CN116395702A - Device and method for preparing high-purity silicon tetrachloride and polysilicon in short process - Google Patents
Device and method for preparing high-purity silicon tetrachloride and polysilicon in short process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 68
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000005049 silicon tetrachloride Substances 0.000 title claims abstract description 49
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 44
- 229920005591 polysilicon Polymers 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 39
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 109
- 239000007789 gas Substances 0.000 claims abstract description 99
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 75
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000009835 boiling Methods 0.000 claims abstract description 60
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 52
- 239000010703 silicon Substances 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 38
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000000460 chlorine Substances 0.000 claims abstract description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 28
- 239000011343 solid material Substances 0.000 claims abstract description 26
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 15
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000003638 chemical reducing agent Substances 0.000 claims description 21
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- 235000019353 potassium silicate Nutrition 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
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- 238000009833 condensation Methods 0.000 claims description 9
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- 238000000746 purification Methods 0.000 claims description 7
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- 229910021487 silica fume Inorganic materials 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
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- 238000002360 preparation method Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 28
- 238000005265 energy consumption Methods 0.000 abstract description 8
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- 238000005243 fluidization Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 39
- 239000002245 particle Substances 0.000 description 32
- 239000002994 raw material Substances 0.000 description 16
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 16
- 239000005052 trichlorosilane Substances 0.000 description 16
- 229910003902 SiCl 4 Inorganic materials 0.000 description 12
- 239000008247 solid mixture Substances 0.000 description 10
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- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 239000011701 zinc Substances 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
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- 229910004298 SiO 2 Inorganic materials 0.000 description 3
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- 238000001125 extrusion Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000542 Sc alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- CAUFKFVKXSZCJW-UHFFFAOYSA-N [Sc].[In] Chemical compound [Sc].[In] CAUFKFVKXSZCJW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000003546 flue gas Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Classifications
-
- 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
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- 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
-
- 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
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/035—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition or reduction of gaseous or vaporised silicon compounds in the presence of heated filaments of silicon, carbon or a refractory metal, e.g. tantalum or tungsten, or in the presence of heated silicon rods on which the formed silicon is deposited, a silicon rod being obtained, e.g. Siemens process
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a device for preparing high-purity silicon tetrachloride and polysilicon in a short process, which is characterized in that an inner cyclone separator is arranged in the upper part of a boiling chlorination furnace, an outer cyclone separator is arranged outside the boiling chlorination furnace, and the air outlet end of the outer cyclone separator is communicated with a gas feed inlet at the bottom of the boiling chlorination furnace through a pipeline, so that the reaction fluidization state can be improved, the circulation of chlorine, hydrogen chloride and solid materials can be realized, and the chlorination reaction rate and the material conversion rate can be promoted. The invention also provides a method for preparing high-purity silicon tetrachloride and polysilicon by using the device, which utilizes the heat released by the reaction to carry out the chlorination reaction of silicon dioxide by adding a proper amount of hydrogen chloride, silicon powder, silicon wafer or silicon carbide, thereby effectively reducing the energy consumption in the reaction process, removing the reaction heat required by the reaction at the beginning and basically not needing additional heating in the follow-up process.
Description
Technical Field
The invention relates to the technical fields of nonferrous metal preparation technology and chemical production, in particular to a device and a method for preparing high-purity silicon tetrachloride and polysilicon in a short process.
Background
Polysilicon is one of the extremely important intermediate products in the silicon product industry chain, is a basic raw material for developing the electronic informatization industry and the solar photovoltaic power generation industry, and is a strategic material in many developed countries. In solar cell module systems, the price of polysilicon affects the photovoltaic power generation cost to a large extent.
The production method of the polysilicon mainly comprises a silane particle silicon method, an improved Siemens method and the like, and the most mainstream technology at present is the improved Siemens method based on the factors of product purity, environmental protection, cost and the like. The main process comprises the following steps: the metallurgical grade industrial silicon and hydrogen chloride are reacted to generate trichlorosilane, the trichlorosilane is deposited into polysilicon in a reducing furnace after rectification and purification, silicon tetrachloride which is a byproduct in the process is converted into the trichlorosilane after cold hydrogenation, and the silicon tetrachloride and the trichlorosilane are used for a reduction procedure after rectification and purification and are key supplementary materials of chlorine and silicon in the whole system. Through years of development, the improved Siemens method has basically made the greatest effect on energy conservation and consumption reduction, but the raw material end has room for cost reduction. The existing metallurgical grade industrial silicon is produced by smelting silicon dioxide and a carbon reducer at high temperature, and is a high-energy-consumption industry, and the power consumption of each ton of industrial silicon is about 12000-14000 kwh. In addition, the silicon smelting process has very strict control requirements on reaction conditions, particularly has requirements on purity, reactivity, antiknock property, air permeability and the like of reactant materials such as silica, petroleum coke, charcoal or coal, which results in narrow adaptation surface of raw materials, limits the regional development of industrial silicon due to high requirements on raw materials and production electricity, and limits the development region of downstream polysilicon due to the consideration of transportation cost and the like. Therefore, if the high-energy-consumption industrial silicon smelting link can be bypassed, the method is beneficial to widening the application range of raw materials, reducing the process difficulty and further reducing the production cost of the polysilicon.
CN106185950B discloses a process for producing silicon tetrachloride using a substance containing more than 90% of silicon dioxide and a carbon reducing agent, comprising grinding a silicon-containing oxide 2 The substances and the carbonaceous substances are chloridized at high temperature to obtain crude silicon tetrachloride, and then the crude silicon tetrachloride is refined to obtain silicon tetrachloride with higher purity. However, as the silicon chlorination reaction is an endothermic reaction, a heating system is required to continuously heat to provide the temperature required by the reaction, and the reaction energy consumption is high. And the technology requires that the purity of the silicon dioxide is generally more than 95 percent, and the silicon dioxide cannot be utilized for raw materials with low silicon content.
CN106379904a discloses a method for preparing silicon tetrachloride, which comprises adding raw material silicon dioxide, excessive carbon and a catalyst into a reactor, and simultaneously introducing chlorine and oxygen to react at 600-1500 ℃ to obtain silicon tetrachloride. The patent proposes that the carbochlorination of silica is an exothermic reaction, but in practice the process is an endothermic reaction; the oxygen is introduced to react with the generated carbon monoxide and the oxygen to generate carbon dioxide, and the excessive carbon reacts with the carbon dioxide to generate carbon monoxide, wherein the process is an endothermic reaction, and the introduced oxygen can also cause the generated silicon tetrachloride to be oxidized into silicon dioxide. Therefore, the reaction of the introduced oxygen and the excessive carbon increases the raw material cost investment and the process control difficulty, the product yield can be reduced without producing beneficial effects, and the added cuprous chloride catalyst further increases the raw material investment and possibly brings copper or cuprous chloride into the product to pollute the product.
US2120261269A1 discloses a method for producing silicon tetrachloride by using silicon dioxide and coke as raw materials, directly reducing and condensing silicon tetrachloride by using metals with strong reducibility such as zinc and the like to prepare polysilicon, and electrolyzing the obtained metal chloride into metal and chlorine by an electrolysis technology for reduction and chlorination respectively. However, the zinc preparing technology by zinc chloride electrolysis is not mature, the purity of the obtained zinc metal is lower, and the zinc metal is also carried into the product polysilicon during reduction, so that the product purity is inferior to that of the improved Siemens method, and therefore, the method is limited in application.
CA1230465A, JP1982042524A, US4490344 and JP1982007813a add part of the catalyst in the silica chlorination process: the chlorination reaction is accelerated by transition metal halides, chlorides of the fifth main group or sub-group of the periodic table, or mixtures thereof, boric acid, diboron trioxide, sodium tetraborate, potassium tetraborate, gaseous boron trichloride, and the like. However, the catalyst is an impurity, so that the difficulty of separation and purification is increased, and the quality of high-purity silicon tetrachloride is greatly influenced.
Although the existing technology for producing polysilicon by the improved Siemens method is disclosed and mature, the following problems still exist in the process of the comprehensive prior art:
(1) The raw materials used in the improved Siemens method are high-energy-consumption industrial silicon, which does not meet the requirements of increasingly strict environmental protection policies in China, and inexpensive and stably supplied silicon raw materials need to be explored;
(2) Silicon dioxide carbochlorination products mainly adopt refined silicon tetrachloride, but impurities such as catalyst, boron, phosphorus, zinc, metal halide and the like can be introduced in the production process, so that the aim of selecting high-purity silica for improving the purity of the product is overcome, and the original purpose of technical development is overcome, so that the process has narrow application range or the purity of the final product is sacrificed.
Disclosure of Invention
Aiming at the defects of the existing silicon tetrachloride and polysilicon production process, the invention provides a method for chlorinating silicon dioxide at high temperature under the action of a reducing agent, adding hydrogen chloride, trace silicon powder, silicon chips or silicon carbide into reaction materials, and carrying out chlorination reaction by utilizing the heat released by the reaction to generate the raw materials of trichlorosilane and silicon tetrachloride required by an improved Siemens method; through condensation separation and rectification refining technology, trichlorosilane enters a reduction system to deposit and produce polysilicon and byproduct high-purity silicon tetrachloride. Meanwhile, the invention comprises devices such as material crushing and conveying, carbonization and chlorination, dust removal, rectification and purification, tail gas recycling and the like, and particularly provides a novel boiling chlorination furnace.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a device for preparing high-purity silicon tetrachloride and polysilicon in a short process comprises a boiling chlorination furnace, an inner cyclone separator, an outer cyclone separator and a three-way control valve,
the boiling chlorination furnace comprises a boiling chlorination reaction section, a transition section and an expansion section from bottom to top, wherein the top of the reaction section is connected with the transition section, and the top of the transition section is connected with the expansion section;
the bottom of the reaction section is provided with a gas distribution chamber, and the bottom of the gas distribution chamber is provided with a slag discharge port; a gas distributor is arranged between the gas distribution chamber and the reaction section and is used for realizing the communication between the gas distribution chamber and the reaction section; the outer wall of the gas distribution chamber is provided with a gas feed port, and mixed gas comprising chlorine and hydrogen chloride is fed into the boiling chlorination furnace; the middle part of the reaction section is provided with a solid material feed inlet, and a heater is arranged outside the inner lining of the reaction section and used for providing heat required by the reaction;
the middle upper part of the expansion section is provided with an inner cyclone separator, and the inner cyclone separator is connected with an outer cyclone separator by extending out of a top cover at the top of the expansion section through a pipeline; the expansion section is also provided with a cooling system;
the gas outlet of the external cyclone separator is connected with a three-way control valve through a pipeline, a part of gas mixture is circulated back to the boiling chlorination furnace, and a part of gas mixture enters the next working procedure from a lower pipeline; and the solid material outlet of the external cyclone separator is connected with the solid material inlet of the reaction section.
According to one embodiment, the height-diameter ratio of the reaction section is more than or equal to 1.5, the transition section accounts for 1/3-1/2 of the total height of the boiling chlorination furnace, and the included angle between the bus of the conical section where the transition section is positioned and the central line is 10-20 degrees; the height-diameter ratio of the expansion section is more than or equal to 1.2, and the diameter of the expansion section is 1.2-2.0 times of the diameter of the reaction section.
According to one embodiment, the reaction section is provided with a bubble breaker, which is located between the gas distributor and the solid material feed opening.
According to one embodiment, the boiling chlorination furnace is provided with more than two gas feed inlets, including a chlorine gas feed inlet, a hydrogen chloride feed inlet and an inert gas feed inlet, and the air inflow of each gas feed inlet is controlled through a three-way control valve.
The method for preparing high-purity silicon tetrachloride and polysilicon by the short process comprises the following steps:
(1) Crushing and conveying materials: crushing silicon ore, mixing the crushed silicon ore with a silicon-containing additive and a reducing agent, and adding water glass as an adhesive to obtain pellets;
(2) Adding carbon for chlorination: feeding the pellets obtained in the step (1) into a boiling chlorination furnace, opening a three-way control valve below the boiling chlorination furnace, introducing chlorine and hydrogen chloride into the furnace, preheating the gas, feeding the preheated gas into a gas distribution chamber, and feeding the preheated gas into a reaction section through a gas distributor and a bubble breaker to react with the pellets conveyed from a solid material feed inlet; the mixed gas generated by the reaction rises to pass through the transition section and the expansion section, enters from the internal cyclone separator, and the carried silicon powder is collected and returned to the reaction section bed layer for continuous reaction.
(3) Gas-solid separation: the gas-solid separation of the materials in the chlorination boiling furnace is realized through the inner cyclone separator and the outer cyclone separator;
(4) And sequentially performing multistage condensation, rectification purification and reduction on the outlet gas separated by the external cyclone separator to obtain silicon tetrachloride and polysilicon.
According to one embodiment, in step (1), the siliceous ore is selected from natural silica sand, silica, quartz sand, quartz, diatomaceous earth, microsilica, or industrial solid wastes and byproducts having a silica content above 50%.
According to one embodiment, the reducing agent is one or more of coal, charcoal, petroleum coke, coke and semi-coke; preferably charcoal and/or coke.
According to one embodiment, the silicon-containing additive is selected from at least one of silicon powder, silicon carbide powder.
According to one embodiment, the material pellets obtained by granulation have a particle size of 0.1-10 mm.
According to one embodiment, the silica ore and the reducing agent are present in a silica to carbon molar ratio of 1: (2-5), preferably 1:3. The addition amount of the silicon-containing additive is 5-20% of the total mass of the silicon ore and the carbon reducer, and the addition amount of the water glass is 5-10% of the total mass of the silicon ore and the carbon reducer.
According to one embodiment, in step (2), the reaction gas is fed at a void bed flow rate of 0.01 to 0.4m/s, preferably 0.01 to 0.03 m/s; the reaction gas includes chlorine and hydrogen chloride.
According to one embodiment, in the mixed gas inlet composition, the mass fraction of the hydrogen chloride in the total mixed gas is 5-50%, preferably 20-25%, and the corresponding molar ratio of the hydrogen chloride to the silicon-containing additive is 2-5:1, preferably 3-4:1.
According to one embodiment, the mixture is heated in the reaction zone to a temperature of 800 to 1600 ℃, preferably 1000 to 1500 ℃.
The invention chlorinates silicon dioxide under the action of the reducing agent, and fully utilizes the reaction waste heat to produce silicon tetrachloride and trichlorosilane. Compared with the traditional chlorination technology, the method has the following obvious advantages and obvious effects:
1. the process provided by the invention does not involve the use of pressurization and concentrated acid, and has high safety coefficient;
2. the process provided by the invention prepares trichlorosilane and silicon tetrachloride simultaneously in the production process, and finally high-purity silicon tetrachloride and polysilicon products can be obtained, and the added value of the products is high;
3. the process provided by the invention is added with a proper amount of hydrogen chloride, silicon powder, silicon wafer or silicon carbide, utilizes the heat released by the reaction to carry out the chlorination reaction of silicon dioxide, effectively reduces the energy consumption in the reaction process, removes the reaction heat required at the beginning of the reaction, and basically does not need additional heating in the follow-up process;
4. the process provided by the invention is suitable for the silicon ore raw material with the silicon dioxide content of more than 50%, and has wide application range;
5. the process provided by the invention can realize recycling of most aluminum chloride, ferric chloride, calcium chloride and magnesium chloride impurities in the flue gas, can realize closed-loop recycling of hydrogen chloride and chlorine gas by means of a two-stage cyclone device and a cooling system, can be used for generating steam by combustion, generating electricity and the like, is finally discharged in a carbon dioxide form, and is less in environmental pollution.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for preparing high purity silicon tetrachloride and polysilicon in a short process of the present invention;
fig. 2 is a schematic diagram of a boiling chlorination furnace for producing polysilicon in a short process according to the present disclosure, wherein reference numerals are as follows:
in the figure: 1-a first gas feed port; 2-a second gas feed port; 3-a slag discharge port; 4-a gas distribution chamber; 5-gas distributor; 6-a bubble breaker; 7-a reaction section; 8-lining the reaction section; 9-a solid material feed inlet; 10-transition section; 11-cooling water inlet; 12-a cooling water outlet; 13-an enlarged section; 14-an internal cyclone separator; 15-internal cyclone gas inlet; 16-an external cyclone separator; 17-a three-way control valve; 18-an induction coil or a microwave heating device.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
The embodiment of the invention provides a device for preparing high-purity silicon tetrachloride and polysilicon in a short process, which is shown in fig. 2 and comprises a boiling chlorination furnace, an inner cyclone separator 14, an outer cyclone separator 16 and a three-way control valve 17.
The inner cyclone separator 14 is arranged inside the upper part of the boiling chlorination furnace, the outer cyclone separator 16 is arranged outside the boiling chlorination furnace, the air outlet end of the inner cyclone separator 14 is communicated with the air inlet end of the outer cyclone separator 16 through a pipeline, the air outlet end of the outer cyclone separator 16 is communicated with the first gas feed inlet 1 and the second gas feed inlet 2 at the bottom of the boiling chlorination furnace through pipelines, and the air inflow is controlled through the three-way control valve 17. The setting mode can improve the reaction fluidization state, realize the circulation of chlorine, hydrogen chloride and solid materials, and promote the chlorination reaction rate and the material conversion rate.
In one embodiment of the invention, the boiling chlorination furnace main body sequentially comprises a boiling chlorination reaction section 7, a transition section 10 and an expansion section 13 from bottom to top, wherein the top of the reaction section 7 is connected with the transition section 10, and the top of the transition section 10 is connected with the expansion section 13;
the bottom of the reaction section 7 is provided with a gas distribution chamber 4, and the bottom of the gas distribution chamber 4 is provided with a slag discharge port 3; a gas distributor 5 is arranged between the gas distribution chamber 4 and the reaction section 7 and is used for realizing the communication between the gas distribution chamber 4 and the reaction section 7; the outer wall of the gas distribution chamber 4 is provided with a first gas feed port 1 and a second gas feed port 2, and mixed gas comprising chlorine and hydrogen chloride is fed into the boiling chlorination furnace; the middle part of the reaction section 7 is provided with a solid material feed port 9, and a heater is arranged outside the inner liner 8 of the reaction section and used for providing heat required by the reaction;
the middle upper part of the expansion section 13 is provided with an inner cyclone separator 14, and the inner cyclone separator 14 is connected with an outer cyclone separator 16 by extending out of the top cover of the expansion section 13 through a pipeline. The internal cyclone separator 14 can directly circulate most of the solid materials back to the bed layer of the reaction section 7 for continuous reaction, so that the solid materials are carried out, the solid particles are prevented from scouring and wearing the pipeline, and no additional conveying is needed; the bottom of the internal cyclone separator 14 is provided with a high-pressure gas flushing system which can clean a discharge hole; the expansion section 13 is also provided with a cooling system for initially reducing the temperature of the reaction gases and reducing the material requirements for the piping and internal cyclone 14.
In one embodiment of the invention, the external cyclone separator 16 is positioned outside the boiling chlorination furnace and further realizes gas-solid separation, a gas outlet of the external cyclone separator 16 is connected with a three-way control valve 17 through a pipeline, a part of gas mixture is circulated back to the boiling chlorination furnace, and a part of gas mixture enters the next working procedure from a lower pipeline; the solid material outlet of the external cyclone separator 16 is connected with the solid material feed inlet 9 of the reaction section 7, and separated materials can be returned into the furnace from the solid material feed inlet 9 or returned to the material granulating system for re-granulation, so that the slag discharge amount of the whole reaction can be reduced, and the reaction conversion rate can be improved.
The reaction section 7, the transition section 10 and the expansion section 13 are the core of the whole boiling chlorination furnace, and the height, diameter and structure directly affect the reaction efficiency. In a preferred embodiment of the invention, the height-diameter ratio of the reaction section 7 is more than or equal to 1.5, the transition section 10 accounts for 1/3-1/2 of the total height of the boiling chlorination furnace, and the included angle between the bus of the conical section where the transition section 10 is positioned and the central line is 10-20 degrees; the height-diameter ratio of the expansion section 13 is more than or equal to 1.2, and the diameter of the expansion section 13 is 1.2-2.0 times of the diameter of the reaction section. The larger the height-diameter ratio of the reaction section 7 is, the more slender the reaction section 7 is, the stable gas speed of the reaction gas can be ensured, the particle fluidization effect is good, and the enough reaction time is provided; by reasonably setting the angle and the height of the transition section 10, the gas speed gradually decreases along with the increase of the diameter, and the particle part carried out by the gas falls back to the reaction section 7; the diameter of the reactor is further enlarged to ensure that the particles carried by the gas are not directly carried out of the boiling chlorination furnace and pass through the internal cyclone separator 14 for sedimentation back mixing, so that the materials have sufficient residence time, and the reaction conversion rate is further improved. The reaction section 7, the transition section 10, the expansion section 13, the inner and outer parts and the like can be manufactured in sections and sealed by flange connection, and can also be manufactured integrally.
In one embodiment of the invention, the boiling chlorination furnace is provided with more than two solid material feed inlets 9, the solid material feed inlets 9 are uniformly distributed along the reaction section 7, the solid material feed inlets 9 are in a conical shape (large outside and small inside) of a round table, so that the material is convenient to add, and meanwhile, the boiling chlorination furnace is provided with a high-pressure gas blowing device, so that the material is convenient to be fed into the furnace and blown.
In one embodiment of the invention, the reaction section 7 is provided with a bubble breaker 6, and the bubble breaker 6 is positioned between the gas distributor 5 and the solid material feed opening 9, so as to prevent bubbles possibly generated by crushing and avoid affecting the reaction fluidization state.
In one embodiment of the invention, the bottom of the reaction section 7 is provided with a slag discharge port 3 for collecting and discharging calcium chloride, magnesium chloride and a small amount of solid materials which are not completely reacted and are generated in the reaction process.
In one embodiment of the invention, the cooling system of the expansion section 13 comprises a cooling water inlet 11 and a cooling water outlet 12, and the overall temperature of the expansion section can be controlled and regulated.
In one embodiment of the present invention, the reaction section 7 is heated by an induction coil or a microwave heater, and the mixed gas preheating mode is implemented by an induction coil or a microwave heating device 18.
In one embodiment of the present invention, the boiling chlorination furnace is provided with more than two gas feed ports, including a chlorine gas feed port, a hydrogen chloride feed port, an inert gas feed port, etc., and the air intake amount of each gas feed port is controlled by a three-way control valve 17.
The flow chart of the method for preparing high-purity silicon tetrachloride and polysilicon by the short flow is shown in fig. 1, and comprises the following steps:
(1) Crushing and conveying materials: crushing silicon ore, mixing the crushed silicon ore with a silicon-containing additive and a reducing agent, and adding water glass as an adhesive to obtain pellets;
because the process is applicable to a wide range of raw materials, the particle sizes of the raw materials are different, and therefore, the process needs to be carried out in a targeted manner. Crushing silicon ore with larger particle size (the main component is silicon dioxide) to 30-200 meshes by adopting a jaw crusher; then, after mixing with silicon-containing additive with smaller particle size and reducer, adding water glass as adhesive. The materials are evenly mixed in a mixer, extruded into pellets in a granulator, dried to constant weight at 150 ℃, and then sent to a boiling chlorination furnace through a screw conveyor.
(2) Adding carbon for chlorination: feeding the pellets obtained in the step (1) into a boiling chlorination furnace, opening a three-way control valve 17 below the boiling chlorination furnace, introducing chlorine (purity is more than 99%) and hydrogen chloride into the furnace, preheating the gas to 200 ℃ by heating through an induction coil or a microwave heating device 18, feeding the gas into a gas distribution chamber 4, and feeding the gas into a reaction section 7 through a gas distributor 5 and a bubble breaker 6 to react with the pellets conveyed from a solid material feed inlet 9; the mixed gas generated by the reaction rises through the transition section 10 and the expansion section 13, enters from the internal cyclone separator 15, and the carried silicon powder is collected and returned to the bed layer of the reaction section 7 for continuous reaction.
Preferably, the integral reaction condition is that the chlorination temperature is 800-1600 ℃, the chlorination time is 10 min-3 h, the air speed of the air bed is 0.01-0.4 m/s, and the mixture of silicon tetrachloride, magnesium chloride, ferric chloride, calcium chloride, aluminum chloride and the like is obtained through the reaction; the reaction of silicon powder and hydrogen chloride, and the reaction of silicon dioxide, silicon, carbon, chlorine and hydrogen chloride are strong exothermic reactions, and are used for providing heat required by the reaction of the silicon dioxide and the chlorine, and the reaction equation is as follows:
SiO 2 +2C+2Cl 2 ＝SiCl 4 +2CO△H＝27.03kJ/mol
SiO 2 +4HCl+2C＝SiCl 4 +2H 2 +2CO△H＝346.74kJ/mol
Si+3HCl＝SiHCl 3 +H 2 △H＝-216.78kJ/mol
3Si+SiO 2 +2HCl+6Cl 2 +2C＝2SiCl 4 +2SiHCl 3 +2CO△H＝-1458.32kJ/mol
CaO+C+Cl 2 ＝CaCl 2 +CO△H＝-246.52kJ/mol
MgO+C+Cl 2 ＝MgCl 2 +CO△H＝-114.57kJ/mol
Fe 2 O 3 +3C+3Cl 2 ＝2FeCl 3 +3CO△H＝-13.04kJ/mol
Al 2 O 3 +3C+3Cl 2 ＝2AlCl 3 +3CO△H＝160.0kJ/mol
the middle part of the boiling chlorination furnace is provided with a cooling water inlet 11 and a cooling water outlet 12 for adjusting the temperature of the furnace body.
The outside of the lining 8 of the reaction section of the boiling chlorination furnace is provided with a heater for providing and maintaining the heat required by partial reaction. It should be noted that when hydrogen chloride and silicon-containing additives are introduced into the reaction, the external heater of the reaction zone liner 8 need only provide the heat required for initial start-up of the reaction; the boiling chlorination furnace can also be used for the chlorination of other materials, such as titanium dioxide, aluminum oxide, zirconium oxide and the like.
(3) Gas-solid separation: the gas-solid separation of the materials in the chlorination boiling furnace is realized through the inner cyclone separator 14 and the outer cyclone separator 16;
(4) The outlet gas separated by the external cyclone separator 16 is sequentially subjected to multistage condensation, rectification purification and reduction to obtain silicon tetrachloride and polysilicon.
The upper part expansion section 13 in the boiling chlorination furnace is provided with an inner cyclone separator 14, the outside of the boiling chlorination furnace is provided with an outer cyclone separator 16, the separation efficiency of solid materials can be regulated and controlled by adjusting the cyclone efficiency, and the solid powder carried out in the reactor is reduced. When the solid powder is more, the outlet of the cyclone separator is easy to be blocked, chlorosilane is easy to leak, the danger is higher, and the separation pressure of the external cyclone separator 16 can be reduced by adopting the two-stage cyclone separator;
the bottom of the boiling chlorination furnace is provided with a slag discharge port 3, when the bed thickness of the reaction section 7 is large and the pressure drop is increased, the furnace is stopped to discharge slag, the main components of the slag are a small amount of unreacted silica sand, a small amount of calcium chloride, magnesium chloride, a reducing agent and the like, the slag is washed by a small amount of lime water, and a filter cake is obtained by filter pressing by a filter press, so that the slag can be used for producing cement and building materials;
(4) Multistage condensation: after the mixed gas generated by the reaction in the step (2) is separated by the external cyclone separator 16, the temperature of the gas outlet is reduced to below 500 ℃. Further, the ferric chloride and aluminum chloride in the mixed gas can be condensed and liquefied through two-stage condensation to be separated from the main product chlorosilane, wherein the primary condensation temperature is 280-300 ℃, the secondary condensation temperature is 160-180 ℃, and the remaining mixed gas outlet is cooled to the temperature required by a rectifying tower after heat exchange between the remaining mixed gas outlet and the liquid product silicon tetrachloride is performed;
(5) And (3) rectifying and purifying: delivering the residual mixed gas obtained in the step (4) into a rectifying process for producing the polycrystalline silicon by using a pipeline, separating the residual mixed gas by using a 10-level rectifying tower to obtain high-purity trichlorosilane (the purity is more than 11N) and high-purity silicon tetrachloride (the purity is more than 11N), and exchanging heat between the silicon tetrachloride (the temperature is 10-30 ℃) product and the residual mixed gas (the temperature is 160-180 ℃) obtained by secondary condensation in the step (4) in a coil heat exchanger to cool the mixed gas to the temperature required by rectification;
(6) And (3) production of polycrystalline silicon: sending the trichlorosilane obtained in the step (5) into a reduction furnace, and reducing and depositing a polycrystalline silicon rod by high-purity hydrogen at the temperature of 1050-1100 ℃; and (3) sending the silicon tetrachloride obtained in the step (5) into a hydrogenation process to react with hydrogen to prepare trichlorosilane, or sending the silicon tetrachloride into a storage tank to prepare optical fibers, gas-phase white carbon black, silicon-based electron gas and the like.
According to one embodiment, in step (1), the siliceous ore may be natural silica sand, silica, quartz sand, quartz, diatomaceous earth, silica fume, or industrial solid waste and byproducts having a silica content above 50%, preferably the siliceous ore has a silica content above 90%, the crystalline type is amorphous silicon, preferably the industrial silicon byproducts are silica fume;
according to one embodiment, the reducing agent is one or more of coal, charcoal, petroleum coke, coke and semi-coke; preferably charcoal and/or coke;
according to one embodiment, the silicon-containing additive is selected from at least one of silicon powder, silicon carbide powder. The method can select polycrystalline silicon, leftover silicon chips, silicon materials, industrial silicon powder, industrial silicon carbide and the like which are left after cutting in a monocrystalline silicon factory, and the leftover silicon chips and the silicon materials are preferred;
according to one embodiment, the particle size of the material pellets obtained by granulation is 0.1-10 mm;
according to one embodiment, the silica ore and the reducing agent are present in a silica to carbon molar ratio of 1: (2-5), preferably 1:3. The addition amount of the silicon-containing additive is 5-20% of the total mass of the silicon ore and the carbon reducer, and the addition amount of the water glass is 5-10% of the total mass of the silicon ore and the carbon reducer.
According to one embodiment, the reaction gas is fed at a void bed flow rate of 0.01 to 0.4m/s, preferably 0.01 to 0.03 m/s; the reaction gas comprises chlorine, hydrogen chloride and an inert carrier gas. According to the reaction principle, the chlorine amount is 1.1-2.0 times, preferably 1.5 times, the theoretical amount of completely converting silicon dioxide, silicon or silicon carbide and other metals in the reactant into chloride, so as to ensure that the reaction is fully carried out and simultaneously reduce the residual amount of the chlorine in the tail gas as much as possible;
according to one embodiment, in the mixed gas inlet composition, the mass fraction of the hydrogen chloride in the total mixed gas is 5-50%, preferably 20-25%, and the corresponding molar ratio of the hydrogen chloride to the silicon-containing additive is 2-5:1, preferably 3-4:1.
According to one embodiment, the reaction may allow for continuous production. However, for single-strand materials, the residence time of the single-strand materials in contact with the reaction gas is 30min to 10h, preferably 60min;
according to one embodiment, the gas feed returned from the external cyclone 16 has a circulation ratio of 1.0 to 5.0, preferably 3.0, i.e. the amount of feed to the reaction cycle is 3 times the amount of feed leaving the reaction system.
According to one embodiment, in step (2), the HCl purity is 99% or more and the chlorine purity is 99% or more;
according to one embodiment, the mixture should be heated to 800-1600 ℃, preferably 1000-1500 ℃, typically not exceeding 1500 ℃, in the reaction section; it should be noted that when the temperature is lower than 800 ℃, the chlorination reaction speed of silica is slower, and when the chlorination temperature exceeds 1500 ℃, the amount of heat absorption accompanying the chlorination reaction increases, the energy consumption of the fluidized bed furnace increases, and the material requirement is high. According to the invention, graphite, silicon nitride, indium scandium alloy or high-silicate bricks and the like are selected as lining materials of a furnace body, and a graphite lining is preferred;
according to one embodiment, the purity of the trichlorosilane product obtained in the step (4-2) is more than 99.999999999 percent, and the purity of the silicon tetrachloride is more than 99.9999999 percent.
Example 1
Respectively crushing microsilica (silicon dioxide content 94.5%), coke (fixed carbon content 81.2%) and silicon wafer into fine particles with the granularity of 100 meshes, and mixing the fine particles according to the microsilica: coke = 10kg:5.1kg (the mol ratio of silicon dioxide to carbon is 1:2.2), the silicon wafer is added in an amount of 5% of the total mass of the micro silicon powder and the coke, the water glass is added in an amount of 5% of the total mass of the micro silicon powder and the coke, the solid mixture is obtained after uniform mixing, and the solid mixture is added into a boiling chlorination furnace after extrusion granulation and drying to constant weight.
The microwave heater 18 is turned on, chlorine and hydrogen chloride (the mass fraction of the hydrogen chloride is 7 percent, and the mass fraction of the chlorine is 93.0 percent) are introduced, the air inlet speed is regulated, so that the particles are kept in a boiling state, the temperature is raised to 1000 ℃, and the material residence time is ensured to be 1h.
CollectingThe solid particles separated from the cyclone separator 16 were detected to have a particle diameter D50 of 4.82. Mu.m, and the product was analyzed by gas chromatography to obtain 11N-grade high purity SiCl 4 24.3kg of product, 3.3kg of 11N grade trichlorosilane product, and 0.6kg of polysilicon is obtained through reduction. The material conversion and yield are shown in Table 1.
TABLE 1 product yield Table
| The particle size D50 μm of the product | SiCl 4 Yield% | SiHCl 3 Yield% |
| 4.82 | 90.74 | 92.4 |
Example 2
Respectively crushing quartz sand (silicon dioxide content 90.5%), activated carbon (fixed carbon content 85.3%) and silicon powder into fine particles with the granularity of 150 meshes, and mixing the fine particles with the quartz sand according to the following steps: activated carbon = 10kg:6.6kg (the mol ratio of silicon dioxide to carbon is 1:3.1), the adding proportion of silicon powder is 20% of the total mass of the active carbon and the quartz sand, the adding proportion of water glass is 10% of the total mass of the active carbon and the quartz sand, the solid mixture is obtained after uniform mixing, and the solid mixture is added into a boiling chlorination furnace after extrusion granulation and drying until the weight is constant.
The microwave heater 18 is turned on, chlorine and hydrogen chloride (the mass fraction of the hydrogen chloride is 44 percent, and the mass fraction of the chlorine is 56 percent) are introduced, the air inlet speed is regulated, so that the particles keep a boiling state, the temperature is increased to 1200 ℃, and the material residence time is ensured to be 1.5h.
The solid particles separated from the outer cyclone 16 are collected,the particle diameter D50 was found to be 3.65. Mu.m. Analyzing the product by gas chromatography to obtain 11N-grade high-purity SiCl 4 22.7kg of product, 14.1kg of 11N grade trichlorosilane product, and 2.6kg of polysilicon is obtained through reduction. The material conversion and yield are shown in Table 2.
TABLE 2 product yields Table
| The particle size D50 μm of the product | SiCl 4 Yield% | SiHCl 3 Yield% |
| 3.65 | 88.7 | 93.1 |
Example 3
Kieselguhr (silicon dioxide content 80.6%), charcoal (fixed carbon content 79.3%) and silicon carbide powder are respectively crushed into fine particles with the granularity of 80 meshes according to the following steps: charcoal = 10kg:11.2kg (the mol ratio of silicon dioxide to carbon is 1:4.9), the silicon carbide is added in an amount which is 11 percent of the total mass of charcoal and diatomite, the water glass is added in an amount which is 10 percent of the total mass of charcoal and diatomite, the mixture is uniformly mixed to obtain a solid mixture, and the solid mixture is extruded, granulated and dried to constant weight and then added into a boiling chlorination furnace.
The microwave heater 18 is turned on, chlorine and hydrogen chloride (the mass fraction of the hydrogen chloride is 23 percent, and the mass fraction of the chlorine is 77 percent) are introduced, the air inlet speed is regulated, so that the particles are kept in a boiling state, the temperature is increased to 950 ℃, and the material residence time is ensured to be 60 minutes. The solid particles separated from the cyclone were collected and the particle diameter D50 was found to be 5.35 μm. Analyzing the product by gas chromatography to obtain 11N-grade high-purity SiCl 4 24kg of product, 10.2kg of 11N grade trichlorosilane product, and 1.9kg of polysilicon is obtained through reduction. The material yields are shown in Table 3.
TABLE 3 product yield Table
| The particle size D50 μm of the product | SiCl 4 Yield% | SiHCl 3 Yield% |
| 5.35 | 93.8 | 95.2 |
Comparative example 1
Diatomaceous earth (silica content 80.6%), charcoal (fixed carbon content 79.3%) and silicon carbide were crushed to fine particles having a particle size of 80 mesh, respectively, according to diatomaceous earth: charcoal = 10kg:11.2kg (the mol ratio of silicon dioxide to carbon is 1:4.9), the silicon carbide is added in an amount which is 11 percent of the total mass of charcoal and diatomite, the water glass is added in an amount which is 10 percent of the total mass of charcoal and diatomite, the mixture is uniformly mixed to obtain a solid mixture, and the solid mixture is extruded, granulated and dried to constant weight and then added into a boiling chlorination furnace.
And (3) turning on the microwave heater 18, introducing chlorine, adjusting the air inlet speed to keep particles in a boiling state, heating to 950 ℃, and ensuring the material residence time to be 60min. The solid particles separated from the cyclone were collected and the particle diameter D50 was found to be 6.28 μm. Analyzing the product by gas chromatography to obtain 11N-grade high-purity SiCl 4 19.5kg of product. The material yields are shown in Table 4.
TABLE 4 product yield Table
| The particle size D50 μm of the product | SiCl 4 Yield% | SiHCl 3 Yield% |
| 6.28 | 76.1 | / |
Comparative example 2
Kieselguhr (silicon dioxide content 80.6%) and charcoal (fixed carbon content 79.3%) were respectively crushed into fine particles having a particle size of 80 mesh, and the kieselguhr was used as follows: charcoal = 10kg:11.2kg (the mol ratio of silicon dioxide to carbon is 1:4.9), the adding proportion of water glass is 10% of the total mass of charcoal and diatomite, the solid mixture is obtained after uniform mixing, and the solid mixture is added into a boiling chlorination furnace after extrusion granulation and drying to constant weight.
The microwave heater 18 is turned on, chlorine and hydrogen chloride (the mass fraction of the hydrogen chloride is 23 percent and the mass fraction of the chlorine is 77 percent) are introduced, the air inlet speed is regulated to keep particles in a boiling state, the temperature is raised to 950 ℃, and the material residence time is ensured to be 60 minutes. The solid particles separated from the cyclone were collected and the particle diameter D50 was found to be 5.85 μm. Analyzing the product by gas chromatography to obtain 11N-grade high-purity SiCl 4 19.5kg of product, 7.4kg of 11N-grade high-purity trichlorosilane and 1.3kg of polysilicon product are obtained through reduction. The material yields are shown in Table 5.
TABLE 5 product yield Table
| The particle size D50 μm of the product | SiCl 4 Yield% | SiHCl 3 Yield% |
| 5.85 | 82.4 | 69.1 |
Comparative examples 1 and 2 demonstrate that the product yield drops dramatically at the same reaction temperature with only chlorine gas added without hydrogen chloride or without the addition of silicon-containing additives.
The present invention is not limited to the above embodiments, but the scope of the invention is defined by the claims.
Claims (10)
1. A device for preparing high-purity silicon tetrachloride and polysilicon in a short process is characterized by comprising a boiling chlorination furnace, an inner cyclone separator, an outer cyclone separator and a three-way control valve,
the boiling chlorination furnace comprises a boiling chlorination reaction section, a transition section and an expansion section from bottom to top, wherein the top of the reaction section is connected with the transition section, and the top of the transition section is connected with the expansion section;
the bottom of the reaction section is provided with a gas distribution chamber, and the bottom of the gas distribution chamber is provided with a slag discharge port; a gas distributor is arranged between the gas distribution chamber and the reaction section and is used for realizing the communication between the gas distribution chamber and the reaction section; the outer wall of the gas distribution chamber is provided with a gas feed port, and mixed gas comprising chlorine and hydrogen chloride is fed into the boiling chlorination furnace; the middle part of the reaction section is provided with a solid material feed inlet, and a heater is arranged outside the inner lining of the reaction section and used for providing heat required by the reaction;
the middle upper part of the expansion section is provided with an inner cyclone separator, and the inner cyclone separator is connected with an outer cyclone separator by extending out of a top cover at the top of the expansion section through a pipeline; the expansion section is also provided with a cooling system;
the gas outlet of the external cyclone separator is connected with a three-way control valve through a pipeline, a part of gas mixture is circulated back to the boiling chlorination furnace, and a part of gas mixture enters the next working procedure from a lower pipeline; and the solid material outlet of the external cyclone separator is connected with the solid material inlet of the reaction section.
2. The device for preparing high-purity silicon tetrachloride and polysilicon by the short process according to claim 1, wherein the height-diameter ratio of the reaction section is more than or equal to 1.5, the transition section accounts for 1/3-1/2 of the total height of the boiling chlorination furnace, and the included angle between the bus of the conical section where the transition section is positioned and the central line is 10-20 degrees; the height-diameter ratio of the expansion section is more than or equal to 1.2, and the diameter of the expansion section is 1.2-2.0 times of the diameter of the reaction section.
3. The apparatus for preparing high-purity silicon tetrachloride and polysilicon by short process according to claim 1, wherein the reaction section is provided with a bubble breaker, and the bubble breaker is positioned between the gas distributor and the solid material feed inlet.
4. The apparatus for preparing high purity silicon tetrachloride and polysilicon by short process according to claim 1, wherein the boiling chlorination furnace is provided with more than two gas feed inlets, including a chlorine gas feed inlet, a hydrogen chloride feed inlet and an inert gas feed inlet, and the air inflow of each gas feed inlet is controlled by a three-way control valve.
5. A process for the short-flow preparation of high-purity silicon tetrachloride and polysilicon, characterized in that it employs the apparatus as claimed in any one of claims 1 to 4, comprising the following steps:
(1) Crushing and conveying materials: crushing silicon ore, mixing the crushed silicon ore with a silicon-containing additive and a reducing agent, and adding water glass as an adhesive to obtain pellets;
(2) Adding carbon for chlorination: feeding the pellets obtained in the step (1) into a boiling chlorination furnace, opening a three-way control valve below the boiling chlorination furnace, introducing chlorine and hydrogen chloride into the furnace, preheating the gas, feeding the preheated gas into a gas distribution chamber, and feeding the preheated gas into a reaction section through a gas distributor and a bubble breaker to react with the pellets conveyed from a solid material feed inlet; the mixed gas generated by the reaction rises to pass through the transition section and the expansion section, enters from the internal cyclone separator, and the carried silicon powder is collected and returned to the reaction section bed layer for continuous reaction;
(3) Gas-solid separation: the gas-solid separation of the materials in the chlorination boiling furnace is realized through the inner cyclone separator and the outer cyclone separator;
(4) And sequentially performing multistage condensation, rectification purification and reduction on the outlet gas separated by the external cyclone separator to obtain silicon tetrachloride and polysilicon.
6. The method for preparing high-purity silicon tetrachloride and polysilicon according to the short process of claim 5, wherein in step (1), the siliceous ore is selected from natural silica sand, silica, quartz sand, quartz, diatomaceous earth, silica fume, or industrial solid waste and byproducts having a silica content of more than 50%;
the reducing agent is one or more of coal, charcoal, petroleum coke, coke and semi-coke;
the silicon-containing additive is at least one selected from silicon powder and silicon carbide powder.
7. The method for preparing high-purity silicon tetrachloride and polysilicon according to the short flow path of claim 5, wherein in step (1), the molar ratio of silicon ore to reducing agent is 1: (2-5) mixing; the addition amount of the silicon-containing additive is 5-20% of the total mass of the silicon ore and the carbon reducer, and the addition amount of the water glass is 5-10% of the total mass of the silicon ore and the carbon reducer.
8. The process for preparing high-purity silicon tetrachloride and polycrystalline silicon according to the short-flow process of claim 5, wherein in step (2), the reaction gas is fed at an empty bed flow rate of 0.01 to 0.4m/s, and the reaction gas comprises chlorine and hydrogen chloride.
9. The method for preparing high-purity silicon tetrachloride and polysilicon by short process according to claim 5, wherein in the step (2), the mass fraction of hydrogen chloride in the total mixed gas is 5% -50% in the mixed gas composition, and the molar ratio of the hydrogen chloride to the silicon-containing additive is 2-5:1.
10. The method for preparing high-purity silicon tetrachloride and polysilicon according to the short process of claim 5, wherein in the step (2), the mixture is heated to 800-1600 ℃.
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