Method and device for preparing dichloromolybdenum dioxide

Abstract

The invention relates to a preparation method of dichloromolybdenum dioxide, which comprises the following steps: S1, putting a raw material metal molybdenum into a reactor, and then vacuumizing the reactor; s2, heating the reactor, controlling the temperature to be 180-600 DEG C, introducing oxygen and hydrogen chloride into the reactor, and reacting for 0.5-3 hours; s3, performing two-stage purification on the reaction product obtained in S2, controlling the temperature of the first-stage purification to be 150-350 DEG C, controlling the temperature of the second-stage purification to be-50-50 DEG C, controlling the pressure to be-0.09-0.05 Mpa, and keeping for 0.5-2 hours; and S4, after the purification is finished, carrying out sampling detection on the dichloromolybdenum dioxide for many times, and collecting the dichloromolybdenum dioxide after the indexes are qualified. According to the method, high-purity hydrogen chloride and oxygen are used as reaction gases to react with metal molybdenum, and the two-stage purification process is performed after the reaction, so that the purity of the product is effectively improved, and the purity of the dichloromolybdenum dioxide prepared by the method can reach 99.99% or above.

Description

Technical Field

[0001] The invention relates to the field of preparation of metal molybdenum oxychloride, and in particular to a method and a device for preparing molybdenum dioxide dichloride. Background Art

[0002] Molybdenum dioxide dichloride, with the chemical formula MoO2Cl2, is an inorganic compound, a yellow-white scaly solid. It can be decomposed by trace amounts of moisture in the air. It is easily soluble in water, ether and ethanol, and easily sublimates when heated. Molybdenum dioxide dichloride is an important transition metal compound. In electronic materials and organic synthesis, it is mainly used as a catalyst for organic synthesis reactions, a raw material for the preparation of other molybdenum compounds, and an ideal material for high-performance electronic devices.

[0003] As a semiconductor material, molybdenum dioxide dichloride has excellent electrical conductivity, good electron transport properties and high carrier mobility, which makes it suitable for use as an electrode material. For example, in devices such as liquid crystal displays, molybdenum dioxide dichloride can be used as a conductive layer material to connect circuits and transmit electrons; in solar cells, molybdenum dioxide dichloride can also be used as a photoelectrode material to absorb sunlight and convert it into electrical energy.

[0004] In addition, molybdenum dioxide dichloride has a wide band gap and high transparency, which enables it to show low absorption and high refractive index in the ultraviolet and visible light ranges, making it an ideal material for preparing optoelectronic devices. For example, molybdenum dioxide dichloride is used as an electrode material for capacitors in electronic ceramic materials, which can provide stable current and voltage output. In addition, in high temperature environments, molybdenum dioxide dichloride can also be used to prepare high-temperature resistant electronic devices, such as high-temperature sensors and power electronic devices.

[0005] Patent CN117208963A provides a novel preparation method of molybdenum dioxide dichloride, which belongs to the technical field of molybdenum dioxide dichloride. The present invention uses molybdenum trichloride, activated carbon and chlorine as reaction raw materials, mixes molybdenum trichloride and activated carbon in a certain proportion, puts them into a tubular reactor and heats them to a certain temperature, then introduces an excess of dry chlorine, reacts to obtain molybdenum dioxide dichloride gas, collects these gases through a cooling chamber and obtains molybdenum dioxide dichloride solid. The crude product is purified by sublimation, and a high-purity molybdenum dioxide dichloride product is finally obtained. However, the purity of the prepared molybdenum dioxide dichloride is not mentioned in the patent, and the cost of molybdenum trichloride is high, which is not suitable for large-scale production. Summary of the invention

[0006] The object of the present invention is to provide a method and device for preparing molybdenum dioxide dichloride. The method and device are relatively simple and can obtain molybdenum dioxide dichloride with high purity, so as to solve the technical problems of high preparation cost of molybdenum dioxide dichloride and unsuitability for large-scale production in the prior art.

[0007] To achieve the purpose of the present invention, the specific technical solutions provided by the present invention are as follows:

[0008] A method for preparing molybdenum dioxide dichloride, the method comprising the following steps:

[0009] S1, placing the raw material metal molybdenum in a reactor, and then vacuuming the reactor;

[0010] S2, heating the reactor to control the temperature to 180-600° C., then introducing oxygen and hydrogen chloride into the reactor to react for 0.5-3 hours;

[0011] S3, the reaction product obtained in S2 is subjected to two-stage purification, the temperature of the first-stage purification is controlled at 150-350°C, and the temperature of the second-stage purification is controlled at -50-5°C;

[0012] S4. After purification, the molybdenum dioxide dichloride is sampled and tested multiple times, and collected after the indicators are qualified.

[0013] Preferably, in step S1, the loading amount of raw material metal molybdenum is 5-40% of the reactor volume.

[0014] Preferably, in step S1, the vacuuming operation is to replace the reactor with nitrogen or an inert gas, and the pressure of the nitrogen or inert gas in the reactor is 0.01 to 0.15 MPa and then vacuumed to -0.1 MPa, and repeated 10 to 20 times, and the inert gas is helium or argon with a purity of 99.0% to 99.999%.

[0015] Preferably, in step S2, the reactor is heated at a heating rate of 10 to 30°C / h.

[0016] Preferably, in step S2, the purity of oxygen and hydrogen chloride is 99.0% to 99.999%, the intake amounts of oxygen and hydrogen chloride are both ≤8.0 kg / h, and the intake ratio of hydrogen chloride to oxygen is 2.0 to 2.5:1.

[0017] Preferably, the heating rate of the primary purification is 10-20°C / min, and the cooling rate of the secondary purification is 10°C / min.

[0018] The present invention also provides a preparation device of molybdenum dioxide dichloride, comprising a reactor, a first purifier and a second purifier, wherein a material inlet is provided at the upper portion of the reactor, a gas inlet and a gas outlet are provided on the side outer wall of the reactor, the first purifier and the second purifier are arranged in series, the gas inlet of the reactor is respectively connected to an oxygen source, a hydrogen chloride gas source and a replacement gas source, the gas outlet of the reactor is connected to a feed port of the first purifier, and a discharge port of the first purifier is connected to a feed port of the second purifier.

[0019] Preferably, the reactor is a reactor with a heating function, or is connected to a heating device, the first purifier has a heating jacket on its periphery, and the second purifier has a cooling jacket on its periphery.

[0020] Preferably, a gas mixing chamber is provided on the connecting pipeline between the reactor and the oxygen source, the hydrogen chloride gas source and the replacement gas source.

[0021] Preferably, the reactor is made of a high temperature resistant and corrosion resistant alloy material, including nickel-based alloy, 316L stainless steel and monel; the first purifier and the second purifier are made of quartz material.

[0022] The method and device for preparing molybdenum dioxide dichloride of the present invention have the following beneficial effects:

[0023] 1. The present application uses high-purity hydrogen chloride and oxygen as reaction gases to react with metallic molybdenum, and after the reaction, a two-stage purification process is performed to effectively improve the purity of the product. The first-stage purification is carried out at high temperature, which helps to remove unreacted raw materials and impurities, while the second-stage purification is carried out at low temperature and low pressure to further purify the product. The purity of molybdenum dioxide dichloride prepared by this method can reach more than 99.99%, which significantly improves its product quality as a precursor material in back-end applications.

[0024] 2. Compared with the prior art, the preparation method of the present application is relatively simple and does not require complex equipment and cumbersome operating steps. By accurately controlling the reaction conditions and purification process, large-scale production can be achieved at a relatively low cost, meeting the needs of industrial applications. At the same time, the preparation device provided by the present invention has a reasonable structure, integrates reaction and purification functions, and improves production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 A schematic diagram of a device for preparing molybdenum dioxide dichloride according to the present invention;

[0026] Explanation of the markings in the figure: 1. Reactor; 2. First purifier; 3. Second purifier; 4. Replacement gas source; 5. Oxygen source; 6. Hydrogen chloride gas source; 7. Gas mixing chamber. DETAILED DESCRIPTION

[0027] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation method, structure, characteristics and effects of the present invention are described in detail below in combination with the preferred embodiments.

[0028] Device Embodiment

[0029] like Figure 1As shown, it is a schematic diagram of a device for preparing molybdenum dioxide dichloride of the present invention. This embodiment provides a device for preparing molybdenum dioxide dichloride, including a reactor 1, a first purifier 2 and a second purifier 3. The reactor 1 is a reactor with a heating function or is connected to a heating device. The first purifier 2 has a heating jacket on the periphery, and the second purifier 3 has a cooling jacket on the periphery. Whether the reactor 1 is externally heated or self-heated, the reactor body can be heated to increase the temperature when the temperature needs to be increased. The material of the reactor 1 is made of high temperature resistant and corrosion resistant alloy materials, including nickel-based alloys, 316L stainless steel and monel.

[0030] The upper part of the reactor 1 is provided with a material inlet for adding raw material molybdenum powder, molybdenum block or molybdenum granules into the reactor 1. The side outer wall of the reactor 1 is provided with a gas inlet and a gas outlet. The gas inlet of the reactor 1 is connected with a gas mixing chamber 7, and the gas mixing chamber 7 is used to mix oxygen and hydrogen chloride uniformly; the gas outlet of the reactor 1 is connected with the first purifier 2, and a valve is provided on the connecting pipeline to control the inlet and outlet of materials.

[0031] One end of the gas mixing chamber 7 is connected to the reactor 1, and the other end is connected to the oxygen source 5, the hydrogen chloride gas source 6 and the replacement gas source 4 respectively.

[0032] The first purifier 2 and the second purifier 3 are arranged in series, and the first purifier 2 and the second purifier 3 are both provided with an air inlet and an air outlet. The air inlet of the first purifier 2 is connected to the gas outlet of the reactor 1, the air outlet of the first purifier 2 is connected to the air inlet of the second purifier 3, and the air outlet of the second purifier 3 is connected to the vacuum pump. The first purifier 2 and the second purifier 3 are made of quartz material and have detachable flanges.

[0033] The device can be used to simultaneously purify molybdenum dichloride during the process of preparing molybdenum dichloride.

[0034] Method Example 1

[0035] This embodiment provides a method for preparing molybdenum dioxide dichloride, which is carried out using the device of the device embodiment, and specifically comprises the following steps:

[0036] S1, reactor 1 selects monel alloy, first raw material metal platinum is placed in the reactor, the charging amount of raw material metal platinum is 5% of the volume of reactor 1, after filling, reactor 1 is connected to gas mixing chamber 7, the other end of gas mixing chamber 7 is connected to nitrogen cylinder 4, oxygen cylinder 5 and hydrogen chloride cylinder 6, then reactor 1 is vacuumized, and reactor 1 is replaced with nitrogen with a purity of 99.99%, and nitrogen is introduced to make the pressure in the reactor within the range of 0.01~0.15Mpa and then vacuumize, pump to -0.1Mpa and stop, introduce nitrogen again, and repeat 10-20 times;

[0037] S2, heating the reactor 1 at a heating rate of 10°C / min, and after the temperature of the reactor 1 reaches 180°C, introducing oxygen and hydrogen chloride with a purity of 99.99% into the reactor, opening the oxygen cylinder 5 and the hydrogen chloride cylinder 6, controlling the intake of hydrogen chloride to 3.3kg / h, the intake of oxygen to 1.32kg / h, and the reaction time to 0.5h;

[0038] S3. The reaction product obtained in S2 is subjected to two-stage purification. The first purifier 2 is heated at a heating rate of 10°C / min to 150°C, and the second purifier 3 is cooled at a rate of 10°C / min to -5°C. Then, the valve between the two is opened, and the gas outlet of the second purifier 3 is evacuated at the same time. The pressure is controlled in the range of -0.09 to 0.05Mpa, and the molybdenum dioxide dichloride is sublimated and purified.

[0039] Sampling was performed from the second purifier 3 and the sampling was tested using ICP-OES and UV-visible spectrophotometer. The test results are shown in Table 1.

[0040] Table 1 Method Example 1 Sample test results (content unit / ppm)

[0041] element Al B Ba Ca Cd Cr Cu Fe K Mg Na Ni Pb Si Zn Li W content 1.7 0.5 0.2 0.9 0.6 0.7 0.9 1.4 3.1 1.1 2.4 0.8 0.5 3.3 0.4 0.8 0.7

[0042] Method Example 2

[0043] This embodiment provides a method for preparing molybdenum dioxide dichloride, which is carried out using the device of the device embodiment, and specifically comprises the following steps:

[0044] S1. Plating raw material metal platinum in a reactor, the loading amount of raw material metal platinum is 25% of the volume of reactor 1. After filling, reactor 1 is connected to gas mixing chamber 7, and the other end of gas mixing chamber 7 is connected to helium cylinder 4, oxygen cylinder 5 and hydrogen chloride cylinder 6, and then the reactor 1 is evacuated, and the reactor 1 is replaced with helium with a purity of 99.9%. Nitrogen is introduced to make the pressure in the reactor within the range of 0.01 to 0.15 MPa, and then evacuation is started, and the pressure is pumped to -0.1 MPa and stopped, and nitrogen is introduced again, and repeated 10-20 times;

[0045] S2, heating the reactor 1 at a heating rate of 30°C / min. After the temperature of the reactor 1 reaches 300°C, oxygen and hydrogen chloride with a purity of 99.9% are introduced into the reactor, and the oxygen cylinder 5 and the hydrogen chloride cylinder 6 are opened. The intake amount of hydrogen chloride is controlled to be 7.2kg / h, the intake amount of oxygen is controlled to be 3.6kg / h, and the reaction time is 2.0h.

[0046] S3. The reaction product obtained in S2 is subjected to two-stage purification. The first purifier 2 is heated at a heating rate of 20°C / min to 250°C, and the second purifier 3 is cooled at a rate of 10°C / min to -25°C. Then, the valve between the two is opened, and the gas outlet of the second purifier 3 is evacuated at the same time. The pressure is controlled in the range of -0.09 to 0.05Mpa, and the molybdenum dioxide dichloride is sublimated and purified.

[0047] Sampling was performed from the second purifier 3 and the sampling was tested using ICP-OES and UV-visible spectrophotometer. The test results are shown in Table 2.

[0048] Table 2 Method Example 2 Sample Test Results (Content Unit / ppm)

[0049] element Al B Ba Ca Cd Cr Cu Fe K Mg Na Ni Pb Si Zn Li W content 2.3 0.2 0.7 1.1 0.6 0.9 0.6 1.1 2.9 0.8 1.5 0.4 0.5 2.3 0.4 0.7 0.9

[0050] Method Example 3

[0051] This embodiment provides a method for preparing molybdenum dioxide dichloride, which is carried out using the device of the device embodiment, and specifically comprises the following steps:

[0052] S1, reactor 1 selects 316L stainless steel, places raw material metal molybdenum in the reactor, and the loading amount of raw material metal molybdenum is 40% of the volume of reactor 1. After filling, reactor 1 is connected to mixing chamber 7, and the other end of mixing chamber 7 is connected to argon cylinder 4, oxygen cylinder 5 and hydrogen chloride cylinder 6, and then the reactor 1 is evacuated, and the reactor 1 is replaced with argon gas with a purity of 99.999%. Nitrogen is introduced to make the pressure in the reactor within the range of 0.01 to 0.15Mpa, and then evacuation is started, and it is stopped when it is evacuated to -0.1Mpa, and nitrogen is introduced again, and repeated 10-20 times;

[0053] S2, heating the reactor 1 at a heating rate of 30°C / min. After the temperature of the reactor 1 reaches 600°C, oxygen and hydrogen chloride with a purity of 99.999% are introduced into the reactor, and the oxygen cylinder 5 and the hydrogen chloride cylinder 6 are opened. The intake amount of hydrogen chloride is controlled to be 8.0kg / h, the intake amount of oxygen is controlled to be 4.0kg / h, and the reaction time is 3h.

[0054] S3. The reaction product obtained in S2 is subjected to two-stage purification. The first purifier 2 is heated at a heating rate of 20°C / min to 350°C, and the second purifier 3 is cooled at a rate of 10°C / min to -50°C. Then, the valve between the two is opened, and the gas outlet of the second purifier 3 is evacuated at the same time. The pressure is controlled in the range of -0.09 to 0.05Mpa, and the molybdenum dioxide dichloride is sublimated and purified.

[0055] Sampling was performed from the second purifier 3 and the sampling was tested using ICP-OES and UV-visible spectrophotometer. The test results are shown in Table 3.

[0056] Table 3 Method Example 3 Sample Test Results (Content Unit / ppm)

[0057] element Al B Ba Ca Cd Cr Cu Fe K Mg Na Ni Pb Si Zn Li W content 1.1 0.4 2.1 2.3 1.6 0.7 1.1 1.2 2.4 1.2 1.5 1.0 0.7 4.2 0.7 1.1 1.2

[0058] As shown in Table 1, Table 2 and Table 3, the test results are basically consistent. According to the test results of Table 1, Table 2 and Table 3, the purity of the molybdenum dioxide dichloride in method embodiments 1 to 3 can be obtained. The test results can illustrate that the purity of the molybdenum dioxide dichloride obtained by the preparation method of molybdenum dioxide dichloride of the present invention is 99.99% or above.

[0059] From the above test results, it can be seen that the molybdenum dichloride prepared by the method for preparing molybdenum dichloride described in the present invention meets the requirements and is stable.

[0060] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing molybdenum dioxide dichloride, characterized in that, The method comprises the following steps: S1, placing the raw material metal molybdenum in a reactor, and then vacuuming the reactor; S2, heating the reactor to control the temperature to 180-600° C., then introducing oxygen and hydrogen chloride into the reactor, reacting for 0.5-3 hours to obtain a reaction product; S3, the reaction product obtained in S2 is subjected to two-stage purification, the temperature of the first-stage purification is controlled at 150-350°C, and the temperature of the second-stage purification is controlled at -50-5°C; S4. After purification, the molybdenum dioxide dichloride is sampled and tested multiple times, and collected after the indicators are qualified.

2. The method for preparing molybdenum dioxide dichloride according to claim 1, wherein: In step S1, the loading amount of raw material metal molybdenum is 5-40% of the reactor volume.

3. A method for preparing molybdenum dioxide dichloride according to claim 1, characterized in that: In step S1, the vacuuming operation is to replace the reactor with nitrogen or an inert gas. The pressure of the nitrogen or inert gas in the reactor is 0.01 to 0.15 MPa and then vacuumed to -0.1 MPa, which is repeated 10 to 20 times. The inert gas is helium or argon with a purity of 99.0% to 99.999%.

4. The method for preparing molybdenum dioxide dichloride according to claim 1, wherein: In step S2, the reactor is heated at a heating rate of 10 to 30°C / h.

5. A method for preparing molybdenum dioxide dichloride according to claim 1, characterized in that: In step S2, the purity of oxygen and hydrogen chloride is 99.0% to 99.999%, the intake amount of oxygen and hydrogen chloride is ≤8.0 kg / h, and the intake amount ratio of hydrogen chloride to oxygen is 2.0 to 2.5:

1.

6. The method for preparing molybdenum dioxide dichloride according to claim 1, wherein: The heating rate of the primary purification is 10-20°C / min, and the cooling rate of the secondary purification is 10°C / min.

7. A device for preparing molybdenum dioxide dichloride used in the method for preparing molybdenum dioxide dichloride according to any one of claims 1 to 6, characterized in that: The invention comprises a reactor, a first purifier and a second purifier, wherein a material inlet is provided on the upper part of the reactor, a gas inlet and a gas outlet are provided on the side of the reactor, the first purifier and the second purifier are arranged in series, the gas inlet of the reactor is respectively connected with an oxygen source, a hydrogen chloride gas source and a replacement gas source, the gas outlet of the reactor is connected with a feed inlet of the first purifier, and a discharge port of the first purifier is connected with a feed inlet of the second purifier.

8. A preparation device for molybdenum dioxide dichloride according to claim 7, characterized in that, The reactor is a reactor with a heating function, or is connected to a heating device. The first purifier is provided with a heating jacket on its periphery, and the second purifier is provided with a cooling jacket on its periphery.

9. A preparation device for molybdenum dioxide dichloride according to claim 7, characterized in that, A gas mixing chamber is arranged on the connecting pipeline between the reactor and the oxygen source, the hydrogen chloride gas source and the replacement gas source.

10. A preparation device for molybdenum dioxide dichloride according to claim 7, characterized in that: The reactor is made of high temperature resistant and corrosion resistant alloy materials, including nickel-based alloy, 316L stainless steel and monel; the first purifier and the second purifier are made of quartz material.

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