A reactor system and method for producing particulate materials

Abstract

The present invention discloses a reactor and a method for producing granular materials. The reactor for producing granular materials includes a reactor cavity, and the reactor cavity is at least provided with a granular material feeding port (hopper), a raw material gas inlet, a granular product discharging port and a tail gas outlet; wherein, a distributor is not arranged on the raw material gas side in the reactor cavity. The reactor cavity is also provided with an internal or external thermal management mechanism for heating (cooling) the reaction zone; the reactor cavity is also provided with an internal or external dynamic generation mechanism. The present invention also discloses a method for producing granular materials by using the above reactor. The present invention overcomes many disadvantages of the prior art and realizes the production of granular materials with high efficiency, energy saving, long-term stability, safety and reliability.

Description

Technical Field

[0001] The present invention relates to the technology of material preparation, in particular to a method for preparing particulate materials by gas-phase (including liquid-phase) to solid-phase deposition, and more particularly to a reactor and a method for preparing particulate materials. Background Art

[0002] In modern industrial production, the demand for particulate materials such as elemental substances like silicon, nickel, and titanium; and compounds such as silicon nitride, silicon carbide, silicon oxide, and silicon suboxide is increasing, while the requirements for their properties are becoming more and more stringent: the particulate materials should meet high purity requirements; have uniform and appropriate particle sizes; and the production cost of the particulate materials should not be too high to meet the needs of large-scale continuous production. At the same time, in many production processes, it is necessary to granulate and coat the products. For example, the production of large-grain urea sulfur and pharmaceutical coatings all belong to the process of gas-phase or liquid-phase to solid-phase particle conversion.

[0003] Currently, the preferred reactor for producing particulate materials is a fluidized bed reactor. A selected raw material gas (a gas that can be decomposed at high temperatures, or undergo reduction, oxidation, nitridation, etc. reactions and whose chemical composition contains the target material element) is used to carry out thermal decomposition or reduction, oxidation, nitridation, etc. processes in the reactor, so that the target element in the raw material gas is continuously deposited on the surface of the particle seeds (previously formed a bed layer in the reactor and supplemented during the reaction process). After reaching the set particle size, it is collected to become the required particulate material.

[0004] Common reaction processes include:

[0005] Thermal decomposition of silane to prepare polysilicon; SiH 4 ---Si + H 2

[0006] Purification by carbonylation, such as decomposition of nickel carbonyl to produce nickel: Ni(CO) 4 ---Ni + CO

[0007] Synthesis of silicon suboxide: SiO2 + ySi --- SiOx (x = (2 + y) / 2)

[0008] Pyrolytic carbon: C-type H ya --- C = H2 and so on.

[0009] As for the precursor raw material gas used, it can be prepared by chemical methods using the corresponding elemental substances of the target material and purified into a raw material gas with a higher purity through a series of physical and chemical means, or it can be a raw material vapor or liquid spray formed at high temperatures, belonging to the production field of raw material gases. What the present invention focuses on is to provide a scientific and effective implementation technology for the industrial production of particulate materials by using these raw material gases through effective process procedures and control conditions.

[0010] The currently adopted fluidized bed process for producing granular materials has at least the following disadvantages:

[0011] After the raw material gas is fed into the reactor cavity, it needs to pass through the provided gas distributor so that the raw material gas can contact and react with the particle surface as fully as possible in the reaction cavity, thereby improving the utilization rate of the raw material gas and the yield of the granular product. In addition to depositing on the surface of the particle seeds, the simple substances decomposed from the raw material gas in the reactor cavity will also form deposits on the inner wall of the cavity, the raw material gas inlet, and the pipeline. While reducing the product yield, it causes blockage at the gas inlet and the gas inlet end of the gas distributor due to excessive deposition, and needs to be cleaned regularly. This not only reduces the product yield but also makes it difficult to meet the requirements of continuous production; it also affects the long-term continuous and stable operation of the fluidized bed.

[0012] When the raw material gas deposits on the particle surface, while the particle seeds grow, it also causes the particles to easily adhere to each other and form agglomerates in the cavity, affecting the collection of the product. Sometimes, production has to be interrupted for necessary treatment;

[0013] When preparing granular materials, the raw material gas is used to suspend solid particles, which consumes a large amount of gas, has a large gas circulation volume, and results in a large amount of free space in the fluidized bed reactor cavity. A large amount of dust is generated by the decomposition of the raw material gas itself, which is difficult to collect, reducing the raw material utilization rate and increasing the cost. Summary of the Invention

[0014] The present invention provides a reactor for preparing granular materials, characterized in that there is no gas distributor on the raw material gas inlet side. The present invention is used to solve the defects in the prior art and achieve the preparation of granular materials with high efficiency, energy saving, long-term stability, safety and reliability.

[0015] A reactor for producing granular materials disclosed by the present invention includes: a reactor cavity; the reactor cavity is at least provided with a granular material feeding hopper (opening), a precursor raw material gas inlet, a granular product discharging port, and a tail gas outlet; wherein,

[0016] There is no gas distributor on the precursor raw material gas inlet side of the reactor cavity. The characteristic is that the raw material gas directly contacts the granular material, deposits the target material in the precursor on the particle surface, enabling the particles to grow continuously and avoiding common problems such as distributor blockage in traditional methods and equipment.

[0017] Preferably, the installation positions of the raw material gas inlet and the tail gas outlet are not higher than the feed inlet and not lower than the granular product discharging port. The granular material feeding hopper is arranged at the upper part of the reactor cavity. The granular material feeding hopper (opening) can be used to add small particle seeds or recycled particles. The granular product discharging port is arranged at the lower part of the reactor cavity for discharging the deposited particles;

[0018] Status of particles in the reactor: There may be no distributor in the reactor cavity, and the particles are in a free-falling particle distribution, a jet-like particle distribution, or a moving distribution.

[0019] 1) The above-mentioned free-falling distribution can be at least one cylinder or multiple polygonal columns, and can be continuous or pulsed falling as Figures 1-3 shown; preferably multiple.

[0020] 2) The above-mentioned jet distribution is at least one as Figure 4 shown, preferably multiple cylinders or multiple polygonal columns or planes or rings, and can be continuous or pulsed;

[0021] 3) Optionally, there can be a tray on the gas outlet side in the reaction chamber, preferably a breathable tray, more preferably a stepped tray, to reduce the particle movement speed, increase the residence time, and improve the conversion efficiency as Figures 5-7 shown. Preferably, there is a gap for gas flow between two steps, and at the same time, heat management of the particle material is provided to reach the temperature and energy required for the reaction. It can be at any angle to the flow direction of the incoming gas. Preferably, the particles stacked on the tray can flow.

[0022] Reactor heat management mechanism: The reactor cavity is also provided with an internal or external heating mechanism for heating the reaction zone (particle seed material); the reactor cavity is also provided with an internal or external heating mechanism for heating the reaction zone, and the selection of the heating mechanism can be determined by the specific reaction, such as a combination of one or more of combustion heating, induction heating, microwave heating, intense light heating, resistance heating, and rotary furnace heating; it can be inside or outside the reactor cavity. Preferably, the heating mechanism is an internal heating mechanism, at least including one of the following mechanisms:

[0023] A heating element disposed in the reaction zone for heating the formed stacked particle bed;

[0024] A heat exchange tube with a heat source inside, the heat exchange tube is disposed in the reaction zone and penetrates through the side wall of the reactor cavity;

[0025] When the particle material is a conductive material, a power source electrically connected to the stacked particle bed.

[0026] Another content of heat management is to minimize deposition in places where deposition should not occur in the reactor, such as the inner wall and pipes; in addition to the air curtain, a cooling (heating) sandwich is used to keep it away from the deposition reaction temperature.

[0027] Dynamic generation mechanism: The reactor cavity is also provided with an internal or external dynamic generation mechanism. The dynamic generation mechanism is used to keep the particle bed layer in the reaction zone in a moving state, which can be spouting, agitation or flow. Preferably, the dynamic generation mechanism is a raw material gas nozzle and / or an auxiliary gas nozzle. The raw material gas nozzle and / or the auxiliary gas nozzle are arranged in the reactor cavity and are respectively connected to the raw material gas inlet and the auxiliary gas inlet provided on the reactor cavity. Or the dynamic generation mechanism is a particle conveying mechanism capable of conveying the particle material located at the lower end of the reactor cavity to the upper end of the reactor cavity. Further, the method for keeping the particle materials in the particle bed layer in a relative motion state includes:

[0028] Injecting auxiliary gas and / or raw material gas into the reactor cavity to agitate the piled particle bed layer; or

[0029] Changing the cross-section of the reactor cavity and changing the speed of supplementing the particle materials to control the residence time of the particle materials in the reactor cavity; or

[0030] Introducing an external force for spouting, rotating, agitating, stirring, vibrating or enabling the particle materials to flow under gravity through the staggered flow comb structure installed on the inner wall of the reactor cavity.

[0031] Particle conveying mechanism: The feeding end of the particle conveying mechanism is connected to the circulating solid discharge port, and the discharging end of the particle conveying mechanism is connected to the particle feeding hopper. In the present invention, the transportation of particles is not limited to gas and can adopt mechanical means, so the reaction has a relatively large operating space.

[0032] Further, the particle transportation mechanism at least includes one of the following mechanisms:

[0033] a) Mechanical lifting (bucket elevator, screw lift, vibration lift, rotation, inversion, etc.);

[0034] b) Further, the particle transportation mechanism includes: a dumping hopper, a lower guide groove and an upper guide groove. The dumping hopper can move back and forth between the upper end and the lower end of the reactor cavity through a lifting device. When the dumping hopper is located at the upper end of the reactor cavity, it can be communicated with the particle feeding hopper through the upper guide groove. The end of the upper guide groove far from the dumping hopper is the discharging end. When the dumping hopper is located at the lower end of the reactor cavity, it can be communicated with the circulating solid discharge port through the lower guide groove. The end of the lower guide groove far from the dumping hopper is the feeding end.

[0035] c) Pneumatic conveying (a combination of positive pressure, negative pressure, dense phase and dilute phase, Venturi, on-line vacuum, etc.).

[0036] Materials inside the reactor: Further, the inner wall of the reactor cavity and all components that can come into contact with the particles are made of the same material as the produced particle material or a material that does not contaminate the particle material. For example, when producing polysilicon materials, high-purity silicon, high-purity silicon carbide, high-purity silicon nitride, quartz, or graphite, etc., materials that will not diffuse impurities into the reactor cavity at high temperatures can be used. This can reduce or avoid contamination of the reactor cavity material to the material and have sufficient mechanical strength under high-temperature conditions.

[0037] Transition deposition prevention mechanism: Optionally, the reactor cavity and all places that may be deposited also include an air curtain mechanism or a cooling / heating sandwich layer that can provide a barrier between the reaction materials and the inner wall of the reactor cavity to prevent excessive deposition on the inner wall of the reactor cavity or other parts, which affects the continuous operation of the reactor; it is characterized in that the air curtain mechanism is a plurality of ventilation openings arranged on the inner wall of the reactor cavity, and the arrangement of the plurality of ventilation openings enables the introduced auxiliary gas to form an air curtain along the inner wall of the reactor cavity; or the reactor cavity further includes an air curtain mechanism that can provide a barrier between the reaction materials and the inner wall of the reactor cavity. The air curtain mechanism is arranged closely against the inner wall of the reactor cavity in the reactor cavity and has a plurality of air outlets, and the arrangement of the air outlets enables the auxiliary gas to form an air curtain along the inner wall of the reaction cavity when ejected.

[0038] Optionally, the reactor cavity is water-cooled or heated. Optionally, the reactor further includes a surface finishing mechanism for finishing the initial product of the obtained particle material. The surface finishing mechanism is a reaction cavity containing a raw material gas with a concentration of 0-10% mol.

[0039] Preheating mechanism: Optionally, the reactor cavity is provided with an internal or external preheating mechanism, which utilizes the waste heat in the reaction tail gas to preheat the raw material gas and / or auxiliary gas and solid particles entering the reactor cavity.

[0040] Gas-solid separation: Optionally, an air-solid separation mechanism is arranged outside the reactor cavity, and the air-solid separation mechanism is used to separate and collect the powder material in the reaction tail gas. Preferably, the air-solid separation mechanism is a bed layer densely packed with the produced particle material, and the filling rate of the densely packed particle material bed layer is more than 20%, preferably more than 50%.

[0041] Sieving and seed preparation mechanism: Optionally, a sieving mechanism is also provided in the reactor cavity corresponding to the particle product discharge port. The qualified particles after sieving enter the surface finishing, the small particles can be returned as seeds, and the over-sized particles can be broken. It also includes a grinder connected to the sieving mechanism for pulverizing the sieved particle material to prepare seeds and break the over-sized particles. A circulating solid discharge port is provided at the bottom of the reactor cavity, which is connected to the particle hopper through a pipeline.

[0042] Surface finishing: Preferably, the reactor further includes a surface finishing mechanism for finishing the initial product of the granular material obtained to obtain granular material with a smooth surface. The surface-treated granular material is cooled, collected, packaged, or directly transported to the downstream production section. The surface finishing mechanism is a reaction cavity containing a raw material gas with a molar concentration of 0-10%.

[0043] Furthermore, 1-1000 reaction units are formed in the reactor cavity.

[0044] Furthermore, the height of the reaction unit is 0.3-100 meters; alternatively, the height of the reactor cavity is 0.5-100 meters.

[0045] Another object of the present invention is to also provide a method for producing granular material using the above reactor, including the following steps:

[0046] a. Add granular material seeds into the reactor cavity through a granular feed hopper, so that the granular material seeds form a stacked granular bed layer in the reaction zone, and the filling rate of the granular material seeds in the stacked granular bed layer is more than 1%, more than 5%, more than 10%, more than 20%, preferably more than 50%; the filling rate is the volume of the granular material seeds in the reaction zone;

[0047] b. Heat the stacked granular bed layer to make the stacked granular bed layer reach the temperature required for the reaction, or it can also be introduced after external heating;

[0048] c. Make the granular material seeds in the stacked granular bed layer in a relative motion state;

[0049] d. Introduce raw material gas and auxiliary gas from the raw material gas inlet, so that the raw material gas deposits on the granular seeds to form an initial product of granular material, and discharge it to the next working area or the granular material outlet;

[0050] e. Recycle the granules and supplement the granular material seeds to maintain the particle size distribution of the stacked granular bed layer, and as much as possible make the total surface area of all particles balanced. When necessary, supplement granules of different sizes;

[0051] The order of the above steps a, b, c, d, and e is not limited. Preferably, the raw material gas is completely reacted before reaching each tray and will not be overly deposited on the tray.

[0052] Thermal management heating: Further, the heating mechanism of the reactor, preferably an internal heating mechanism, includes at least one of the following methods: a heating element disposed in the reaction zone for heating the formed packed particle bed; a heat exchange tube with a heat source inside, the heat exchange tube being disposed in the reaction zone and passing through the side wall of the reactor cavity; when the particulate material is a conductive material, preferably, the packed particulate bed is electrically connected to a power source for heating; the method further includes: using the internal heating mechanism to heat the formed packed particulate bed so that the introduced raw material gas reacts. Further, the method for making the particulate material seeds in the packed particulate bed in a relative motion state includes:

[0053] Dynamic generation: Injecting auxiliary gas and / or raw material gas into the reactor cavity to agitate the packed particulate bed; or

[0054] Using a variable-diameter reactor cavity and changing the speed of replenishing particulate material seeds to control the residence time of the particulate material seeds in the reactor cavity;

[0055] Introducing an external force for spouting, rotating, agitating, stirring, vibrating or allowing the particulate material seeds to flow under gravity through a cross-flow comb structure installed on the inner wall of the reactor cavity;

[0056] Circulating particulate material: Further, the method for pollution prevention and control during the reaction process includes:

[0057] The particulate material is silicon, nickel, iron and titanium, and the raw material gas is a compound containing silicon, nickel or titanium. The particulate material is a single substance that can exist independently in nature such as silicon, germanium, carbon, etc. and their nitrides, silicon carbide or oxides, etc. The raw material gas is a compound containing target materials such as silicon, nickel or titanium, etc. and a gas that can undergo chemical reactions such as redox carbonization with it.

[0058] Preferably, it further includes: separating powder material from the reaction tail gas and adding the powder material to the packed particulate bed; or

[0059] Seed preparation: Bursting part of the produced particulate material into small particulate material and adding the small particulate material to the packed particulate bed.

[0060] Gas-solid separation: Further, the process of separating powder material from the reaction tail gas is specifically: passing the reaction tail gas through a gas-solid separation mechanism with a densely packed particulate bed, collecting the powder material, and the filling rate of the densely packed particulate bed is more than 20%. The reaction tail gas after separating the powder material can also be separated according to the gas components, and the separated auxiliary gas is transported back to the reactor cavity for recycling.

[0061] Optionally, it further includes a process of surface-treating the as-produced initial granular material: subjecting the initial granular material to gas-phase airflow polishing in a reaction chamber containing a raw material gas with a concentration of 0-10% mol.

[0062] Optionally, a screening mechanism is further provided in the reactor chamber corresponding to the discharge port of the granular product, and a circulating solid discharge port is provided at the bottom of the reactor chamber, which is connected to the granular feed hopper through a pipeline; the method further includes:

[0063] Screening the as-produced initial granular material obtained by the reaction, discharging the initial granular material with a size not reaching the specified size from the circulating solid discharge port, and returning it as supplementary granular material seeds to the reactor chamber to participate in the reaction; subjecting the initial granular material with a size reaching the specified size to surface treatment.

[0064] Prevention of excessive deposition: Further, the auxiliary gas is an inert or non-reactive gas, and the auxiliary gas can be used to dilute the raw material gas, stir the accumulated granular bed to prevent caking, and generate an air curtain to prevent the deposition of solid materials at the raw material gas inlet and the inner wall of the reactor chamber; the method of forming the air curtain is to introduce the auxiliary gas into the reactor chamber through the air curtain mechanism, so that the auxiliary gas flows along the inner wall of the reactor chamber, realizing the barrier between the obtained initial granular material and the inner wall of the reactor chamber, and / or between the raw material gas and the inner wall of the reactor chamber, or achieving the effect of reducing deposition through heat management of the chamber inner wall such as heating or passing a cooling water jacket.

[0065] The reactor and method for producing granular materials provided by the present invention mainly have the following advantages compared with the currently adopted fluidized bed process for producing granular materials:

[0066] After the raw material gas is fed into the reactor chamber, the raw material gas can be fully contacted with the granular material seeds without setting a gas distributor, overcoming or reducing the blockage formed at the raw material gas inlet due to granular deposition, and realizing the stable and continuous operation of the reactor;

[0067] In addition, part of the reaction tail gas rises and mixes with the raw material gas, acting as an auxiliary gas, reducing the consumption of the auxiliary gas while also reducing the tail gas emission. In summary, the present invention realizes energy-saving, continuous, low-cost and long-time continuous and stable production of granular materials. Description of the Drawings

[0068] The drawings are used to provide a further understanding of the present invention, and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention, and do not constitute a limitation to the present invention. In the drawings:

[0069] Figure 1 Schematic diagram of a multi-reaction zone reactor for producing granular materials with external heating of the reaction chamber provided for Example 1;

[0070] Figure 2 It is a schematic structural diagram of a reactor for producing granular materials with pneumatic conveying circulation in the second embodiment;

[0071] Figure 3 It is a schematic structural diagram of a reactor for producing granular materials with symmetric handling of granules in the third embodiment;

[0072] Figure 4 It is a schematic structural diagram of a reactor for producing granular materials with multiple spouted reaction zones in the fourth embodiment;

[0073] Figure 5 It is a schematic diagram of a single reaction zone reactor for producing silicon suboxide materials provided in the fifth embodiment;

[0074] Figure 6 It is a schematic diagram of a reactor for producing high-purity silicon granules with multiple reaction zones provided in the sixth embodiment;

[0075] Figure 7 It is a schematic structural diagram of a spiral reactor in the seventh embodiment;

[0076] Figure 8 It is a schematic diagram of a reactor for producing high-purity silicon granules with multiple wedge-shaped reaction zones in the eighth embodiment. Detailed implementation manners

[0077] Example 1, Droplet type Granular polycrystalline silicon is prepared by the droplet method. The reactor for producing granular materials provided in this example is used for reducing raw material gases (trichlorosilane) and hydrogen to produce granular silicon materials, for decomposing silane to prepare granular silicon, and for collecting silicon suboxide vapor to form granules or powders.

[0078] Figure 1It is a reactor for producing granular materials. 100 is the reactor chamber, 101 is the granular inlet, 102 is the granular outlet. 103 is the reaction gas inlet, 104 is the tail gas outlet. 131, 132, 133 are heating ducts. 105 is the granular feed hopper and granular disperser. The granular screening, small granular seed addition and recycling mechanism are not shown. The specific operation is that the granules enter through the feed hopper 105 by the circulating feeder. The granules after entering 105 then pass through the heating ducts 131, 132, 133, and then enter the reactor chamber 100 through the inlet 101 (the other two are 101b and c), forming granular columnar reaction zones (units) 111, 112, 113. At this time, the heated seed granules in the reaction zone contact the raw material gas entering from the inlet 103, and the raw material gas decomposes on the surface of the granules to generate the target material which is deposited on the surface of the granules. The granules descend to the receiving hopper 106 and are discharged through the granular discharge port 102, and then are conveyed to the top 105 of the reactor by the granular recycling system to achieve a complete cycle. The granules that have grown and met the standard are separated from the recycling system through screening as products, and the small granules continue to recycle and grow until they meet the standard. At the same time, finer granules are added to the system as seeds. The height of the reaction unit is 0.3 - 100 meters; the height of the reactor chamber is 0.5 - 100 meters. It can be understood that according to the needs of the reaction, the number of feed inlets in the reactor chamber can be adjusted, at least one, preferably more than 3, so that 1 - 1000 reaction units are correspondingly formed in the reactor chamber. The ducts 131, 132, 133 for heating the granules are used to continuously add the granules as seeds to the reaction system, and at the same time heat the seeds. The heating method is a heater outside the tube or applying voltage at both ends of the tube to generate current, or heating by other means, forming a continuous process production process.

[0079] Example 2, a falling - type granular reactor with pneumatic conveying circulation for preparing granular polysilicon. The reactor for producing granular materials provided in this embodiment is used for reducing raw material gas (trichlorosilane) with hydrogen to generate granular silicon materials, for decomposing silane to prepare granular silicon, and for collecting silicon monoxide vapor to form granules or powders.

[0080] Figure 2 It is a granular reactor with a recycling system. 200 is the reaction chamber, 201 is the granular feed inlet, 202 is the granular discharge outlet, 203 is the raw material gas feed inlet, 204 is the reaction tail gas discharge outlet. 205 is the heating barrel, 206 is the receiving hopper, 207 is the valve, 208 is the gas sending tank, 209 is the conveying gas interface. 231 and 232 are resistance heaters.

[0081] The operating principle of the reactor is as follows: Granular materials are added from the top and heated above the reaction temperature by resistors 231 and 232 in 205. Then, they are continuously discharged by 201abc into the reactor cavity 200, forming three granular columnar reaction zones 211, 212, and 213. At this time, the heated granules will come into contact with the raw material gas entering from 203 in 211, 212, and 213, and the silicon material in the gas will be deposited on the surface of these granules. The granules sink downward over time and fall into the collector 206, completing the reaction cycle.

[0082] When 206 has collected a certain amount of granules, the valve 207 opens to inject the granules into the sending tank, and then the valve is closed. At this time, high-pressure gas is introduced into the sending tank under pressure from 209 to send the granules to the top of the reactor to form a cycle. At the same time, granule screening and seed addition are carried out, but not shown. Similarly, the height of the reaction unit is 0.3 - 100 meters; the height of the reactor cavity is 0.5 - 100 meters. It can be understood that according to the reaction requirements, the number of feed ports in the reactor cavity can be adjusted, at least one, preferably more than 2, so that 1 - 1000 reaction units are formed in the reactor cavity. Example 3: Symmetrical falling particle type. The reactor for producing granular materials provided in this embodiment is used for reducing raw material gas (trichlorosilane) and hydrogen to produce granular silicon materials, for decomposing silane to produce granular silicon, and for collecting silicon monoxide vapor to form granules or powders.

[0083] Figure 3 It is a granular reactor composed of two symmetrical heating chambers in the embodiment. The upper and lower parts have exactly the same form and are symmetrical about the central plane. 300 is the reaction cavity, 301 is the granular feed port, 302 is the granular discharge port, 303 is the raw material gas feed port, and 304 is the reaction tail gas discharge port. 305 and 306 are heating barrels and also hoppers, and 331, 332, 333, and 334 are resistance heaters in a Siemens furnace.

[0084] Small raw material particles are added to the reactor from the top 341, with the amount being one-third to one-fourth of 306. Start heating 333 and 334 so that the particles are heated to a temperature above the set reaction temperature. Then, rotate the reactor 180 degrees as shown by the arrow to reverse the positions of the upper and lower parts. At this time, the heated particles will flow into the reaction chamber 300 from the particle discharge port, forming particle columns 311, 312, and 313. The gas flowing in from the raw material gas inlet 303 will deposit on the surface of the particles in the reaction zones 311, 312, and 313, causing the particles to grow and fall into the lower heater to be continuously heated. When almost all the particles in the top heater have dropped, the bottom heater can be rotated 180 degrees to the top, and the top one to the bottom for circulation, so that the particles are continuously heated, discharged, deposited, and then reheated to achieve the purpose of growing large particles. The operation of this method is to stop the reaction after growing from a small amount of seed particles to large particles to achieve the purpose of producing large particles. The height of the reaction unit is 0.3 - 10 meters; the height of the reactor cavity is 0.5 - 10 meters, depending on the height of the rotatable space. It can be understood that according to the needs of the reaction, the number of feed ports in the reactor cavity can be adjusted, at least one, preferably more than 2, so that 1 - 1000 reaction units are correspondingly formed in the reactor cavity.

[0085] Example 4, Spouted bed operation is used for a reactor for preparing granular polysilicon from trichlorosilane. The reactor provided in this embodiment for producing granular materials is used to produce granular silicon materials by reducing raw material gas (trichlorosilane) with hydrogen.

[0086] Figure 4 It is a spouted bed granular reactor. 400 is the reactor cavity. The starting point is that small particle seeds enter the reactor cavity 400 from 401. On the left side 403 of the reactor is the reaction gas inlet, and on the right side 404 is the reaction tail gas outlet. At the bottom of the reactor, there is a bed layer 430 formed by piled-up particles. There are electrodes 431 and 432 on both sides of 430 to heat the particle bed layer. There are multiple injection ports 405 below the particle bed layer through which inert gas or non-reacting gas is injected to generate a particle column reaction zone (unit) 411, 412, and 413. The height of the reaction unit is 0.3 - 10 meters; the height of the reactor cavity is 0.5 - 10 meters. It can be understood that according to the needs of the reaction, the number of feed ports in the reactor cavity can be adjusted, at least one, preferably more than 2, so that 1 - 1000 reaction units are correspondingly formed in the reactor cavity.

[0087] The particles in the reaction zones 411, 412, and 413 will come into contact with the reaction raw material gas entering from 403, causing material deposition on the particle surface. Then, the particles fall back onto the heating bed, are heated, and then spouted up again. The surface is continuously deposited, and finally grows. By continuously adding and circulating in this way, the particle seeds finally grow and are discharged from the discharge port 402, while the reaction tail gas is discharged from 404, achieving circulation. Figure 4 a is the dot matrix horizontal distribution diagram of the injection ports at the bottom of the reactor; b and 4c are the distribution diagrams of another type of strip-shaped injection ports at the bottom of the reactor; Figure 4 d is the schematic diagram of the linear injection ports at the bottom of the annular reactor, and at the same time, it can also be an annular injection port. Other components of the reactor for producing high-purity silicon particle materials provided in this embodiment, such as the particle transport mechanism, screening mechanism, seed preparation and addition, and surface finishing mechanism, etc., are the same as those in Embodiments 1-3 and are not shown in the figure.

[0088] Embodiment 5: A reactor with a tray is used for the decomposition of silane to prepare granular silicon, nickel carbonyl pellets, and collect silicon monoxide vapor to form particles or powders.

[0089] As Figure 5 shown in a, using the same sample as in Embodiment 6, silicon monoxide precursor particles with a particle size of 3-10 mm are made and added to the reactor through the double-lock hopper 501 and fall into the crucible 503. The crucible is heated to 1400 °C by the graphite heating element 502. The sublimated silicon monoxide 507 overflows from the crucible and drifts to the collection chamber and deposits on the surface of the granular silicon monoxide substrate 508. 505 is the vacuum outlet, and there is also a louver-shaped baffle on the left of the vacuum outlet 505 (see Figure 5 b), and 506 is the particle circulator, which transports the particles from the bottom storage tank to the top of the equipment. Figure 5 In b, the reactor cavity 511 has a silicon monoxide inlet 510 and an outlet 513, and a stepped tray 512 is installed inside the reactor cavity 511. The bottom of the reactor cavity 511 is connected to a vacuum feeder 516 through a pipeline; while the top of the reactor cavity 511 is connected to a particle disperser 514, (see Figure 5 c is a folding fan. A particle screening device 515 is installed in the pipeline between the particle disperser 514, the stepped tray 512, and the vacuum feeder 516. The particles are evenly distributed on the stepped tray 512 through the particle disperser 514, and then the particles move to the bottom and circulate continuously. Inside the reactor cavity 511, its surface is in full contact with the silicon monoxide gas and its own particle size continuously grows. There is also a screening device 504 between the particle circulator 506 and the top, which leaves the large particles and discharges them, while the small particles are transported to the top and continue to circulate in the reactor and grow continuously. When there are too few small particle seeds in the system, they can be added to ensure the system operates in a stable state.

[0090] The stepped pallet on the gas outlet side has a stepped structure, whose function is to reduce the particle movement speed, increase the residence time, and improve the conversion efficiency. As shown in Figure 5 Figure b, there is a gap for gas flow between the two steps, and at the same time, it provides thermal management for the particulate material to reach the temperature and energy required for the reaction. It can be at any angle with the flow direction of the incoming gas or in a Figure 7 spiral distribution as shown. All chemical reactions are completed before the raw material gas reaches the pallet on the outlet side, and no solid material will be deposited on the pallet to eventually block the pallet.

[0091] Example 6, The reactor with multiple reaction zones is used for the decomposition of silane to prepare granular silicon, nickel carbonyl pellets, and collect silicon monoxide vapor to form particles or powders.

[0092] Figure 6 Schematic diagram of the reactor for producing high-purity silicon particulate material in the reactor with multiple reaction zones in Example 6. Figure 6 Figure a shows a reactor with single-sided gas inlet, where 600 is the reaction chamber, 601 is the feed inlet, which is divided into three paths to enter the reaction chamber; 602 is the particulate material outlet, 603 is the raw material gas inlet, and the reaction tail gas converges to the reaction tail gas outlet 604. Particulates enter the reaction chamber 600 from 601, descend along the pallet 611 into 621, and are heated (or cooled) by the heating mechanism provided by 621 at the same time, maintaining the reaction temperature and moving down to the pallet 612, then passing through 622 to 613, until reaching the outlet 602, and finally being circulated and transported to the top 601. During this period, the particulates contact the raw material gas at 611, 612, and 613 respectively, and the surface is deposited, and the particulates grow continuously. At the same time, the particulates are heated or cooled when passing through 621 and 622 for the next-stage reaction. Figure 6 Figure b shows a reactor with side-side gas inlet, and the principle is the same as Figure 6 Figure a, except that there is no separate heating tube, and the thermal management and the pallet form an integrated unit.

[0093] Example 7, The reactor with a spiral reaction zone is used for the decomposition of silane to prepare granular silicon, nickel carbonyl pellets, and collect silicon monoxide vapor to form particles or powders. Figure 7 Schematic diagram of the structure of the spiral stepped reactor. The spiral steps divide the space formed by the inner and outer cylinders into two spaces: above the steps and below the steps. The particulate material and the raw material gas enter from the space above the steps. After the raw material gas deposits the target material on the particulates, the generated tail gas flows into the space below the steps through the gaps between the steps and is then discharged from the gas outlet of the reactor. The particulates fall from the steps to the particulate outlet and are taken to screening. The large particulates enter the surface finishing device and are then output as products, while the small particulates are circulated back to the reactor to continue growing.

[0094] Example 8. A wedge-shaped reactor with multiple reaction zones is used for decomposing silane to prepare granular silicon, nickel carbonyl pellets, and collecting silicon monoxide vapor to form particles or powders.

[0095] Figure 8 It is a schematic diagram of the reactor of the multi-stage wedge-shaped reactor in Example 8 for producing high-purity silicon particulate material. Figure 8 a is a schematic diagram of the reactor for producing particulate material provided in Example 1; Figure 8 b is Figure 8 a schematic diagram of the wedge-shaped pallet structure in a; Figure 8 c is Figure 8 a schematic diagram of another inverted wedge-shaped pallet structure in a. The reactor for producing particulate material provided in this embodiment is used for pyrolyzing a raw material gas (silane) to generate a particulate material (silicon). As Figure 8 shown in a, the reactor for producing particulate material includes: a reactor cavity 801;

[0096] The reactor cavity 801 is at least provided with a particulate feed hopper 802, a raw material gas inlet 803, a particulate product outlet 804, and a tail gas outlet 805; among them, three wedge-shaped pallets 807 are further arranged in the reactor cavity 1, and are arranged at intervals from top to bottom along the reactor cavity 801. Thus, 3 reaction units are correspondingly formed in the reactor cavity. The height of the reaction unit is 0.3 - 100 meters; the height of the reactor cavity is 0.5 - 100 meters. It can be understood that according to the needs of the reaction, the number of wedge-shaped pallets in the reactor cavity can be adjusted. The number of wedge-shaped pallets in the reactor cavity is preferably 1 - 100 pairs, so that 1 - 100 reaction units are correspondingly formed in the reactor cavity.

[0097] As Figure 8 shown in b, the wedge-shaped pallet 807 is composed of 3 coaxial open-ended flat plates (the number of flat plates is determined by the width of the reactor cavity, and the larger the width of the reactor cavity, the more the number of flat plates), and the wide-mouth end of the wedge-shaped pallet 807 faces upward. The adjacent two flat plates are fixed together by the lower edge of the upper flat plate and the inner side wall of the lower flat plate, and a gas channel is formed. The upper edge of the uppermost flat plate is fixed to the inner side wall of the reactor cavity 801, and a gas channel is formed. And there is a gap for gas flow between the side walls of the adjacent two flat plates. The setting position of the wedge-shaped pallet 807 in the reactor cavity 801 is lower than the setting position of the raw material gas inlet 803. The upper region of the wedge-shaped pallet 807 can provide a reaction zone formed by stacking a particulate bed layer;

[0098] The cross-section of the flat plate of the wedge-shaped pallet 807 and the cross-section of the reactor cavity 801 are both rectangular. The cross-section of the flat plate of the corresponding wedge-shaped pallet 807 can reduce or prevent the initial product of the particulate material from flowing through the gap between the wedge-shaped pallet 807 and the reactor cavity 801, so that as much particulate material as possible passes through the central region of the wedge-shaped pallet 807.

[0099] The adjacent flat plates of the wedge-shaped support plate 807 are fixed by welding. The welding method is that the lower edge of the upper flat plate is fixed to the inner side wall of the lower flat plate by intermittent spot welding, and an air flow channel is formed in the area between the solder joints; the upper most flat plate of the wedge-shaped support plate 807 is fixed to the inner wall of the reactor cavity 801 by intermittent spot welding, and an air flow channel is formed in the area between the solder joints. In addition to welding fixation, other fixation methods can also be used, such as bolt connection.

[0100] In this embodiment, there are also three raw material gas inlets 803, which are correspondingly arranged above each wedge-shaped support plate 807;

[0101] The tail gas outlet 805 is arranged on the side wall of the reactor cavity 801 below the lowermost wedge-shaped support plate 807. The tail gas outlet 805 is used to discharge the tail gas, and the tail gas includes the gas decomposed from the reaction gas (H 2 ) and the auxiliary gas (H 2 ). When the reactor runs smoothly due to power failure or other reasons, the tail gas may also contain a small amount of raw material gas;

[0102] The particle hopper 802 is arranged at the upper part of the reactor cavity 801, and the particle product discharge port 804 is arranged at the lower part of the reactor cavity 801;

[0103] The reactor cavity 801 further includes an air curtain mechanism that can provide a barrier between the reaction material and the inner wall of the reactor cavity 801; the air curtain mechanism is a plurality of ventilation openings arranged on the inner wall of the reactor cavity, and the arrangement of the plurality of ventilation openings can make the introduced auxiliary gas form an air curtain along the inner wall of the reactor cavity 801. In addition, the air curtain mechanism can also be arranged on the raw material gas inlet pipeline connected to the raw material gas inlet. The raw material gas inlet pipeline is provided with ventilation holes, and the auxiliary gas is introduced into the raw material inlet pipeline through the ventilation holes, so that the auxiliary gas flows in a parallel or spiral manner along the pipeline, separating the raw material gas from the inner wall of the pipeline; the air curtain mechanism can also be an annular pipe arranged at the top or bottom in the reactor cavity 801 and surrounding the inner wall of the reactor cavity 801. The annular pipe is communicated with the auxiliary gas source, and a plurality of air outlets are arranged on the annular pipe. The arrangement of the air outlets can make the auxiliary gas form an air curtain along the inner wall of the reaction cavity when spraying out.

[0104] Such as Figure 8As shown, within the reactor cavity 801, built-in heating mechanisms 808 are provided in the reaction zones on the second and third wedge-shaped pallets. The heating mechanism 808 is a heating element embedded in the stacked particle bed layer. In addition to the built-in heating mechanism, an external heating mechanism can also be provided on the outer wall of the reactor cavity corresponding to the reaction zone. However, for large-sized reactors, the preferred heating method is the built-in heating mechanism. The built-in heating mechanism is at least one of the following: a heating element provided in the reaction zone for heating the formed stacked particle bed layer; or a heat exchange tube with a heat source inside, the heat exchange tube is provided in the reaction zone and penetrates through the side wall of the reactor cavity, and the heat source can be combustion heating or electric heating; or when the particulate material is a conductive material, a power source electrically connected to the stacked particle bed layer.

[0105] The reactor cavity 801 is also provided with an external dynamic generating mechanism, and the dynamic generating mechanism is used to keep the stacked particle bed layer in the reaction zone in a moving state. The dynamic generating mechanism adopted in this embodiment is a particle conveying mechanism capable of conveying the particulate material located at the lower end of the reactor cavity to the upper end of the reactor cavity.

[0106] In the present invention, the transport of particles is not limited by gas, but mechanical means are adopted, so the reaction has a relatively large operating space.

[0107] In addition, the dynamic generating mechanism can also adopt: a raw material gas nozzle and / or an auxiliary gas nozzle, the raw material gas nozzle and / or the auxiliary gas nozzle are arranged in the reactor cavity and are respectively connected to the raw material gas inlet and the auxiliary gas inlet provided on the reactor cavity.

[0108] The reactor cavity 801 is also provided with an external preheating mechanism for preheating the raw material gas and / or the auxiliary gas entering the reactor cavity 1, effectively utilizing the reaction waste heat and reducing the production cost.

[0109] An air-solid separation mechanism connected to the preheating mechanism is also provided outside the reactor cavity 801, and the air-solid separation mechanism is used to separate and collect the powder material in the reaction tail gas. The air-solid separation mechanism is a densely packed particle material bed layer, and the filling rate of the densely packed particle material bed layer is above 20% or above 50%.

[0110] A screening mechanism 810 is also provided in the reactor cavity 801 corresponding to the particle product discharge port 804. It also includes a grinder connected to the screening mechanism 810 for pulverizing the screened particulate material. When the particulate material seeds are insufficient, a part of the particulate material can be pulverized and sent back into the reactor cavity 801 as particulate material seeds. A circulating solid discharge port 809 is provided at the bottom of the reactor cavity 801, and it is communicated with the particle feed hopper 802 through a particle transport mechanism.

[0111] The inner wall of the reactor cavity 801 is made of high-purity silicon. It can be understood that other materials that are the same as the produced particulate material or do not contaminate the particulate material can also be selected. The inner wall of the reactor cavity 801 can also be made of high-purity silicon carbide, high-purity silicon nitride, quartz, graphite, etc., which do not diffuse impurities into the reactor cavity 801 at high temperatures.

[0112] The reactor also includes a surface finishing mechanism for finishing the initial product of the obtained particulate material to obtain a particulate material with a smooth surface. The surface-treated particulate material is cooled, collected, packaged, or directly transported to the downstream production section. The surface finishing mechanism is a reaction cavity containing a raw material gas with a molar concentration of 0-10%. When there is no raw material gas in the reaction cavity (i.e., 0% raw material gas), the initial products of each particulate material become smooth by rubbing against each other; when there is raw material gas in the reaction cavity, in addition to the mutual friction between the initial products of each particulate material, the decomposed low-concentration raw material gas is deposited on the surface of the initial products of the particulate material, further making the surface of the initial products of the particulate material smooth; the initial products of the surface-treated particulate material become particulate materials, and the particulate materials are cooled, collected, packaged, or directly transported to the downstream production section.

[0113] In order to further separate and recycle the effective components in the tail gas, a tail gas treatment mechanism is also provided outside the reactor cavity 801. The tail gas treatment structure is arranged between the preheating mechanism and the raw material gas inlet 803 to separate and recycle the available gas.

[0114] The following takes Embodiment VIII in combination with the attached Figures 1-8 , and describes the method for producing particulate materials using the reactor of the present invention, including the following steps:

[0115] a. Add particulate material seeds (the particulate material seeds can be purchased particulate materials, powder materials separated from the reaction tail gas, particulate materials with unqualified sizes sent back by the particulate transport mechanism, or pulverized particulate materials) into the reactor cavity 801 through the particulate hopper 802, so that the particulate material seeds form a stacked particulate bed layer in the reaction zone, and the filling rate of the particulate material seeds in the stacked particulate bed layer is above 20% or above 50%.

[0116] In order to make the free space between the particulate materials in the stacked particulate bed layer smaller, thereby increasing the filling rate, operations such as pressurization, spouted bed, and downward moving bed can be adopted. Specific measures can also include moving beds (vertical, horizontal, inclined) to increase the particulate packing density, reduce the free space, thereby reducing the generation of gas-phase powder and accelerating the polymerization of powder into particles.

[0117] b. The granular conveying mechanism is used to make the granular material seeds in the stacked granular bed in a relative motion state. The working steps of the granular conveying mechanism are as follows: The granular material that has not reached the product size requirement at the lower end of the reactor cavity is uploaded from the circulating solid discharge port 809 to the feed port 802 through the conveying device. When producing granular materials by the traditional fluidized bed, raw material gas is used to suspend the granular material seeds, which requires a large amount of gas support. Usually, the fluidized bed needs to have a minimum fluidization velocity Umf to maintain the operation. In this embodiment, however, a mechanical method is used to move the granular material seeds without relying on gas. The flow rates of the auxiliary gas and the raw material gas are not restricted by the minimum floating velocity of the traditional fluidized bed, and the gas flow can be less than the critical fluidization velocity. The gas flow velocity can be controlled between 0.01Umf and 10Umf. This can bring the following benefits: saving gas flow, reducing heating and energy losses, reducing the amount of tail gas treatment, and reducing pollution; enabling a large operating range during the production of the present invention, where the gas can be more or less, and the production will not stop due to a temporary reduction in raw materials.

[0118] In addition, the method for making the granular material seeds in the stacked granular bed in a relative motion state further includes: 1) injecting the auxiliary gas and / or the raw material gas into the reactor cavity to make the stacked granular bed in a motion state; 2) introducing an external force for spouting, rotating, stirring, agitating, vibrating or flowing under gravity through the staggered flow comb structure installed on the inner wall of the reactor cavity; 3) placing the reactor under other gravitational fields (such as a centrifugal force field, etc.); 4) using a stirred bed; 5) using a vibrating bed (including mechanical vibration, acoustic or ultrasonic vibration, inserted vibration, etc.); 6) controlling the residence time of the granular material seeds in the reactor cavity by changing the cross-sectional area of the reactor cavity and the speed of supplementing the granular material seeds.

[0119] The stacked granular bed is heated by a heating element buried in the stacked granular bed to make the stacked granular bed reach the temperature required for the reaction, so that the introduced raw material gas undergoes a decomposition reaction. The optimal reaction temperature for the decomposition of silane to generate silicon is 300 - 1200 degrees;

[0120] c. An auxiliary gas (hydrogen) and a raw material gas (silane) are introduced from the raw material gas inlet 803. The auxiliary gas and the raw material gas are added to the reactor cavity together to dilute the raw material gas and stir the stacked granular bed to prevent caking;

[0121] The three wedge-shaped pallets 807 in the reactor cavity form three reaction units. Each reaction unit is provided with a reaction zone formed by a packed particle bed. The raw material gas contacts the particle material seeds (or the produced particle material) in a co-current manner. The raw material gas undergoes a decomposition reaction and deposits on the particle seeds to form the initial product of the particle material with an increased size. The initial product of the particle material and the tail gas move from the wide mouth to the narrow mouth direction of the wedge-shaped pallet 807. The radius of the flow path of the initial product of the particle material and the tail gas gradually decreases, bringing the following benefits: on the one hand, the particle material with a larger density squeezes the reaction tail gas with a smaller density, and the gas in the gas channels between the flat plates of the tail gas jets out of the wedge-shaped reactor. The jetting tail gas forms an air curtain that separates the inner wall of the reactor cavity 801 from the packed particle bed, preventing the deposition of materials on the inner wall of the reactor cavity; on the other hand, when the initial product of the particle material moves from the wide mouth to the narrow mouth direction of the wedge-shaped pallet, it is squeezed by the inner wall of the wedge-shaped pallet, increasing the friction between the initial products of the particle materials, thereby reducing the agglomeration between the initial products of the particle materials and improving the quality of the particle materials; on the other hand, the particle material with a larger density squeezes the reaction tail gas with a smaller density, and the tail gas flows out of the wedge-shaped reactor through the gas channels between the flat plates, realizing the separation of solid materials and gas materials, improving the yield of the particle materials, reducing the powder material content in the tail gas, reducing the generation and overflow of dust, increasing the utilization rate of the raw material gas, and reducing the operating cost;

[0122] The initial product of the particle material is discharged through the center of the wedge-shaped pallet 807 to the next reaction unit; the initial product of the particle material from the last (third) reaction unit is screened. The initial product of the particle material whose size does not reach the specified size is discharged from the circulating solid discharge port and transported by the particle conveying mechanism and returned to the reactor cavity 801 as supplementary particle material seeds to participate in the reaction; through screening treatment, the size of the product particles can also be controlled within the required optimal size range, which can not only reduce possible surface contamination (when the particles are small, they are prone to contamination due to their large surface area), but also be more conducive to application in downstream production;

[0123] In order to improve the quality of the particle material, the initial product of the particle material with a size reaching the specified size obtained by screening also needs to be surface-treated: the initial product of the particle material discharged from the particle product discharge port 804 passes through a reaction cavity containing the raw material gas with a molar concentration of 0 - 10%. The raw material gas with a lower concentration performs a dense coating on the surface of the particle material, making the surface of each particle material bright and clean. After the produced particle material is surface-treated, it enters a cooler and is cooled by an inert gas, and finally is collected and packaged or directly transported to the downstream production section;

[0124] After the raw material gas is fed into the reactor cavity, it contacts the granular material seeds in a co-current manner and descends for a certain distance. Without setting a gas distributor, sufficient contact between the raw material gas and the granular material seeds can be achieved, overcoming or reducing the blockage formed at the raw material gas inlet due to particle deposition, and realizing the stable and continuous operation of the reactor;

[0125] d. Supplement the granular material seeds to maintain the dynamic balance of the stacked granular bed, and enable the filled granular material seeds to contact the raw material gas in a co-current manner when descending;

[0126] The order of the above steps a, b, c, and d is not limited, and the raw material gas is completely decomposed before reaching the wedge-shaped support plate 807. The complete decomposition of the raw material gas before reaching the wedge-shaped support plate 807 is achieved by controlling reaction conditions such as reaction temperature and raw material gas flow rate.

[0127] The granular material seeds in this embodiment mainly come from the granular materials with unqualified sizes at the lower end circulating solid discharge port of the reactor. In addition, powder materials can also be separated from the reaction tail gas and added to the stacked granular bed; when the unqualified granular materials and powder materials cannot meet the requirements, some of the produced granular materials can also be burst or crushed into small granular materials by passing them through a grinder, and the small granular materials are then added to the stacked granular bed. In order to better capture the powder materials in the reaction tail gas and use them as supplementary granular material seeds, the method for producing granular materials in this embodiment can also include: passing the tail gas through a gas-solid separation mechanism with a densely packed granular material bed, collecting the powder materials, and the filling rate of the densely packed granular material bed is above 20% or above 50%. This process can not only prevent the powder materials from entering the downstream of the reaction, but also simply and pollution-free produce granular material seeds. The reaction tail gas after separating the powder materials can also be separated according to the gas components, and the separated auxiliary gas is transported back to the reactor cavity for recycling. The tail gas can also be used as a heat source in the preheating mechanism to exchange heat with the granular material seeds, raw material gas, or auxiliary gas.

[0128] This embodiment discloses a method for producing granular materials using a reactor for producing granular materials. Taking the thermal decomposition of nickel carbonyl to prepare nickel granular materials as an example, it is described in combination with Figure 8 a and 8c. The method includes the following steps:

[0129] a. Add heated nickel granular material seeds into the reactor cavity 850 through the granular material feeding port 851, so that the nickel granular material seeds form a stacked granular bed 860 (above the inverted wedge-shaped air-permeable baffle 861) in the reaction zone, and the filling rate of the nickel granular material seeds in the stacked granular bed is above 60%; the filling rate is the volume of the nickel granular material seeds in the reaction zone. 855 is the reactor outer wall, and 856 is the reactor inner tank.

[0130] b. Control the residence time of nickel particulate material seeds in the reactor cavity by changing the velocity of the particulate material discharged from the bottom 584, and keep the nickel particulate material seeds in the packed particulate bed in a relative motion state;

[0131] c. Heat the packed particulate bed. The heating method is to connect the packed nickel particulate bed to the power supply electrode 584, i.e., apply a voltage to the packed nickel particulate bed. Since the filling rate of the packed nickel particulate bed is as high as 60%, the distance between nickel particulate materials is small, and the heat can be generated by the resistance of the nickel particulate materials themselves through electrification to heat the packed particulate bed to the thermal decomposition temperature of nickel carbonyl;

[0132] d. Feed the raw material gas (nickel carbonyl) from the raw material gas inlet 582, so that the raw material gas undergoes a decomposition reaction and deposits on the nickel particulate seeds to form primary nickel particulate materials, and then discharges them to the next heating zone; a tail gas outlet 853 is provided at a position corresponding to the inside of each inverted wedge-shaped baffle; each reaction unit is provided with a reaction zone formed by a packed particulate bed, so that the primary nickel particulate materials from the previous reaction zone are in co-current contact with the fed raw material gas, and the raw material gas undergoes further decomposition and deposition to obtain primary nickel particulate materials with increased size; the primary nickel particulate materials from the last reaction unit are screened by a screening mechanism provided at the particulate product discharge port, and the primary nickel particulate materials whose size does not reach the specified size are discharged from the circulating solid discharge port and returned to the reactor cavity as supplementary nickel particulate material seeds to participate in the reaction; the primary nickel particulate materials whose size reaches the specified size are surface-treated to obtain particulate materials.

[0133] e. Supplement the nickel particulate material seeds, maintain the dynamic balance of the packed particulate bed, and make the supplemented nickel particulate material seeds in co-current contact with the raw material gas when they move downward;

[0134] There is no limitation on the order of the above steps a, b, c, d, and e, and the raw material gas is completely decomposed before reaching the baffle.

[0135] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A reactor for producing granular materials, characterized in that, the reactor comprises: a reactor cavity, the reactor cavity is respectively provided with at least one granular material feeding port, a raw material gas inlet, a granular product discharging port and a reaction tail gas outlet; wherein, there is at least one reaction zone in the reactor cavity for reacting the granular materials entering from the granular material feeding port, and the reaction zone can communicate with the raw material gas inlet and the reaction tail gas outlet, so that the granular materials contact with the raw material gas, and further enable the raw material gas to directly deposit on the surface of the granular materials and cause the granular materials to grow; there is no gas distributor on the raw material gas inlet side in the reactor cavity, and a breathable support plate is provided on the gas outlet side in the reactor cavity, which can support the granular materials in the reaction zone. The breathable support plate has gaps for gas flow and provides thermal management for the granular materials at the same time. The top of the reaction zone is connected to a granular disperser, and the granular disperser is fan-shaped. The dispersed granular materials are evenly distributed on one side of the breathable support plate. All the raw material gas experiences the same reaction area and reaction conditions. The raw material gas inlet is located on one side of the reactor cavity. The installation positions of the raw material gas inlet and the reaction tail gas outlet are not higher than the granular material feeding port and not lower than the granular product discharging port. The reaction tail gas outlet is located on the opposite side of the raw material gas inlet in the reactor cavity. The granular material feeding port and the granular product discharging port are respectively arranged at the top and bottom of the reactor cavity. There are gaps at the butt joints of the breathable support plate with the two adjacent breathable support plates above and below for the granular materials to flow. Above and below each breathable support plate, there is respectively a raw material gas inlet and a reaction tail gas outlet corresponding to it.

2. The reactor according to claim 1, characterized in that, the reactor further comprises: an internal or external thermal management mechanism for heating the granular materials in the reaction zone; the thermal management mechanism at least includes one of the following methods: a. A heating element arranged in the reaction zone, and the heating element is used for heating the accumulated granular material bed layer formed in the reaction zone to make the granular materials in the reaction zone reach the temperature required for the reaction; b. When the granular material is a conductive material, the thermal management mechanism is a power source electrically connected to the accumulated granular material bed layer; c. A heater arranged outside the reaction zone, and the heater heats the granular materials and then allows the granular materials to enter the reaction zone.

3. The reactor according to claim 2, characterized in that, the heating method of the heating element for heating the granular materials at least includes one of combustion heating, induction heating, microwave heating, light heating and resistance heating.

4. The reactor according to claim 1, characterized in that, the reactor further comprises: an internal or external dynamic generating mechanism, and the dynamic generating mechanism is used for making the accumulated granular material bed layer in the reaction zone in a moving state.

5. The reactor according to claim 4, characterized in that, the dynamic generating mechanism is a raw material gas nozzle and / or an auxiliary gas nozzle, and the raw material gas nozzle and / or the auxiliary gas nozzle are arranged in the reactor cavity to make the granular material bed layer in the reaction zone be spouted, stirred or flowed.

6. The reactor according to claim 4, wherein, the dynamic generation mechanism is a particle conveying mechanism capable of conveying particles to the upper end of the reactor cavity.

7. The reactor according to claim 6, wherein, the form of the particle conveying mechanism includes one of the following forms: mechanical lifting, vibration lifting, pneumatic conveying; the mechanical lifting at least includes one of the following mechanisms: bucket elevator, screw elevator.

8. The reactor according to claim 1, wherein, the reactor further includes: a built-in or external preheating mechanism for preheating the raw material gas and / or auxiliary gas entering the reactor cavity.

9. The reactor according to claim 1, wherein, the reactor further includes: a gas-solid separation mechanism arranged outside the reactor cavity, the gas-solid separation mechanism is used for separating and collecting powder materials in the reaction tail gas discharged from the reaction tail gas outlet, the gas-solid separation mechanism is a densely packed particle material bed layer, and the filling rate of the densely packed particle material bed layer is more than 50%.

10. The reactor according to claim 1, wherein, the reactor further includes: a screening mechanism for discharging qualified parts of the particles discharged from the particle product outlet from the reaction circulation system.

11. The reactor according to claim 1, wherein, the reactor further includes: a transition deposition prevention mechanism, which includes an air curtain mechanism or a cooling and heating interlayer that plays a blocking role between the reaction material and the inner wall of the reactor cavity, so as to prevent excessive deposition on the inner wall of the reactor cavity from affecting the continuous operation of the reactor.

12. The reactor according to claim 1, wherein, the reactor further includes: a surface finishing mechanism for finishing the initial product of the obtained particle material, and the surface finishing mechanism polishes the particle surface with a raw material gas containing a concentration of 0-10%.

13. The reactor according to claim 1, wherein, the inner wall of the reactor cavity and / or the components in contact with the particle material are prepared from the same material as the produced particle material or a non-polluting material.

14. A method for producing particle materials using the reactor according to any one of claims 1 to 13, wherein, it includes the following steps: Adding particle material seeds into the reactor cavity through the particle feeding port, so that the particle material seeds form a stacked particle bed layer in the reaction zone, and the filling rate of the particle material seeds in the stacked particle bed layer is more than 10%; Putting the particle material seeds in the stacked particle bed layer in a relative motion state; Heating the stacked particle bed layer internally or externally to make the stacked particle bed layer reach the temperature required for the reaction; Introducing auxiliary gas and raw material gas from the raw material gas inlet, so that the raw material gas undergoes a decomposition reaction and deposits on the particle seeds to form an initial product of the particle material; Supplying particle material seeds to the stacked particle bed layer, and screening out the particle materials that meet the requirements from the initial product of the particle material, so as to maintain the dynamic balance of the stacked particle bed layer.

15. The method for producing granular materials according to claim 14, characterized in that, the heating method of the stacked granular bed layer is a combination of one or more of combustion heating, induction heating, microwave heating, light heating, and resistance heating by an internal or external thermal management mechanism.

16. The method for producing granular materials according to claim 14, characterized in that, the ways to make the granular material seeds in the stacked granular bed layer in a relative motion state include at least one of the following: injecting auxiliary gas and / or raw material gas into the reactor cavity to stir the stacked granular bed layer; using a variable-diameter reactor cavity and changing the speed of replenishing granular material seeds to control the residence time of the granular material seeds in the reactor cavity; introducing an external force for spouting, rotating, stirring, mixing, vibrating, or making the granular material seeds flow under gravity.

17. The method for producing granular materials according to claim 14, characterized in that, it further includes the following steps: after the raw material gas reacts with the granular material seeds, reaction tail gas is formed, powder materials are separated from the reaction tail gas discharged from the reaction tail gas outlet, and the powder materials are added to the stacked granular bed layer.

18. The method for producing granular materials according to claim 17, characterized in that, the reaction tail gas discharged from the reaction tail gas outlet passes through a gas-solid separation mechanism with a densely packed granular material bed layer to collect powder materials, and the filling rate of the densely packed granular material bed layer is above 20%.

19. The method for producing granular materials according to claim 14, characterized in that, it further includes the following steps: bursting part of the produced granular materials into smaller-sized granular materials, and adding the burst smaller-sized granular materials to the stacked granular bed layer.

20. The method for producing granular materials according to claim 14, characterized in that, it further includes the following steps: performing a surface treatment process on the initial product of the produced granular materials, and passing the initial product of the granular materials through a reaction cavity containing a raw material gas with a molar concentration of 0-10%.

Images