A novel preparation method of molybdenum dioxide dichloride

Abstract

The present invention provides a novel method for preparing molybdenum dioxide dichloride, belonging to the technical field of molybdenum dioxide dichloride. The method uses molybdenum trichloride, activated carbon, and chlorine as reaction raw materials. The molybdenum trichloride and activated carbon are mixed in a certain proportion, placed in a tubular reactor, heated to a certain temperature, and then an excess of dry chlorine is introduced to react to produce molybdenum dioxide dichloride gas. This gas is collected in a cooling chamber to obtain molybdenum dioxide dichloride solid. The crude product is then sublimated and purified to ultimately obtain a high-purity molybdenum dioxide dichloride product. This method has a high yield, improves raw material utilization and product yield, reduces production costs, and is conducive to industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of molybdenum dioxide dichloride, in particular to a novel preparation method of molybdenum dioxide dichloride. Background Art

[0002] Molybdenum, a Group VI metal element, is characterized by an extremely high melting point, low coefficient of thermal expansion, low resistivity, and high thermal conductivity. It is widely used in the manufacture of semiconductor devices, including diffusion barriers, electrodes, photomasks, power electronics substrates, low-resistivity gates, and interconnects. Molybdenum dioxide dichloride is a yellow-white solid and is often used as a molybdenum source for chemical vapor deposition of molybdenum-containing materials. The application of this type of molybdenum thin film deposition lies primarily in its high conformality and efficient deposition rates that can accommodate high-volume processing operations.

[0003] Molybdenum dioxide dichloride was synthesized by Berzelius in 1826, and Colton and Tomkins reported the preparation of MoO2Cl2 in 1965. A mixture of dry oxygen and chlorine reacts with molybdenum powder at 250-350°C. The resulting yellow-white solid is purified by sublimation of volatile products to obtain MoO2Cl2.

[0004]

[0005] Colton and Tomkins also reported a method for synthesizing molybdenum oxides and molybdenum chloride compounds in 1965.

[0006]

[0007] Vernon proposed another synthesis method in 1988. Molybdenum tetrachloride and bis(trimethylsilyl)oxy react in dichloromethane to produce molybdenum dichloride and trimethylchlorosilane.

[0008] MoOCl4+O(Si(CH3)3)2→MoO2Cl2+2ClSi(CH3)3

[0009] In 1990, Richard R. Schrock proposed the synthesis of molybdenum dioxide dichloride by reacting molybdenum dioxide and chlorine in an inert gas atmosphere.

[0010] MoO2+Cl2→MoO2Cl2

[0011] In 2003, Ojeda and Rivarola analyzed the kinetics of the chlorination of MoO₃ in the presence of carbon. The experiments were conducted in a fixed-bed isothermal reactor, operating at atmospheric pressure between 543 K and 603 K, and varying feed flow rates and chlorine concentrations. Based on the analysis of the experimental data, thermodynamic results from other authors, and observations, three fundamental stages were distinguished: 1) the chlorinating agent; 2) the chlorination of molybdenum trioxide; and 3) carbon oxidation. This mechanism explains the greater reactivity of carbon chlorination at low temperatures compared to direct chlorination. Kinetic studies revealed the involvement of 22 stages in this complex reaction. The data were then analyzed using various kinetic models, and the "nucleation and growth" model, conveniently applicable to non-catalyzed heterogeneous reactions, was found to be a better fit for the experimental data.

[0012] EP3656741 provides an apparatus and method for producing high-purity molybdenum dioxide dichloride. The method involves sublimating and reaggregating the raw material molybdenum dioxide dichloride in a reduced-pressure atmosphere, or retaining gaseous molybdenum dioxide dichloride within a certain temperature range to grow crystals to obtain high-purity molybdenum dioxide dichloride. However, this method requires temperatures exceeding 700°C and a reduced-pressure atmosphere, making it unsuitable for industrial production.

[0013] WO2021171742 provides a method for preparing molybdenum dioxide dichloride. Molybdenum dioxide dichloride is synthesized by heating molybdenum trioxide and chlorine at 800-1000°C in a reaction chamber. This method is characterized by the placement of an impurity trap between the reaction chamber and the recovery chamber to remove impurities. This method has a high reaction temperature and consumes a lot of energy, making it unsuitable for industrial production.

[0014] CN114174216A provides a method for preparing molybdenum and tungsten oxyhalide compounds suitable for depositing thin films containing molybdenum and tungsten on various surfaces of microelectronic devices. In this invention, a reaction is carried out with molybdenum trioxide or tungsten trioxide under reduced pressure in a solid medium or in a melt phase containing a eutectic blend of an alkali metal salt and / or an alkaline earth metal salt. The resulting molybdenum or tungsten oxyhalide can be separated as a vapor and crystallized to provide a high-purity precursor compound. However, this method utilizes reduced pressure reaction and requires relatively high heating temperatures, resulting in high raw material costs, making it unsuitable for industrial production.

[0015] The raw material molybdenum dioxide used in the above method is relatively expensive, or a reduced pressure reaction is required, and the heating reaction temperature is very high, which has high energy consumption and increases production costs, making it unfavorable for industrial production.

[0016] In view of this, the present invention proposes a novel preparation method of molybdenum dioxide dichloride. Summary of the Invention

[0017] 1. Technical problem to be solved by the invention

[0018] The problem to be solved by the present invention is to provide a novel synthesis method of molybdenum dioxide dichloride to overcome the above-mentioned defects in the prior art.

[0019] The present invention is a one-step reaction: activated carbon and molybdenum trioxide are mixed in a certain proportion, placed in a tubular reactor and heated to a certain temperature, and then dry chlorine is introduced to react to obtain molybdenum dioxide dichloride gas, which is collected in a cooling chamber to obtain molybdenum dioxide dichloride solid, and the crude product is sublimated and purified to finally obtain a high-purity molybdenum dioxide dichloride product.

[0020] 2. Technical solution

[0021] A novel preparation method of molybdenum dioxide dichloride is characterized in that it comprises the following steps:

[0022] S1: According to parts by mass, 10-20 parts of molybdenum trichloride and 10-80 parts of activated carbon are mixed in a certain proportion, placed in a tubular reactor, heated to a certain temperature, and then an excess of dry chlorine is introduced to react to obtain molybdenum dioxide dichloride gas;

[0023] S2: The gases are collected in a cooling chamber to obtain molybdenum dioxide dichloride solid. The crude product is purified by sublimation to obtain a high-purity molybdenum dioxide dichloride product.

[0024] Furthermore, the molar mass ratio of the molybdenum trichloride to the activated carbon is 1:1-4.

[0025] Furthermore, the heating temperature of the tubular reactor is 200-400°C.

[0026] Furthermore, the flow rate of the chlorine gas is 200-400 mL / min.

[0027] Furthermore, the reaction time is 1-4 hours.

[0028] Furthermore, the molybdenum dioxide dichloride gas produced in S1 is passed into an adsorption tower, which is filled with 10-30% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0029] Furthermore, the molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 0.5-2 BV / h.

[0030] Furthermore, the temperature of the adsorption tower is 180-200°C.

[0031] Furthermore, the preparation method of the high temperature resistant metal impurity adsorbent is:

[0032] According to weight parts, 0.003-0.04 parts of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 5-16 parts of (4-bromo-2-butenyl)triphenylphosphine bromide, 50-100 parts of thiol-modified MCM-41 mesoporous molecular sieve, 500-1000 parts of N,N-dimethylformamide, and 2-5 parts of triethanolamine are added to a stirring kettle, stirred at 70-90° C. for 100-150 minutes, and then benzoyl peroxide is added. The mixture is stirred for 20-60 minutes, filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0033] Furthermore, the 5-16 parts of (4-bromo-2-butenyl)triphenylphosphine bromide are optimized to 5-9 parts;

[0034] Furthermore, the preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is:

[0035] According to the mass ratio, 10-15 parts of mercaptosiloxane, 120-150 parts of MCM-41 mesoporous molecular sieve, and 300-500 parts of deionized water are stirred at 70-80° C. for 50-100 minutes, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0036] The adsorbent reaction mechanism is:

[0037] The mercapto-modified MCM-41 mesoporous molecular sieve undergoes a mercapto-ene addition reaction with 20-tetrakis(4-vinylphenyl)porphyrin and (4-bromo-2-butenyl)triphenylphosphine bromide to obtain a high-temperature resistant metal impurity adsorbent grafted with phenylporphyrin and triphenylphosphine on the mesoporous molecular sieve.

[0038] 3. Beneficial effects

[0039] Compared with the prior art, the present invention has significant advantages and beneficial effects, which are specifically reflected in the following aspects:

[0040] 1. Compared with the traditional method, the use of molybdenum trioxide as the reaction raw material is cheaper and reduces production costs.

[0041] 2. Using activated carbon as a reaction booster can reduce the reaction heating temperature, reduce energy consumption, and reduce the risk of the reaction. It is safer for industry and is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is a diagram of the experimental setup of the present invention. DETAILED DESCRIPTION

[0043] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0044] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0045] In a specific embodiment, ICP-OES / MS is used to analyze and detect the metal ion impurity content of the product.

[0046] Example 1

[0047] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 0.83 g of activated carbon (molar mass ratio of 1:1) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 200°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2 hours to obtain molybdenum dioxide dichloride gas.

[0048] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 10% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0049] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 0.5 BV / h.

[0050] The temperature of the adsorption tower is 180°C.

[0051] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0052] 0.01 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 5 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 50 g of thiol-modified MCM-41 mesoporous molecular sieve, 500 g of N,N-dimethylformamide, and 2 g of triethanolamine were added to a stirring vessel and stirred at 70°C for 100 min. Then, benzoyl peroxide was added and stirring was continued for 20 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0053] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0054] 10 g of mercaptosiloxane, 120 g of MCM-41 mesoporous molecular sieve, and 300 g of deionized water were stirred at 70° C. for 50 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0055] These gases are collected by a cooling chamber and a molybdenum dioxide dichloride solid is obtained. The crude product is purified by sublimation in a sublimator to obtain 10 g of molybdenum dioxide dichloride product.

[0056] Example 2

[0057] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 0.83 g of activated carbon (molar mass ratio of 1:1) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 300°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2.5 hours to obtain molybdenum dioxide dichloride gas.

[0058] Molybdenum dioxide dichloride gas is introduced into an adsorption tower filled with 15% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0059] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 1 BV / h.

[0060] The temperature of the adsorption tower is 180°C.

[0061] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0062] 0.02 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 8 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 70 g of thiol-modified MCM-41 mesoporous molecular sieve, 650 g of N,N-dimethylformamide, and 3 g of triethanolamine were added to a stirring kettle and stirred at 75° C. for 120 min. Then, benzoyl peroxide was added and stirring was continued for 30 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0063] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0064] 12 g of mercaptosiloxane, 130 g of MCM-41 mesoporous molecular sieve, and 375 g of deionized water were stirred at 70° C. for 65 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0065] The gases were collected by cooling chamber and molybdenum dioxide dichloride solid was obtained. The crude product was purified by sublimation in a sublimator to obtain 11.1 g of molybdenum dioxide dichloride product.

[0066] Example 3

[0067] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 0.83 g of activated carbon (molar mass ratio of 1:1) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 400°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2 hours to obtain molybdenum dioxide dichloride gas.

[0068] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 20% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0069] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 1.5 BV / h.

[0070] The temperature of the adsorption tower is 200°C.

[0071] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0072] 0.03 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 12 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 85 g of thiol-modified MCM-41 mesoporous molecular sieve, 800 g of N,N-dimethylformamide, and 4 g of triethanolamine were added to a stirring kettle and stirred at 80° C. for 135 min. Then, benzoyl peroxide was added and stirring was continued for 50 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0073] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0074] 14 g of mercaptosiloxane, 140 g of MCM-41 mesoporous molecular sieve, and 450 g of deionized water were stirred at 80° C. for 85 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0075] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid will be obtained. The crude product is purified by sublimation in a sublimator to obtain 10.9 g of molybdenum dioxide dichloride product.

[0076] Example 4

[0077] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 1.67 g of activated carbon (molar mass ratio of 1:2) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 200°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 3 hours to obtain molybdenum dioxide dichloride gas.

[0078] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 30% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0079] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 2 BV / h.

[0080] The temperature of the adsorption tower is 200°C.

[0081] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0082] 0.04 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 16 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 100 g of thiol-modified MCM-41 mesoporous molecular sieve, 100 g of N,N-dimethylformamide, and 5 g of triethanolamine were added to a stirring vessel and stirred at 90° C. for 150 min. Then, benzoyl peroxide was added and stirred for 60 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0083] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0084] 15 g of mercaptosiloxane, 150 g of MCM-41 mesoporous molecular sieve, and 500 g of deionized water were stirred at 80° C. for 100 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0085] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid will be obtained. The crude product is purified by sublimation in a sublimator to obtain 12.0 g of molybdenum dioxide dichloride product.

[0086] Example 5

[0087] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 1.67 g of activated carbon (molar mass ratio of 1:2) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 300°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2.5 hours to obtain molybdenum dioxide dichloride gas.

[0088] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 10% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0089] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 0.5 BV / h.

[0090] The temperature of the adsorption tower is 180°C.

[0091] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0092] 0.01 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 5 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 50 g of thiol-modified MCM-41 mesoporous molecular sieve, 500 g of N,N-dimethylformamide, and 2 g of triethanolamine were added to a stirring vessel and stirred at 70°C for 100 min. Then, benzoyl peroxide was added and stirring was continued for 20 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0093] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0094] 10 g of mercaptosiloxane, 120 g of MCM-41 mesoporous molecular sieve, and 300 g of deionized water were stirred at 70° C. for 50 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0095] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid is obtained. The crude product is purified by sublimation in a sublimator to obtain 13.7 g of molybdenum dioxide dichloride product.

[0096] Example 6

[0097] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 1.67 g of activated carbon (molar mass ratio of 1:2) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 400°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2 hours to obtain molybdenum dioxide dichloride gas.

[0098] Molybdenum dioxide dichloride gas is introduced into an adsorption tower filled with 15% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0099] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 1 BV / h.

[0100] The temperature of the adsorption tower is 180°C.

[0101] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0102] 0.02 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 8 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 70 g of thiol-modified MCM-41 mesoporous molecular sieve, 650 g of N,N-dimethylformamide, and 3 g of triethanolamine were added to a stirring kettle and stirred at 75° C. for 120 min. Then, benzoyl peroxide was added and stirring was continued for 30 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0103] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0104] 12 g of mercaptosiloxane, 130 g of MCM-41 mesoporous molecular sieve, and 375 g of deionized water were stirred at 70° C. for 65 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0105] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid will be obtained. The crude product is purified by sublimation in a sublimator to obtain 13.5 g of molybdenum dioxide dichloride product.

[0106] Example 7

[0107] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 0.50 g of activated carbon (molar mass ratio of 1:3) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 200 ° C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2 hours to obtain molybdenum dioxide dichloride gas.

[0108] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 20% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0109] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 1.5 BV / h.

[0110] The adsorption tower temperature is 200°C.

[0111] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0112] 0.03 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 12 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 85 g of thiol-modified MCM-41 mesoporous molecular sieve, 800 g of N,N-dimethylformamide, and 4 g of triethanolamine were added to a stirring kettle and stirred at 80° C. for 135 min. Then, benzoyl peroxide was added and stirring was continued for 50 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0113] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0114] 14 g of mercaptosiloxane, 140 g of MCM-41 mesoporous molecular sieve, and 450 g of deionized water were stirred at 80° C. for 85 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0115] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid is obtained. The crude product is purified by sublimation in a sublimator to obtain 15.6 g of molybdenum dioxide dichloride product.

[0116] Example 8

[0117] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 0.50 g of activated carbon (molar mass ratio of 1:3) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 300 ° C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 3 hours to obtain molybdenum dioxide dichloride gas.

[0118] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 30% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0119] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 2 BV / h.

[0120] The adsorption tower temperature is 200°C.

[0121] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0122] 0.04 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 16 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 100 g of thiol-modified MCM-41 mesoporous molecular sieve, 100 g of N,N-dimethylformamide, and 5 g of triethanolamine were added to a stirring vessel and stirred at 90° C. for 150 min. Then, benzoyl peroxide was added and stirred for 60 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0123] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0124] 15 g of mercaptosiloxane, 150 g of MCM-41 mesoporous molecular sieve, and 500 g of deionized water were stirred at 80° C. for 100 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0125] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid will be obtained. The crude product is purified by sublimation in a sublimator to obtain 16.9 g of molybdenum dioxide dichloride product.

[0126] Example 9

[0127] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 0.50 g of activated carbon (molar mass ratio of 1:3) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 400°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2 hours to obtain molybdenum dioxide dichloride gas.

[0128] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 10% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0129] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 0.5 BV / h.

[0130] The temperature of the adsorption tower is 180°C.

[0131] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0132] 0.01 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 5 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 50 g of thiol-modified MCM-41 mesoporous molecular sieve, 500 g of N,N-dimethylformamide, and 2 g of triethanolamine were added to a stirring vessel and stirred at 70°C for 100 min. Then, benzoyl peroxide was added and stirring was continued for 20 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0133] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0134] 10 g of mercaptosiloxane, 120 g of MCM-41 mesoporous molecular sieve, and 300 g of deionized water were stirred at 70° C. for 50 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0135] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid will be obtained. The crude product is purified by sublimation in a sublimator to obtain 14.8 g of molybdenum dioxide dichloride product.

[0136] Example 10

[0137] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 3.33 g of activated carbon (molar mass ratio of 1:4) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 200°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 3 hours to obtain molybdenum dioxide dichloride gas.

[0138] Molybdenum dioxide dichloride gas is introduced into an adsorption tower filled with 15% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0139] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 1 BV / h.

[0140] The temperature of the adsorption tower is 180°C.

[0141] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0142] 0.02 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 8 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 70 g of thiol-modified MCM-41 mesoporous molecular sieve, 650 g of N,N-dimethylformamide, and 3 g of triethanolamine were added to a stirring kettle and stirred at 75° C. for 120 min. Then, benzoyl peroxide was added and stirring was continued for 30 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0143] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0144] 12 g of mercaptosiloxane, 130 g of MCM-41 mesoporous molecular sieve, and 375 g of deionized water were stirred at 70° C. for 65 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0145] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid will be obtained. The crude product is purified by sublimation in a sublimator to obtain 14.2 g of molybdenum dioxide dichloride product.

[0146] Example 11

[0147] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 3.33 g of activated carbon (molar mass ratio of 1:4) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 300 ° C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2 hours to obtain molybdenum dioxide dichloride gas.

[0148] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 20% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0149] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 1.5 BV / h.

[0150] The adsorption tower temperature is 200°C.

[0151] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0152] 0.03 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 12 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 85 g of thiol-modified MCM-41 mesoporous molecular sieve, 800 g of N,N-dimethylformamide, and 4 g of triethanolamine were added to a stirring kettle and stirred at 80° C. for 135 min. Then, benzoyl peroxide was added and stirring was continued for 50 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0153] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0154] 14 g of mercaptosiloxane, 140 g of MCM-41 mesoporous molecular sieve, and 450 g of deionized water were stirred at 80° C. for 85 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0155] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid will be obtained. The crude product is purified by sublimation in a sublimator to obtain 14.3 g of molybdenum dioxide dichloride product.

[0156] Example 12

[0157] Under an inert gas atmosphere, 20 g of molybdenum trichloride and 3.33 g of activated carbon (molar mass ratio of 1:4) were mixed and placed in a boat made of borosilicate glass. The boat was then placed in a tubular reactor and heated to 400°C. An excess of dry chlorine was slowly introduced at a chlorine flow rate of 300 mL / min. The reaction was continued for 2.5 hours to obtain molybdenum dioxide dichloride gas.

[0158] Molybdenum dioxide dichloride gas is introduced into an adsorption tower, which is filled with 30% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities.

[0159] The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 2 BV / h.

[0160] The adsorption tower temperature is 200°C.

[0161] The preparation method of the high temperature resistant metal impurity adsorbent is:

[0162] 0.04 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 16 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 100 g of thiol-modified MCM-41 mesoporous molecular sieve, 100 g of N,N-dimethylformamide, and 5 g of triethanolamine were added to a stirring vessel and stirred at 90° C. for 150 min. Then, benzoyl peroxide was added and stirred for 60 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities.

[0163] The preparation method of the allyl-modified MCM-41 mesoporous molecular sieve is as follows:

[0164] 15 g of mercaptosiloxane, 150 g of MCM-41 mesoporous molecular sieve, and 500 g of deionized water were stirred at 80° C. for 100 min, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

[0165] These gases will be collected by a cooling chamber and a molybdenum dioxide dichloride solid will be obtained. The crude product is purified by sublimation in a sublimator to obtain 13.8 g of molybdenum dioxide dichloride product.

[0166] The information in the above Examples 1-12 is shown in Table 1 and Table 2:

[0167] Table 1

[0168]

[0169]

[0170] Table 2 Metal ion impurity content of purified product of Example 8

[0171] element Content (ppb) element Content (ppb) Be ＜10 Zr ＜10 Li ＜10 Au ＜10 Na ＜50 Hf ＜10 Mg ＜50 Cu ＜10 Al ＜10 Zn ＜10 K ＜50 Ga ＜10 Ca ＜50 Sr ＜10 Cr ＜10 Ag ＜10 Mn ＜10 Cd ＜50 Fe ＜50 Ba ＜10 Co ＜10 Pb ＜10 Ni ＜10 U ＜10 Ta ＜10 V ＜10 Ge ＜10 As ＜10 W ＜10 Ti ＜10 In ＜10 Bi ＜10 Sc ＜10 Se ＜10

[0172] The present invention uses molybdenum trichloride, activated carbon, and chlorine as reaction raw materials. The molybdenum trichloride and activated carbon are mixed in a certain proportion, placed in a tubular reactor, heated to a certain temperature, and then an excess of dry chlorine is introduced to react to produce molybdenum dioxide dichloride gas. This gas is collected in a cooling chamber to obtain molybdenum dioxide dichloride solid. The crude product is then sublimated and purified to ultimately obtain a high-purity molybdenum dioxide dichloride product. This method has a high yield, improves raw material utilization and product yield, reduces production costs, and is conducive to industrial production.

[0173] The above are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or any direct or indirect application in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing molybdenum dioxide dichloride, characterized in that, The steps include: S1: 20g of molybdenum trioxide and 0.50g of activated carbon were mixed, placed in a tubular reactor and heated to a certain temperature, and then an excess of dry chlorine was introduced to react to produce molybdenum dioxide dichloride gas; S2: These gases are collected through a cooling chamber to obtain molybdenum dioxide dichloride solid, which is purified by sublimation to obtain a high-purity molybdenum dioxide dichloride product with a purity of 6N. The molybdenum dioxide dichloride gas produced in S1 is passed into an adsorption tower filled with 30% by volume of a high-temperature resistant metal impurity adsorbent to adsorb the metal impurities; The preparation method of the high temperature resistant metal impurity adsorbent is: 0.04 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 16 g of (4-bromo-2-butenyl)triphenylphosphine bromide, 100 g of thiol-modified MCM-41 mesoporous molecular sieve, 100 g of N,N-dimethylformamide, and 5 g of triethanolamine were added to a stirred tank and stirred at 90° C. for 150 min. Benzoyl peroxide was then added and stirred for 60 min. The mixture was filtered, washed with deionized water until neutral, and dried to obtain a high-temperature resistant adsorbent for metal impurities. The heating temperature of the tubular reactor is: 300°C; The adsorption tower temperature is 200°C; The molybdenum dioxide dichloride gas enters the adsorption tower at a space velocity of 2 BV / h.

2. The method for preparing molybdenum dioxide dichloride according to claim 1, wherein The flow rate of the chlorine gas is 200-400 mL / min.

3. The method for preparing molybdenum dioxide dichloride according to claim 1, wherein The reaction time is 1-4 hours.

4. The method for preparing molybdenum dioxide dichloride according to claim 1, wherein The preparation method of the thiol-modified MCM-41 mesoporous molecular sieve is: According to the mass ratio, 10-15 parts of mercaptosiloxane, 120-150 parts of MCM-41 mesoporous molecular sieve, and 300-500 parts of deionized water are stirred at 70-80° C. for 50-100 minutes, filtered, and dried to obtain mercapto-modified MCM-41 mesoporous molecular sieve.

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