Antimony particle preparation method and device used by same

Abstract

The invention provides a preparation method of antimony particles and a device used by the preparation method, and belongs to the field of antimony preparation. The invention provides a preparation method of antimony particles, which comprises the following steps: continuously introducing a mixed gas containing gaseous antimony trichloride and hydrogen and a carrier gas into a vertical fluidized bed reactor filled with antimony micro powder for reduction reaction, and adjusting the flow of the mixed gas and the carrier gas to obtain the antimony particles with target particle size, antimony particles are obtained at a bottom discharge hole of the vertical fluidized bed reactor. The antimony particles are prepared by adopting the vertical fluidized bed reactor, and the gravity of the generated antimony particles is larger than the borne suspension force by adjusting the flow of the mixed gas and the carrier gas in the preparation process, so that the antimony particles with controllable and uniform particle sizes are directly synthesized.

Description

Technical Field

[0001] The invention relates to the field of antimony preparation, and in particular to a method for preparing antimony particles and a device for using the same. Background Art

[0002] High-purity antimony is mainly used as dopant for semiconductor materials, antimony compound semiconductor materials and antimony alloys.

[0003] At present, the main preparation method of high-purity antimony is to use industrial antimony as raw material, and then mix the antimony trichloride obtained by chlorination and rectification with high-temperature hydrogen (>850°C) to produce a hydrogen reduction reaction to obtain a molten antimony solution. The molten antimony solution is collected to obtain a 4-5N high-purity antimony product, and then the regional melting method and vacuum distillation method are used for secondary purification to obtain 6N and above high-purity antimony. There is also a method of directly preparing high-purity 6N antimony material by using high-purity antimony trichloride (purity of 4N) as raw material through hydrogen reduction. However, the disadvantages of the above method are also obvious. The antimony material obtained is a tiny fine powder, and the tiny fine powder antimony material is inconvenient to use directly, and needs to be processed by granulation and other reprocessing processes, which increases the production and purity control costs. Summary of the invention

[0004] The invention provides a method for preparing antimony particles and a device for using the same. The method can directly prepare antimony particles with a target particle size, thereby reducing the cost.

[0005] The present invention provides a method for preparing antimony particles, comprising the following steps:

[0006] A mixed gas containing gaseous antimony trichloride and hydrogen and a carrier gas are continuously introduced into a vertical fluidized bed reactor 3 filled with antimony micropowder for reduction reaction. Antimony particles with a target particle size are obtained by adjusting the flow rates of the mixed gas and the carrier gas, and antimony particles are obtained at the bottom discharge port of the vertical fluidized bed reactor 3.

[0007] Preferably, the method for preparing the mixed gas containing gaseous antimony trichloride and hydrogen comprises the following steps:

[0008] Under a protective atmosphere, antimony trichloride is melted to obtain an antimony trichloride melt;

[0009] Passing high-temperature hydrogen into the antimony trichloride melt for bubbling to obtain a mixed gas containing gaseous antimony trichloride and hydrogen;

[0010] The temperature of the high temperature hydrogen is 90-300°C;

[0011] The temperature of the mixed gas containing gaseous antimony trichloride and hydrogen is 90-300°C.

[0012] Preferably, the purity of the antimony trichloride is ≥6N.

[0013] Preferably, the molar ratio of gaseous antimony trichloride to hydrogen in the mixed gas is 1:2 to 10;

[0014] The temperature of the carrier gas is 100-350°C.

[0015] Preferably, the temperature of the reduction reaction is 400-630°C.

[0016] Preferably, the particle size of the antimony micropowder is 50 to 1000 μm;

[0017] The purity of the antimony micropowder is ≥5N.

[0018] Preferably, the preparation method obtains small-sized antimony particles having a particle size smaller than that of the antimony particles and gaseous antimony trichloride gas at the top of the vertical fluidized bed reactor 3; the preparation method further comprises: subjecting the gas containing small-sized antimony particles and gaseous antimony trichloride to sedimentation separation to obtain small-sized antimony particles and gas containing gaseous antimony trichloride;

[0019] The small-size antimony particles are introduced into a vertical fluidized bed reactor 3 to continue preparing antimony particles of a target particle size; the gas containing gaseous antimony trichloride is condensed to obtain antimony trichloride;

[0020] The antimony trichloride is used to prepare a mixed gas containing gaseous antimony trichloride and hydrogen.

[0021] The present invention also provides a device used in the preparation method described in the above technical solution, comprising a vertical fluidized bed reactor 3;

[0022] a volatilizer 2 connected to the inlet of the vertical fluidized bed reactor 3, the volatilizer 2 being used for preparing a mixed gas containing gaseous antimony trichloride and hydrogen;

[0023] a high-temperature hydrogen storage device connected to the volatilizer 2;

[0024] A carrier gas storage device connected to the inlet of the vertical fluidized bed reactor 3.

[0025] Preferably, it also includes: a pretreatment tank 1, used for preparing liquid antimony trichloride;

[0026] A cyclone dust collector 4 connected to the top discharge port of the vertical fluidized bed reactor 3, used for settling small-size antimony particles;

[0027] A micro powder bin 5 connected to the bottom discharge port of the cyclone dust collector 4.

[0028] Preferably, it further comprises: a tail gas condensation unit 6 connected to the tail gas outlet of the cyclone dust collector 4;

[0029] A condensate collection tank 7 connected to the bottom discharge port of the tail gas condensation unit 6;

[0030] The bottom discharge port of the condensate collecting tank 7 is connected to the first raw material inlet of the volatilizer 2;

[0031] A product particle bin 8 connected to the bottom discharge port of the vertical fluidized bed reactor 3 .

[0032] The present invention adopts a vertical fluidized bed reactor 3 to prepare antimony particles. The antimony particles are affected by their own gravity and the suspension force generated by the gas flow rate in the vertical fluidized bed reactor 3. During the preparation process, the flow rates of the mixed gas and the carrier gas are adjusted so that the gravity of the generated antimony particles is greater than the suspension force, so that antimony particles with controllable and uniform particle size can be directly synthesized. The antimony particles are solid and do not melt. They do not dissolve and corrode the wall of the vertical fluidized bed reactor 3, are not easily introduced with impurities and pollution, and the purity of the antimony particle product is guaranteed. No secondary purification is required, and secondary pollution, secondary purification, reprocessing and other processes in the production process are avoided, thereby reducing the production cost of antimony metal materials. The preparation method is simple and has the characteristics of continuous production, small equipment scale, low investment, large output and scalability.

[0033] Furthermore, the present invention recovers and reuses antimony particles smaller than the target particle size and unreacted antimony trichloride, thereby ensuring full utilization of antimony trichloride and miniaturization of the device.

[0034] Furthermore, a particle collection bin is provided at the lower part of the vertical fluidized bed reactor 3, and the grown antimony particles continuously settle to the bottom of the vertical fluidized bed reactor 3 and are discharged from the lower end, thereby achieving the effect of continuous production and output. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Schematic diagram of the device used in the embodiment. DETAILED DESCRIPTION

[0036] The present invention provides a method for preparing antimony particles, comprising the following steps:

[0037] A mixed gas containing gaseous antimony trichloride and hydrogen and a carrier gas are continuously introduced into a vertical fluidized bed reactor 3 filled with antimony micropowder for reduction reaction. Antimony particles with a target particle size are obtained by adjusting the flow rates of the mixed gas and the carrier gas, and antimony particles are obtained at the bottom discharge port of the vertical fluidized bed reactor 3.

[0038] In the present invention, the method for preparing the mixed gas containing gaseous antimony trichloride and hydrogen comprises the following steps:

[0039] Under a protective atmosphere, antimony trichloride is melted to obtain an antimony trichloride melt;

[0040] High-temperature hydrogen is introduced into the antimony trichloride melt for bubbling to obtain a mixed gas containing gaseous antimony trichloride and hydrogen.

[0041] The invention melts antimony trichloride under a protective atmosphere to obtain an antimony trichloride melt.

[0042] In the present invention, the purity of the antimony trichloride is ≥6N.

[0043] In the present invention, the protective atmosphere preferably includes a nitrogen atmosphere.

[0044] In the present invention, the melting temperature is preferably 90°C.

[0045] After obtaining the antimony trichloride melt, the present invention introduces high-temperature hydrogen into the antimony trichloride melt for bubbling to obtain a mixed gas containing gaseous antimony trichloride and hydrogen.

[0046] In the present invention, the temperature of the high temperature hydrogen is preferably 115-120°C.

[0047] In the present invention, the molar ratio of gaseous antimony trichloride to hydrogen in the mixed gas is preferably 1:2-10. In a specific embodiment of the present invention, the molar ratio of gaseous antimony trichloride to hydrogen can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0048] In the present invention, the temperature of the mixed gas containing gaseous antimony trichloride and hydrogen is preferably 90-300° C. In a specific embodiment of the present invention, the temperature of the mixed gas containing gaseous antimony trichloride and hydrogen can be 90° C., 150° C., 200° C., 250° C. or 300° C. In the present invention, the temperature of the mixed gas containing gaseous antimony trichloride and hydrogen is preferably consistent with the temperature of the high-temperature hydrogen.

[0049] In the present invention, the temperature of the carrier gas is preferably 100-350°C. In a specific embodiment of the present invention, the temperature of the carrier gas can be 100°C, 150°C, 200°C, 250°C, 300°C or 350°C. The height of the carrier gas is preferably higher than the temperature of the mixed gas containing gaseous antimony trichloride and hydrogen. The carrier gas preferably includes one or more of hydrogen, nitrogen and argon. The function of the carrier gas is to achieve fluidization of antimony solid particles.

[0050] The size of the target antimony particles is controlled by the flow rate of the carrier gas containing the mixed gas of gaseous antimony trichloride and hydrogen.

[0051] When the vertical fluidized bed reactor 3 contains antimony powder, the carrier gas flow rate of the carrier gas and the mixed gas containing gaseous antimony trichloride and hydrogen can be adjusted by conventional methods. In a specific embodiment of the present invention, the flow rate of the carrier gas is kept unchanged, and the flow rate of the mixed gas containing gaseous antimony trichloride and hydrogen is slowly increased from 0. The particles continue to grow, and the mixed gas is also slowly increased, and the carrier gas can remain unchanged. When the mixed gas reaches the maximum value, if the particles still need to grow, the carrier gas flow rate can be increased at this time to maintain the force required for particle suspension.

[0052] The present invention has no special limitation on the carrier gas flow rate, and it can be adjusted according to the particle size of the antimony particles obtained at the bottom discharge port. In a specific embodiment of the present invention, the carrier gas flow rate gradually increases from an initial value of 0 and reaches a constant value. During the continuous production process, it remains unchanged or the initial introduction rate of the carrier gas is 3L / min, and then slowly increases to 5L / min and remains constant.

[0053] In the present invention, the temperature of the reduction reaction is preferably 400-630°C. In a specific embodiment of the present invention, the temperature of the reduction reaction may be 400°C, 450°C, 500°C, 550°C, 600°C or 630°C.

[0054] In the present invention, the reduction reaction is preferably carried out in a hydrogen atmosphere.

[0055] In the present invention, the vertical fluidized bed reactor 3 contains antimony powder, and the particle size of the antimony powder is preferably 50 to 1000 μm. In a specific embodiment of the present invention, the particle size of the antimony powder can be 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm or 1000 μm.

[0056] In the present invention, the purity of the antimony micropowder is ≥5N.

[0057] The preparation method obtains small-sized antimony particles having a particle size smaller than that of the antimony particles and gaseous antimony trichloride gas at the top of the vertical fluidized bed reactor 3. The present invention preferably separates the small-sized antimony particles and the gaseous antimony trichloride gas by sedimentation to obtain small-sized antimony particles and gas containing gaseous antimony trichloride.

[0058] In the present invention, the temperature of the gas containing gaseous antimony trichloride is preferably 300-600°C.

[0059] After the gas containing gaseous antimony trichloride is obtained, the present invention preferably condenses the gas containing gaseous antimony trichloride to obtain antimony trichloride.

[0060] After obtaining antimony trichloride, the present invention preferably uses the antimony trichloride to prepare a mixed gas containing gaseous antimony trichloride and hydrogen.

[0061] After obtaining the small-sized antimony particles, the present invention preferably introduces the small-sized antimony particles into a vertical fluidized bed reactor 3 to continue preparing antimony particles of target particle size.

[0062] In the present invention, the purity of the antimony particles of the target particle size and the small-size antimony particles is preferably 6N to 7N.

[0063] The present invention also provides a device used in the preparation method described in the above technical solution, comprising a vertical fluidized bed reactor 3;

[0064] The volatilizer 2 connected to the vertical fluidized bed reactor 3 is used for preparing a mixed gas containing gaseous antimony trichloride and hydrogen;

[0065] A carrier gas storage device 9 connected to the vertical fluidized bed reactor 3 .

[0066] In the present invention, the device comprises: a vertical fluidized bed reactor 3;

[0067] The function of the vertical fluidized bed reactor 3 is to realize the reaction of hydrogen and antimony trichloride to produce antimony particles. The antimony particles are in a suspended or fluidized state under the action of the airflow. As the reaction continues, the antimony particles continue to grow. As the antimony particles continue to grow and reach the desired particle size, the gravity of the antimony particles is greater than the suspension force of the airflow, and the antimony particles settle and are enriched at the bottom of the vertical fluidized bed reactor 3.

[0068] In the present invention, the device comprises: a volatilizer 2 connected to the vertical fluidized bed reactor 3, the volatilizer 2 is used to prepare a mixed gas containing gaseous antimony trichloride and hydrogen; the volatilizer 2 preferably comprises a bubbling volatilizer 2. The function of the volatilizer 2 is to prepare gaseous antimony trichloride using high-temperature hydrogen and antimony trichloride melt, and to achieve mixing of hydrogen and gaseous antimony trichloride in a specific ratio, and then the mixed hydrogen and gaseous antimony trichloride are fed into the vertical fluidized bed reactor 3.

[0069] In the present invention, the top discharge port of the volatilizer 2 is preferably connected to the first feed port of the vertical fluidized bed reactor 3 .

[0070] In the present invention, the top feed port of the volatilizer 2 is preferably a hydrogen feed port. When preparing gaseous antimony trichloride using high-temperature hydrogen and antimony trichloride melt, the hydrogen feed port is preferably sunk below the liquid level of the antimony trichloride melt.

[0071] In the present invention, the device comprises: a carrier gas storage device 9 connected to the vertical fluidized bed reactor 3 .

[0072] In the present invention, the carrier gas storage device 9 is preferably connected to the second feed port of the vertical fluidized bed reactor 3 .

[0073] In the present invention, the device preferably comprises: a pretreatment tank 1 connected to a volatilizer 2, used for melting antimony trichloride. The function of the pretreatment tank 1 is to achieve the addition and pretreatment of antimony trichloride.

[0074] In the present invention, the bottom of the volatilizer 2 is preferably connected to the pretreatment tank 1. The bottom of the volatilizer 2 is connected to the pretreatment tank 1 so that the antimony trichloride melt can be continuously transported to the volatilizer 2.

[0075] A material pretreatment tank 1 and a volatilizer 2 are arranged in front of the vertical fluidized bed reactor 3 to realize continuous material supply in the continuous production process.

[0076] In the present invention, the device preferably further comprises: a cyclone dust collector 4 connected to the top discharge port of the vertical fluidized bed reactor 3, for settling small-size antimony particles;

[0077] In the present invention, the device preferably further comprises: a powder bin 5 connected to the bottom discharge port of the cyclone dust collector 4; after the antimony particles that have finished growing are discharged into the product particle bin 8, the antimony particle product with the required particle size can be obtained.

[0078] The micro powder bin 5 is preferably connected to the third feed inlet of the vertical fluidized bed reactor 3 .

[0079] In the present invention, the device preferably further comprises: a tail gas condensation unit 6 connected to the tail gas outlet of the cyclone dust collector 4; the tail gas condensation unit 6 is preferably composed of a single or multiple shell-and-tube heat exchangers, and the heat exchange refrigerant is preferably water at room temperature. The condensed antimony trichloride melt is transported to the condensate collection tank 7, and finally sent to the volatilizer 2 again. The function of the tail gas condensation unit 6 is to cool the high-temperature tail gas, so that the gaseous antimony trichloride that has not reacted completely in the tail gas is condensed and liquefied, and the non-condensable gas components are hydrogen, carrier gas and by-product hydrogen chloride, and the collected antimony trichloride melt is sent to the condensate collection tank 7.

[0080] In the present invention, the device preferably further comprises: a condensate collecting tank 7 connected to the bottom outlet of the tail gas condensation unit 6 ; the bottom outlet of the condensate collecting tank 7 is connected to the first raw material inlet of the volatilizer 2 .

[0081] In the present invention, the device preferably further comprises: a product particle bin 8 connected to the bottom discharge port of the vertical fluidized bed reactor 3 .

[0082] In the present invention, when the device includes a pretreatment tank 1, a volatilizer 2, a vertical fluidized bed reactor 3, a carrier gas storage device 9, a cyclone dust collector 4, a micro powder bin 5, a tail gas condensation unit 6 and a condensate collection tank 7, the preparation method preferably includes the following steps:

[0083] Antimony trichloride is placed in a pretreatment tank 1 and melted, and the obtained melt is sent to a volatilizer 2, and then hydrogen is introduced into the volatilizer 2 to bubble the melt in the volatilizer 2 to obtain a mixed gas containing gaseous antimony trichloride and hydrogen;

[0084] Passing a carrier gas into a vertical fluidized bed reactor 3 containing antimony seed crystals, and then passing the mixed gas containing gaseous antimony trichloride and hydrogen into the vertical fluidized bed reactor 3 for reduction reaction, obtaining antimony particles of target particle size at the bottom discharge port of the vertical fluidized bed reactor 3, and obtaining a mixed gas containing small-size antimony particles and antimony trichloride vapor at the top discharge port;

[0085] The mixed gas is passed into a cyclone dust collector 4 for sedimentation to obtain small-sized antimony particles and tail gas containing antimony trichloride vapor;

[0086] The small-size antimony particles are introduced into the micro powder bin 5 and then into the vertical fluidized bed reactor 3 to continue preparing antimony particles of target particle size;

[0087] The tail gas is passed into the tail gas condensation unit 6 for condensation to obtain antimony trichloride.

[0088] The present invention places antimony trichloride in a pretreatment tank 1 for melting, sends the obtained melt into a volatilizer 2, and then introduces hydrogen into the volatilizer 2 to bubble the melt in the volatilizer 2 to obtain a mixed gas containing gaseous antimony trichloride and hydrogen.

[0089] In the present invention, the melting is preferably carried out in a protective atmosphere. The present invention has no particular limitation on the method of forming the protective atmosphere, and a solution familiar to those skilled in the art may be used. Specifically, in a specific embodiment of the present invention, antimony trichloride is placed in the pretreatment tank 1 and then replaced with nitrogen several times to exhaust the air and impurity atmosphere inside the pretreatment tank 1.

[0090] In the present invention, the temperature of the volatilizer 2 is preferably 90-300° C., and in a specific embodiment of the present invention, the temperature of the volatilizer 2 may be 90, 100, 150, 200, 250 or 300° C.; the pressure is preferably 0.1-10 bar, and in a specific embodiment of the present invention, the pressure may be 0.1 bar, 1.5 bar, 5 bar, 8 bar or 10 bar.

[0091] After obtaining a mixed gas containing gaseous antimony trichloride and hydrogen, the present invention passes a carrier gas into a vertical fluidized bed reactor 3 containing antimony seeds, and then passes the mixed gas containing gaseous antimony trichloride and hydrogen into the vertical fluidized bed reactor 3 for a reduction reaction, and antimony particles of a target particle size are obtained at the bottom discharge port of the vertical fluidized bed reactor 3, and a mixed gas containing small-size antimony particles and antimony trichloride vapor is obtained at the top discharge port.

[0092] During the reduction reaction, the mixed gas of hydrogen and antimony trichloride undergoes a reduction reaction and deposits on the surface of the antimony particles. When the gravity effect is greater than the suspension effect of the airflow, the antimony particles are deposited and enriched at the bottom of the vertical fluidized bed reactor 3 .

[0093] After a mixed gas containing small-sized antimony particles and antimony trichloride vapor is obtained at the top discharge port, the mixed gas is passed into a cyclone dust collector 4 for sedimentation to obtain small-sized antimony particles and tail gas containing antimony trichloride vapor.

[0094] After obtaining the small-sized antimony particles, the present invention passes the small-sized antimony particles into the micro powder bin 5 and then into the vertical fluidized bed reactor 3 to continue preparing antimony particles of target particle size.

[0095] After obtaining the tail gas containing antimony trichloride vapor, the present invention passes the tail gas into a tail gas condensation unit 6 for condensation to obtain antimony trichloride.

[0096] In the present invention, antimony trichloride raw material is preferably supplemented during the preparation process so that the liquid level of the volatilizer 2 is maintained between two-thirds and one-half.

[0097] The schematic diagram of the device used in the embodiment of the present invention is as follows Figure 1 Shown: vertical fluidized bed reactor 3;

[0098] A volatilizer 2 connected to the vertical fluidized bed reactor 3, wherein the top discharge port of the volatilizer 2 is preferably connected to the first feed port of the vertical fluidized bed reactor 3;

[0099] The top feed port of the volatilizer 2 is a hydrogen feed port;

[0100] A carrier gas storage device 9 connected to the vertical fluidized bed reactor 3;

[0101] The carrier gas storage device 9 is connected to the second feed port of the vertical fluidized bed reactor 3;

[0102] A pretreatment tank 1 is connected to a volatilizer 2 , and the bottom of the volatilizer 2 is connected to the pretreatment tank 1 .

[0103] A cyclone dust collector 4 connected to the top discharge port of the vertical fluidized bed reactor 3,

[0104] A micro powder bin 5 connected to the bottom discharge port of the cyclone dust collector 4;

[0105] The micro powder bin 5 is connected to the third feed inlet of the vertical fluidized bed reactor 3 .

[0106] A tail gas condensation unit 6 connected to the tail gas outlet of the cyclone dust collector 4;

[0107] A condensate collecting tank 7 is connected to the bottom discharge port of the tail gas condensation unit 6 ; the bottom discharge port of the condensate collecting tank 7 is connected to the first raw material inlet of the volatilizer 2 .

[0108] A product particle bin 8 connected to the bottom discharge port of the vertical fluidized bed reactor 3 .

[0109] The method for preparing the antimony particles provided by the present invention and the device used therein are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0110] Example 1

[0111] 10 g of antimony powder with a particle size of 1 mm (the purity of the antimony powder is 99.9998%) is placed in a vertical pipe fluidized bed reactor with an inner diameter of 200 mm and a length of 1500 mm, and the vertical fluidized bed reactor 3 is evacuated and replaced with a hydrogen atmosphere, and then the vertical fluidized bed reactor 3 is heated to 550°C and kept warm.

[0112] Then, hydrogen gas at a temperature of 350° C. was introduced into the vertical fluidized bed reactor 3 . Hydrogen gas was used as a carrier gas with a flow rate of 3 L / min, so that the antimony powder in the vertical fluidized bed reactor 3 was in a fluidized state.

[0113] After antimony trichloride solid (the purity of antimony trichloride solid is 99.9999%) is loaded into the pretreatment tank 1, it is replaced with nitrogen several times to exhaust the air and impurity atmosphere inside the pretreatment tank 1, heated to 90° C. to melt into liquid, and then sent to the bubbling evaporator 2. The temperature of the evaporator 2 is controlled to be stable at 115° C. and the pressure is constant at 1.5 bar.

[0114] Hydrogen preheated to 115°C was introduced into the volatilizer 2 for bubbling, and the hydrogen feed port pipeline was sunk below the antimony trichloride liquid level. During the particle growth process, the mixed gas flow rate increased uniformly from 0 over 20 hours and was finally controlled to be constant at 2L / min. The mixed gas temperature at the outlet of the volatilizer 2 was always 115°C. The gas components were hydrogen and gaseous antimony trichloride, and the molar ratio was 3:1.

[0115] The mixed gas is slowly introduced into the vertical fluidized bed reactor 3, and the mixed gas of hydrogen and gaseous antimony trichloride undergoes chemical vapor deposition reaction on the surface of the antimony particles. During the deposition and growth of the antimony particles, the carrier gas flow rate, the temperature and pressure of the volatilizer 2 are always kept constant. The mixed gas flow rate is adjusted as the antimony particles grow slowly, increasing from the initial 0 L / min to 2 L / min, and then remains unchanged. At this time, the total gas flow rate of the carrier gas and the mixed gas is 5 L / min.

[0116] After the antimony particles in the vertical fluidized bed reactor 3 grow to a diameter of 5 mm, they are deposited and enriched at the bottom of the vertical fluidized bed reactor 3 because the gravity is greater than the suspension effect of the airflow. After the particles are accumulated, the channel between the bottom of the vertical fluidized bed reactor 3 and the product particle bin 8 is opened, and the antimony particle products enter the product particle bin 8.

[0117] The tail gas after the reaction first enters the cyclone dust collector 4, and the tail gas after settling is then sent to the tail gas condensation unit 6. The tail gas condensation unit 6 is composed of a single or multiple tube-and-tube heat exchangers, and the heat exchange refrigerant is room temperature water. The condensed liquid is transported to the condensate collection tank 7 through a pipeline, and finally sent to the volatilizer 2 again.

[0118] The antimony powder obtained after the tail gas is settled is first stored in the powder bin 5 temporarily, and then sent to the vertical fluidized bed reactor 3 for further growth.

[0119] During the reaction, antimony trichloride raw material is added to the pretreatment tank 1 for many times, and raw material is added to the volatilizer 2. The liquid level of the volatilizer 2 is maintained between two-thirds and one-half. According to the above process, continuous production is carried out, and antimony particles in the product particle bin 8 are collected. The particle size is 4 to 6 mm. After GDMS detection, the purity is 99.99997%.

[0120] Example 2

[0121] 10 g of antimony powder with a particle size of 1 mm (the purity of the antimony powder is 99.9998%) is placed in a vertical pipe fluidized bed reactor with an inner diameter of 200 mm and a length of 1500 mm, and the vertical fluidized bed reactor 3 is evacuated and replaced with a nitrogen atmosphere, and then the vertical fluidized bed reactor 3 is heated to 550°C and kept warm.

[0122] Then, nitrogen gas at a temperature of 350° C. was introduced into the vertical fluidized bed reactor 3 . The nitrogen gas was used as a carrier gas with a flow rate of 3 L / min, so that the antimony powder in the vertical fluidized bed reactor 3 was in a fluidized state.

[0123] After antimony trichloride solid (the purity of antimony trichloride solid is 99.9999%) is loaded into the pretreatment tank 1, it is replaced with nitrogen several times to exhaust the air and impurity atmosphere inside the pretreatment tank 1, heated to 90° C. to melt into liquid, and then sent to the bubbling evaporator 2. The temperature of the evaporator 2 is controlled to be stable at 115° C. and the pressure is constant at 1.5 bar.

[0124] Hydrogen preheated to 115°C was introduced into the volatilizer 2 for bubbling, and the hydrogen feed port pipeline was sunk below the antimony trichloride liquid level. During the particle growth process, the mixed gas flow rate increased uniformly from 0 over 20 hours and was finally controlled to be constant at 2L / min. The mixed gas temperature at the outlet of the volatilizer 2 was always 115°C. The gas components were hydrogen and gaseous antimony trichloride, and the molar ratio was 3:1.

[0125] The mixed gas is slowly introduced into the vertical fluidized bed reactor 3, and the mixed gas of hydrogen and gaseous antimony trichloride undergoes chemical vapor deposition reaction on the surface of the antimony particles. During the deposition and growth of the antimony particles, the carrier gas flow rate, the temperature and pressure of the volatilizer 2 are always kept constant. The mixed gas flow rate is adjusted as the antimony particles grow slowly, increasing from the initial 0 L / min to 2 L / min, and then remains unchanged. At this time, the total gas flow rate of the carrier gas and the mixed gas is 5 L / min.

[0126] After the antimony particles in the vertical fluidized bed reactor 3 grow to a diameter of 5 mm, they are deposited and enriched at the bottom of the vertical fluidized bed reactor 3 because the gravity is greater than the suspension effect of the airflow. After the particles are accumulated, the channel between the bottom of the vertical fluidized bed reactor 3 and the product particle bin 8 is opened, and the antimony particle products enter the product particle bin 8.

[0127] The tail gas after the reaction first enters the cyclone dust collector 4, and the tail gas after settling is then sent to the tail gas condensation unit 6. The tail gas condensation unit 6 is composed of a single or multiple tube-and-tube heat exchangers, and the heat exchange refrigerant is room temperature water. The condensed liquid is transported to the condensate collection tank 7 through a pipeline, and finally sent to the volatilizer 2 again.

[0128] The antimony powder obtained after the tail gas is settled is first stored in the powder bin 5 temporarily, and then sent to the vertical fluidized bed reactor 3 for further growth.

[0129] During the reaction, antimony trichloride raw material is added to the pretreatment tank 1 for multiple times, and raw material is replenished into the volatilizer 2. The liquid level of the volatilizer 2 is maintained between two-thirds and one-half.

[0130] According to the above process, continuous production is carried out to collect antimony particles in the product particle bin 8. The particle size is 4 to 6 mm. After GDMS detection, the purity is 99.99995%.

[0131] Example 3

[0132] 10 g of antimony powder with a particle size of 1 mm (the purity of the antimony powder is 99.9998%) is placed in a vertical pipe fluidized bed reactor with an inner diameter of 200 mm and a length of 1500 mm, and the vertical fluidized bed reactor 3 is evacuated and replaced with a nitrogen atmosphere, and then the vertical fluidized bed reactor 3 is heated to 550°C and kept warm.

[0133] Then, nitrogen gas at a temperature of 350° C. was introduced into the vertical fluidized bed reactor 3 . The nitrogen gas was used as a carrier gas with a flow rate of 3 L / min, so that the antimony powder in the vertical fluidized bed reactor 3 was in a fluidized state.

[0134] After antimony trichloride solid (the purity of antimony trichloride solid is 99.99999%) is loaded into the pretreatment tank 1, it is replaced with nitrogen several times to exhaust the air and impurity atmosphere inside the pretreatment tank 1, heated to 90° C. to melt into liquid, and then sent to the bubbling evaporator 2. The temperature of the evaporator 2 is controlled to be stable at 115° C. and the pressure is constant at 1.5 bar.

[0135] Hydrogen preheated to 115°C was introduced into the volatilizer 2 for bubbling, and the hydrogen feed port pipeline was sunk below the antimony trichloride liquid level. During the particle growth process, the mixed gas flow rate increased uniformly from 0 over 20 hours and was finally controlled to be constant at 2L / min. The mixed gas temperature at the outlet of the volatilizer 2 was always 115°C. The gas components were hydrogen and gaseous antimony trichloride, and the molar ratio was 3:1.

[0136] The mixed gas is slowly introduced into the vertical fluidized bed reactor 3, and the mixed gas of hydrogen and gaseous antimony trichloride undergoes chemical vapor deposition reaction on the surface of the antimony particles. During the deposition and growth of antimony particles, the carrier gas flow rate, the temperature and pressure of the volatilizer 2 are always kept constant. The mixed gas flow rate is adjusted as the antimony particles grow slowly, from the initial 0L / min to 2L / min, and then remains unchanged. When the mixed gas flow rate reaches 2L / min, the carrier gas flow rate begins to increase, from 3L / min to 5L / min at a uniform rate over 10h. At this time, the total gas flow rate of the carrier gas and the mixed gas is 7L / min.

[0137] After the antimony particles in the vertical fluidized bed reactor 3 grow to a diameter of 8 mm, they are deposited and enriched at the bottom of the vertical fluidized bed reactor 3 because the gravity is greater than the suspension effect of the airflow. After the particles are accumulated, the channel between the bottom of the vertical fluidized bed reactor 3 and the product particle bin 8 is opened, and the antimony particle products enter the product particle bin 8.

[0138] The tail gas after the reaction first enters the cyclone dust collector 4, and the tail gas after settling is then sent to the tail gas condensation unit 6. The tail gas condensation unit 6 is composed of a single or multiple tube-and-tube heat exchangers, and the heat exchange refrigerant is room temperature water. The condensed liquid is transported to the condensate collection tank 7 through a pipeline, and finally sent to the volatilizer 2 again.

[0139] The antimony powder obtained after the tail gas is settled is first stored in the powder bin 5 temporarily, and then sent to the vertical fluidized bed reactor 3 for further growth.

[0140] During the reaction, antimony trichloride raw material is added to the pretreatment tank 1 for multiple times, and raw material is replenished into the volatilizer 2. The liquid level of the volatilizer 2 is maintained between two-thirds and one-half.

[0141] According to the above process, continuous production is carried out to collect antimony particles in the product particle bin 8, the particle size of which is 6-8 mm. After GDMS detection, the purity is 99.999995%.

[0142] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing antimony particles, characterized in that: The following steps are involved: A mixed gas containing gaseous antimony trichloride and hydrogen and a carrier gas are continuously introduced into a vertical fluidized bed reactor (3) containing antimony micropowder for a reduction reaction, and antimony particles with a target particle size are obtained by adjusting the flow rates of the mixed gas and the carrier gas, and antimony particles are obtained at the bottom discharge port of the vertical fluidized bed reactor (3).

2. The preparation method according to claim 1, characterized in that: The method for preparing the mixed gas containing gaseous antimony trichloride and hydrogen comprises the following steps: Under a protective atmosphere, antimony trichloride is melted to obtain an antimony trichloride melt; Passing high-temperature hydrogen into the antimony trichloride melt for bubbling to obtain a mixed gas containing gaseous antimony trichloride and hydrogen; The temperature of the high temperature hydrogen is 90-300°C; The temperature of the mixed gas containing gaseous antimony trichloride and hydrogen is 90-300°C.

3. The preparation method according to claim 2, characterized in that: The purity of the antimony trichloride is ≥6N.

4. The preparation method according to claim 1 or 2, characterized in that: The molar ratio of gaseous antimony trichloride to hydrogen in the mixed gas is 1:2-10; The temperature of the carrier gas is 100-350°C.

5. The preparation method according to claim 1 or 2, characterized in that: The temperature of the reduction reaction is 400-630°C.

6. The preparation method according to claim 1, characterized in that: The particle size of the antimony micropowder is 50 to 1000 μm; The purity of the antimony micropowder is ≥5N.

7. The preparation method according to claim 1, characterized in that: The preparation method obtains small-sized antimony particles having a particle size smaller than that of the antimony particles and gaseous antimony trichloride gas at the top of the vertical fluidized bed reactor (3), and the preparation method further comprises: subjecting the gas containing the small-sized antimony particles and the gaseous antimony trichloride to sedimentation separation to obtain small-sized antimony particles and gas containing gaseous antimony trichloride; Passing the small-size antimony particles into a vertical fluidized bed reactor (3) to continue preparing antimony particles of target particle size; condensing the gas containing gaseous antimony trichloride to obtain antimony trichloride; The antimony trichloride is used to prepare a mixed gas containing gaseous antimony trichloride and hydrogen.

8. The device used in the preparation method according to any one of claims 1 to 7, characterized in that: It comprises a vertical fluidized bed reactor (3); a volatilizer (2) connected to the inlet of the vertical fluidized bed reactor (3), the volatilizer (2) being used for preparing a mixed gas containing gaseous antimony trichloride and hydrogen; a high-temperature hydrogen storage device connected to the volatilizer (2); A carrier gas storage device connected to the inlet of the vertical fluidized bed reactor (3).

9. The device according to claim 8, characterized in that Also includes: A pretreatment tank (1) for preparing liquid antimony trichloride; A cyclone dust collector (4) connected to the top discharge port of the vertical fluidized bed reactor (3) for settling small-size antimony particles; A micro powder bin (5) connected to the bottom discharge port of the cyclone dust collector (4).

10. The device according to claim 8 or 9, characterized in that Also includes: A tail gas condensation unit (6) connected to the tail gas outlet of the cyclone dust collector (4); A condensate collection tank (7) connected to the bottom discharge port of the tail gas condensation unit (6); The bottom discharge port of the condensate collection tank (7) is connected to the first raw material inlet of the volatilizer (2); A product particle bin (8) connected to the bottom discharge port of the vertical fluidized bed reactor (3).

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