Large-scale black phosphorus preparation device
By combining a carrier protection system and microwave heating with a multi-stage catalyst reaction chamber, the purity and stability issues in black phosphorus preparation have been resolved, achieving high-purity and high-efficiency black phosphorus preparation, suitable for large-scale industrial production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- SHAANXI TITANIUM CHAORUN NEW MATERIAL TECH CO LTD
- Filing Date
- 2025-06-09
- Publication Date
- 2026-05-15
AI Technical Summary
Existing black phosphorus preparation technologies face challenges such as stringent preparation conditions, high costs, introduction of toxic substances, insufficient process stability, and difficulties in improving purity, making it difficult to meet the needs of high-end applications and large-scale industrial production.
The system employs a carrier protection system, a feeding system, a vibration transmission system, a microwave-assisted heating box, a multi-stage catalyst reaction box, and a black phosphorus partition crystallization device. Combined with inert gas protection and microwave heating, it achieves uniform fluidization and efficient catalytic reaction of red phosphorus, and forms black phosphorus products of different purities through multi-stage crystallization.
It achieves high purity (≥99.5%) and high utilization rate (≥92%) of black phosphorus, ensuring production safety and stability, and adapting to large-scale industrial production.
Smart Images
Figure CN224236114U_ABST
Abstract
Description
Technical Field
[0001] This utility model belongs to the field of smelting equipment technology, and further to the field of black phosphorus smelting equipment technology, specifically relating to a black phosphorus large-scale preparation device with simple structure and reliable operation. Background Technology
[0002] Black phosphorus, an allotrope of phosphorus, exhibits broad application prospects in semiconductor devices, energy storage, biomedicine, and catalysis due to its unique layered structure, high anisotropy, tunable direct band gap, and excellent electrical and optical properties. In recent years, with the rapid development of new energy and nanomaterials technologies, the large-scale preparation of high-purity black phosphorus has become crucial for its industrial application. However, existing black phosphorus preparation technologies still face many bottlenecks. Current methods mainly include traditional high-pressure methods, bismuth melting methods, mercury catalysis methods, ball milling methods, fixed-bed reactors combined with alternating double crystallizer systems, calcination processes, and gas separation methods. However, these methods have the following shortcomings:
[0003] 1. Traditional high-pressure methods rely on ultra-high-pressure equipment, which requires stringent preparation conditions and is costly;
[0004] 2. Although methods such as bismuth melting and mercury catalysis can improve purity, they require the introduction of toxic metals, posing environmental and safety risks.
[0005] 3. Although ball milling is simple to operate, the resulting black phosphorus has poor crystallinity, which makes it difficult to meet the needs of high-end applications.
[0006] 4. While a fixed-bed reactor combined with a dual-crystallizer alternating system can achieve continuous production to a certain extent, the solid catalyst is easily consumed during the reaction, the unreacted gas circulation efficiency is low, and the switching of the dual crystallizers requires frequent valve opening and closing, resulting in insufficient process stability and difficulty in meeting the needs of large-scale industrial production.
[0007] 5. The limitations of the calcination process (high-temperature, long-term calcination) and gas separation methods (cyclone separation or ceramic filtration) further restrict the improvement of black phosphorus purity and cost control.
[0008] Therefore, developing a simple and reliable device for the large-scale preparation of black phosphorus is key to solving this problem. Utility Model Content
[0009] The purpose of this invention is to provide a simple and reliable device for the large-scale preparation of black phosphorus.
[0010] The purpose of this utility model is achieved as follows: it includes a carrier protection system, a feeding system, a vibration transmission system, a microwave-assisted heating chamber, a multi-stage catalyst reaction chamber, a black phosphorus partitioned crystallization device, and a tail gas collection system. The feeding system has a carrier protection system at its inlet end; the feeding system has a vibration transmission system, a microwave-assisted heating chamber, and a multi-stage catalyst reaction chamber arranged sequentially at its outlet end; the multi-stage catalyst reaction chamber has a black phosphorus partitioned crystallization device at its outlet end; the black phosphorus partitioned crystallization device has a tail gas collection system at its exhaust end; the carrier protection system is a positive pressure gas system and includes an inert gas; the feeding system is a positive pressure system and includes a screw feeder and a mass flow meter; the vibration transmission system includes a screening device; the microwave-assisted heating chamber contains a magnetron; the multi-stage catalyst reaction chamber contains a magnetron and a porous distribution plate; the black phosphorus partitioned crystallization device includes multiple black phosphorus crystallization chambers, each with an independent temperature control system.
[0011] This invention comprises a carrier protection system, a feeding system, a vibration transmission system, a microwave-assisted heating chamber, a multi-stage catalyst reaction chamber, a black phosphorus zone crystallization device, and a tail gas collection system. The carrier protection system is a positive pressure gas system and is equipped with an inert gas supply, a flow control valve, and a high-purity supply device. Its functions are as follows:
[0012] (1) Isolate oxidation reaction
[0013] By continuously introducing inert gas to replace the air in the reaction system, the oxidation reaction of red phosphorus (P) and black phosphorus (BP) with oxygen at high temperatures is avoided (such as the generation of impurities such as P2O5), ensuring that the purity of the product is >99.5%.
[0014] (2) Maintaining fluidized state stability
[0015] Precise control of the carrier gas flow rate ensures that the red phosphorus particles form a uniform fluidized state (fluidization velocity 0.2–0.8 m / s) within the microwave fluidized bed, thereby improving gas-solid contact efficiency.
[0016] (3) Process environment safety assurance
[0017] The positive pressure design effectively prevents external air from flowing back in. Combined with the gas purification module, the oxygen concentration in the system is controlled at <10 ppm, preventing flammable phosphorus vapors (such as P4) from spontaneously combusting or exploding at high temperatures.
[0018] (4) Integration of dual functions of carrier gas
[0019] Inert gas not only serves as a protective medium but also as a reactant transport carrier, efficiently transferring red phosphorus vapor to the multi-stage catalyst reaction chamber, reducing raw material retention and loss (raw material utilization rate increased to over 92%).
[0020] The feeding system is a positive pressure system to prevent air from entering; the vibration transmission system is equipped with a screening device to remove excessively large particles, ensuring that red phosphorus enters the microwave-assisted heating box in small particles (<150μm) uniformly; the magnetrons I of the microwave-assisted heating box are spirally distributed on the inner wall of box I, with each layer of magnetrons having a different phase angle to increase energy utilization; a layer of microwave-absorbing material is set at the bottom of the inner cavity of box I, which can prevent excess energy from forming standing waves and causing energy loss, and absorb excess energy to be discharged from the bottom; a parabolic reflector is set at the top of the inner cavity of box I to ensure that energy is uniformly covered within the inner cavity of box I; the black phosphorus partition crystallization device is equipped with multiple black phosphorus crystallization boxes, each with an independent temperature control system, which can form different cooling rates and crystallization temperatures to form different black phosphorus crystal products.
[0021] This invention involves red phosphorus entering a microwave-assisted heating chamber and, after heating, forming red phosphorus vapor. Driven by an inert gas in a carrier protection system, this vapor enters a multi-stage catalyst reaction chamber (with a gas flow control valve at the bottom) from the bottom. The multi-stage catalyst reaction chamber contains a magnetron II and a multi-layer porous distribution plate. The magnetron II is microwave-heated (microwaves have a certain catalytic promoting effect), and the porous distribution plate is loaded with catalyst particles. The fluidized state of the catalyst particles on the multi-layer porous distribution plate enhances gas-solid contact and increases the conversion rate of intermediate transition state gas molecules (red phosphorus forms intermediate transition state gas molecules after reacting with the catalyst particles). After reacting for a certain period in the multi-stage catalyst reaction chamber, the phosphorus enters a black phosphorus partitioned crystallization device. This device contains multiple black phosphorus crystallization boxes, each with an independent temperature control system. The intermediate transition state gas molecules, upon entering different black phosphorus crystallization boxes, are cooled at different rates and crystallized at different temperatures by each independent temperature control system, resulting in different black phosphorus crystal products. The exhaust gas collection system is connected in parallel to the exhaust end of the black phosphorus crystallization box of the black phosphorus partition crystallization device. The unreacted carrier gas is separated by a cyclone separator and then returned to the gas purification unit for reuse through a circulating compressor to reduce the consumption of inert gas.
[0022] This invention has a simple structure, reliable operation, and can realize the large-scale preparation of black phosphorus. Attached Figure Description
[0023] Figure 1 This is a schematic diagram of the overall structure of this utility model;
[0024] Figure 2 This is a schematic diagram of the microwave-assisted heating box of this utility model;
[0025] Figure 3 This is a schematic diagram of the multi-stage catalyst reaction chamber of this utility model.
[0026] In the diagram: 1-Carrier protection system, 2-Feeding system, 3-Vibration transmission system, 4-Microwave-assisted heating box, 41-Box I, 42-Magnetron I, 43-Wave absorption material layer, 44-Parabolic reflector, 5-Multi-stage catalyst reaction box, 51-Box II, 52-Magnetron II, 53-Porous distribution plate, 54-Catalyst particles, 6-Black phosphorus zoned crystallization device, 61-Black phosphorus crystallization box I, 62-Black phosphorus crystallization box II, 63-Black phosphorus crystallization box III, 64-The nth black phosphorus crystallization box, 7-Tail gas collection system. Detailed Implementation
[0027] The present invention will be further described below with reference to the accompanying drawings, but this does not limit the present invention in any way. Any modifications made based on the teachings of the present invention shall fall within the protection scope of the present invention.
[0028] like Figures 1-3 As shown, this utility model includes a carrier protection system 1, a feeding system 2, a vibration transmission system 3, a microwave-assisted heating box 4, a multi-stage catalyst reaction box 5, a black phosphorus partitioned crystallization device 6, and a tail gas collection system 7. The carrier protection system 1 is installed at the feeding end of the feeding system 2; the vibration transmission system 3, the microwave-assisted heating box 4, and the multi-stage catalyst reaction box 5 are sequentially installed at the discharge end of the feeding system 2; the black phosphorus partitioned crystallization device 6 is installed at the discharge end of the multi-stage catalyst reaction box 5; and the tail gas collection system 7 is installed at the exhaust end of the black phosphorus partitioned crystallization device 6. The carrier protection system 1 is a positive pressure gas system and is equipped with an inert gas; the feeding system 2 is a positive pressure system and is equipped with a screw feeder and a mass flow meter; the vibration transmission system 3 is equipped with a screening device; a magnetron is installed inside the microwave-assisted heating box 4; a magnetron and a porous distribution plate are installed inside the multi-stage catalyst reaction box 5; and the black phosphorus partitioned crystallization device 6 is equipped with multiple black phosphorus crystallization boxes, each with an independent temperature control system.
[0029] The carrier protection system 1 includes an inert gas, a flow control valve, and a high-purity supply device.
[0030] The microwave-assisted heating box 4 is equipped with a PLC intelligent temperature control system.
[0031] The microwave-assisted heating box 4 includes a box body I 41, a magnetron I 42, a microwave absorbing material layer 43, and a parabolic reflector 44; the magnetron I 42 is installed on the inner wall of the box body I 41; the microwave absorbing material layer 43 is installed at the bottom of the inner cavity of the box body I 41; the parabolic reflector 44 is installed at the top of the inner cavity of the box body I 41; the bottom of the box body I 41 is provided with a feed hole, and the top is provided with a discharge hole.
[0032] The magnetrons I42 are spirally distributed on the inner wall of the housing I41, with each layer of magnetrons having a different phase angle.
[0033] The multi-stage catalyst reaction chamber 5 includes a chamber body II 51, a magnetron II 52, a porous distribution plate 53, and catalyst particles 54; the magnetron II 52 is installed on the inner wall of the chamber body II 51; multiple porous distribution plates 53 are installed vertically in the inner cavity of the chamber body II 51; catalyst particles 54 are installed on the porous distribution plates 53; a feed hole is provided at the bottom of the chamber body II 51, and a discharge hole is provided at the top.
[0034] The magnetrons II52 are spirally distributed on the inner wall of the housing II51, with each layer of magnetrons having a different phase angle.
[0035] The porous distribution plate 53 consists of 6 pieces, with a gradient distribution of pore size. From the bottom layer to the top layer, the pore sizes are 1nm, 0.9nm, 0.8nm, 0.7nm, 0.6nm, and 0.5nm respectively.
[0036] The black phosphorus partition crystallization device 6 includes black phosphorus crystallization box I 61, black phosphorus crystallization box II 62, black phosphorus crystallization box III 63, and the nth black phosphorus crystallization box 64; the black phosphorus crystallization box I 61, black phosphorus crystallization box II 62, black phosphorus crystallization box III 63, and the nth black phosphorus crystallization box 64 are respectively connected in parallel at the discharge end of the multi-stage catalyst reaction box 5.
[0037] The working principle and process of this utility model:
[0038] This utility model consists of a carrier protection system 1, a feeding system 2, a vibration transmission system 3, a microwave-assisted heating box 4, a multi-stage catalyst reaction box 5, a black phosphorus zone crystallization device 6, and a tail gas collection system 7. The carrier protection system 1 is a positive pressure gas system and is equipped with an inert gas supply, a flow control valve, and a high-purity supply device. Its functions are as follows:
[0039] (1) Isolate oxidation reaction
[0040] By continuously introducing inert gas to replace the air in the reaction system, the oxidation reaction of red phosphorus (P) and black phosphorus (BP) with oxygen at high temperatures is avoided (such as the generation of impurities such as P2O5), ensuring that the purity of the product is >99.5%.
[0041] (2) Maintaining fluidized state stability
[0042] Precise control of the carrier gas flow rate ensures that the red phosphorus particles form a uniform fluidized state (fluidization velocity 0.2–0.8 m / s) within the microwave fluidized bed, thereby improving gas-solid contact efficiency.
[0043] (3) Process environment safety assurance
[0044] The positive pressure design effectively prevents external air from flowing back in. Combined with the gas purification module, the oxygen concentration in the system is controlled at <10 ppm, preventing flammable phosphorus vapors (such as P4) from spontaneously combusting or exploding at high temperatures.
[0045] (4) Integration of dual functions of carrier gas
[0046] Inert gas not only serves as a protective medium but also as a reactant transport carrier, efficiently transferring red phosphorus vapor to the multi-stage catalyst reaction chamber, reducing raw material retention and loss (raw material utilization rate increased to over 92%).
[0047] The feeding system 2 is a positive pressure system to prevent air from entering; the vibration transmission system 3 is equipped with a screening device to remove excessively large particles, ensuring that red phosphorus enters the microwave-assisted heating box 4 in small particles (<150μm) uniformly; the magnetrons I 42 of the microwave-assisted heating box 4 are spirally distributed on the inner wall of the box body I 41, with each layer of magnetrons having a different phase angle to increase energy utilization; a microwave-absorbing material layer 43 is set at the bottom of the inner cavity of the box body I 41, which can prevent excess energy from forming standing waves and causing energy loss, and absorb excess energy to be discharged from the bottom; a parabolic reflector 44 is set at the top of the inner cavity of the box body I 41 to ensure that energy is uniformly covered in the inner cavity of the box body I 41; the black phosphorus partition crystallization device 6 is equipped with multiple black phosphorus crystallization boxes, each with an independent temperature control system, which can form different cooling rates and crystallization temperatures to form different black phosphorus crystal products.
[0048] In this invention, red phosphorus enters a microwave-assisted heating chamber 4 and, after heating, forms red phosphorus vapor. Driven by the inert gas in the carrier protection system 1, it enters a multi-stage catalyst reaction chamber 5 (with a gas flow control valve at the bottom) from the bottom. The multi-stage catalyst reaction chamber 5 is equipped with a magnetron II 52 and a multi-layer porous distribution plate 53. The magnetron II 52 is microwave-heated (microwaves have a certain catalytic promoting effect). The porous distribution plate 53 is loaded with catalyst particles 54. The fluidized state of the catalyst particles 54 on the multi-layer porous distribution plate 53 enhances the gas-solid contact and increases the conversion rate of intermediate transition state gas molecules (red phosphorus forms intermediate transition state gas molecules after reacting with the catalyst particles). After reacting for a certain period in the multi-stage catalyst reaction chamber 5, the phosphorus enters a black phosphorus partitioned crystallization device 6. The black phosphorus partitioned crystallization device 6 is equipped with multiple black phosphorus crystallization boxes, each with an independent temperature control system. The intermediate transition state gas molecules, upon entering different black phosphorus crystallization boxes, are subjected to different cooling rates and crystallization temperatures through each independent temperature control system, resulting in different black phosphorus crystal products. The exhaust gas collection system 7 is connected in parallel to the exhaust end of the black phosphorus crystallization box of the black phosphorus partition crystallization device 6. After the unreacted carrier gas is separated by a cyclone, it is returned to the gas purification unit for reuse through a circulating compressor to reduce the consumption of inert gas.
Claims
1. A large-scale black phosphorus preparation apparatus, comprising a carrier protection system (1), a feeding system (2), a vibration transmission system (3), a microwave-assisted heating box (4), a multi-stage catalyst reaction box (5), a black phosphorus partition crystallization device (6), and a tail gas collection system (7), characterized in that: The feeding system (2) is equipped with a carrier protection system (1) at the feeding end; the feeding system (2) is equipped with a vibration transmission system (3), a microwave-assisted heating box (4), and a multi-stage catalyst reaction box (5) in sequence at the discharge end; the multi-stage catalyst reaction box (5) is equipped with a black phosphorus partition crystallization device (6) at the discharge end; the black phosphorus partition crystallization device (6) is equipped with a tail gas collection system (7) at the exhaust end; the carrier protection system (1) is a positive pressure gas system and is equipped with an inert gas; the feeding system (2) is a positive pressure system and is equipped with a screw feeder and a mass flow meter; the vibration transmission system (3) is equipped with a screening device; the microwave-assisted heating box (4) is equipped with a magnetron; the multi-stage catalyst reaction box (5) is equipped with a magnetron and a porous distribution plate; the black phosphorus partition crystallization device (6) is equipped with multiple black phosphorus crystallization boxes, and each black phosphorus crystallization box has an independent temperature control system.
2. The apparatus for large-scale preparation of black phosphorus according to claim 1, characterized in that: The carrier protection system (1) includes an inert gas, a flow control valve, and a high-purity supply device.
3. The apparatus for large-scale preparation of black phosphorus according to claim 1, characterized in that: The microwave-assisted heating box (4) is equipped with a PLC intelligent temperature control system.
4. The apparatus for large-scale preparation of black phosphorus according to claim 1, characterized in that: The microwave-assisted heating box (4) includes a box body I (41), a magnetron I (42), a microwave absorbing material layer (43), and a parabolic reflector (44); the magnetron I (42) is installed on the inner wall of the box body I (41); the microwave absorbing material layer (43) is installed at the bottom of the inner cavity of the box body I (41); the parabolic reflector (44) is installed at the top of the inner cavity of the box body I (41); the bottom of the box body I (41) is provided with a feed hole, and the top is provided with a discharge hole.
5. The apparatus for large-scale preparation of black phosphorus according to claim 4, characterized in that: The magnetrons I (42) are spirally distributed on the inner wall of the housing I (41), and the phase angles of each layer of magnetrons are different.
6. The apparatus for large-scale preparation of black phosphorus according to claim 1, characterized in that: The multi-stage catalyst reaction box (5) includes a box body II (51), a magnetron II (52), a porous distribution plate (53), and catalyst particles (54); the magnetron II (52) is installed on the inner wall of the box body II (51); multiple porous distribution plates (53) are installed in the vertical direction in the inner cavity of the box body II (51); catalyst particles (54) are installed on the porous distribution plates (53); the bottom of the box body II (51) is provided with a feed hole, and the top is provided with a discharge hole.
7. The apparatus for large-scale preparation of black phosphorus according to claim 6, characterized in that: The magnetrons II (52) are spirally distributed on the inner wall of the housing II (51), and the phase angles of each layer of magnetrons are different.
8. The apparatus for large-scale preparation of black phosphorus according to claim 6, characterized in that: The porous distribution plate (53) consists of 6 pieces with a gradient distribution of pore size. From the bottom layer to the top layer, the pore sizes are 1nm, 0.9nm, 0.8nm, 0.7nm, 0.6nm, and 0.5nm respectively.
9. The apparatus for large-scale preparation of black phosphorus according to claim 1, characterized in that: The black phosphorus partition crystallization device (6) includes black phosphorus crystallization box I (61), black phosphorus crystallization box II (62), black phosphorus crystallization box III (63), and nth black phosphorus crystallization box (64); the black phosphorus crystallization box I (61), black phosphorus crystallization box II (62), black phosphorus crystallization box III (63), and nth black phosphorus crystallization box (64) are respectively connected in parallel at the discharge end of the multi-stage catalyst reaction box (5).