically 0.01% or more by weight of Cr, and 1% or less by weight; Not less than 0.01% by weight of Fe, and not more than 1% by weight of Fe; And not less than 0.01% by weight of Ti, and not more than 1% by weight of Ti as metal impurities. In addition to the above-mentioned metallic impurities, scrap may contain oil such as cutting oil used in the turning process as an impurity.

Next, in step S20, the scrap is washed. The oil contained as impurities in the scrap can be removed in step S20. Specifically, the scrap can be immersed in a volatile organic solvent to remove oil fractions. At this time, the volatile organic solvent may be one containing methanol, ethanol, ethyl ether, acetone, or a combination thereof.

 However, the present invention is not limited thereto, and any volatile organic solvent suitable for oil removal can be used. More specifically, the scrap can be immersed in acetone and subjected to ultrasonic treatment to remove oil fractions.

Impurities such as oil may not be completely removed even in step S20. In this case, although not shown in Fig. 1, the step S20 may further include washing with acid. Impurities such as Cr, Fe, Ti, and Al can be removed by reaction with the acid by treating the scrap with an acid. As an example, in citric acid treatment, Fe can be removed in the form of iron citrate. In this case, any acid may be used as long as it is suitable for removing impurities.

Next, in step S30, the scrap is crushed. This is to vaporize metal impurities more easily when scrap is heat-treated in step S40. If the scrap is directly heat-treated without applying the step S30, unnecessarily large energy may be consumed to vaporize the metal impurities. If a scrap of a sufficiently small size is prepared in step S10, step S30 may be omitted. Although an example of performing step S30 after step S20 in FIG. 1 is shown, step S20 may be performed after step S30. However, it is more preferable to carry out step S20 first in terms of impurity removal efficiency such as oil.

In step S30, the scrap may be crushed to have a particle size of 1 cm or more and 5 cm or less. When scrap is crushed too small, unnecessarily large amounts of energy may be consumed. If the scrap is crushed too much, then unnecessarily much energy may be consumed in vaporizing the metal impurities in step S40. Therefore, scrap can be crushed in the above-mentioned range.

Next, in step S40, the scrap is heat-treated to vaporize the metal impurities to obtain a high-purity tantalum ingot. Cr, Fe, and Ti, which are major metal impurities in tantalum scrap, have a significantly lower vaporization temperature than tantalum. Therefore, when heat treatment is performed at an appropriate temperature, metal impurities are vaporized and separated to obtain high purity tantalum.

Specifically, the heat treatment temperature may be 3,200 ° C or higher and 3,500 ° C or lower. If the heat treatment temperature is too low, metal impurities may remain without vaporization. If the heat treatment temperature is too high, energy may be unnecessarily consumed. Therefore, the heat treatment can be performed in the above-mentioned range.

Step (S40) is 10 ^- may be performed at a vacuum degree of less than ³ torr ^{- 5} torr or higher, and 10. By performing at a low pressure in the above-mentioned range, metal impurities can be more easily vaporized and removed.

Step S40 can be repeated three to five times. At this time, the repetition means that the impurity metal is vaporized and removed by heat treatment to coagulate the molten tantalum, and then the coagulated tantalum is heat-treated again. By repeating the heat treatment the above-mentioned number of times, tantalum having higher purity can be obtained. It may be difficult to increase the purity even if it is repeated over the above-mentioned range.

By the manufacturing steps up to this point, it is possible to recover high purity tantalum ingots containing 0.0001 wt% or less of Cr, 0.005 wt% or less of Fe, 0.01 wt% or less of Ti and tantalum as the impurities.

In step S50, hydrogen chloride (HCl) in a gaseous state at a high temperature is brought into contact with the surface of the tantalum ingot to produce gaseous tantalum chloride (TaCl ₅ ). The tantalum chloride thus produced can be recycled as an industrial raw material. The production of tantalum chloride by the reaction of hydrogen chloride and tantalum can be carried out by the reaction shown in the following reaction formula (1).

[Reaction Scheme 1]

2Ta (s) + 10HCl (g ) → 2TaCl 5 (g) + 5H 2 (g)

At this time, the reaction temperature may be at 239.4 DEG C or higher, and 500 DEG C or lower. The reaction temperature is preferably 239.4 DEG C or higher, which is the boiling point of the tantalum chloride in order to obtain the product tantalum chloride as a gaseous state. When the temperature is too high, the increase in the reaction efficiency is insignificant, but the increase in the process cost is undesirably increased.

Vaporization of an aqueous solution of hydrogen chloride (HCl) prior to step S50, although not shown in FIG. This is to supply gaseous hydrogen chloride that can react and contact the surface of the tantalum ingot. At this time, the temperature for vaporizing the hydrogen chloride (HCl) aqueous solution is preferably 239.4 ° C or higher. More specifically, not less than 239.4 占 폚, and not more than 500 占 폚.

At a temperature within this range, hydrogen chloride (HCl) is vaporized and fed to the surface of the tantalum ingot, so that an appropriate temperature range in which gaseous tantalum chloride can be produced can be maintained. In this case, the aqueous solution of hydrogen chloride (HCl) used may contain hydrogen chloride (HCl) in an amount of 20 wt% or more and 35 wt% or less based on 100 wt% of the total weight of the aqueous hydrogen chloride solution.

If the amount of hydrogen chloride in the aqueous solution of hydrogen chloride is too small, the chlorination reaction of tantalum may be slowed down. On the other hand, when the amount of hydrogen chloride in the aqueous hydrogen chloride solution is too large, the solubility of hydrogen chloride in water as a solvent is exceeded, making it difficult to produce an aqueous solution of hydrogen chloride.

In step S60, the generated gaseous tantalum chloride is condensed; Or condensation and solidification to obtain a liquid or solid tantalum chloride. The temperature in step S60 can be adjusted to 65 deg. C or higher, and 239.4 deg. C or lower. If the temperature is too low, the hydrogen chloride gas may condense and the recovery of unreacted hydrogen chloride may become difficult. On the other hand, if the temperature is too high, the tantalum chloride may be vaporized, making it impossible to obtain tantalum chloride.

The melting point of tantalum chloride is known to be about 216 ° C. Thus, when the temperature of the condenser is 216 DEG C or higher and 239.4 DEG C or lower, tantalum chloride can be condensed and obtained in a liquid state. In this case, it is possible to further carry out the step of further solidifying the temperature-reduced and condensed tantalum chloride to obtain solid tantalum chloride. When the temperature of the condenser is lower than 216 캜, gaseous tantalum chloride can be obtained as a solid phase through condensation and solidification.

Although not shown in FIG. 1, the method for producing tantalum chloride according to an embodiment of the present invention may further include recovering unreacted hydrogen chloride (HCl). When the hydrogen chloride gas is supplied to the surface of the tantalum ingot, excess hydrogen chloride gas may be supplied relative to the reaction equivalent. Accordingly, unreacted hydrogen chloride gas may be generated. This unreacted hydrogen chloride gas can be recovered and recycled to reduce the process cost.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example

Recovery of tantalum metal

Tantalum turning scraps obtained from the tantalum turning process were prepared. The tantalum turning scrap is shown in Fig. The components of the tantalum turning scrap were analyzed by an X-ray fluorescence analyzer (XRF, manufacturer: RIGAKU, model name: SIMULTIX12) and found to contain 0.1 wt% Cr, 0.5 wt% Fe and 0.5 wt% Ti.

The tantalum turning scrap was immersed in acetone and washed with ultrasonic wave for 5 minutes to remove oil. Thereafter, the ultrasonic cleaned tantalum turning scrap was cut to a size of about 1.5 cm and vacuum-dried at a vacuum of 10 ^-4 torr using a vacuum arc remelter (VAR) equipped with a water-cooled copper mold and at 3300 ° C. The metal impurities were removed by volatilization three times by heat treatment. The obtained tantalum ingots are shown in Fig.

The obtained tantalum ingot was sampled and analyzed for metal impurity content using glow discharge mass spectrometry (GD-MS, manufactured by Thermo, model: Element GD). As a result, Cr: 0.11 ppm, Fe: Ti: 56ppm, and thus the purity of the tantalum ingot was confirmed to be over 99.9%.

The removal rate (%) of the metal impurity was calculated to be 99.989% Cr, 99.72% Fe, and 98.88% Ti.

As confirmed in the examples, it was confirmed that Cr, Fe, and Ti, which are major metal impurities other than tantalum, were removed by 98% or more through the method according to one embodiment of the present invention.

Manufacture of tantalum chloride

4 is a schematic diagram of a tantalum chlorination apparatus 100 used for chlorination of tantalum in this embodiment.

First, the high purity tantalum ingot 1 obtained above was charged into the tantalum ingot reservoir 2, and a 25% aqueous solution of hydrogen chloride (containing 25 wt% of hydrogen chloride per 100 wt% of the aqueous hydrogen chloride solution) (4). Thereafter, hydrogen chloride gas is supplied to the tantalum ingot reservoir 2 by heating the hydrogen chloride reservoir 3 and the tantalum ingot reservoir 2 to 400 DEG C, thereby contacting and reacting with the surface of the tantalum ingot 1, Tantalum was produced.

The generated gaseous tantalum chloride was introduced into the condenser 5, and the temperature of the condenser 5 was maintained at 100 캜. The gaseous tantalum chloride introduced into the condenser 5 solidified and solidified on the inner wall of the condenser 5 (6).

The excess unreacted hydrogen chloride gas was recovered into the hydrogen chloride storage 3 through the unreacted hydrogen chloride recovery pipe 7. After completion of the reaction, the temperature was lowered to room temperature to recover the tantalum chloride 6 adhering to the surface of the condenser Respectively.

The recovered tantalum chloride powder was subjected to X-ray diffraction (XRD) using an X-ray diffractometer (manufacturer: Rigaku model name: D / Max-2500V) .

The tantalum chloride phase was confirmed in FIG. 5, and it was confirmed that high purity tantalum chloride was produced.

As has been confirmed in the above-mentioned examples, Cr, Fe, and Ti, which are major metal impurities other than tantalum, were found to have a removal effect of 98% or more through the above-described processes. Based on this, tantalum chloride can be produced, .

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

1: Tantalum ingot 2: Tantalum ingot storage
3: HCl storage tank 4: HCl aqueous solution
5: condenser 6: tantalum chloride
7: unreacted hydrogen chloride recovery pipe 100: tantalum chloride device

Claims (18)

Preparing a scrap comprising tantalum;
Washing the scrap;
Crushing the scrap;
Heat treating the scrap to vaporize metal impurities and obtain a tantalum ingot;
Contacting gaseous hydrogen chloride (HCl) on the surface of the tantalum ingot to produce gaseous tantalum chloride; And
Condensing said gaseous tantalum chloride; Or condensation and solidification to obtain tantalum chloride;
Method of manufacturing tantalum chloride. The method of claim 1,
The scrap comprising tantalum may comprise:
And at least one of Cr, Fe, and Ti is contained as a metal impurity.
Method of manufacturing tantalum chloride. 3. The method of claim 2,
The scrap comprising tantalum may comprise:
At least 0.01% Cr, and at most 1% Cr;
Not less than 0.01% by weight of Fe, and not more than 1% by weight of Fe; And
At least 0.01% by weight of Ti, and at most 1% by weight of Ti as metal impurities.
Method of manufacturing tantalum chloride. The method of claim 1,
The scrap comprising tantalum may comprise:
Which is a scrap generated during the turning of tantalum,
Method of manufacturing tantalum chloride. The method of claim 1,
Heat treating the scrap to vaporize metal impurities and obtain a tantalum ingot;
The heat-
3200 ° C and 3500 ° C,
Method of manufacturing tantalum chloride. The method of claim 1,
Heat treating the scrap to vaporize metal impurities and obtain a tantalum ingot;
10 ^{- 5} torr, and 10 ^{- 3} torr.
Method of manufacturing tantalum chloride. The method of claim 1,
Heat treating the scrap to vaporize metal impurities and obtain a tantalum ingot;
3 times, and 5 times or less.
Method of manufacturing tantalum chloride. The method of claim 1,
Washing the scrap,
The scrap is immersed in a volatile organic solvent and then subjected to ultrasonic treatment.
Method of manufacturing tantalum chloride. 9. The method of claim 8,
The volatile organic solvent may be,
Wherein the solvent comprises methanol, ethanol, ethyl ether, acetone, or a combination thereof.
Method of manufacturing tantalum chloride. The method of claim 1,
Washing the scrap; Since the,
And washing the scrap with an acid.
Method of manufacturing tantalum chloride. The method of claim 1,
And crushing the scrap,
Wherein the scrap is ground to a particle size of 1 cm or more and 5 cm or less,
Method of manufacturing tantalum chloride. The method of claim 1,
Contacting the surface of the tantalum ingot with gaseous hydrogen chloride (HCl) to produce gaseous tantalum chloride,
Lt; RTI ID = 0.0 > 1, < / RTI >
Method of manufacturing tantalum chloride.
[Reaction Scheme 1]
2Ta (s) + 10HCl (g ) → 2TaCl 5 (g) + 5H 2 (g) The method of claim 1,
Contacting the surface of the tantalum ingot with gaseous hydrogen chloride (HCl) to produce gaseous tantalum chloride,
239.4 DEG C, and 500 DEG C or less.
Method of manufacturing tantalum chloride. The method of claim 1,
Condensing said gaseous tantalum chloride; Or condensation and solidification to obtain tantalum chloride;
≪ RTI ID = 0.0 > 65 C, < / RTI &
Method of manufacturing tantalum chloride. The method of claim 1,
Contacting gaseous hydrogen chloride (HCl) on the surface of the tantalum ingot to produce gaseous tantalum chloride; Before,
Further comprising the step of vaporizing an aqueous solution of hydrogen chloride (HCl)
Method of manufacturing tantalum chloride. 16. The method of claim 15,
Vaporizing the hydrogen chloride (HCl) aqueous solution,
The content of hydrogen chloride relative to 100 wt% of the total weight of the aqueous solution of hydrogen chloride,
20 wt% or more, and 35 wt% or less.
Method of manufacturing tantalum chloride. 16. The method of claim 15,
Vaporizing the hydrogen chloride (HCl) aqueous solution,
239.4 DEG C, and 500 DEG C or less.
Method of manufacturing tantalum chloride. The method of claim 1,
Recovering unreacted hydrogen chloride < RTI ID = 0.0 > (HCI) < / RTI &
Method of manufacturing tantalum chloride.

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