Low-oxygen vanadium carbide and method for producing the same

Abstract

The present invention provides a low-oxygen vanadium carbide and a method for producing the same, which is formed by reducing the oxygen content, mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy milling apparatus, followed by vacuum heat treatment and a carbonization reduction reaction.

Description

[Technical Field]

[0001] The present invention relates to a low-oxygen vanadium carbide and a method for producing the same, which is formed by reducing the oxygen content, mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy milling apparatus, followed by vacuum heat treatment and a carbonization reduction reaction. [Background technology]

[0002] Vanadium metal is a substance that readily forms carbides, nitrides, or oxides due to its high affinity for nonmetallic components such as carbon, nitrogen, or oxygen.

[0003] Therefore, although vanadium carbides, produced by the bonding of vanadium and carbon, are easy to synthesize, due to vanadium's strong affinity for oxygen, it is not easy to synthesize pure (low-oxygen) carbides.

[0004] That is, V(C x O 1-x Because x<1 form oxycarbides are readily formed, the production of vanadium carbides with low oxygen content is not easily carried out.

[0005] In particular, hypoxic vanadium carbides, which are said to be formable from a thermodynamic theory perspective, are compounds in which vacancies exist at some carbon positions in the VCx form. In reality, many vacancies exist within the lattice, and oxygen penetration into these vacancies occurs frequently, resulting in V(C) x O 1-x Because this transformation is likely to occur, synthesizing low-oxygen vanadium carbide is very difficult.

[0006] Therefore, the applicant of the present application has, through long-term painstaking efforts and various studies, reduced the oxygen content, mixed vanadium oxide and a carbon compound, and then, through a high-energy milling device, refined the particle size by high-energy milling, subjected it to vacuum heat treatment, and caused a carbonization reduction reaction to obtain a low-oxygen vanadium carbide formed thereby and a method for producing the same, thus completing the present invention. Summary of the Invention Problems to be Solved by the Invention

[0007] Therefore, an object of the present invention is to provide a low-oxygen vanadium carbide formed by reducing the oxygen content, mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling through a high-energy milling device, subjecting it to vacuum heat treatment, and causing a carbonization reduction reaction.

[0008] Another object of the present invention is to provide a method for producing a low-oxygen vanadium carbide, which comprises mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling through a high-energy milling device, subjecting it to vacuum heat treatment, and causing a carbonization reduction reaction.

[0009] Another object of the present invention is to provide the use of a low-oxygen vanadium carbide formed by mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling through a high-energy milling device, subjecting it to vacuum heat treatment, and causing a carbonization reduction reaction.

[0010] Another object of the present invention is to provide a low-oxygen vanadium carbide having a particle size of 2 nm to 50 μm produced by the method for producing a low-oxygen vanadium carbide.

[0011] Another object of the present invention is to provide a low-oxygen vanadium carbide having the chemical formula VCx produced by the method for producing a low-oxygen vanadium carbide, wherein the range of x is 0.3 < x < 1.

[0012] Another object of the present invention is to provide an application of a low-oxygen vanadium carbide having a particle size of 2 nm to 50 μm produced by the method for producing a low-oxygen vanadium carbide.

[0013] Another object of the present invention is to provide an application of a low-oxygen vanadium carbide having a chemical formula of VCx produced by the method for producing a low-oxygen vanadium carbide, wherein the range of x is 0.3 < x < 1.

[0014] The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

Means for Solving the Problems

[0015] According to one aspect of the present invention for solving the above problems, a low-oxygen vanadium carbide, including a low-oxygen vanadium carbide in which the oxygen content is reduced and the particle size is refined by high-energy milling with 0.6 to 2.4 J / g·s of high energy input, the low-oxygen vanadium carbide is formed by mixing a vanadium oxide and a carbon compound, then refining the particle size by the high-energy milling through a high-energy milling device and subjecting to vacuum heat treatment for carbonization reduction reaction, and is characterized in that, a low-oxygen vanadium carbide is provided.

[0016] According to one embodiment of the present invention, the oxygen content may be 10 ppm to 10,000 ppm.

[0017] According to one embodiment of the present invention, the low-oxygen vanadium carbide has a chemical formula of VCx, and the range of x may be 0.3 < x < 1.

[0018] According to one embodiment of the present invention, the molar ratio (B / A) of the carbon compound (B) to the vanadium oxide (A) may be 6.1 to 7.5.

[0019] According to an embodiment of the present invention, the particle size of the mixed powder of the vanadium oxide or the carbon compound may be 2 nm to 50 μm.

[0020] According to an embodiment of the present invention, the vanadium oxide may be at least any one selected from vanadium pentoxide (V2O5), sodium metavanadate (NaVO3), vanadium trioxide (V2O3), vanadium oxychloride (VOCl3), and ammonium metavanadate (H4NVO3).

[0021] According to an embodiment of the present invention, the carbon compound is at least any one selected from industrial carbon powder, coke, coal, coal tar, activated carbon, graphite, natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, industrial diamond, and carbon fiber.

[0022] According to an embodiment of the present invention, the high-energy milling is After mixing the vanadium oxide and the carbon compound, the mixed powder is put into a rotating container in a high-energy milling device together with steel balls, and then In an atmosphere of air, vacuum, nitrogen or argon, high energy of 0.6 to 2.4 J / g·s is input, the rotating shaft is rotated at 500 to 1500 rpm, and the rotating container is rotated in the opposite direction to the rotation direction of the rotating shaft at 2000 to 3500 rpm, and high-energy milling can be performed in a short time of 10 to 100 minutes.

[0023] According to an embodiment of the present invention, the high-energy milling device is a planetary ball mill, a SPEX mill or an attritor.

[0024] According to an embodiment of the present invention, the heat treatment temperature of the vacuum heat treatment may be 800°C to 1600°C, The heat treatment time may range from 10 minutes to 24 hours.

[0025] According to one embodiment of the present invention, the carbonization reduction reaction is carried out as follows: By using the high-energy milling method to refine the vanadium oxide and carbon compound, the contact area can be increased, thereby increasing the rate of the carbon reduction reaction.

[0026] Furthermore, according to another aspect of the present invention, A method for producing low-oxygen vanadium carbide, (a-1) A step of mixing vanadium oxide and a carbon compound to produce a mixed powder; (a-2) The step of introducing the mixed powder together with steel balls into a rotating container in a high-energy milling apparatus; (a-3) A step of producing fine powder by high-energy milling in an atmosphere of air, vacuum, nitrogen or argon, applying a high energy of 0.6 to 2.4 J / g·s and rotating the rotating shaft and rotating vessel in different directions from each other; and, (a-4) The step of producing low-oxygen vanadium carbide is to perform a vacuum heat treatment on the fine powder to cause a carbonization reduction reaction, A method for producing low-oxygen vanadium carbide can be provided.

[0027] According to one embodiment of the present invention, in the step of mixing (a-1) vanadium oxide and a carbon compound to produce a mixed powder, The mixing ratio of the vanadium oxide and the carbon compound may be 1:0.2 to 1:0.7 by weight.

[0028] According to one embodiment of the present invention, in the step of introducing the (a-2) mixed powder into a rotating container in a high-energy milling apparatus together with steel balls, The steel ball may be at least one selected from ceramic balls, metal balls, and cemented carbide.

[0029] According to an embodiment of the present invention, in the step of manufacturing fine powder by introducing high energy of 0.6 to 2.4 J / g·s in an atmosphere of air, vacuum, nitrogen or argon and rotating the rotating shaft and the rotating container in different directions from each other for high energy milling, the rotating shaft may be rotated at 500 to 1500 rpm, and the rotating container may be rotated in a direction opposite to the rotation direction of the rotating shaft at 2000 to 3500 rpm for high energy milling during a short time of 10 to 100 minutes.

[0030] According to an embodiment of the present invention, in the step of manufacturing low-oxygen vanadium carbide by subjecting the fine powder to vacuum heat treatment for a carboreduction reaction, for the vacuum heat treatment the heat treatment temperature may be 800°C to 1600°C, and the heat treatment time may be 10 minutes to 24 hours.

[0031] According to an embodiment of the present invention, the high energy milling device may be a planetary ball mill, a SPEX mill or an attritor.

[0032] Also, according to another aspect of the present invention, it is possible to provide low-oxygen vanadium carbide whose use is a MAX precursor, a raw material for cemented carbide, a catalyst or a semiconductor material.

[0033] Also, according to another aspect of the present invention, it is possible to provide low-oxygen vanadium carbide having a particle size of 2 nm to 50 μm produced by the method for producing low-oxygen vanadium carbide.

[0034] According to another aspect of the present invention, it is possible to provide low-oxygen vanadium carbide having the chemical formula of VCx produced by the method for producing low-oxygen vanadium carbide, wherein the range of x is 0.3 < x < 1.

[0035] According to another aspect of the present invention, there is provided a low-oxygen vanadium carbide produced by the method for producing a low-oxygen vanadium carbide, which is used as a MAX precursor, a raw material for cemented carbide materials, a catalyst or a semiconductor material.

Advantages of the Invention

[0036] According to the present invention, in order to provide a low-oxygen vanadium carbide formed by reducing the oxygen content, mixing a vanadium oxide and a carbon compound, and then subjecting the particle size to high-energy milling through a high-energy milling device to be refined and vacuum heat-treated to cause a carbothermal reduction reaction, the low-oxygen vanadium carbide has a low oxygen content, a small particle size, excellent physical properties, and can be used in various applications such as a MAX precursor, a raw material for cemented carbide materials, a catalyst or a semiconductor material.

[0037] In addition, the present invention provides a method for producing a low-oxygen vanadium carbide, which comprises mixing a vanadium oxide and a carbon compound, then subjecting the particle size to high-energy milling through a high-energy milling device to be refined and vacuum heat-treated to cause a carbothermal reduction reaction. Therefore, the method has excellent process stability, can be mass-produced, and is economical.

[0038] In addition, the present invention provides a low-oxygen vanadium carbide having a particle size of 2 nm to 50 μm produced by the method for producing a low-oxygen vanadium carbide. Therefore, the low-oxygen vanadium carbide has a low oxygen content, a small particle size, excellent physical properties, and can be used in various applications such as a MAX precursor, a raw material for cemented carbide materials, a catalyst or a semiconductor material.

[0039] In addition, the present invention provides a low-oxygen vanadium carbide having the chemical formula VCx and the range of x being 0.3 < x < 1 produced by the method for producing a low-oxygen vanadium carbide. Therefore, the low-oxygen vanadium carbide has a low oxygen content, a small particle size, excellent physical properties, and can be used in various applications such as a MAX precursor, a raw material for cemented carbide materials, a catalyst or a semiconductor material.

[0040] The effects of the present invention are not limited to those described above, but should be understood to include all effects that can be inferred from the detailed description of the present invention or the configuration of the invention as described in the claims. [Brief explanation of the drawing]

[0041]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

[0042] In the following, preferred embodiments of the present invention will be described in detail with reference to the attached drawings.

[0043] The advantages and features of the present invention, and the methods for achieving them, will become clear when you refer to the embodiments described in detail below, along with the accompanying drawings.

[0044] However, the present invention is not limited to the embodiments disclosed below, but can be embodied in a variety of different forms. These embodiments are provided to complete the disclosure of the present invention and to fully inform those who are ordinary skill in the art to which the invention pertains, and the present invention is defined only by the scope of the claims.

[0045] Furthermore, in describing the present invention, if it is determined that related known technologies or other elements would obscure the gist of the present invention, a detailed explanation thereof will be omitted.

[0046] The present invention will be described in detail below.

[0047] Low-oxygen vanadium carbide The present invention provides a low-oxygen vanadium carbide formed by reducing the oxygen content, mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy milling apparatus, followed by vacuum heat treatment and a carbonization reduction reaction.

[0048] The present invention relates to a low-oxygen vanadium carbide, It contains low-oxygen vanadium carbide, whose oxygen content has been reduced and whose particle size has been refined by high-energy milling with high energy input of 0.6~2.4 J / g·s. The low-oxygen vanadium carbide is formed by mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy milling apparatus, followed by vacuum heat treatment and a carbonization reduction reaction.

[0049] The present invention provides a low-oxygen vanadium carbide formed by reducing the oxygen content, mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy milling apparatus, followed by vacuum heat treatment and a carbonization reduction reaction. As a result, the low-oxygen vanadium carbide has a low oxygen content, small particle size, and excellent physical properties, making it suitable for various applications such as a max precursor, a raw material for cemented carbide materials, a catalyst, or a semiconductor material.

[0050] Vanadium metal is a substance that readily forms carbides, nitrides, or oxides due to its high affinity for nonmetallic components such as carbon, nitrogen, or oxygen.

[0051] Therefore, although vanadium carbide produced by the combination of vanadium and carbon is an easy-to-produce compound, due to the property of vanadium having a high affinity for oxygen, it is not easy to synthesize a pure (low-oxygen-content) carbide.

[0052] That is, since oxycarbides in the form of V(C x O 1-x ), where x < 1, are readily formed, the production of vanadium carbide with a low oxygen content is not easily achieved.

[0053] In particular, theoretically thermodynamically, low-oxygen vanadium carbide, which is said to be formable, is a compound in the form of VCx with vacancies in some carbon positions, and in reality, there are many vacancies in the lattice, and oxygen intrusion into the vacancies readily occurs, and thus it is very difficult to synthesize low-oxygen vanadium carbide because it easily changes to V(C x O 1-x ).

[0054] Therefore, the applicant has, through long-term painstaking efforts and various studies, reduced the oxygen content, mixed vanadium oxide and carbon compound, and then refined the particle size through high-energy milling and subjected it to vacuum heat treatment and carbonization reduction reaction through a high-energy milling device, thereby obtaining a low-oxygen vanadium carbide and its manufacturing method and completing the present invention.

[0055] In addition, the low-oxygen vanadium carbide of the present invention can be formed by mixing vanadium oxide and carbon compound, then refining the particle size through high-energy milling through a high-energy milling device, subjecting it to vacuum heat treatment, and performing a carbonization reduction reaction.

[0056] At this time, the oxygen content may be 10 ppm to 10,000 ppm.

[0057] Here, when the oxygen content is within the above range, V(C x O 1-x)The oxygen carbide of the form may not be easily formed.

[0058] At this time, the content of the oxygen may preferably be 30 ppm to 8,000 ppm, and more preferably 100 ppm to 2,000 ppm.

[0059] And the low-oxygen vanadium carbide has a chemical formula of VCx, The range of x may be 0.3 < x < 1.

[0060] Here, when the range of x is within the above range, the low-oxygen vanadium carbide may not easily form the oxygen carbide of the V(C x O 1-x ) form.

[0061] At this time, the range of x may preferably be 0.4 < x < 0.9, and more preferably 0.45 < x < 0.8.

[0062] Also, the molar ratio (B / A) of the carbon compound (B) to the vanadium oxide (A) may be 6.1 to 7.5.

[0063] Here, when the molar ratio (B / A) of the carbon compound (B) to the vanadium oxide (A) is within the above range, the low-oxygen vanadium carbide may not easily form the oxygen carbide of the V(C x O 1-x ) form.

[0064] At this time, the molar ratio (B / A) of the carbon compound (B) to the vanadium oxide (A) may preferably be 6.3 to 7.0, and more preferably 6.45 to 6.8.

[0065] And the particle size of the mixed powder of the vanadium oxide or the carbon compound may be 2 nm to 50 μm.

[0066] Here, if the particle size of the mixed powder of the vanadium oxide or the carbon compound is within the above range, the contact area between the vanadium oxide and the carbon compound increases, and the rate of the carbonization reduction reaction may increase.

[0067] In this case, the particle size of the mixed powder of vanadium oxide or carbon compound may preferably be 2 nm to 48 μm, and more preferably 2 nm to 45 μm.

[0068] In other words, the present invention increases the reaction rate by reducing the particle size of the raw material, a mixed powder of vanadium oxide and carbon compound, to 2 nm to 50 μm through a high-energy milling process. As a result, a low-oxygen vanadium carbide with a particle size of 2 nm to 50 μm and low oxygen content is produced.

[0069] Furthermore, the vanadium oxide may be at least one selected from vanadium pentoxide (V2O5), sodium metavanadate (NaVO3), vanadium trioxide (V2O3), vanadium oxychloride (VOCl3), and ammonium metavanadate (H4NVO3).

[0070] Here, when vanadium oxide (V2O5) is used as a raw material for synthesizing vanadium carbide, the vanadium carbide is formed by the reaction of vanadium oxide with carbon, i.e., by carbon reduction, as shown in Chemical Formula 1 below.

[0071] V2O5+7C→2VC+5CO -----(chemical 1)

[0072] In this process, theoretically, by adjusting the amount of carbon to less than 7 moles per mole of vanadium oxide, a VCx form of hypoxic vanadium carbide may be synthesized.

[0073] However, in actual processes, reducing the amount of carbon that acts as a reducing agent decreases the reaction rate for reduction, and V(C) has a high oxygen content. x O 1-xAcid carbides of the ) form can be easily formed.

[0074] Furthermore, in order to form vanadium carbides, it is necessary not only to adjust the amount of carbon, but also to perform treatments to increase the rate of the carbonization reduction reaction.

[0075] In this invention, the particle size of the mixed powder of vanadium oxide and carbon, which are the raw materials, is reduced to the above range through a high-energy milling process, thereby increasing the reaction rate. This resulted in the synthesis of low-oxygen vanadium carbide with a low oxygen content.

[0076] Furthermore, the carbon compound is It may be at least one selected from industrial carbon powder, coke, coal, coal tar, activated carbon, graphite, natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, industrial diamond, and carbon fiber.

[0077] Here, the carbon compound may further include biomass, which is at least one selected from coffee grounds, fallen leaves, and discarded wood.

[0078] Furthermore, the carbon compound may further contain a reducing gas containing carbon, which is at least one of carbon monoxide, methane, and hydrocarbons.

[0079] And the high-energy milling described above is After mixing the vanadium oxide and carbon compound, the mixed powder is placed together with steel balls into a rotating container in a high-energy milling apparatus. In an atmosphere of air, vacuum, nitrogen, or argon, by applying a high energy of 0.6 to 2.4 J / g·s, the rotating shaft is rotated at 500 to 1500 rpm, and the rotating vessel is rotated at 2000 to 3500 rpm in the opposite direction to the rotation of the rotating shaft, enabling high-energy milling in a short time of 10 to 100 minutes.

[0080] Furthermore, the high-energy milling apparatus may be a planetary ball mill, a SPEX mill, or an attritor.

[0081] In this planetary ball mill, steel balls are loaded into a container along with the raw materials, and the container rotates and revolves at high speed, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0082] Furthermore, in the SPEX mill, steel balls are loaded into the container along with the raw materials, and the container vibrates at high speed up and down and left and right, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0083] Furthermore, the attritor is loaded with steel balls together with the raw materials into a container, and energy is transmitted by the rotational force of the rotor, thereby reducing the particle size of the mixed powder of vanadium oxide and the carbon compound to the above range.

[0084] Furthermore, the high-energy milling apparatus can reduce the particle size of the mixed powder of vanadium oxide and carbon compound to the above range by rotating the rotating container containing the mixed powder of vanadium oxide and carbon compound on the rotating plate in opposite directions to the rotation direction of the rotation axis of the rotating plate.

[0085] And the vacuum heat treatment The heat treatment temperature may be between 800°C and 1600°C. The heat treatment time may range from 10 minutes to 24 hours.

[0086] Here, if the heat treatment temperature of the vacuum heat treatment is within the above range, the low-oxygen vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0087] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus can be subjected to vacuum heat treatment at the heat treatment temperature of the vacuum heat treatment to produce a low-oxygen vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

[0088] In this case, the heat treatment temperature for the vacuum heat treatment may preferably be 850°C to 1600°C, and more preferably 900°C to 1600°C.

[0089] Furthermore, if the heat treatment time for the vacuum heat treatment is within the above range, the low-oxygen vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0090] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus is subjected to vacuum heat treatment during the heat treatment time of the vacuum heat treatment to produce a low-oxygen vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

[0091] In this case, the heat treatment time for the vacuum heat treatment may preferably be 20 minutes to 24 hours, and more preferably 30 minutes to 24 hours.

[0092] Furthermore, the carbonization reduction reaction is By using the high-energy milling method to refine the vanadium oxide and carbon compound, the contact area can be increased, thereby increasing the rate of the carbon reduction reaction.

[0093] Figure 1 is a schematic diagram of the reaction of a low-oxygen vanadium carbide produced by the carbon-reduction reaction of a vanadium oxide and a carbon compound according to one embodiment of the present invention.

[0094] Referring to Figure 1, the reaction equation for low-oxygen vanadium carbide produced by the carbon-reduction reaction of vanadium oxide and carbon compounds is shown in Chemical Formula 2 below.

[0095] VOa+(x+a)C→VCx+aCO ------(C2)

[0096] For example, when vanadium oxide (V2O5) is used as a raw material for synthesizing low-oxygen vanadium carbide, the vanadium carbide is formed by the reaction of vanadium oxide with carbon, i.e., by carbonization reduction, as shown in Chemical Formula 3 below.

[0097] V2O5+(5+2x)C→2VCx+5CO -----(C3)

[0098] Here, formula 3 above is a combination of the two chemical formulas shown in Figure 1.

[0099] Method for producing low-oxygen vanadium carbide The present invention provides a method for producing low-oxygen vanadium carbide, which involves mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy milling apparatus, followed by vacuum heat treatment to induce a carbonization reduction reaction.

[0100] The present invention is a method for producing low-oxygen vanadium carbide, (a-1) A step of mixing vanadium oxide and a carbon compound to produce a mixed powder; (a-2) The step of introducing the mixed powder together with steel balls into a rotating container in a high-energy milling apparatus; (a-3) A step of producing fine powder by high-energy milling in an atmosphere of air, vacuum, nitrogen or argon, applying a high energy of 0.6 to 2.4 J / g·s and rotating the rotating shaft and rotating vessel in different directions from each other; and, (a-4) The step of vacuum heat treatment of the fine powder to cause a carbonization reduction reaction to produce low-oxygen vanadium carbide.

[0101] The present invention provides a method for producing low-oxygen vanadium carbide by mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy milling apparatus, followed by vacuum heat treatment to induce a carbonization reduction reaction. This method offers excellent process stability, enables mass production, and is economical.

[0102] Furthermore, in the step of mixing vanadium oxide and a carbon compound to produce a mixed powder, The mixing ratio of the vanadium oxide and the carbon compound may be 1:0.2 to 1:0.7 by weight.

[0103] Here, if the mixing ratio of the vanadium oxide and the carbon compound is within the above range by weight, then V(C) has a high oxygen content. x O 1-x ) Acid carbides of this form may not be easily formed.

[0104] In this case, the mixing ratio of the vanadium oxide and the carbon compound may preferably be 1:0.4 to 1:0.6 by weight, and more preferably 1:0.45 to 1:0.55 by weight.

[0105] Then, in the step of introducing the (a-2) mixed powder into a rotating container in a high-energy milling apparatus together with steel balls, The steel ball may be at least one selected from ceramic balls, metal balls, and cemented carbide balls.

[0106] Specifically, the material of the steel ball may be iron, tungsten, or zirconia.

[0107] Here, the shape of the steel ball may be at least one selected from spherical, star-shaped, angular, and columnar.

[0108] Furthermore, in the step of producing fine powder by high-energy milling in an atmosphere of air, vacuum, nitrogen, or argon, by applying a high energy of 0.6 to 2.4 J / g·s and rotating the rotating shaft and rotating container in opposite directions, The rotating shaft may be rotated at 500 to 1500 rpm, and the rotating container may be rotated at 2000 to 3500 rpm in the opposite direction to the rotation of the rotating shaft, thereby performing high-energy milling over a short period of time of 10 to 100 minutes.

[0109] Here, the high-energy milling may be a process in which energy is applied at a rate of 0.6 to 2.4 J / g·s to rotate the rotating shaft and the rotating container in opposite directions, and the steel balls placed in the rotating container are milled by friction between them and the mixed powder of vanadium oxide and the carbon compound, thereby pulverizing the particles of the mixed powder of vanadium oxide and the carbon compound and reducing the average particle size of the mixed powder to 2 nm to 50 μm.

[0110] Furthermore, the high-energy milling apparatus may be a planetary ball mill, a SPEX mill, or an attritor.

[0111] In this planetary ball mill, steel balls are loaded into a container along with the raw materials, and the container rotates and revolves at high speed, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0112] Furthermore, in the SPEX mill, steel balls are loaded into the container along with the raw materials, and the container vibrates at high speed up and down and left and right, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0113] Furthermore, the attritor is loaded with steel balls together with the raw materials into a container, and energy is transmitted by the rotational force of the rotor, thereby reducing the particle size of the mixed powder of vanadium oxide and the carbon compound to the above range.

[0114] Furthermore, the high-energy milling apparatus can reduce the particle size of the mixed powder of vanadium oxide and carbon compound to the above range by rotating the rotating container containing the mixed powder of vanadium oxide and carbon compound on the rotating plate in opposite directions to the rotation direction of the rotation axis of the rotating plate.

[0115] Then, in the step of producing low-oxygen vanadium carbide by vacuum heat treatment of the (a-4) fine powder to cause a carbonization reduction reaction, The vacuum heat treatment The heat treatment temperature may be between 800°C and 1600°C. The heat treatment time may range from 10 minutes to 24 hours.

[0116] Here, if the heat treatment temperature of the vacuum heat treatment is within the above range, the low-oxygen vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0117] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus can be subjected to vacuum heat treatment at the heat treatment temperature of the vacuum heat treatment to produce a low-oxygen vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

[0118] In this case, the heat treatment temperature for the vacuum heat treatment may preferably be 850°C to 1600°C, and more preferably 900°C to 1600°C.

[0119] Furthermore, if the heat treatment time for the vacuum heat treatment is within the above range, the low-oxygen vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0120] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus is subjected to vacuum heat treatment during the heat treatment time of the vacuum heat treatment to produce a low-oxygen vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

[0121] In this case, the heat treatment time for the vacuum heat treatment may preferably be 20 minutes to 24 hours, and more preferably 30 minutes to 24 hours.

[0122] Figure 2 is a flowchart of the process for producing low-oxygen vanadium carbide according to one embodiment of the present invention.

[0123] Referring to Figure 2, first, a mixed powder is produced by mixing vanadium oxide and a carbon compound (S110).

[0124] Subsequently, the mixed powder is fed into a rotating container in a high-energy milling apparatus along with steel balls (S120).

[0125] Subsequently, in an atmosphere of air, vacuum, nitrogen, or argon, a high energy of 0.6 to 2.4 J / g·s is applied, and the rotating shaft and rotating vessel are rotated in opposite directions to produce fine powder by high-energy milling (S130).

[0126] Subsequently, the fine powder is subjected to vacuum heat treatment to induce a carbonization reduction reaction, thereby producing low-oxygen vanadium carbide (S140).

[0127] Figure 3 is a schematic diagram of a rotating plate of a high-energy milling apparatus according to one embodiment of the present invention.

[0128] Referring to Figure 3, the rotation direction of the main spindle of the rotating plate of the high-energy milling apparatus and the rotation direction of the rotating container containing the mixed powder of vanadium oxide and carbon compound are opposite to each other. This opposite rotational force can reduce the particle size of the mixed powder of vanadium oxide and carbon compound to 2 nm to 50 μm.

[0129] Use of low-oxygen vanadium carbide The present invention provides applications for low-oxygen vanadium carbide, which is formed by mixing vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy milling apparatus, followed by vacuum heat treatment and a carbonization reduction reaction.

[0130] The present invention can provide a low-oxygen vanadium carbide whose applications include being a max precursor, a raw material for cemented carbide materials, a catalyst, or a semiconductor material.

[0131] Low-oxygen vanadium carbide with a particle size of 2 nm to 50 μm The present invention provides low-oxygen vanadium carbide, which has a particle size of 2 nm to 50 μm, produced by the method for producing low-oxygen vanadium carbide described above.

[0132] The present invention can provide a low-oxygen vanadium carbide having a particle size of 2 nm to 50 μm, which is produced by the method for producing the low-oxygen vanadium carbide.

[0133] In order to provide a low-oxygen vanadium carbide having a particle size of 2 nm to 50 μm, which is produced by the method for producing the low-oxygen vanadium carbide, the present invention provides a low-oxygen vanadium carbide having a low oxygen content, a small particle size, excellent physical properties, and can be used in various applications such as a MAX precursor, a raw material for cemented carbide, a catalyst, or a semiconductor material.

[0134] The present invention can provide a low-oxygen vanadium carbide having a use as a MAX precursor, a raw material for cemented carbide, a catalyst, or a semiconductor material, which is the low-oxygen vanadium carbide produced by the method for producing the low-oxygen vanadium carbide.

[0135] Through the high-energy ball milling process, the present invention reduces the particle size of the mixed powder of vanadium oxide and carbon compound as raw materials to 2 nm to 50 μm, increases the reaction rate, and thereby can produce a low-oxygen vanadium carbide having a particle size of 2 nm to 50 μm and a low oxygen content.

[0136] Low-oxygen vanadium carbide having the chemical formula VCx, where the range of x is 0.3 < x < 1 The present invention provides a low-oxygen vanadium carbide having the chemical formula VCx, where the range of x is 0.3 < x < 1, which is produced by the method for producing the low-oxygen vanadium carbide.

[0137] The present invention can provide a low-oxygen vanadium carbide having the chemical formula VCx, where the range of x is 0.3 < x < 1, which is produced by the method for producing the low-oxygen vanadium carbide.

[0138] The present invention can provide a low-oxygen vanadium carbide having a use as a MAX precursor, a raw material for cemented carbide, a catalyst, or a semiconductor material, which is the low-oxygen vanadium carbide produced by the method for producing the low-oxygen vanadium carbide.

[0139] The present invention provides a low-oxygen vanadium carbide having a chemical formula of VCx produced by the method for producing the low-oxygen vanadium carbide, where the range of x is 0.3 < x < 1. The low-oxygen vanadium carbide has a low oxygen content, a small particle size, excellent physical properties, and can be used in various applications such as a MAX precursor, a raw material for cemented carbide materials, a catalyst, or a semiconductor material.

[0140] The present invention reduces the particle size of the mixed powder of vanadium oxide and carbon compound as raw materials to 2 nm to 50 μm through a high-energy milling process, increasing the reaction rate, thereby enabling the production of a low-oxygen vanadium carbide having a chemical formula of VCx, where the range of x is 0.3 < x < 1.

[0141] Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are for more specifically explaining the present invention, and the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified and changed by those skilled in the art within the scope of the present invention.

[0142] <Example> <Examples 1 to Examples 7> Production of low-oxygen vanadium carbide A mixed powder of vanadium oxide and carbon compound was produced with the components and contents shown in Table 1 below.

[0143] Thereafter, the mixed powder was put into a rotating container in a high-energy milling apparatus shown in Table 1 below together with steel balls.

[0144] Thereafter, under an atmosphere of air, vacuum, nitrogen, or argon, which is the gas condition when pulverizing particles with the high-energy milling apparatus shown in Table 1 below, high energy shown in Table 1 below was input, the rotating shaft and the rotating container were rotated in different directions from each other, and high-energy milling was performed to produce fine powder.

[0145] Subsequently, the fine powder was subjected to a vacuum heat treatment under the conditions shown in Table 1 below to induce a carbonization reduction reaction, thereby producing low-oxygen vanadium carbide.

[0146] <Comparative Example> Production of vanadium carbide The comparative example vanadium carbide was produced in the same manner as in Example 1, except that the high-energy milling apparatus used in Example 1 was employed.

[0147] [Table 1]

[0148] Referring to Table 1 above, the oxygen content of the low-oxygen vanadium carbides in Examples 1 to 7 ranged from 1440 ppm to 3870 ppm, which was significantly lower than the 12000 ppm oxygen content of the vanadium carbide in the comparative example.

[0149] Therefore, it is shown that the low-oxygen vanadium carbides of Examples 1 to 7 contain little oxygen.

[0150] Furthermore, the average particle size of the low-oxygen vanadium carbides in Examples 1 to 7 is 20 nm, which is significantly smaller than the average particle size of the vanadium carbides in the comparative example, which is 10 μm.

[0151] Therefore, it was confirmed that the low-oxygen vanadium carbides of Examples 1 to 7 have a significantly lower oxygen content and a significantly smaller average particle size compared to the comparative examples.

[0152] <Examples 8 to Examples 13> Production of low-oxygen vanadium carbide A mixed powder of vanadium oxide and carbon compounds was prepared using the components and content shown in Table 2 below.

[0153] Subsequently, the mixed powder was placed together with steel balls into a rotating container in the high-energy milling apparatus shown in Table 2 below.

[0154] Subsequently, using the high-energy milling apparatus shown in Table 2 below, fine powder was produced by high-energy milling under the gas conditions of air, vacuum, nitrogen, or argon, which are used when grinding particles, and by applying the high energy shown in Table 2 below, while rotating the rotating shaft and rotating container in opposite directions.

[0155] Subsequently, the fine powder was subjected to a vacuum heat treatment under the conditions shown in Table 2 below to induce a carbonization reduction reaction, thereby producing low-oxygen vanadium carbide.

[0156] [Table 2]

[0157] <Example of experiment> <Experimental Example 1> TEM image of vanadium oxide-graphite mixture refined by high-energy milling Figure 4 shows a TEM image of the vanadium oxide-graphite mixture that was refined by high-energy milling as described in Example 1.

[0158] Figure 4 is a TEM image of the vanadium oxide-graphite mixture refined by high-energy milling according to Example 1.

[0159] Referring to Figure 4, the vanadium oxide-graphite mixture refined by high-energy milling according to Example 1 showed vanadium oxide nanocrystalline grain sizes of approximately 20 nm and amorphous carbon (graphite-derived) particle sizes of approximately 100 nm.

[0160] <Experimental Example 2> Figure 5 shows the crystal structure (XRD) graph of the low-oxygen vanadium carbide produced in Example 1.

[0161] Figure 5 is a crystal structure graph of the low-oxygen vanadium carbide according to Example 1.

[0162] Referring to Figure 5, the crystal structure of the low-oxygen vanadium carbide according to Example 1 showed that as the vacuum heat treatment temperature increased from 1000°C to 1500°C, the oxygen content decreased and the carbide content increased, and at 1500°C, both were confirmed to be low-oxygen vanadium carbide.

[0163] Specific examples relating to the low-oxygen vanadium carbide and the method for producing the low-oxygen vanadium carbide according to the present invention have been described so far, but it is clear that various modifications are possible as long as they do not deviate from the scope of the present invention.

[0164] Therefore, the scope of the present invention should not be limited to the embodiments described, but should be defined not only by the claims described later, but also by equivalent claims, etc.

[0165] In other words, the embodiments described above should be understood to be illustrative and not limiting, and the scope of the present invention is indicated by the claims described below rather than by the detailed description, and all modifications or variations conceived from the meaning and scope of those claims and their equivalent concepts should be interpreted as being included within the scope of the present invention. [Industrial applicability]

[0166] This invention can be used in the production of vanadium carbides with low oxygen content.

Claims

1. It is a low-oxygen vanadium carbide, It contains low-oxygen vanadium carbide, whose oxygen content has been reduced and whose particle size has been refined by high-energy milling with high energy input of 0.6 to 2.4 J / g·s. The low-oxygen vanadium carbide is formed by mixing vanadium oxide and a carbon compound, then milling the particles through a high-energy milling apparatus using high energy of 0.6 to 2.4 J / g·s, rotating the rotating shaft and rotating container in opposite directions, followed by vacuum heat treatment and a carbonization reduction reaction. Low-oxygen vanadium carbide.

2. The oxygen content is characterized by being between 10 ppm and 10,000 ppm. The low-oxygen vanadium carbide according to claim 1.

3. The aforementioned hypoxic vanadium carbide has the chemical formula VCx, The range of x is characterized in that 0.3 < x < 1. The low-oxygen vanadium carbide according to claim 1.

4. The molar ratio (B / A) of the carbon compound (B) to the vanadium oxide (A) is characterized by being 6.1 to 7.

5. The low-oxygen vanadium carbide according to claim 1.

5. The particle size of the mixed powder of the vanadium oxide or the carbon compound is characterized by being 2 nm to 50 μm. The low-oxygen vanadium carbide according to claim 1.

6. The vanadium oxide is vanadium pentoxide (V ２ O ５ ), sodium metavanadate (NaVO ３ ), vanadium trioxide (V ２ O ３ ), vanadium oxychloride (VOCl ３ ), and ammonium metavanadate (H ４ NVO ３ It is characterized by being at least one of the following selected from: The low-oxygen vanadium carbide according to claim 1.

7. The aforementioned carbon compound, It is characterized by being at least one selected from industrial carbon powder, coke, coal, coal tar, activated carbon, graphite, natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, industrial diamond, and carbon fiber. The low-oxygen vanadium carbide according to claim 1.

8. The aforementioned high-energy milling is After mixing the vanadium oxide and carbon compound, the mixed powder is placed together with steel balls into a rotating container in a high-energy milling apparatus. The method is characterized by applying a high energy of 0.6 to 2.4 J / g·s in an atmosphere of air, vacuum, nitrogen, or argon, rotating the rotating shaft at 500 to 1500 rpm, and rotating the rotating vessel at 2000 to 3500 rpm in the opposite direction to the rotation of the rotating shaft, thereby performing high-energy milling in a short period of time of 10 to 100 minutes. The low-oxygen vanadium carbide according to claim 1.

9. The high-energy milling apparatus described above is Characterized by being a planetary ball mill, SPEX mill, or atritine, The low-oxygen vanadium carbide according to claim 1.

10. The vacuum heat treatment The heat treatment temperature is 800°C to 1600°C. The heat treatment time is characterized by being between 10 minutes and 24 hours. The low-oxygen vanadium carbide according to claim 1.

11. The aforementioned carbonization-reduction reaction is The vanadium oxide and carbon compound are refined by high-energy milling to increase the contact area and thereby increase the rate of the carbon reduction reaction. The low-oxygen vanadium carbide according to claim 1.

12. A method for producing low-oxygen vanadium carbide, (a-1) A step of mixing vanadium oxide and a carbon compound to produce a mixed powder; (a-2) The step of introducing the mixed powder together with steel balls into a rotating container in a high-energy milling apparatus; (a-3) A step of producing fine powder by high-energy milling in an atmosphere of air, vacuum, nitrogen, or argon, by applying a high energy of 0.6 to 2.4 J / g·s and rotating the rotating shaft and rotating vessel in opposite directions; and, (a-4) A step in which the fine powder is subjected to vacuum heat treatment to cause a carbonization reduction reaction in order to produce low-oxygen vanadium carbide. including, A method for producing low-oxygen vanadium carbide.

13. In the step of (a-1) mixing vanadium oxide and a carbon compound to produce a mixed powder, The mixing ratio of the vanadium oxide and the carbon compound is characterized by being 1:0.2 to 1:0.7 by weight. A method for producing low-oxygen vanadium carbide according to claim 12.

14. In the step of introducing the (a-2) mixed powder into a rotating container in a high-energy milling apparatus together with steel balls, The steel ball is characterized by being at least one selected from ceramic balls, metal balls, and cemented carbide balls. A method for producing low-oxygen vanadium carbide according to claim 12.

15. In the step of producing fine powder by high-energy milling in an atmosphere of air, vacuum, nitrogen, or argon, by applying a high energy of 0.6 to 2.4 J / g·s and rotating the rotating shaft and rotating container in opposite directions, The rotating shaft is rotated at 500 to 1500 rpm, and the rotating container is rotated at 2000 to 3500 rpm in the opposite direction to the rotation of the rotating shaft, characterized in that high-energy milling is performed in a short time of 10 to 100 minutes. A method for producing low-oxygen vanadium carbide according to claim 12.

16. In the step of producing low-oxygen vanadium carbide by vacuum heat treatment of the fine powder (a-4) to cause a carbonization reduction reaction, The vacuum heat treatment The heat treatment temperature is 800°C to 1600°C. The heat treatment time is characterized by being between 10 minutes and 24 hours. A method for producing low-oxygen vanadium carbide according to claim 12.

17. The low-oxygen vanadium carbide, having an oxygen content of 10 ppm to 10,000 ppm as described in any one of claims 1 to 11, has applications as a max precursor, a raw material for cemented carbide, a catalyst, or a semiconductor material. Low-oxygen vanadium carbide.

18. A low-oxygen vanadium carbide produced by the method for producing low-oxygen vanadium carbide according to any one of claims 12 to 16, having a particle size of 2 nm to 50 μm and an oxygen content of 10 ppm to 10,000 ppm. Low-oxygen vanadium carbide.

19. A low-oxygen vanadium carbide produced by the method for producing low-oxygen vanadium carbide according to any one of claims 12 to 16, having the chemical formula VCx, wherein the range of x is 0.3 < x < 1, and the oxygen content is 10 ppm to 10,000 ppm. Low-oxygen vanadium carbide.

20. The low-oxygen vanadium carbide produced by the method for producing low-oxygen vanadium carbide according to any one of claims 12 to 16 is used as a max precursor, a raw material for cemented carbide materials, a catalyst, or a semiconductor material, and has an oxygen content of 10 ppm to 10,000 ppm. Low-oxygen vanadium carbide.

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