Device for efficiently preparing black phosphorus

Abstract

The utility model discloses a device for efficiently preparing black phosphorus, which belongs to the technical field of phosphorus chemical new materials and comprises a reactor, a reaction area is arranged in the reactor, a charging mechanism is arranged in the reaction area and comprises an outer lining reaction kettle arranged in the reaction area, a first sealing mechanism is arranged on the top surface of the outer lining reaction kettle, and a lining is arranged in the outer lining reaction kettle. A plurality of flat bottom pipes are arranged in the lining at equal intervals, supporting nets are arranged in the flat bottom pipes, a heating resistance wire is arranged in the reaction area, and a second sealing mechanism is arranged outside the reaction area. The supporting net is placed in the flat-bottom pipe, the catalyst is filled in the flat-bottom pipe under the inert atmosphere condition, then the flat-bottom pipe is placed in the lining, and the phosphorus source is evenly distributed at the bottom of the lining. After the filling is completed, putting the whole lining into an outer lining reaction kettle, sealing the outer lining reaction kettle, and carrying out high-temperature heat treatment in a reaction system through accurately controlled temperature; after the reaction is finished, black phosphorus is deposited and grows in an internal flat-bottom tube, and high-quality black phosphorus crystals are obtained.

Description

Technical Field

[0001] The utility model belongs to the technical field of new phosphorus chemical materials, and particularly relates to a device for efficiently preparing black phosphorus. Background Art

[0002] Black phosphorus is a stable allotrope of phosphorus, with a corrugated layered structure similar to that of graphite. In this structure, phosphorus atoms are closely connected by covalent bonds, and the layers interact with each other through van der Waals forces. This unique structure endows black phosphorus with a series of excellent physical and chemical properties, including high carrier mobility, significant anisotropy, adjustable direct bandgap, and broad light absorption range. These properties make black phosphorus show great application potential in many fields such as optoelectronic devices, electrochemical energy storage, photocatalysis, flame retardant materials, and biomedicine.

[0003] However, due to its harsh preparation conditions, the current industrial scale-up production of black phosphorus is still in its initial stage. How to improve the conversion rate and quality of black phosphorus to promote its efficient preparation is a key problem that needs to be solved urgently. At present, researchers mainly focus on the mineralization method, a preparation technology with great development potential. In the existing preparation technologies based on the mineralization method, most preparation process technologies such as patents CN218422705U and CN218621134U directly mix the phosphorus source, catalyst, and transport agent to prepare black phosphorus. Although this mixing method is convenient, when producing in large quantities, heat conduction is easily limited, resulting in material agglomeration, thus leading to low material conversion rate and product purity, and the catalyst is difficult to recycle, increasing the preparation cost. Although patent CN220579442U proposes an internal support to distribute the phosphorus source, catalyst, and transport agent in isolated areas, during the growth process of black phosphorus, the combination of the phosphorus source with the catalyst and transport agent to form other compounds (such as phosphorus tin compounds, phosphorus iodine compounds, etc.) still affects the conversion rate and purity of black phosphorus. In addition, the above series of patents do not solve the key problem of heat transfer imbalance caused by the endothermic vaporization of the phosphorus source and the large heat release during black phosphorus growth. This imbalance phenomenon leads to blocked internal heat conduction, making it difficult for the material to be effectively converted, increasing production energy consumption and cost, and restricting the production scale, thus hindering the large-scale and low-cost efficient production of black phosphorus.

[0004] Therefore, the utility model develops a device for efficiently preparing black phosphorus to solve the key problems of the decline in product purity caused by the mixing of materials and catalysts and the imbalance of heat transfer in each section in the existing black phosphorus preparation technology. Summary of the Utility Model

[0005] The purpose of the utility model is to provide a device for efficiently preparing black phosphorus to solve the problems existing in the above-mentioned prior art.

[0006] To achieve the above object, the present utility model provides the following solution: The present utility model provides a device for efficiently preparing black phosphorus, including a reactor. A reaction zone is provided inside the reactor, and a loading mechanism is provided in the reaction zone. The loading mechanism includes an outer lining reaction kettle disposed in the reaction zone. A first sealing mechanism is provided on the top surface of the outer lining reaction kettle. An inner lining is provided inside the outer lining reaction kettle. A plurality of flat-bottomed tubes are equidistantly arranged inside the inner lining. A support mesh is provided inside the flat-bottomed tubes. Heating resistance wires are provided in the reaction zone, and a second sealing mechanism is provided outside the reaction zone.

[0007] Preferably, the first sealing mechanism includes a reaction kettle upper cover, which is fixedly connected to the outer lining reaction kettle through flange bolts. A sealing graphite gasket is provided inside the reaction kettle upper cover.

[0008] Preferably, an air inlet probe tube is provided in the reaction zone, which is located between the heating resistance wires and the outer lining reaction kettle. A radiator is provided on the furnace wall of the reactor.

[0009] Preferably, the second sealing mechanism includes a reactor upper cover disposed outside the reactor, and a buckle is provided outside the reactor upper cover.

[0010] Preferably, the material thickness of the outer lining reaction kettle is 5 - 15 mm.

[0011] Preferably, the inner lining and the flat-bottomed tubes are made of the same material, and the material thickness of the inner lining and the flat-bottomed tubes is 1 - 5 mm.

[0012] Preferably, the diameter of the support mesh is the same as the inner diameter of the flat-bottomed tube, and the pore size of the support mesh ≥ 200 mesh.

[0013] The present utility model discloses the following technical effects: The present utility model not only solves the problems of low conversion rate, low purity caused by the mixing of raw materials and catalysts and the difficulty of recycling catalysts in the existing black phosphorus preparation technology, but also solves the problem of unbalanced heat transfer caused by the endothermic vaporization of the phosphorus source and the exothermic nucleation of black phosphorus, realizes the effective matching of heat transfer in each section during the reaction process, thereby improving the conversion rate and product quality, reducing the preparation energy consumption and cost, improving the safety of the preparation process, and enhancing the production capacity and quality of black phosphorus. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The drawings constituting a part of this application are used to provide a further understanding of this application. The schematic embodiments of this application and their descriptions are used to explain this application and do not constitute an improper limitation to this application. In the drawings:

[0015] Figure 1 is a schematic structural diagram of the inner lining of the present utility model;

[0016] Figure 2 This is a schematic structural diagram of the outer lining reactor of the present utility model;

[0017] Figure 3 This is a schematic structural diagram of the reactor of the present utility model.

[0018] In the figure: 1, loading mechanism; 11, inner lining; 12, flat-bottom tube; 13, support mesh; 14, outer lining reactor; 15, reactor upper cover; 16, flange bolt; 2, reactor; 21, reaction zone; 22, heating resistance wire; 23, air inlet probe tube; 24, reactor upper cover; 25, buckle; 26, radiator. Specific embodiments

[0019] Next, the technical solutions in the embodiments of the present utility model will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present utility model. Obviously, the described embodiments are only a part of the embodiments of the present utility model, rather than all the embodiments. Based on the embodiments of the present utility model, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present utility model.

[0020] To make the above objects, features, and advantages of the present utility model more obvious and understandable, the present utility model will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0021] Referring to Figures 1 - 3 As shown, this embodiment provides a device for efficiently preparing black phosphorus, including a reactor 2. A reaction zone 21 is provided inside the reactor 2, and a loading mechanism 1 is provided inside the reaction zone 21. The loading mechanism 1 includes an outer lining reactor 14 provided inside the reaction zone 21. A first sealing mechanism is provided on the top surface of the outer lining reactor 14. An inner lining 11 is provided inside the outer lining reactor 14. A plurality of flat-bottom tubes 12 are equidistantly provided inside the inner lining 11. A support mesh 13 is provided inside the flat-bottom tube 12. A heating resistance wire 22 is provided inside the reaction zone 21, and a second sealing mechanism is provided outside the reaction zone 21.

[0022] Place the support mesh 13 into the flat-bottom tube 12. Under the condition of an inert atmosphere, fill the catalyst into it, and then place the flat-bottom tube 12 into the inner lining 11. The phosphorus source is evenly distributed at the bottom of the inner lining 11. After the above loading is completed, place the entire inner lining 11 into the outer lining reactor 14 and seal the outer lining reactor 14. Perform high-temperature heat treatment in the reaction system by precisely controlling the temperature; after the reaction is completed, black phosphorus deposits and grows in the internal flat-bottom tube 12 to obtain high-quality black phosphorus crystals.

[0023] Through a material separation and precise heat matching mechanism, the present utility model utilizes a large amount of heat generated during the growth stage of black phosphorus to reduce the thermal energy consumption required for the vaporization of the phosphorus source, thereby achieving efficient utilization of the overall thermal field and high conversion rate of the material during the preparation process, efficiently balancing the heat transfer between the raw material and the product, and saving energy consumption. The present utility model is of great significance for improving the material conversion rate and product quality, reducing energy consumption and costs, enhancing production safety, and expanding the preparation scale of black phosphorus, facilitating the industrial application of black phosphorus materials in various fields, and also providing strong support for the technological progress and industrial upgrading of related fields.

[0024] In a further optimized solution, the first sealing mechanism includes a reaction kettle upper cover 15, the reaction kettle upper cover 15 is fixedly connected to the outer lining reaction kettle 14 through flange bolts 16, and a sealing graphite gasket is provided inside the reaction kettle upper cover 15.

[0025] In a further optimized solution, an air inlet probe tube 23 is provided inside the reaction zone 21, the air inlet probe tube 23 is located between the heating resistance wire 22 and the outer lining reaction kettle 14, and a radiator 26 is provided on the furnace wall of the reactor 2.

[0026] In a further optimized solution, the second sealing mechanism includes a reactor upper cover 24 provided outside the reactor 2, and a buckle 25 is provided outside the reactor upper cover 24.

[0027] In a further optimized solution, the outer lining reaction kettle is a reaction kettle made of 304, 316 stainless steel or Hastelloy, the material of the flange bolts 16 is the same as that of the outer lining reaction kettle, and the material thickness of the outer lining reaction kettle is 5 - 15 mm.

[0028] In a further optimized solution, the inner lining 11 and the flat bottom tube 12 are made of the same material, which is 304 or 316 stainless steel, and the material thickness of the inner lining 11 and the flat bottom tube 12 is 1 - 5 mm.

[0029] In a further optimized solution, the material of the support mesh 13 is a pore-containing material that does not react with phosphides, such as stainless steel mesh, nickel foam, cobalt foam, titanium foam, etc. The diameter of the support mesh 13 is the same as the inner diameter of the flat bottom tube 12, and the pore size of the support mesh 13 ≥ 200 mesh.

[0030] In a further optimized solution, the number of flat bottom tubes 12 ≥ 1, and increases with the increase of the bottom area of the inner lining 11. The height of the flat bottom tube 12 is (3 - 4) / 5 of the inner lining 11, and the outer diameter of the flat bottom tube 12 is 1 / (3 - 10) of the inner lining 11.

[0031] In a further optimized solution, the support mesh 13 is placed at 2 / 3 from the bottom upwards of a plurality of flat bottom tubes 12.

[0032] The reactor 2 is a vertical heating device with two temperature zones.

[0033] The steps of its operation method are as follows:

[0034] (1) Place the support mesh 13 at the 2 / 3 position from the bottom to the top of the flat-bottomed tube 12, which can stably support the catalyst. Place an appropriate proportion of the catalyst on the support mesh 13 under an inert gas. Then place multiple assembled flat-bottomed tubes 12 equidistantly in the inner liner 11. Add an appropriate amount of phosphorus source to the bottom of the inner liner 11, and then place the inner liner 11 into the outer liner reaction kettle 14 and seal the outer liner reaction kettle 14.

[0035] (2) The sealed reaction is placed in the reactor 2 and undergoes a high-temperature reaction through an optimized heating program. After the reaction ends, high-quality black phosphorus crystals are finally obtained.

[0036] In the above solution, the phosphorus source in step (1) is any one or a combination of two of red phosphorus or yellow phosphorus, and the purity is above 98%; the catalyst is Sn 24 P 19.3 I 8 catalyst or Sn 24 P 19.3 I 8 catalyst containing additives. The morphology of the catalyst is one or a combination of at least two of any shapes such as powder, granule, flake, spherical, etc., and the purity of the catalyst is above 99%; the feeding ratio of the phosphorus source and the catalyst is 100:(1 - 50).

[0037] In the above solution, the heating program of the reactor 2 in step (2) is as follows: the high-temperature end is heated from room temperature to 490 - 530 °C in 1 - 2 h and then kept warm for 10 - 18 h, and then cooled to room temperature within 4 - 8 h; the low-temperature end is heated from room temperature to 480 - 520 °C in 1 - 2 h and then kept warm for 10 h - 18 h, and then cooled to room temperature within 4 h - 8 h.

[0038] Compared with the production device of direct mixing used in the actual large-scale production process, the present utility model has the following remarkable beneficial effects:

[0039] 1. The present utility model provides a device for efficiently preparing black phosphorus. This device physically isolates the reaction raw materials from the catalyst, significantly reducing the risks of decreased material conversion rate, decreased product purity, and difficulty in recycling the catalyst caused by the mixing of raw materials and the catalyst. At the same time, the device utilizes a large amount of heat energy released during the nucleation and growth of black phosphorus to balance the heat energy required for the vaporization of the phosphorus source, realizing an efficient match of heat transfer between the materials and the products, saving the energy consumption in the production process. This design not only optimizes the utilization efficiency of the thermal field but also significantly improves the conversion rate and utilization rate of the materials, reduces the production energy consumption and cost, and provides strong technical support for the large-scale, high-quality and efficient preparation of black phosphorus.

[0040] 2. The present utility model provides a unique internal heat exchange device, which has a remarkable effect on solving the problem of a large amount of heat release during the preparation of black phosphorus. By improving the heat transfer mechanism, this device not only optimizes the heat transfer in the preparation process, but also uses the large amount of heat energy released during the growth of black phosphorus to balance the energy consumption required for the vaporization of the phosphorus source, reduces the conversion rate and utilization rate of materials affected by uneven heat transfer, significantly reduces energy consumption and costs, and enhances the safety performance of the entire preparation system, providing a solid foundation for the further development and optimization of black phosphorus preparation technology.

[0041] 3. The related components such as the inner lining 11, the outer lining reaction kettle 14 and the reactor 2 in the present utility model are all made of easily obtainable materials, are simple to assemble and easy to operate, and the scale of the device can be flexibly adjusted according to production requirements. In addition, the preparation method involved in the present utility model adopts simplified raw materials and process flows, improves the utilization rate of materials, effectively reduces the energy consumption and costs during the synthesis process, simplifies the operation steps, and provides convenient conditions for realizing the large-scale production of black phosphorus.

[0042] In the description of the present utility model, it should be understood that the orientation or positional relationship indicated by the terms "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present utility model, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation to the present utility model.

[0043] The embodiments described above are only for describing the preferred mode of the present utility model, and do not limit the scope of the present utility model. Without departing from the design spirit of the present utility model, various deformations and improvements made by those of ordinary skill in the art to the technical solution of the present utility model should all fall within the protection scope determined by the claims of the present utility model.

Claims

1. A device for efficiently preparing black phosphorus, characterized in that: The invention comprises a reactor (2), wherein a reaction zone (21) is arranged in the reactor (2), wherein a charging mechanism (1) is arranged in the reaction zone (21), wherein the charging mechanism (1) comprises an outer-lined reactor (14) arranged in the reaction zone (21), wherein a first sealing mechanism is arranged on the top surface of the outer-lined reactor (14), wherein an inner lining (11) is arranged in the outer-lined reactor (14), wherein a plurality of flat-bottomed tubes (12) are arranged at equal intervals in the inner lining (11), wherein a supporting net (13) is arranged in the flat-bottomed tube (12), wherein a heating resistance wire (22) is arranged in the reaction zone (21), and a second sealing mechanism is arranged outside the reaction zone (21).

2. The device for efficiently preparing black phosphorus according to claim 1, characterized in that: The first sealing mechanism comprises a reactor upper cover (15), the reactor upper cover (15) is fixedly connected to the outer liner reactor (14) via flange bolts (16), and a sealing graphite gasket is arranged inside the reactor upper cover (15).

3. The device for efficiently preparing black phosphorus according to claim 1, characterized in that: An air intake probe (23) is provided in the reaction zone (21), and the air intake probe (23) is located between the heating resistance wire (22) and the outer lining reaction kettle. A radiator (26) is provided on the furnace wall of the reactor (2).

4. The device for efficiently preparing black phosphorus according to claim 1, characterized in that: The second sealing mechanism comprises a reactor upper cover (24) arranged on the outside of the reactor (2), and a buckle (25) is provided on the outside of the reactor upper cover (24).

5. The device for efficiently preparing black phosphorus according to claim 1, characterized in that: The material thickness of the outer lining reactor is 5 to 15 mm.

6. The device for efficiently preparing black phosphorus according to claim 1, characterized in that: The inner lining (11) and the flat-bottomed tube (12) are made of the same material, and the thickness of the inner lining (11) and the flat-bottomed tube (12) is 1 to 5 mm.

7. The device for efficiently preparing black phosphorus according to claim 1, characterized in that: The diameter of the support net (13) is the same as the inner diameter of the flat-bottomed tube (12), and the aperture of the support net (13) is ≥200 meshes.

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