CN115385338A - Preparation method and device of silicon material - Google Patents

Preparation method and device of silicon material Download PDF

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Publication number
CN115385338A
CN115385338A CN202210916057.0A CN202210916057A CN115385338A CN 115385338 A CN115385338 A CN 115385338A CN 202210916057 A CN202210916057 A CN 202210916057A CN 115385338 A CN115385338 A CN 115385338A
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reaction
hydrogen
silicon
heat exchanger
reaction device
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王体虎
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Qinghai Asia Silicon Silicon Material Engineering Technology Co Ltd
Asia Silicon Qinghai Co Ltd
Qinghai Asia Silicon Semiconductor Co Ltd
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Qinghai Asia Silicon Silicon Material Engineering Technology Co Ltd
Asia Silicon Qinghai Co Ltd
Qinghai Asia Silicon Semiconductor Co Ltd
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Priority to CN202210916057.0A priority Critical patent/CN115385338A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/002—Component parts of these vessels not mentioned in B01J3/004, B01J3/006, B01J3/02 - B01J3/08; Measures taken in conjunction with the process to be carried out, e.g. safety measures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/02—Feed or outlet devices therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00065—Pressure measurement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00139—Controlling the temperature using electromagnetic heating
    • B01J2219/00146—Infrared radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention discloses a preparation method and a device of a silicon material, belonging to the technical field of production of polycrystalline silicon. The preparation method comprises the following steps: silicon source containing silicon dioxide and excessive dry hydrogen gas are subjected to high-temperature reduction reaction in a reaction device at the temperature of 600-3000 ℃ and the pressure of 0.3-100 MPa. The method has the advantages of short process chain, less carbon emission and environmental friendliness, and can effectively prepare the solar-grade silicon. The corresponding preparation device has simple structure, low cost and easy control.

Description

Preparation method and device of silicon material
Technical Field
The invention relates to the technical field of production of polycrystalline silicon, in particular to a preparation method and a device of a silicon material.
Background
Metallurgical grade silicon is a raw material for producing polycrystalline silicon, and is traditionally produced by reducing quartz sand in an electric arc furnace by using carbon, and the method has high carbon emission. The hydrogen is adopted to replace carbon as a reducing agent, and is an important way for realizing carbon reduction in the current metallurgical industry.
However, in the temperature range of 1200-1700 ℃, silicon dioxide can be reduced into stable silicon monoxide by hydrogen, silicon cannot be directly obtained, and silicon is required to be obtained by silicon monoxide disproportionation. Therefore, in the prior art, silicon dioxide is reduced by using high-purity hydrogen to prepare silicon monoxide, and then disproportionation reaction of the silicon monoxide is utilized to prepare solar grade silicon.
The above preparation process is cumbersome and it is difficult to obtain silicon directly from the reaction of silicon dioxide and hydrogen.
In view of this, the invention is particularly proposed.
Disclosure of Invention
One objective of the present invention is to provide a method for preparing a silicon material, so as to solve the above technical problems.
The second object of the present invention is to provide a manufacturing apparatus used in the above manufacturing method.
The application can be realized as follows:
in a first aspect, the present application provides a method for preparing a silicon material, comprising the following steps: silicon source containing silicon dioxide and excessive dry hydrogen are subjected to high-temperature reduction reaction in a reaction device at the temperature of 600-3000 ℃ and the pressure of 0.3-100 MPa.
In an alternative embodiment, the materials in the reaction apparatus are heated to a desired temperature during the high temperature reduction reaction by at least one of electromagnetic induction heating and infrared heating.
In an alternative embodiment, electromagnetic field excitation is also assisted during the high-temperature reduction reaction.
In an alternative embodiment, the conditions of the electromagnetic field excitation include: the electric field intensity is 0.1-200kV/mm, and the magnetic field frequency is 100Hz-1000kHz.
In an alternative embodiment, the silicon source comprises a quartz product.
In an alternative embodiment, the quartz product comprises at least one of quartz sand, quartz glass sand, and waste quartz crucible powder.
In an alternative embodiment, the silicon source has a particle size of 1 to 1000nm.
In a second aspect, the present application provides a production apparatus used in the production method according to any one of the preceding embodiments, the production apparatus including a reaction device and a heating device;
the reaction device is internally provided with a reaction chamber, the top of the reaction device is provided with a silicon source inlet, the bottom of the reaction device is provided with a hydrogen inlet and a silicon product outlet, and the silicon source inlet, the hydrogen inlet and the silicon product outlet are communicated with the reaction chamber;
the heating device is arranged in the reaction device or outside the reaction device and is used for providing the temperature required by the high-temperature reduction reaction.
In an alternative embodiment, the reaction apparatus is a fixed bed reactor or a fluidized bed reactor.
In an optional embodiment, the preparation apparatus further includes a heat exchanger, the heat exchanger is provided with a first hydrogen inlet of the heat exchanger and a hydrogen outlet of the heat exchanger, and the hydrogen outlet of the heat exchanger is communicated with the hydrogen inlet of the reaction apparatus so as to introduce the preheated hydrogen into the reaction apparatus to react with the silicon source.
In an optional embodiment, the top of the reaction device is further provided with a hydrogen outlet of the reaction device, the heat exchanger is further provided with a second hydrogen inlet of the heat exchanger, and the hydrogen outlet of the reaction device is connected with the second hydrogen inlet of the heat exchanger.
In an alternative embodiment, the inner wall of the reaction apparatus is provided with an inner lining.
In alternative embodiments, the liner is a film or coating.
In alternative embodiments, the material of the liner comprises silicon nitride, silicon carbide or aluminum oxide.
In an alternative embodiment, the thickness of the liner is 0.01 to 1mm.
In an alternative embodiment, the bottom inside the reactor is also provided with a gas distribution plate, the periphery of which is connected with the inner wall of the reactor.
In an alternative embodiment, the preparation apparatus further comprises a silo, and the outlet of the silo is connected with the silicon source inlet.
The beneficial effect of this application includes:
the silicon source and excessive hydrogen gas are subjected to high-temperature reduction reaction under the conditions of specific temperature and pressure, and in the whole reaction process, the silicon dioxide powder is always kept in a solid state and is subjected to gas-solid reaction with the hydrogen gas on the surface of the silicon dioxide powder; at the initial reaction, the reaction of silicon dioxide to generate silicon monoxide through hydrogen reduction is inhibited under high-pressure conditions, meanwhile, under high-temperature and high-pressure conditions, the activity of hydrogen on the surface of the silicon dioxide is increased, a hydrogen-silicon dioxide gas-solid interface reaction zone with high activity is formed, the silicon dioxide at the interface is directly reduced into silicon by the hydrogen, and the process of directly obtaining the silicon from the silicon dioxide is realized.
The method can realize the reaction of silicon dioxide and hydrogen to directly obtain silicon, and has the advantages of short process chain, low carbon emission and environmental friendliness. The corresponding preparation device has simple structure, low cost and easy control.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic structural diagram of a device for preparing a silicon material provided by the present application.
Icon: 1-a reaction device; 11-a reaction chamber; 12-silicon source inlet; 13-a hydrogen inlet; 14-a silicon product outlet; 15-hydrogen outlet of the reaction device; 2-a heat exchanger; 21-heat exchanger first hydrogen inlet; 22-heat exchanger hydrogen outlet; 23-heat exchanger second hydrogen inlet; and 3-a storage bin.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the method and apparatus for preparing silicon material provided in the present application.
The application provides a preparation method of a silicon material, which comprises the following steps: a silicon source containing silicon dioxide is subjected to a high temperature reduction reaction with an excess of dry hydrogen gas in a reaction apparatus 1 (shown in fig. 1) at a temperature of 600 to 3000 c and a pressure of 0.3 to 100 MPa.
By reference, the silicon source used in the present application is primarily a quartz product (to provide SiO) 2 ) Specifically, the quartz product may include at least one of quartz sand (preferably in powder form), quartz glass sand (preferably in powder form), and waste quartz crucible powder.
The particle size of the silicon source may be 1-1000nm, such as 1nm, 2nm, 5nm, 10nm, 20nm, 50nm, 100nm, 200nm, 500nm or 1000nm, or may be any other value within the range of 1-1000nm.
By controlling the particle size of the silicon source within the above range, sufficient contact with hydrogen is facilitated, and the reaction is ensured to be sufficiently carried out.
Preferably, the hydrogen used for the reaction is high-purity dried and preheated hydrogen, and the temperature of the preheated hydrogen can be, for example, 100-500 ℃.
By preheating, on the one hand, the time for heating the material in the reactor to the desired temperature can be shortened, and on the other hand, the reactivity can be increased.
The high-temperature reduction reaction time may be 600 ℃, 800 ℃, 1000 ℃, 1200 ℃, 1500 ℃, 1800 ℃, 2000 ℃, 2200 ℃, 2500 ℃, 2800 ℃, 3000 ℃ or the like, or may be any other value within the range of 600-3000 ℃.
The pressure of the high-temperature reduction reaction may be 0.3MPa, 0.5MPa, 1MPa, 2MPa, 5MPa, 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 70MPa, 80MPa, 90MPa, 100MPa or the like, or may be any other value within the range of 0.3 to 100 MPa.
In some preferred embodiments, during the high-temperature reduction reaction, the material in the reaction apparatus 1 is heated to a desired temperature by at least one of electromagnetic induction heating and infrared heating.
In the preparation method of the silicon material provided by the application, under the action of high-temperature hydrogen and reactor heating, the temperature of a reaction zone of the reactor is kept at 600-3000 ℃, the atmosphere pressure is kept at 0.3-100MPa, and in the whole reaction process, silicon dioxide powder is always kept in a solid state and generates gas-solid reaction with hydrogen on the surface; at the initial reaction, the reaction of silicon dioxide to generate silicon monoxide through hydrogen reduction is inhibited under high-pressure conditions, meanwhile, under high-temperature and high-pressure conditions, the activity of hydrogen on the surface of the silicon dioxide is increased, a hydrogen-silicon dioxide gas-solid interface reaction zone with high activity is formed, the silicon dioxide at the interface is directly reduced into silicon by the hydrogen, and the process of directly obtaining the silicon from the silicon dioxide is realized.
The chemical reaction equation of the above process is as follows:
SiO 2 +2H 2 ＝Si+2H 2 O↑。
wherein H 2 As a reducing agent.
That is, the preparation method provided by the application can directly obtain silicon from silicon dioxide, and the process does not generate carbon emission.
Furthermore, in the high-temperature reduction reaction process, electromagnetic field excitation can be assisted. The "electromagnetic field" is the coupling field of the electric field and the magnetic field.
The conditions for electromagnetic field excitation include: the electric field intensity is 0.1-200kV/mm, and the magnetic field frequency is 100Hz-1000kHz.
The electric field strength may, for example, be 0.1kV/mm, 0.2kV/mm, 0.5kV/mm, 1kV/mm, 2kV/mm, 5kV/mm, 10kV/mm, 20kV/mm, 50kV/mm, 100kV/mm, 150kV/mm or 200kV/mm, or the like, or may be any other value within the range of 0.1 to 200 kV/mm.
The magnetic field frequency may be 100Hz, 200Hz, 500Hz, 800Hz, 1kHz, 2kHz, 5kHz, 8kHz, 10kHz, 20kHz, 50kHz, 80kHz, 100kHz, 200kHz, 500kHz, 800kHz, 1000kHz, etc., or any other value within the range of 100Hz to 1000kHz.
It should be noted that hydrogen gas is converted into hydrogen gas plasma having high-energy electrons and high-activity hydrogen radicals under the excitation action of the electromagnetic field in the reaction device 1, the high-energy electrons strike the O-Si-O bond at the interface of the silicon dioxide, oxygen radicals in the active silicon dioxide are combined with the active hydrogen radicals to generate water under the strong attraction action of the hydrogen radicals, and the silicon radicals are combined and agglomerated to form silicon particles.
Accordingly, the present application also provides a production apparatus (as shown in fig. 1) used in the above production method, the production apparatus comprising a reaction apparatus 1 and a heating apparatus (not shown).
Reaction unit 1's inside has reaction chamber 11, and reaction unit 1's top is equipped with silicon source entry 12, and reaction unit 1's bottom is equipped with hydrogen inlet 13 and silicon product export 14, and silicon source entry 12, hydrogen inlet 13 and silicon product export 14 all communicate with reaction chamber 11.
The raw material silicon source required by the reaction enters from the silicon source inlet 12, the hydrogen gas is introduced from the hydrogen gas inlet 13, the raw material silicon source and the hydrogen gas react in the reaction chamber 11, and after the reaction is finished, the obtained silicon product is output from the silicon product outlet 14.
The reactor apparatus 1 used in the present application is, by reference, a fixed bed reactor or a fluidized bed reactor.
In the method, a silicon source (silicon dioxide powder) is placed in a fluidized bed reactor or a fixed bed reactor, high-temperature hydrogen enters a reaction zone (reaction chamber 11) of the reactor from the bottom of the reactor, and the hydrogen and the silicon dioxide powder interact with each other in the fluidized bed reactor to enable the silicon dioxide powder to be in a fluidized state; in a fixed bed reactor, the silica powder is in a relatively quiescent state, and this feature is aimed at increasing the activity of the silica and increasing the reaction area.
Since the Si-O bond energy in the SiO is greater than the Si-O bond energy in the SiO, the higher activation energy is obtained in the above way, so that the gaseous SiO can react with hydrogen, and the condition that the SiO is reduced into gaseous SiO by hydrogen in the temperature range of 1200-1700 ℃ but can not directly obtain Si is effectively avoided.
Preferably, a valve or a switch can be further disposed at the silicon product outlet 14 of the reaction device 1 to control the discharge of the product according to the requirement.
The heating device provided by the present application may be disposed inside the reaction device 1 or outside the reaction device 1, so as to provide the temperature required by the high-temperature reduction reaction.
When the heating mode is electromagnetic induction heating, the corresponding heating device can be an electromagnetic induction heater; when the heating mode is infrared heating, the corresponding heating device is an infrared heater.
It should be noted that the electromagnetic induction heater and the infrared heater can be purchased directly.
When the heating device is an electromagnetic induction heater, the electromagnetic field excitation can be assisted in the high-temperature reduction reaction process and can also be provided by the heating device. When the heating device is an infrared heater, the electromagnetic field excitation can be assisted in the high-temperature reduction reaction process by arranging an electromagnetic induction heater in the reaction device 1.
In an alternative embodiment, the inner wall of the reaction apparatus 1 is lined to prevent contamination.
The lining may, by reference, be in particular in the form of a film or a coating. The material may be silicon nitride, silicon carbide or aluminum oxide. The thickness may be 0.01-1mm.
Further, the bottom of the reaction apparatus 1 (specifically, the bottom of the reaction chamber 11) is further provided with a gas distribution plate (not shown), and the periphery of the gas distribution plate is connected with the inner wall of the reaction apparatus 1.
By providing a gas distribution plate, the incoming hydrogen gas can be distributed more evenly within the reaction apparatus 1.
The gas distribution plate may be a commercially available gas distribution plate.
Further, the preparation device of the present application further comprises a silo 3, and an outlet of the silo 3 is connected with the silicon source inlet 12.
Preferably, a crusher (not shown) may be further disposed between the bin 3 and the reaction equipment, and the silicon source is output from the bin 3, enters the crusher, is crushed into a predetermined particle size, and then enters the reaction equipment to react with the hydrogen gas.
Further, the preparation device further comprises a heat exchanger 2, the heat exchanger 2 is provided with a first hydrogen inlet 21 and a hydrogen outlet 22 of the heat exchanger, and the hydrogen outlet 22 of the heat exchanger is communicated with the hydrogen inlet 13 of the reaction device 1 so as to introduce the preheated hydrogen into the reaction device 1 to react with the silicon source.
The hydrogen is preheated by the heat exchanger 2 and then enters the reaction device 1.
Further, the top of the reaction device 1 is also provided with a reaction device hydrogen outlet 15, the heat exchanger 2 is also provided with a heat exchanger second hydrogen inlet 23, and the reaction device hydrogen outlet 15 is connected with the heat exchanger second hydrogen inlet 23.
In the reaction process, the amount of hydrogen is excessive, so that part of redundant hydrogen is left in the reactor after the reaction, the part of hydrogen can be introduced into the heat exchanger 2 together with tail gas, and the fresh hydrogen in the heat exchanger 2 is heated by the waste heat of the part of hydrogen, so that the hydrogen can be recycled, and the effect of saving energy consumption is achieved.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation device for preparing silicon materials, which comprises a reaction device 1 (fixed bed reactor), a heating device (electromagnetic induction heater), a storage bin 3, a crusher and a heat exchanger 2.
Fixed bed reactor's inside has reaction chamber 11, and fixed bed reactor's top is equipped with silicon source entry 12, and fixed bed reactor's bottom is equipped with hydrogen inlet 13 and silicon product export 14, and silicon source entry 12, hydrogen inlet 13 and silicon product export 14 all communicate with reaction chamber 11.
The inner wall of the fixed bed reactor is provided with a film with the thickness of 0.01nm, and the material of the film is silicon nitride. The bottom of the reaction chamber 11 of the fixed bed reactor is also provided with a gas distribution disc, and the periphery of the gas distribution disc is connected with the inner wall of the fixed bed reactor.
The electromagnetic induction heater is disposed in the reaction apparatus 1.
A valve is arranged at the silicon product outlet 14.
The outlet of the silo 3 is connected to the inlet of the crusher, and the outlet of the crusher is connected to the silicon source inlet 12.
The heat exchanger 2 is provided with a first hydrogen inlet 21 and a hydrogen outlet 22 of the heat exchanger, and the hydrogen outlet 22 of the heat exchanger is communicated with the hydrogen inlet 13 of the reaction device 1; the top of the fixed bed reactor is also provided with a hydrogen outlet 15 of the reaction device, the heat exchanger 2 is also provided with a second hydrogen inlet 23 of the heat exchanger, and the hydrogen outlet 15 of the reaction device is connected with the second hydrogen inlet 23 of the heat exchanger.
The structures related to material conveying are connected through pipelines.
Example 2
This example differs from example 1 in that: a fluidized bed reactor is used instead of a fixed bed reactor.
Example 3
This example differs from example 1 in that: the heating device is an infrared heater and is arranged outside the reaction device 1; an electromagnetic induction heater is built into the reaction apparatus 1 to provide electromagnetic field excitation.
Example 4
This example provides a method for preparing a silicon material, which is performed by using the apparatus provided in example 1.
The method specifically comprises the following steps: quartz sand powder with the particle size of 1nm enters a reaction chamber 11 of a fixed bed reactor through a silicon source inlet 12, excessive high-purity dry hydrogen (with the temperature of 200 ℃) preheated by a heat exchanger 2 is introduced into the reaction chamber 11 of the fixed bed reactor through a hydrogen inlet 13 and a gas distribution disc, and high-temperature reduction reaction is carried out under the conditions that the temperature is 1200 ℃ and the pressure is 80 MPa.
In the high-temperature reduction reaction process, the materials in the reaction device 1 are heated to the required temperature in an electromagnetic induction heating mode.
In the high-temperature reduction reaction process, electromagnetic field excitation is assisted. The conditions for electromagnetic field excitation include: the electric field strength was 100kV/mm and the magnetic field frequency was 50kHz.
After the reaction is finished, the redundant hydrogen enters the heat exchanger 2 through the hydrogen outlet 15 of the reaction device and the second hydrogen inlet 23 of the heat exchanger for cyclic utilization, and the silicon product is collected through the silicon product outlet 14.
Example 5
This embodiment provides a method for preparing a silicon material, which is performed by using the apparatus provided in embodiment 2.
The method specifically comprises the following steps: quartz sand powder with the particle size of 10nm enters a reaction chamber 11 of a fluidized bed reactor through a silicon source inlet 12, excessive high-purity dry hydrogen (the temperature is 350 ℃) preheated by a heat exchanger 2 is introduced into the reaction chamber 11 of the fluidized bed reactor through a hydrogen inlet 13 and a gas distribution disc, and high-temperature reduction reaction is carried out under the conditions that the temperature is 600 ℃ and the pressure is 100 MPa.
In the high-temperature reduction reaction process, the materials in the reaction device 1 are heated to the required temperature in the mode of an electromagnetic induction heater.
In the high-temperature reduction reaction process, electromagnetic field excitation is assisted. The conditions for electromagnetic field excitation include: the electric field strength was 0.1kV/mm, and the magnetic field frequency was 1000kHz.
After the reaction is finished, the redundant hydrogen enters the heat exchanger 2 through the hydrogen outlet 15 of the reaction device and the second hydrogen inlet 23 of the heat exchanger for cyclic utilization, and the silicon product is collected through the silicon product outlet 14.
Example 6
This example provides a method for preparing a silicon material, which is performed by using the apparatus provided in example 3.
The method specifically comprises the following steps: quartz sand powder with the particle size of 1000nm enters a reaction chamber 11 of a fluidized bed reactor through a silicon source inlet 12, excessive high-purity dry hydrogen (with the temperature of 500 ℃) preheated by a heat exchanger 2 is introduced into the reaction chamber 11 of the fluidized bed reactor through a hydrogen inlet 13 and a gas distribution disc, and high-temperature reduction reaction is carried out under the conditions that the temperature is 3000 ℃ and the pressure is 0.3 MPa.
In the high-temperature reduction reaction process, the materials in the reaction device 1 are heated to the required temperature in an infrared heater mode.
In the high-temperature reduction reaction process, electromagnetic field excitation is assisted. The conditions for electromagnetic field excitation include: the electric field strength was 200kV/mm and the magnetic field frequency was 100Hz.
After the reaction is finished, the redundant hydrogen enters the heat exchanger 2 through the hydrogen outlet 15 of the reaction device and the second hydrogen inlet 23 of the heat exchanger for cyclic utilization, and the silicon product is collected through the silicon product outlet 14.
The yields of silicon prepared by the above examples 4-6 were all > 25%.
In summary, the preparation method of the silicon material provided by the application has the advantages of short process chain, less carbon emission and environmental friendliness, and can be used for effectively preparing the solar-grade silicon. The corresponding preparation device has simple structure, low cost and easy control.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a silicon material is characterized by comprising the following steps: silicon source containing silicon dioxide and excessive dry hydrogen gas are subjected to high-temperature reduction reaction in a reaction device at the temperature of 600-3000 ℃ and the pressure of 0.3-100 MPa.
2. The method according to claim 1, wherein during the high-temperature reduction reaction, the material in the reaction apparatus is heated to a desired temperature by at least one of electromagnetic induction heating and infrared heating.
3. The preparation method according to claim 2, wherein electromagnetic field excitation is also assisted in the high-temperature reduction reaction process;
preferably, the conditions of electromagnetic field excitation include: the electric field intensity is 0.1-200kV/mm, and the magnetic field frequency is 100Hz-1000kHz.
4. The method of any one of claims 1-3, wherein the silicon source comprises a quartz product;
preferably, the quartz product comprises at least one of quartz sand, quartz glass sand and waste quartz crucible powder;
preferably, the particle size of the silicon source is 1-1000nm.
5. The production apparatus used in the production method according to any one of claims 1 to 4, wherein the production apparatus comprises a reaction apparatus and a heating apparatus;
the reaction device is internally provided with a reaction chamber, the top of the reaction device is provided with a silicon source inlet, the bottom of the reaction device is provided with a hydrogen inlet and a silicon product outlet, and the silicon source inlet, the hydrogen inlet and the silicon product outlet are all communicated with the reaction chamber;
the heating device is arranged in the reaction device or outside the reaction device and is used for providing the temperature required by the high-temperature reduction reaction;
preferably, the reaction apparatus is a fixed bed reactor or a fluidized bed reactor.
6. The preparation device according to claim 5, further comprising a heat exchanger, wherein the heat exchanger is provided with a first hydrogen inlet of the heat exchanger and a hydrogen outlet of the heat exchanger, and the hydrogen outlet of the heat exchanger is communicated with the hydrogen inlet of the reaction device so as to introduce the preheated hydrogen into the reaction device to react with the silicon source.
7. The preparation device of claim 6, wherein a reaction device hydrogen outlet is further arranged at the top of the reaction device, the heat exchanger is further provided with a heat exchanger second hydrogen inlet, and the reaction device hydrogen outlet is connected with the heat exchanger second hydrogen inlet.
8. The manufacturing apparatus as set forth in claim 5, wherein the inner wall of the reaction apparatus is provided with an inner liner;
preferably, the liner is a film or coating;
preferably, the material of the liner comprises silicon nitride, silicon carbide or aluminum oxide;
preferably, the thickness of the liner is 0.01-1mm.
9. A preparation device as claimed in claim 5, characterized in that the bottom of the reaction device is further provided with a gas distribution plate, and the periphery of the gas distribution plate is connected with the inner wall of the reaction device.
10. The manufacturing apparatus of claim 5, further comprising a silo, wherein an outlet of the silo is connected to the silicon source inlet.
CN202210916057.0A 2022-08-01 2022-08-01 Preparation method and device of silicon material Pending CN115385338A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE8702065D0 (en) * 1985-12-26 1987-05-19 Dow Corning A PLASMA MELTING PROCESS FOR SILICON
JP2001039708A (en) * 1999-05-21 2001-02-13 Kobe Steel Ltd High purity metal silicon and its production
CN101857232A (en) * 2009-04-07 2010-10-13 瑞贤科技股份有限公司 Manufacturing method of high-purity silicon material
CN103058194A (en) * 2008-09-16 2013-04-24 储晞 Reactor for producing high-purity particulate silicon
CN111056556A (en) * 2019-12-26 2020-04-24 黄冈师范学院 Method for preparing polycrystalline silicon by taking silicon dioxide and hydrogen as raw materials
US20220041457A1 (en) * 2020-08-07 2022-02-10 6K Inc. Synthesis of silicon products

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE8702065D0 (en) * 1985-12-26 1987-05-19 Dow Corning A PLASMA MELTING PROCESS FOR SILICON
JP2001039708A (en) * 1999-05-21 2001-02-13 Kobe Steel Ltd High purity metal silicon and its production
CN103058194A (en) * 2008-09-16 2013-04-24 储晞 Reactor for producing high-purity particulate silicon
CN101857232A (en) * 2009-04-07 2010-10-13 瑞贤科技股份有限公司 Manufacturing method of high-purity silicon material
CN111056556A (en) * 2019-12-26 2020-04-24 黄冈师范学院 Method for preparing polycrystalline silicon by taking silicon dioxide and hydrogen as raw materials
US20220041457A1 (en) * 2020-08-07 2022-02-10 6K Inc. Synthesis of silicon products

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