CN113387359A - Method and system for preparing polycrystalline silicon by crystalline silicon dioxide - Google Patents
Method and system for preparing polycrystalline silicon by crystalline silicon dioxide Download PDFInfo
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- CN113387359A CN113387359A CN202110668864.0A CN202110668864A CN113387359A CN 113387359 A CN113387359 A CN 113387359A CN 202110668864 A CN202110668864 A CN 202110668864A CN 113387359 A CN113387359 A CN 113387359A
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- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
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- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10715—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material
- C01B33/10721—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material with the preferential formation of tetrachloride
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Abstract
In order to solve the problem that the purity of polycrystalline silicon is difficult to control due to the introduction of impurities into the initial raw materials in the existing production process of the polycrystalline silicon, the invention provides a method for preparing the polycrystalline silicon by using crystalline silicon dioxide, which comprises the following operation steps: obtaining crystalline silicon dioxide, and placing the crystalline silicon dioxide under the irradiation of high-energy particles to convert the crystalline silicon dioxide into amorphous silicon dioxide; reacting amorphous silicon dioxide with reducing carbon and chlorine to obtain silicon tetrachloride; reacting silicon tetrachloride with hydrogen at high temperature to generate the polysilicon. Meanwhile, the invention also discloses a system for preparing polycrystalline silicon by using the crystalline silicon dioxide. The method and the system for preparing the polysilicon by using the crystalline silicon dioxide irradiated by the high-energy particles as the initial raw material not only ensure the high purity and the low impurity content of the initial raw material and realize the high-purity production of the silicon tetrachloride which is the direct raw material for preparing the polysilicon, but also ensure the high chemical activity of the initial raw material, effectively improve the reaction efficiency and reduce the energy consumption.
Description
Technical Field
The invention belongs to the technical field of polycrystalline silicon preparation, and particularly relates to a method and a system for preparing polycrystalline silicon by crystalline silicon dioxide.
Background
Polycrystalline silicon is an important raw material of high-tech products and is widely applied to semiconductor and photovoltaic industries. At present, the industrial production method of polycrystalline silicon mainly comprises an improved Siemens method and a silane methodAnd vapor-liquid deposition methods. The silane method for preparing the polycrystalline silicon by taking silane gas as a silicon source has the main advantages of convenient purification, and the silane gas belongs to flammable and explosive dangerous goods and can cause accidents once the control is not proper. The polycrystalline silicon prepared by the improved Siemens method occupies the main market, but because the production process is limited by thermodynamics, a plurality of inherent defects such as high energy consumption, low efficiency and the like exist all the time, so that the production cost is high. The gas-liquid deposition method is a more advanced polysilicon production technology, and the action temperature condition is controlled at 1500 ℃, so that liquid silicon is directly generated in gas. In the conventional modified Siemens process, the polysilicon is generally made of SiHCl3Directly reacts with hydrogen to generate, and because the reaction temperature of a gas-liquid deposition method is high, the direct raw material generated by polycrystalline silicon is not limited to SiHCl with higher activity3Silicon tetrachloride can also be used as a direct raw material, and the deposition rate is higher and the production efficiency is higher. The silicon tetrachloride can be SiO2Is obtained by chemical reaction as the initial raw material. Compared with the improved Siemens method, the initial raw material of the gas-liquid deposition method process is not industrial silicon but SiO2Omitting the SiO step2The smelting to the industrial silicon greatly shortens the production flow. Compared with silane method, gas-liquid deposition method uses SiO as raw material2And the potential safety hazard of flammability and explosiveness is avoided.
The major disadvantage of the current gas-liquid deposition process is the high metal impurity content of the resulting polysilicon, due in part to the starting SiO material2At present, diatomite (amorphous SiO as the main component) is mostly selected2) While general diatomaceous earth SiO2The content is only 80-90%, the rest impurity metal oxides are abundant, impurities are easily introduced into the generated polycrystalline silicon, and the production purity of the polycrystalline silicon is influenced. While the common crystalline SiO2The starting material, such as quartz sand, is in the form of crystals, which facilitates the separation of impurities, and also has a high initial purity, which is theoretically more suitable as a starting material, but crystalline SiO2The raw material exists in a crystal structure with a silicon-oxygen tetrahedron configuration, has low chemical activity, has strict reaction requirements with carbon and chlorine gas, requires a reaction temperature of over 1100 ℃, and simultaneously needs to use crystalline SiO2The raw materials are ground to be in a sufficiently fine state, the reaction efficiency is low, the problem of incomplete reaction is easy to occur, and the method is not beneficial to expanding production.
Disclosure of Invention
Aiming at the problem that the purity of polycrystalline silicon is difficult to control due to the introduction of impurities into initial raw materials in the existing production process of polycrystalline silicon, the invention provides a method and a system for preparing polycrystalline silicon by using crystalline silicon dioxide.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a method for preparing polysilicon by using crystalline silicon dioxide, which comprises the following operation steps:
obtaining crystalline silicon dioxide, and placing the crystalline silicon dioxide under the irradiation of high-energy particles to convert the crystalline silicon dioxide into amorphous silicon dioxide;
reacting amorphous silicon dioxide with reducing carbon and chlorine to obtain silicon tetrachloride;
reacting silicon tetrachloride with hydrogen at high temperature to generate the polysilicon.
Optionally, the high-energy particle irradiation includes one or more of electron irradiation, neutron irradiation, and ion irradiation.
Optionally, the irradiation of the high-energy particles is performed by an electron accelerator, the energy range of the irradiated electrons is 1500keV-2250keV, and the irradiation time is 25-40 s.
Optionally, the crystalline silicon dioxide is in a granular structure with an average particle size of 1000-3000 meshes, and the stacking thickness of the crystalline silicon dioxide is 3.0-3.5 mm when high-energy particle irradiation is performed.
Optionally, the crystalline silica is selected from SiO2High-purity quartz sand with the content of more than or equal to 99.99 percent.
Optionally, amorphous silica, reducing carbon and chlorine are introduced into the fluidized bed reactor to react to generate silicon tetrachloride and CO2The reaction temperature is 750-900 ℃, wherein metal oxide impurities in the amorphous silicon dioxide are chloridized to generate metal chloride, and the silicon tetrachloride is separated from CO2And separating and purifying from metal chloride.
Alternatively, reacting silicon tetrachloride and hydrogen at high temperature to produce polycrystalline silicon comprises:
introducing silicon tetrachloride and hydrogen into a gas-liquid deposition reactor, wherein the introduction molar ratio of the silicon tetrachloride to the hydrogen is 1: 2.5-3.0, generating a plasma reaction zone with the temperature of 1500-1650 ℃ through the heating structure, reacting silicon tetrachloride and hydrogen in the plasma reaction zone to generate polycrystalline silicon and HCl gas, and condensing and liquefying the polycrystalline silicon to obtain polycrystalline silicon liquid.
Optionally, tail gas generated by the reaction of the silicon tetrachloride and the hydrogen at a high temperature is recovered by a tail gas dry method, unreacted silicon tetrachloride and hydrogen are separated, and the purified silicon tetrachloride and hydrogen are introduced into the gas-liquid deposition reactor again to participate in the reaction.
In another aspect, the present invention provides a system for preparing polysilicon from crystalline silicon dioxide, comprising a high-energy particle irradiation device, a fluidized bed reactor and a gas-liquid deposition reactor, wherein the high-energy particle irradiation device is used for converting crystalline silicon dioxide into amorphous silicon dioxide under the irradiation of high-energy particles; the fluidized bed reactor is used for introducing the amorphous silicon dioxide obtained by the high-energy particle irradiation device and reacting the amorphous silicon dioxide with reducing carbon and chlorine to obtain silicon tetrachloride; the gas-liquid deposition reactor is used for introducing silicon tetrachloride generated by the fluidized bed reactor and reacting the silicon tetrachloride with hydrogen at high temperature to generate polycrystalline silicon.
Optionally, the high-energy particle irradiation device is an electron accelerator, the electron accelerator includes a feeding and discharging structure, a shielding body, a high-voltage power supply, a high-voltage electrode, an electron gun, an accelerating tube, a magnetic focusing lens, a vacuum tube, and a scanning system, the high-voltage electrode, the electron gun, the accelerating tube, the magnetic focusing lens, the vacuum tube, and the scanning system are located in the shielding body, the feeding and discharging structure is a quartz glass conveying platform, the feeding and discharging structure is used for guiding crystalline silica into the shielding body and guiding amorphous silica out, the high-voltage power supply is electrically connected with the high-voltage electrode, the electron gun, the accelerating tube, the magnetic focusing lens, the vacuum tube, and the scanning system are sequentially arranged along an electron emission direction, and the feeding and discharging structure is located in a direction of the scanning system.
According to the method for preparing the polysilicon by the crystalline silicon dioxide, the crystalline silicon dioxide is adopted as the initial material for preparing the polysilicon, the crystal structure with ultrahigh purity and ultralow impurity content provides a good basis for improving the purity of the generated polysilicon, the crystal structure of the crystalline silicon dioxide is changed in a high-energy particle irradiation mode, the molecular distribution of the crystalline silicon dioxide can be changed into a disordered state, and then amorphous silicon dioxide is obtained, the intermolecular bridge oxygen bond energy is lower, the chemical activity is higher, the high purity and the low impurity content of the initial raw material are ensured, the high-purity production of the direct raw material silicon tetrachloride for preparing the polysilicon is realized, the metal pollution caused by adopting diatomite as the initial raw material in the prior art is reduced, the high chemical activity of the initial raw material is also ensured, the full reaction can be ensured to generate the silicon tetrachloride at lower temperature, effectively improves the reaction efficiency and reduces the energy consumption.
Drawings
FIG. 1 is a flow chart of a process for preparing polysilicon from crystalline silicon dioxide provided by an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a high-energy particle irradiation device provided by an embodiment of the invention;
fig. 3 is a schematic structural diagram of a gas-liquid deposition reactor provided in an embodiment of the present invention.
The reference numbers in the drawings of the specification are as follows:
1. an electron accelerator; 11. a high voltage power supply; 12. high voltage electrode, 13, electron gun; 14. an accelerating tube; 15. a magnetic focusing lens; 16. a vacuum tube; 17. a scanning system; 18. a shield; 19. a feeding and discharging structure;
2. a gas-liquid deposition reactor; 21. a laser; 22. a lens group; 23. a plasma reaction zone; 24. cooling the cavity; 241. a condensing agent inlet; 242. a condensing agent outlet; 25. a reactor body; 26. a condensation zone; 27. a tail gas outlet; 28. and (4) a discharge port.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, "a plurality" means two or more unless otherwise specified.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing polysilicon from crystalline silicon dioxide, including the following steps:
obtaining crystalline silicon dioxide, and placing the crystalline silicon dioxide under the irradiation of high-energy particles to convert the crystalline silicon dioxide into amorphous silicon dioxide;
reacting amorphous silicon dioxide with reducing carbon and chlorine to obtain silicon tetrachloride;
reacting silicon tetrachloride with hydrogen at high temperature to generate the polysilicon.
The preparation method adopts the crystalline silicon dioxide as the initial material for preparing the polysilicon, the crystal structure with ultrahigh purity and ultralow impurity content provides a good basis for improving the purity of the generated polysilicon, the crystal structure of the crystalline silicon dioxide is changed by the irradiation of high-energy particles, the molecular distribution of the crystalline silicon dioxide can be changed into a disordered state, and then amorphous silicon dioxide is obtained, the intermolecular bridge oxygen bond energy is lower, the chemical activity is higher, the high purity and the low impurity content of the initial raw material are ensured, the high purity production of the silicon tetrachloride which is the direct raw material of the preparation reaction of the polysilicon is realized, the metal pollution caused by adopting diatomite as the initial raw material in the prior art is reduced, the high chemical activity of the initial raw material is also ensured, can ensure the full reaction to generate the silicon tetrachloride at a lower temperature, effectively improves the reaction efficiency and reduces the energy consumption.
In some embodiments, the high energy particle irradiation comprises one or more of electron irradiation, neutron irradiation, and ion irradiation.
In some embodiments, the high-energy particle irradiation is electron accelerator irradiation, the irradiation electron energy range is 1500keV-2250keV, and the irradiation time is 25-40 s. It should be noted that the irradiation time of the electron accelerator can be adjusted according to the particle size and the amount of the crystalline silica and the size of the irradiated electron energy, so as to achieve the purpose of generating amorphous silica, and theoretically, the longer the irradiation time is, the more beneficial the generation of amorphous silica is.
Compared with other high-energy particle irradiation modes, the method has the advantages that the electron accelerator is adopted for irradiation of the crystalline silicon dioxide, and introduction of impurities can be avoided.
In some embodiments, the crystalline silicon dioxide is a granular structure with an average particle size of 1000-3000 meshes, and the stacking thickness of the crystalline silicon dioxide is 3.0-3.5 mm when the high-energy particle irradiation is carried out.
The smaller the average particle size of the crystalline silicon dioxide is, the larger the specific surface area of the crystalline silicon dioxide is, the more beneficial the crystalline silicon dioxide can receive the irradiation of the high-energy particles to generate crystal structure transformation, when the average particle size of the selected crystalline silicon dioxide is too large, the crystalline silicon dioxide can be dispersed into smaller particles by crushing or grinding and the like, but the requirement of the undersized crystalline silicon dioxide on raw material grinding is higher, and the energy consumption is higher, so when the average particle size of the crystalline silicon dioxide is in the range, the crushing difficulty is lower, and the requirement of the irradiation transformation of the high-energy particles can be met.
In some embodiments, the crystalline silica is selected from SiO2High-purity quartz sand with the content of more than or equal to 99.99 percent.
In some embodiments, when the selected crystalline silica has insufficient purity, the crystalline silica may be pretreated to increase the purity of the crystalline silica, for example, by water quenching, pulverizing, sieving, acid washing, water washing, magnetic separation, and the like.
In some embodiments, amorphous silica is introduced into a fluidized bed reactor with reducing carbon and chlorine gas to react to form silicon tetrachloride and CO2The reaction temperature is 750-900 ℃, wherein metal oxide impurities in the amorphous silicon dioxide are chloridized to generate metal chloride, and tetrachloro is carried outSilicon from CO2And separating and purifying from metal chloride.
The reaction in the fluidized bed reactor mainly generates silicon tetrachloride and CO2The reaction equation is: SiO 22+C+2Cl2＝SiCl4+CO2(ii) a Meanwhile, the raw material high-purity quartz sand contains very little metal oxide impurities (Fe)2O3、CaO、MgO、Al2O3Etc., total content less than 50ppm) will be chlorinated to metal chlorides (FeCl)3、CaCl2、MgCl2、AlCl3Etc.). According to the difference of physical properties (boiling point, melting point and the like), the silicon tetrachloride can be obtained by separation and purification through condensation and other methods.
In some embodiments, the reducing carbon comprises one or more of carbon black, carbon powder, charcoal, petroleum coke, graphite powder.
In a preferred embodiment, the reducing carbon is selected from carbon powder.
In a preferred embodiment, the reaction temperature of the amorphous silica with the reducing carbon and chlorine gas is 840 ℃ to 860 ℃.
In some embodiments, "reacting silicon tetrachloride and hydrogen at elevated temperatures to form polycrystalline silicon" includes:
introducing silicon tetrachloride and hydrogen into a gas-liquid deposition reactor, wherein the introduction molar ratio of the silicon tetrachloride to the hydrogen is 1: 2.5-3.0, generating a plasma reaction zone with the temperature of 1500-1650 ℃ through the heating structure, reacting silicon tetrachloride and hydrogen in the plasma reaction zone to generate polycrystalline silicon and HCl gas, and condensing and liquefying the polycrystalline silicon to obtain polycrystalline silicon liquid.
In some embodiments, multiple laser beams are used to converge to form a plasma reaction zone at the point of convergence.
Gas molecules in the plasma reaction area are ionized at the intersection of laser beams to form laser plasma, the partially ionized laser plasma can more rapidly absorb laser energy, the energy absorbed by the partially ionized laser plasma is transferred to other gas molecules to further cause the ionization of peripheral molecules so as to generate plasma clusters with higher ionization degree, the existence of the plasma clusters can be maintained through smaller laser power, the plasma clusters continuously absorb the energy from the laser, the temperature is increased, and a heat source is formed.
Because the reaction of the silicon tetrachloride and the hydrogen is positioned in the plasma reaction zone, the reaction is difficult to carry out because the temperature in the outer space of the plasma reaction zone does not meet the reaction requirement, and the polysilicon liquid generated by the reaction in the plasma reaction zone is deposited to the bottom of the gas-liquid deposition reactor, the reaction process of the silicon tetrachloride and the hydrogen does not need to be contacted with the gas-liquid deposition reactor, the area of the chemical reaction is effectively controlled, and a contact type heating device does not need to be additionally arranged, so that the risks of pollution and impurity introduction caused by the material of the gas-liquid deposition reactor or the contact of the heating device can be effectively reduced, and the purity of the prepared polysilicon is improved.
In some embodiments, the different laser beams are focused by a lens group and then meet in the plasma reaction region, and the lens group can collect the laser beams on a focal point, thereby facilitating the improvement of energy at the meeting point.
In some embodiments, the laser power of the laser beam is 1500-2000W.
In some embodiments, a condensation zone is formed in the gas-liquid deposition reactor, the condensation zone is located below the plasma reaction zone, polycrystalline silicon liquid formed by reaction in the plasma reaction zone is settled and collected in the condensation zone, and the temperature of the condensation zone is 1410-1450 ℃.
The condensation zone accessible sets up condensing agent circulation heat transfer's mode and carries out temperature control to make the polycrystalline silicon that generates be in liquid, can collect the discharge in unison after gathering a certain amount of polycrystalline silicon liquid, on the other hand, set up the condensation zone is used for controlling the heating range in plasma reaction zone, leads to the pipe wall high temperature of gas-liquid deposition reactor to prevent that thermal radiation from leading to, does benefit to the going on of reaction in the stable plasma reaction zone.
In some embodiments, tail gas generated by the reaction of silicon tetrachloride and hydrogen at high temperature is subjected to tail gas dry recovery, unreacted silicon tetrachloride and hydrogen are separated, purified silicon tetrachloride and hydrogen are introduced into the gas-liquid deposition reactor again to participate in the reaction, and the utilization efficiency of materials is improved.
The recovery method of silicon tetrachloride and hydrogen from the tail gas generated by the reaction can adopt the existing substance separation method, and particularly, in some embodiments, the dry recovery of the tail gas comprises bubbling leaching, pressurized condensation, absorption desorption and activated carbon adsorption processes.
Another embodiment of the present invention provides a system for preparing polysilicon from crystalline silicon dioxide, comprising a high-energy particle irradiation device, a fluidized bed reactor and a gas-liquid deposition reactor, wherein the high-energy particle irradiation device is used for converting crystalline silicon dioxide into amorphous silicon dioxide under the irradiation of high-energy particles; the fluidized bed reactor is used for introducing the amorphous silicon dioxide obtained by the high-energy particle irradiation device and reacting the amorphous silicon dioxide with reducing carbon and chlorine to obtain silicon tetrachloride; the gas-liquid deposition reactor is used for introducing silicon tetrachloride generated by the fluidized bed reactor and reacting the silicon tetrachloride with hydrogen at high temperature to generate polycrystalline silicon.
According to the system for preparing the polycrystalline silicon from the crystalline silicon dioxide, the crystalline silicon dioxide is pretreated by adopting the high-energy particle irradiation device, so that the crystalline silicon dioxide can be converted into the amorphous silicon dioxide, the temperature required by reaction in a subsequent fluidized bed reactor is effectively reduced, and the reaction efficiency and the yield of silicon tetrachloride are improved.
As shown in fig. 2, in an embodiment, the high-energy particle irradiation apparatus is an electron accelerator 1, the electron accelerator 1 includes a loading and unloading structure 19, a shielding body 18, a high-voltage power supply 11, a high-voltage electrode 12, an electron gun 13, an acceleration tube 14, a magnetic focusing lens 15, a vacuum tube 16, and a scanning system 17, the high-voltage electrode 12, the electron gun 13, the acceleration tube 14, the magnetic focusing lens 15, the vacuum tube 16, and the scanning system 17 are located in the shielding body 18, the loading and unloading structure 19 is a quartz glass conveying platform, the loading and unloading structure 19 is used for introducing crystalline silica into the shielding body 18 and guiding amorphous silica out, and the quartz glass conveying platform is used as the loading and unloading structure 19, so that the crystalline silica can be prevented from being contaminated during the high-energy particle irradiation process; the high voltage power supply 11 is electrically connected with the high voltage electrode 12, the electron gun 13, the accelerating tube 14, the magnetic focusing lens 15, the vacuum tube 16 and the scanning system 17 are sequentially arranged along an electron emission direction, and the feeding and discharging structure 19 is located in a direction facing the scanning system 17.
The high-voltage power supply 11 is electrically connected with the high-voltage electrode 12 through a cable, the high-voltage electrode 12 is electrically connected with the electron gun 13, so that the electron gun 13 is in a negative high-voltage state to generate a large amount of free electrons, the accelerating tube 14 is used for generating an accelerating electric field, the free electrons pass through the accelerating tube 14 and are accelerated to form a high-energy electron beam, then the high-energy electron beam is focused under the magnetic control action of the magnetic focusing lens 15, an electron beam spot is formed through the vacuum tube 16, and the scanning system 17 is provided with a longitudinal scanner and a transverse scanner and is used for forming an electron beam with a certain irradiation range when the electron beam spot is irradiated on the surface of crystalline silicon dioxide so as to realize the amorphization transformation of the crystalline silicon dioxide. The shield 18 serves to prevent the electron beam from escaping and also to prevent external environmental factors from interfering with the electron beam irradiation.
As shown in fig. 3, in an embodiment, the gas-liquid deposition reactor 2 includes a reactor body 25 and a plurality of lasers 21, wherein laser beams emitted from the plurality of lasers 21 are converged in the reactor body 25 to form a plasma reaction zone 23 at a convergence point.
In an embodiment, a lens group 22 is disposed in a laser emitting direction of the laser 21, the lens group 22 is configured to adjust a focusing position of the laser beam emitted by the laser 21, and the laser beams emitted by the lasers 21 are collected and converged in the plasma reaction region 23 by the plurality of lens groups 22.
In an embodiment, a condensation zone 26 is formed in the gas-liquid deposition reactor 2, the condensation zone 26 is located below the plasma reaction zone 23, a cooling cavity 24 is arranged on the outer wall of the gas-liquid deposition reactor 2, the cooling cavity 24 is located outside the condensation zone 26, and the cooling cavity 24 is provided with a condensing agent inlet 241 for introducing a condensing agent and a condensing agent outlet 242 for leading out the condensing agent.
In an embodiment, a discharge port 28 is arranged below the gas-liquid deposition reactor 2, the discharge port 28 is used for guiding out the polysilicon liquid, a tail gas outlet 27 is arranged on a side wall of the gas-liquid deposition reactor 2, and the tail gas outlet 27 is used for guiding out the tail gas after reaction.
In one embodiment, the reactor body 25 is made of quartz glass, which is chemically stable and can avoid product contamination.
Wherein, the heat source of the gas-liquid deposition reactor 2 comes from plasma generated by the laser 21, and the lens group 22 can adjust the focusing position of the laser beam in the reactor body 25, namely the plasma generating position. H2And SiCl4The gas enters a reactor and reacts at a heat source (higher than 1500 ℃) formed by plasma to generate polycrystalline silicon and HCl gas. Residual H not reacted completely2And SiCl4Discharging gas and HCl gas from tail gas discharge port, recovering residual H by tail gas dry method2And SiCl4The gases are respectively recovered and enter the reactor body 25 again for reaction and recycling. Flowing condensing agent is introduced into the cooling cavity 24 on the outer layer of the reactor body 25 for cooling, and the polycrystalline silicon is condensed and liquefied in the condensation area 26 of the reactor body 25 and can be collected from a discharge hole 28 below the condensation area 26.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for preparing polysilicon by using crystalline silicon dioxide is characterized by comprising the following operation steps:
obtaining crystalline silicon dioxide, and placing the crystalline silicon dioxide under the irradiation of high-energy particles to convert the crystalline silicon dioxide into amorphous silicon dioxide;
reacting amorphous silicon dioxide with reducing carbon and chlorine to obtain silicon tetrachloride;
reacting silicon tetrachloride with hydrogen at high temperature to generate the polysilicon.
2. The method of claim 1, wherein the high energy particle irradiation comprises one or more of electron irradiation, neutron irradiation, and ion irradiation.
3. The method for preparing polysilicon from crystalline silicon dioxide as claimed in claim 1, wherein the high energy particle irradiation is electron accelerator irradiation, the irradiation electron energy is in the range of 1500keV-2250keV, and the irradiation time is 25-40 s.
4. The method for preparing polysilicon from crystalline silica according to claim 1, wherein the crystalline silica has a granular structure with an average particle size of 1000 to 3000 mesh, and the crystalline silica has a bulk thickness of 3.0 to 3.5mm when subjected to high energy particle irradiation.
5. Method for the preparation of polysilicon from crystalline silicon dioxide as claimed in claim 1, wherein the crystalline silicon dioxide is selected from SiO2High-purity quartz sand with the content of more than or equal to 99.99 percent.
6. The method for preparing polysilicon from crystalline silica as claimed in claim 1, wherein amorphous silica, reducing carbon and chlorine are introduced into the fluidized bed reactor to react to form silicon tetrachloride and CO2The reaction temperature is 750-900 ℃, wherein metal oxide impurities in the amorphous silicon dioxide are chloridized to generate metal chloride, and the silicon tetrachloride is separated from CO2And separating and purifying from metal chloride.
7. The method of claim 1, wherein reacting silicon tetrachloride and hydrogen at an elevated temperature to form polysilicon comprises:
introducing silicon tetrachloride and hydrogen into a gas-liquid deposition reactor, wherein the introduction molar ratio of the silicon tetrachloride to the hydrogen is 1: 2.5-3.0, generating a plasma reaction zone with the temperature of 1500-1650 ℃ through the heating structure, reacting silicon tetrachloride and hydrogen in the plasma reaction zone to generate polycrystalline silicon and HCl gas, and condensing and liquefying the polycrystalline silicon to obtain polycrystalline silicon liquid.
8. The method for preparing polysilicon from crystalline silica as claimed in claim 7, wherein the tail gas generated by the reaction of silicon tetrachloride and hydrogen at high temperature is recovered by a tail gas dry method, unreacted silicon tetrachloride and hydrogen are separated, and the purified silicon tetrachloride and hydrogen are introduced into the gas-liquid deposition reactor again to participate in the reaction.
9. The system for preparing the polycrystalline silicon by using the crystalline silicon dioxide is characterized by comprising a high-energy particle irradiation device, a fluidized bed reactor and a gas-liquid deposition reactor, wherein the high-energy particle irradiation device is used for converting the crystalline silicon dioxide into amorphous silicon dioxide under the irradiation of high-energy particles; the fluidized bed reactor is used for introducing the amorphous silicon dioxide obtained by the high-energy particle irradiation device and reacting the amorphous silicon dioxide with reducing carbon and chlorine to obtain silicon tetrachloride; the gas-liquid deposition reactor is used for introducing silicon tetrachloride generated by the fluidized bed reactor and reacting the silicon tetrachloride with hydrogen at high temperature to generate polycrystalline silicon.
10. The system for preparing polysilicon from crystalline silica as claimed in claim 9, wherein the high energy particle irradiation device is an electron accelerator, the electron accelerator comprises a loading/unloading structure, a shielding body, a high voltage power supply, a high voltage electrode, an electron gun, an accelerating tube, a magnetic focusing lens, a vacuum tube and a scanning system, the high voltage electrode, the electron gun, the accelerating tube, the magnetic focusing lens, the vacuum tube and the scanning system are located in the shielding body, the loading/unloading structure is a quartz glass conveying platform, the loading/unloading structure is used for guiding crystalline silica into the shielding body and guiding amorphous silica out, the high voltage power supply is electrically connected with the high voltage electrode, the electron gun, the accelerating tube, the magnetic focusing lens, the vacuum tube and the scanning system are sequentially arranged along an electron emission direction, the feeding and discharging structure is located in the direction of the scanning system.
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