CN114180578A - Production process and production system for ultra-pure polycrystalline silicon and silicon derivatives - Google Patents
Production process and production system for ultra-pure polycrystalline silicon and silicon derivatives Download PDFInfo
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- CN114180578A CN114180578A CN202210141190.3A CN202210141190A CN114180578A CN 114180578 A CN114180578 A CN 114180578A CN 202210141190 A CN202210141190 A CN 202210141190A CN 114180578 A CN114180578 A CN 114180578A
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- China
- Prior art keywords
- tower
- trichlorosilane
- dichlorosilane
- silicon
- silicon tetrachloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 131
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 123
- 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 claims abstract description 121
- 230000009467 reduction Effects 0.000 claims abstract description 67
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000000746 purification Methods 0.000 claims abstract description 55
- 238000001179 sorption measurement Methods 0.000 claims abstract description 53
- 229920005591 polysilicon Polymers 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 claims abstract description 26
- 239000013307 optical fiber Substances 0.000 claims abstract description 23
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 102
- 239000001257 hydrogen Substances 0.000 claims description 100
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 94
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 92
- 239000007789 gas Substances 0.000 claims description 89
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 71
- 238000000926 separation method Methods 0.000 claims description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000005984 hydrogenation reaction Methods 0.000 claims description 52
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 43
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims description 43
- 239000005046 Chlorosilane Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 41
- 238000002360 preparation method Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000007323 disproportionation reaction Methods 0.000 claims description 31
- 239000011863 silicon-based powder Substances 0.000 claims description 29
- 238000011084 recovery Methods 0.000 claims description 28
- 150000003376 silicon Chemical class 0.000 claims description 26
- 238000005660 chlorination reaction Methods 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 230000008878 coupling Effects 0.000 claims description 22
- 238000010168 coupling process Methods 0.000 claims description 22
- 238000005859 coupling reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 239000003463 adsorbent Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 238000002386 leaching Methods 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 11
- 230000005587 bubbling Effects 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 6
- 244000060011 Cocos nucifera Species 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229940049953 phenylacetate Drugs 0.000 claims description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 claims description 4
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 3
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 3
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical group 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 61
- 238000005516 engineering process Methods 0.000 abstract description 13
- 239000006227 byproduct Substances 0.000 abstract description 12
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 101
- 239000012535 impurity Substances 0.000 description 66
- 238000006722 reduction reaction Methods 0.000 description 55
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000010992 reflux Methods 0.000 description 21
- 238000001816 cooling Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000004857 zone melting Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000010791 quenching Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 230000000171 quenching effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- -1 styrene-polyethylene styrene Chemical class 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- 229910015844 BCl3 Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- QQAHAGNPDBPSJP-UHFFFAOYSA-N 1,1,1,2,2,3,3,3-octachloropropane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl QQAHAGNPDBPSJP-UHFFFAOYSA-N 0.000 description 1
- 229910015395 B-O-Si Inorganic materials 0.000 description 1
- 229910015403 B—O—Si Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C01B33/02—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
-
- 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
-
- 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
- C01B33/10773—Halogenated silanes obtained by disproportionation and molecular rearrangement of halogenated silanes
-
- 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
- C01B33/10778—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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Abstract
The invention provides a production process and a production system of ultra-pure polysilicon and silicon derivatives, which are characterized in that an electronic-grade trichlorosilane is prepared by developing an adsorption complexation-efficient rectification trichlorosilane purification technology, the electronic-grade trichlorosilane is further prepared by taking the electronic-grade trichlorosilane as a raw material, optical fiber silicon tetrachloride is prepared by developing a photocatalytic reaction-efficient rectification purification technology, and the electronic-grade ethyl orthosilicate is further prepared by taking the optical fiber silicon tetrachloride as a raw material. The invention takes the manufacture of high-purity zone-melting-stage polysilicon as a center, and carries out internal circulation and reutilization on material flow, thereby realizing the reduction and resource utilization of byproducts, forming a synergistic product chain, exerting the synergistic effect, integrating a public and auxiliary system, realizing the sharing of related product manufacturing devices, and reducing the number of devices and the system investment.
Description
Technical Field
The invention relates to the technical field of polycrystalline silicon production, in particular to a production process and a production system of ultra-high purity polycrystalline silicon and silicon derivatives.
Background
High purity polysilicon and silicon derivatives are key raw materials in optical fiber and semiconductor manufacturing, and over 95% of semiconductor chips and devices are produced with silicon as the substrate functional material worldwide. The floating-zone grade polysilicon is a key base material for the entire semiconductor industry chain. Photovoltaic grade polysilicon has entered into resource and cost competition, but high purity zone melting grade polysilicon preparation is still the key direction of attack.
The preparation of the high-purity polysilicon is mainly influenced by the quality of the trichlorosilane and the hydrogen as raw materials, the structure and the process of the reduction furnace, the control system, the cleanliness of the system and the like.
The quality of the high-purity polysilicon is improved by optimizing the structure or process of the reduction furnace. However, in the prior art, the adaptability of the furnace types with different specifications is often not fully considered, the application is limited, and meanwhile, the optimization measures of the thermal field in the reduction furnace are not considered, so that the separation of the thermal field in the equipment and the recycling of the capacity are not facilitated.
Trichlorosilane:
the purification mainly adopts modes of rectification, adsorption, complexation and the like, the rectification mostly adopts a series-connection multiple purification method to purify raw materials, the purification of trichlorosilane by rectification has the advantages of realizing industrial production, reducing the energy consumption of a purification unit, having multiple series-connection stages, high investment, high difficulty in stable operation control, easily influencing the product quality by operating conditions, and mostly adopting differential pressure thermal coupling to recover energy and reduce the energy consumption and equipment investment at present. But the quality assurance is the premise, the rectification belongs to physical purification, and the separation limit of trace impurities exists due to the rectification efficiency, the number of theoretical plates and the existence of impurity azeotrope.
At present, adsorption and impurity removal are widely applied to preparation of photovoltaic-grade products, and are mainly used for adsorption and separation of ppm-grade impurities, but the separation limit difficulty of ppb and even ppt-grade trace impurities is very high, and meanwhile, impurities are easily introduced into the adsorbent to cause pollution. But also by adsorption capacity, selectivity, attrition product fines, etc. In addition, the adsorption method and the configuration of the adsorber have a great influence on the adsorption effect.
The reaction impurity removal is to add corresponding reagents into raw materials to react with target impurities to realize physical property conversion, so that separation is facilitated, but the reaction reagents have low selectivity and low conversion rate, and are impurities and need to be separated.
Hydrogen gas:
at present, the hydrogen purification in the preparation of polycrystalline silicon mainly adopts an activated carbon physical adsorption technology, the hydrogen is purified through cyclic adsorption and desorption, the purified hydrogen is returned to a system for reuse, the product purity can meet the preparation quality requirement of solar-grade polycrystalline silicon, the activated carbon adsorption is physical adsorption, the pertinence and the selectivity are not strong, the removal capacity of trace impurities is limited, and the hydrogen quality cannot be guaranteed. Which makes it unsatisfactory for the preparation of high purity polysilicon and still requires further purification.
The patent [201921786204.7 composite hydrogen purification system using molecular sieve adsorption and metal hydride purification ] uses a composite hydrogen purification system using molecular sieve adsorption and metal hydride purification, and the method realizes further purification of hydrogen, but the purity can not meet the requirement. According to the patent [201110200460.5 method for purifying and processing circulating hydrogen for producing polycrystalline silicon by reducing trichlorosilane ] two groups of metal palladium composite membrane hydrogen purifiers connected in series are adopted to purify and process circulating hydrogen for reducing trichlorosilane to obtain two qualities of hydrogen, high-purity 5N hydrogen returns to a reduction furnace, and low-quality hydrogen is hydrogenated. However, there is an index requirement for the hydrogen chloride content in the raw material gas, and an adsorption and hydrogen chloride removal device needs to be additionally arranged, so that the adaptability is limited. Therefore, the hydrogen purification method and process which are suitable for the high-purity polysilicon manufacturing process and are large-scale and qualified in quality still need to be further improved.
The number of the special electronic gases is about 110, and the number of the special electronic gases is 30 in common use, and accounts for 3-5% of the manufacturing cost; the product has multiple varieties and strict quality requirements, the control requirement of element impurities is in ppb level, the influence factors of the manufacturing process are multiple, and the separation and manufacturing difficulty of trace impurities is high. The electronic speciality is various, the products of the manufacturing enterprises are distributed in a point mode, each product independently and repeatedly establishes a preparation system, public and auxiliary facilities are not effectively integrated, the investment is large, product clusters are not formed, and the synergistic effect cannot be formed.
For example, the polysilicon production process involves various intermediate products and by-products, and cannot be effectively utilized or is simply utilized, and further extension application is not performed, and the added value is low. Meanwhile, part of byproducts need to be specially treated, so that the operation cost and the environmental protection pressure are increased. In addition, the conventional separation and purification technology is limited in the aspect of trace impurity separation, core technologies such as key component and metal impurity separation and purification, intersystem cooperative integration and the like are not formed and mastered, and product indexes cannot reach downstream use indexes.
Trichlorosilane, silicon tetrachloride, dichlorosilane, tetraethoxysilane and the like are difficult to remove to a trace level only by means of rectification, adsorption and the like because impurities in the trichlorosilane are close to the boiling point of a target product or azeotrope is easily formed, and the indexes of electronic-grade products cannot be reached. It is considered that impurities are converted by a specific and selective method, and the impurities are easily separated by increasing the physical differences such as boiling points with the target product.
The electronic speciality is various, the products of the manufacturing enterprise are distributed in a point mode, each product independently and repeatedly establishes a preparation system, the investment is large, a product cluster is not formed, and a synergistic effect cannot be formed; key technologies such as key component and metal impurity separation, material purification, process control, high-purity product filling, system cleaning control, preparation devices and modular systems are not formed and mastered, and product indexes cannot reach downstream use indexes.
Disclosure of Invention
The invention aims to provide a production process and a production system of ultra-pure polysilicon and silicon derivatives, which take the manufacture of high-purity zone-melting-level polysilicon as a center, carry out internal circulation and reutilization on material flows, realize the reduction and resource utilization of byproducts, form a synergistic product chain, play a synergistic effect, integrate a public and auxiliary system, share related product manufacturing devices, and reduce the number of devices and the system investment.
One aspect of the application provides a production process of ultra-pure polysilicon and silicon derivatives, trichlorosilane, dichlorosilane and hydrogen are introduced into a reduction furnace to prepare polysilicon, and tail gas containing chlorosilane and hydrogen is recycled; conveying one part of the recovered hydrogen after deep purification to a reduction furnace to participate in preparation of polysilicon, conveying the other part of the recovered hydrogen to a hydrogenation fluidized bed to participate in synthesis of trichlorosilane, introducing the recovered chlorosilane into a dividing wall rectifying tower, and extracting dichlorosilane, trichlorosilane, silicon tetrachloride and hexachlorodisilane; conveying dichlorosilane extracted from the dividing wall rectifying tower to a reducing furnace to participate in preparing polycrystalline silicon; preparing electronic-grade trichlorosilane from trichlorosilane extracted by a dividing wall rectifying tower, conveying one part of the prepared electronic-grade trichlorosilane to a reduction furnace to participate in preparation of polycrystalline silicon, and preparing electronic-grade dichlorosilane from the other part of the prepared electronic-grade trichlorosilane by a catalytic disproportionation reaction method; conveying one part of silicon tetrachloride extracted from a dividing wall rectifying tower to a hydrogenation fluidized bed to participate in synthesizing electronic-grade trichlorosilane, purifying the other part of silicon tetrachloride to prepare optical fiber silicon tetrachloride, and reacting the prepared optical fiber silicon tetrachloride with ethanol to synthesize electronic-grade ethyl orthosilicate; and (3) preparing electronic-grade hexachlorodisilane from the hexachlorodisilane extracted from the dividing wall rectifying tower.
In some embodiments, the preparation method of the electronic-grade trichlorosilane comprises the following steps: trichlorosilane extracted from the dividing wall rectifying tower is sequentially introduced into an adsorption reactor, a trichlorosilane lightness-removing tower and a trichlorosilane weight-removing tower, wherein the adsorption reactor is filled with an adsorbent loaded with a reagent, and oxygen, ozone or a mixture of the oxygen and the ozone are introduced into the adsorption reactor.
In some embodiments, the reagent is diphenylthiocarbazone, triphenylchloromethane, phenyl acetate, diphenyl sulfide, aluminum chloride, benzaldehyde, cinnamaldehyde and a mixture of any one or more of the above derivatives, the loading amount of the reagent is 0.5-10% by weight, and the water content is less than 0.5%.
In some embodiments, the hydrogen is firstly introduced into an activated carbon adsorber for preliminary purification, part of the purified hydrogen is conveyed to a hydrogenation fluidized bed to participate in synthesis of trichlorosilane, and the other part of the purified hydrogen firstly enters a first-stage purifier and a second-stage purifier for deep purification, then enters a mixer to be mixed with dichlorosilane and trichlorosilane, and then is introduced into a reduction furnace for preparation of polycrystalline silicon.
In some embodiments, spherical coconut shell activated carbon is used in the activated carbon adsorber, and HNO is used3、H2SO4、H2O2The mixed acid system is used for carrying out oxidation modification on the coconut shell activated carbon.
In some embodiments, the first purifier is internally provided with a deoxygenation adsorbent, the deoxygenation adsorbent is a metal oxide, and the second purifier is filled with a metal alloy.
In some embodiments, the number of pairs of silicon rods in the reduction furnace is 12, 24, 36, 48 or 64, the inner wall of the reduction furnace is treated by silver plating, and the molar ratio of hydrogen to silicon trichloride fed into the reduction furnace is as follows: 2-5: 1, wherein the addition amount of dichlorosilane is 2-10% of that of trichlorosilane, the internal temperature of the reducing furnace is 900-1200 ℃, and the pressure is 30-1000 Kpa.
In some embodiments, the tail gas of the reduction furnace is recovered by a dry cryogenic process, a double-effect heat exchanger is arranged to exchange heat between the tail gas and the reduction furnace raw material hydrogen, trichlorosilane and dichlorosilane, the tail gas after heat exchange enters a bubbling leaching tower, the tail gas is leached by chlorosilane, the chlorosilane in the tail gas is liquefied and separated from gas, and the separated chlorosilane is extracted from the bottom of the leaching tower and enters a dividing wall rectifying tower for purification; and introducing unseparated tail gas into a tail gas compressor and a first step cryogenic heat exchange system in sequence to separate hydrogen from chlorosilane, introducing the separated hydrogen into an activated carbon adsorber for purification and recycling, and introducing the separated chlorosilane into a dividing wall rectifying tower.
In some embodiments, silicon tetrachloride and hexachlorodisilane extracted from a tower kettle of the dividing wall rectifying tower are introduced into a silicon tetrachloride separating tower, and the separated hexachlorodisilane sequentially enters a hexachlorodisilane lightness-removing tower and a hexachlorodisilane weight-removing tower to prepare electronic-grade hexachlorodisilane; preheating a part of the separated silicon tetrachloride along with hydrogen and silicon powder, then introducing the preheated silicon tetrachloride into a hydrogenation reactor, returning the prepared chlorosilane to a dividing wall rectifying tower for component separation, and returning the recovered hydrogen to the hydrogenation reactor for continuous cyclic utilization; and the other part of the separated silicon tetrachloride sequentially passes through a photocatalysis chlorination coupling rectifying tower, a silicon tetrachloride lightness-removing tower and a silicon tetrachloride heaving-removing tower to prepare the optical fiber silicon tetrachloride.
In some embodiments, the preparation method of the electronic grade tetraethoxysilane comprises the following steps: and (2) introducing the prepared optical fiber silicon tetrachloride and ethanol into an ethyl orthosilicate reactor, introducing the reacted materials into an ethyl orthosilicate separation tower, returning the separated excessive ethanol to the ethyl orthosilicate reactor for recycling, and sequentially introducing the separated ethyl orthosilicate into an ethyl orthosilicate lightness-removing tower and an ethyl orthosilicate heaving-removing tower to prepare the electronic grade ethyl orthosilicate.
In some embodiments, the preparation method of the electronic-grade dichlorosilane comprises the following steps: introducing the prepared electronic grade trichlorosilane into a disproportionation reactor, introducing the reacted materials into a dichlorosilane separation tower, separating dichlorosilane from the tower top of the dichlorosilane separation tower, and separating trichlorosilane and silicon tetrachloride from the tower kettle;
wherein, dichlorosilane is sequentially introduced into a dichlorosilane lightness-removing tower and a dichlorosilane heavy-removing tower to prepare electronic-grade dichlorosilane;
trichlorosilane and silicon tetrachloride are fed into a dichlorosilane recovery tower to separate trichlorosilane and silicon tetrachloride, the separated trichlorosilane returns to the disproportionation reactor again for cyclic utilization, and the separated silicon tetrachloride is fed into the hydrogenation reactor or the photocatalytic chlorination coupling rectifying tower for cyclic utilization.
Another embodiment of the present application provides a system for producing ultra-high purity polysilicon and silicon derivatives, comprising a mixer, a reduction furnace, a tail gas recovery device, a hydrogen purification device, a dividing wall rectifying tower, a hydrogenation fluidized bed, an adsorption reactor, a photocatalytic chlorination coupling rectifying tower, an ethyl orthosilicate reactor and a disproportionation reactor;
an outlet of the mixer is connected with an inlet of the reduction furnace, an outlet of the reduction furnace is connected with a tail gas recovery device, the tail gas recovery device is respectively connected with an inlet of the dividing wall rectifying tower and an inlet of the hydrogen purification device, the top of the dividing wall rectifying tower is connected with an inlet of the mixer, an adsorption reactor, a trichlorosilane lightness-removing tower and a trichlorosilane heavy-removing tower are sequentially connected in the dividing wall rectifying tower, and a tower kettle of the dividing wall rectifying tower is connected with a silicon tetrachloride separation tower;
the hydrogen purification device is respectively connected with the inlet of the mixer and the inlet of the hydrogenation fluidized bed, and the outlet of the hydrogenation fluidized bed is connected with the inlet of the dividing wall rectifying tower;
the top of the silicon tetrachloride separation tower is connected with an inlet of a hydrogenation fluidized bed and an inlet of a photocatalytic chlorination coupling rectifying tower, an outlet of the photocatalytic chlorination coupling rectifying tower is sequentially connected with a silicon tetrachloride lightness-removing tower and a silicon tetrachloride heavy-removing tower, and a tower kettle of the silicon tetrachloride separation tower is sequentially connected with a hexachlorodisilane lightness-removing tower and a hexachlorodisilane heavy-removing tower;
the outlet of the silicon tetrachloride heavy-duty removal tower is sequentially connected with an ethyl orthosilicate reactor, an ethyl orthosilicate separation tower, an ethyl orthosilicate light-duty removal tower and an ethyl orthosilicate heavy-duty removal tower;
the outlet of the trichlorosilane de-heavy tower is sequentially connected with a disproportionation reactor and a dichlorosilane separation tower, the tower top of the dichlorosilane separation tower is sequentially connected with a dichlorosilane light-ends removal tower and a dichlorosilane de-heavy tower, the tower kettle of the dichlorosilane separation tower is connected with the inlet of a dichlorosilane recovery tower, the tower top of the dichlorosilane recovery tower is connected with the inlet of the disproportionation reactor, and the tower kettle of the dichlorosilane recovery tower is connected with the inlet of a photocatalytic chlorination coupling rectifying tower.
The invention has the beneficial effects that:
1. developing a production process and a production system of zone-melting-grade polycrystalline silicon and silicon derivatives, taking 'silicon' as a center, performing closed-loop circulation and radiation derivatization on product materials to realize product clustering, and forming preparation of high-purity zone-melting silicon and silicon-based electronic special gas of multiple products to form a synergistic effect;
2. the production system is in green internal circulation, and intermediate products and byproducts in the production process of the high-purity zone-melting silicon are reduced and recycled;
3. the electronic grade trichlorosilane is prepared by developing an adsorption complexation-efficient rectification trichlorosilane purification technology, an adsorption reaction device has the functions of adsorption and reaction complexation, and a load complexing agent is preferably selected to realize the separation of trace impurities in the trichlorosilane. Meanwhile, a high-purity hydrogen purification technology is carried out to realize the preparation of zone-melting-grade polysilicon, and the purity reaches 13N;
4. the prepared electronic-grade trichlorosilane is taken as a raw material, electronic-grade dichlorosilane is further prepared, and the purity of a product reaches 4N;
5. starting a luminescent catalytic reaction-efficient rectification purification technology, effectively converting and removing hydrogen-containing impurities, realizing the preparation of optical fiber silicon tetrachloride, and further synthesizing and preparing electronic grade ethyl orthosilicate by taking high-purity silicon tetrachloride as a raw material;
6. the system has openness and extensibility, related products and materials of the system are high-purity media, and corresponding intermediate products and byproducts have low impurity content.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent from and readily appreciated by reference to the following description of the embodiments taken in conjunction with the accompanying drawings,
wherein:
FIG. 1 is a flow chart of an ultra-high purity polysilicon and silicon derivative production system in an embodiment of the present invention;
reference numerals:
1-a reduction furnace; 2-double effect heat exchanger; 3-a bubbling leaching tower; 4-a tail gas compressor; 5-a first step deep cooling heat exchange system; 6-dry cryogenic recovery system; 7-dividing wall rectifying tower; 8-an adsorption reactor; 9-trichlorosilane lightness removing tower; 10-trichlorosilane de-heavy column; 11-a disproportionation reactor; a 12-dichlorosilane separation tower; 13-dichlorosilane light component removal tower; 14-dichlorosilane de-heavy tower; 15-a mixer; 16-a secondary purifier; 17-a primary purifier; 18-an activated carbon adsorber; 19-a silicon tetrachloride separation column; 20-a dense phase conveying device for silicon powder; 21-a preheater; 22-a hydrogenation reactor; 23-hydrogenation quench tower; 24-a second step cryogenic heat exchange system; a 25-dichlorosilane recovery tower; 26-hexachlorodisilane de-weighting tower; 27-hexachlorodisilane lightness-removing tower; 28-a photocatalytic chlorination coupled rectifying tower; 29-silicon tetrachloride lightness-removing tower; 30-silicon tetrachloride de-weighting tower; 31-ethyl orthosilicate reactor; a 32-tetraethoxysilane separation column; 33-ethyl orthosilicate lightness-removing tower; 34-ethyl orthosilicate de-weighting tower.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The high-purity zone melting level polysilicon and silicon derivatives are key raw materials in the manufacture of optical fibers and semiconductors, the product quality requirement is strict, the variety is multiple, the purity requirement of the zone melting level polysilicon reaches 13N, and the impurity requirement of silicon-based electronic special gas is less than 1 ppb. At present, most units adopt an improved Siemens method or a silane method to prepare the polycrystalline silicon, and the product meets the indexes of photovoltaic grade polycrystalline silicon and cannot reach the indexes of zone-melting grade polycrystalline silicon. Meanwhile, the preparation process of the polycrystalline silicon has long system flow, relates to various byproducts, does not utilize the byproducts effectively or only utilizes the byproducts simply, has low added value, and is easy to cause the problems of environmental protection and cost.
In addition, the related unit products mostly adopt point type layout, each product independently and repeatedly builds a preparation system, public and auxiliary facilities are not effectively integrated, the investment is large, product clusters are not formed, and the synergistic effect cannot be formed. Core technologies such as key component and metal impurity separation and purification, intersystem collaborative integration and the like are not formed and mastered, and product indexes cannot reach downstream use indexes.
Therefore, the invention provides a production process and a system of high-purity zone-melting-level polycrystalline silicon and silicon derivatives, which develop a high-efficiency vapor deposition technology and series equipment of the high-purity polycrystalline silicon, a chlorosilane photocatalysis reaction-adsorption complexation-high-efficiency rectification purification technology and a silicon derivative high-efficiency catalytic synthesis purification technology, take 'silicon' as a center, perform radiation derivatization, reduce and recycle intermediate products and byproducts in the production process of the high-purity zone-melting silicon, realize green internal circulation of the system, realize closed circulation of product materials, and design of the system and the process in a modularized way, form product clusters and realize the full-flow supply of silicon materials. The color filter has the characteristics of greenness, cyclicity and integration.
The ultra-high purity polysilicon and silicon derivative production process and system according to the embodiment of the present invention will be described with reference to the drawings.
As shown in fig. 1, an embodiment of an aspect of the present application provides a process for producing ultra-high purity polysilicon and silicon derivatives, comprising the following steps:
(1) introducing trichlorosilane, dichlorosilane and hydrogen into a reduction furnace 1 to prepare polycrystalline silicon, and recovering tail gas containing chlorosilane and hydrogen;
(2) one part of the recovered hydrogen is deeply purified and then is conveyed to a reduction furnace 1 to participate in the preparation of polysilicon, the other part of the recovered hydrogen is conveyed to a hydrogenation fluidized bed to participate in the synthesis of trichlorosilane, the recovered chlorosilane is introduced into a dividing wall rectifying tower 7, and dichlorosilane, trichlorosilane, silicon tetrachloride and hexachlorodisilane are extracted;
(3) conveying dichlorosilane extracted from the dividing wall rectifying tower 7 to a reducing furnace 1 to participate in preparing polycrystalline silicon;
(4) preparing electronic-grade trichlorosilane from trichlorosilane extracted by a dividing wall rectifying tower 7, conveying one part of the prepared electronic-grade trichlorosilane to a reduction furnace 1 to participate in preparation of polycrystalline silicon, and preparing electronic-grade dichlorosilane from the other part of the prepared electronic-grade trichlorosilane by a catalytic disproportionation reaction method;
(5) conveying one part of silicon tetrachloride extracted from the dividing wall rectifying tower 7 to a hydrogenation fluidized bed to participate in synthesizing trichlorosilane, purifying the other part of silicon tetrachloride to prepare optical fiber silicon tetrachloride, and reacting the prepared optical fiber silicon tetrachloride with ethanol to synthesize electronic-grade ethyl orthosilicate;
(6) the hexachlorodisilane extracted from the dividing wall rectifying tower 7 is subjected to the preparation of electronic-grade hexachlorodisilane.
In the step (1), trichlorosilane is purified to ppb level by adopting a chemical reaction combined adsorption and rectification process, firstly trichlorosilane enters an adsorption reactor 8 in a liquid or gaseous state, an adsorbent loaded with a reagent is filled in the adsorption reactor 8, and an adsorbent carrier has a large specific surface area, specifically 400-1000 m2The water-soluble polymer is/g and has good chemical stability, such as one or a mixture of alumina, artificial zeolite, activated carbon, styrene-polyethylene styrene resin, silica gel and the like. The reagent is any one or more of diphenylthiocarbazone, triphenylchloromethane, phenyl acetate, diphenyl sulfide, aluminum chloride, benzaldehyde, cinnamaldehyde and derivatives of the above substances, the proportion of the mixture is not required, and the proportion can be any, so that the protection is not important in the scheme. Soaking, mixing and roasting a carrier and a reagent with a certain content to ensure that the loading capacity of the reagent is 0.5-10 wt% and the water content is less than 0.5%.
The bottom of the adsorption reactor 8 is provided with a gas phase or liquid phase inlet, and oxygen, ozone or a mixture of the oxygen and the ozone are introduced at the same time, so that the adsorption reactor has two main functions: the method is characterized in that trivalent phosphorus in trichlorosilane is oxidized into pentavalent phosphorus, so that the phosphorus exists in the form of phosphorus pentachloride or phosphorus oxychloride, and the existence forms of impurities such as phosphorus and the like are converted. The boron impurity mainly exists in the form of boron trichloride, forms covalent coordination bonds with oxygen atoms and nitrogen atoms in a reagent, is converted into a high-boiling-point and macromolecular compound, and increases the boiling point difference with trichlorosilane. Secondly, oxygen reacts with Si-H bonds in the trichlorosilane to form SiOH intermediate substances, and the intermediate substances and trivalent boron in the trichlorosilane exist in the form of BCl3Carrying out complex reaction to form high boiling point substance containing B-O-Si bond, and separating by a rectifying tower.
Wherein the addition amount of oxygen, ozone or the mixture of oxygen and ozone is 1-10000 times of the molar content of impurities in trichlorosilane, and the oxygen, ozone or the mixture of the oxygen and the ozone is added into the mixtureThe proportion of oxygen and ozone is not required, and any proportion can be adopted, which is not the key point to be protected in the scheme. Wherein the impurities in the trichlorosilane include B, P and other impurities, such as BCl3、BCl5、PCl3、PCl5And the like. The operation pressure of the adsorption reactor 8 is 50-3000 KPa, the operation temperature is 5-300 ℃, and the adsorption and complexation reaction effect is better under the temperature and pressure. The inlet of the adsorption reactor 8 is provided with a preheater 21 for preheating the raw material trichlorosilane, so that the trichlorosilane can enter the adsorption reactor 8 in the form of liquid, gas or gas-liquid mixture, and can be easily in full contact with the adsorbent, and the reaction is more sufficient.
The adsorption reactor 8 is provided with a jacket or a heat exchange pipe, hot water, steam or heat conducting oil is used as a heat source, temperature measuring devices are arranged at different positions of the upper part, the middle part and the lower part of the adsorption reactor 8 and are interlocked with the heat source, and the accurate control of the temperature of the adsorption reactor 8 is realized.
The trichlorosilane after reaction and adsorption enters a trichlorosilane lightness removing tower 9 and a trichlorosilane heaving removing tower 10 to respectively carry out first-level lightness removing and first-level heaving removing, 50-100 theoretical plates of the two towers have the operation pressure of 50-500 KPa and the reflux feed ratio of 5-20: 1, and high-purity trichlorosilane, namely electronic-level trichlorosilane, is obtained from the top of the heaving removing tower, wherein boron impurities in the trichlorosilane are less than 0.02ppb, phosphorus impurities are less than 0.05ppb, and the total amount of metal impurities is less than 1 ppb. The high-purity trichlorosilane can be used as a raw material of high-purity zone-melting-grade polycrystalline silicon to prepare zone-melting-grade polycrystalline silicon on one hand, and can be directly used as electronic special gas for silicon epitaxial film deposition on the other hand.
The input hydrogen and the hydrogen recovered by reduction are purified. Firstly, performing primary purification by using an activated carbon adsorber 18, preferably selecting coconut shell activated carbon with large surface area from the activated carbon, and performing high-temperature anoxic activation on the activated carbon at 800-1500 ℃ to form abundant micropores in the activated carbon, wherein the pore diameter is 1-5 nm, and the specific surface area is 800-1500 m2The activated carbon can be in various forms such as column, granule, block and sphere, preferably spherical activated carbon to reduce fluid resistance and increase packing density, the particle size of the spherical activated carbon is 0.5-5 mm, and HNO is adopted3、H2SO4、H2O2Mixed acid bodyThe active carbon is oxidized and modified, so that the content of carboxyl and nitro is improved, and the trapping capacity of impurities is improved. Simultaneously, for further promoting the adsorption effect and the active carbon loading of active carbon adsorber 18, the bionic design is carried out to the active carbon inner structure, sets up regular hexagon honeycomb shape distributor for active carbon evenly distributed, simultaneously, the inside gas flow distribution is more even during the operation, effectively gets rid of impurity such as trichlorosilane, silicon tetrachloride, hydrogen chloride in the hydrogen.
In the step (2), part of the hydrogen purified by the activated carbon adsorber 18 is sent to a hydrogenation fluidized bed to participate in the synthesis of trichlorosilane, and part of the hydrogen is further purified deeply and is sent to the reduction furnace 1 to prepare zone-melting silicon (i.e. polysilicon). Wherein the hydrogen deep purification adopts two-stage purification, the first-stage purifier 17 is internally provided with a deoxygenation adsorbent to deeply remove trace O in the gas2、H2O、CO、CO2When impurities are contained, the primary purifier 17 can be provided with a plurality of parallel connection modes, and can work and regenerate alternately, so that the raw material gas can be purified continuously, and the continuous operation of the system is ensured. After adsorption saturation, regeneration can be carried out, wherein the regeneration gas is hydrogen, and the regeneration temperature is 100-500 ℃. The deoxidized adsorbent is metal oxide, specifically one or mixture of manganese oxide, nickel oxide, copper oxide, aluminum oxide, magnesium oxide and zinc oxide. The operation temperature of the primary purifier 17 is-30-300 ℃, and the pressure is 50-5000 KPa.
Preheating the hydrogen after the first-stage adsorption and purification, and then feeding the hydrogen into a second-stage purifier 16, wherein the operation temperature is 300-700 ℃, the pressure is 50-5000 KPa, and the N in the gas is treated2、CH4Deep removal is carried out, and the secondary purifier 16 is filled with metal alloy consisting of zinc, nickel, vanadium, iron, zirconium and platinum. After purification, O2、H2O、CO、CO2、N2、CH4And the content of other impurities is less than 1 ppb.
The high-purity trichlorosilane and the hydrogen are introduced into a reduction furnace 1, the hydrogen and the trichlorosilane are independently measured by a mass flow meter, the proportion of the hydrogen and the trichlorosilane can be accurately controlled, and the molar ratio of the hydrogen to the trichlorosilane is as follows: 2-5: 1. In order to improve the deposition efficiency and reduce the operation power consumption, high-purity dichlorosilane can be introduced, and the addition amount of the dichlorosilane is 2-10% of that of the trichlorosilane. Trichlorosilane, dichlorosilane and hydrogen react on the surface of the silicon rod, simple substance silicon is deposited on the surface of the silicon rod, and the deposition rate on the surface of the silicon rod is 0.2-2 mm/h.
The number of pairs of silicon rods in the reduction furnace 1 may be 12, 24, 36, 48, 64, and the reduction furnace 1 is increased in size as the number of silicon rods increases. The inner wall of the reduction furnace 1 is treated by silver plating, the thickness of a plating layer is 0.5-5 mm, the silver plating on the inner wall of the furnace barrel can reduce the precipitation of metal impurities of the furnace barrel to pollute the product quality, and meanwhile, the radiation effect of heat inside the furnace barrel is increased, so that the distribution of a thermal field is more uniform, and the reduction power consumption is reduced. The temperature in the reducing furnace 1 is 900-1200 ℃, and the pressure is 30-1000 KPa. The diameter of a silicon rod of the product is more than or equal to 100mm, the N-type resistivity is more than or equal to 1000 omega-cm, the total amount of metal impurities is less than or equal to 1ppb, and the purity of the product reaches 99.99999999999%.
The tail gas extracted from the reducing furnace 1 is recovered by adopting a dry deep cooling process, and a double-effect heat exchanger 2 is arranged. The heat exchange is carried out on the reduction tail gas and the raw material hydrogen, trichlorosilane and dichlorosilane of the reduction furnace 1, on one hand, the reduction tail gas is cooled, on the other hand, the raw material of the reduction furnace 1 is preheated, and the double-effect heat exchanger 2 is provided with a temperature difference of 2-10 ℃, so that the heat recovery is realized, and meanwhile, the heat exchange efficiency is ensured.
And (3) feeding the heat-exchanged reduction tail gas into a bubbling leaching tower 3, bubbling the reduction tail gas in chlorosilane in a tower kettle of a bubbling rectifying tower, leaching the reduction tail gas by using the chlorosilane, improving the gas-liquid exchange effect, separating the chlorosilane from gas in the tail gas by liquefaction, and collecting the separated chlorosilane from the bottom of the leaching tower to enter a dividing wall rectifying tower 7 for purification. The temperature of the leacheate ranges from-5 ℃ to 10 ℃, and the operating pressure of the bubbling leaching tower 3 ranges from 20 KPa to 100 KPa.
The method comprises the steps of pressurizing the washed reduced tail gas to 50-1000 KPa by using a tail gas compressor 4, increasing the pressure to be beneficial to improving the saturation temperature and reducing the grade of a tail gas cooling cold source, arranging a first step deep cooling heat exchange system 5 according to the difference of the saturated vapor pressure of each component in the tail gas, wherein the first step deep cooling heat exchange system 5 comprises a deep cooling and middle double-effect heat exchanger adopting refrigerants of different grades, and realizing the purpose of energy recovery while carrying out gas-liquid (chlorosilane and hydrogen) separation. The gas continuously enters a primary water cooler, a secondary water cooler, an intermediate double-effect heat exchanger and a terminal cooler, after-55 ℃ Freon is cooled in the terminal cooler, chlorosilane in the gas is basically and completely cooled, the intermediate double-effect heat exchanger exchanges heat with the compressed gas by using the gas after deep cooling, and the purpose of energy conservation is achieved.
And the dry cryogenic recovery system 6 separates out chlorosilane and hydrogen, wherein the chlorosilane comprises trichlorosilane, silicon tetrachloride, dichlorosilane and hexachlorodisilane. And separating the chlorosilane recovered by the dry method and synthesized by hydrogenation by using a dividing wall rectifying tower 7. Wherein chlorosilane firstly enters a dividing wall rectifying tower 7, the operation pressure is 50-500 KPa, and the reflux feed ratio is 5-20: 1. The feeding amount is controlled by controlling the temperature of the feeding measurement sensitive plate, the line extraction amount is controlled by controlling the temperature of the extraction measurement sensitive plate, the extraction of materials is carried out at the tower top and the tower kettle according to the temperature, the separation of dichlorosilane at the tower top is realized, trichlorosilane is extracted from the tower, and silicon tetrachloride and hexachlorodisilane are extracted from the tower kettle. Compared with the conventional method for separating two medium materials by one rectifying tower, the method can greatly reduce the number of the rectifying towers and reduce the investment and the operating cost.
In the step (3), dichlorosilane extracted from the top of the dividing wall rectifying tower 7 is returned to the reducing furnace 1 for utilization and participates in the preparation of polycrystalline silicon.
In the step (4), the trichlorosilane extracted from the tower enters the adsorption reactor 8 and the rectification process in the step (1) for purification to the PPb level, electronic grade trichlorosilane is generated, one part of the prepared electronic grade trichlorosilane is conveyed to the reduction furnace 1 for preparation of high-purity zone melting grade polycrystalline silicon, and the other part of trichlorosilane is synthesized to prepare electronic grade dichlorosilane by a catalytic disproportionation reaction method.
In the step (5), the mixture of silicon tetrachloride and hexachlorodisilane extracted from the tower kettle enters a silicon tetrachloride separation tower 19 for component separation, the theoretical plates are 70-120, the operating pressure is 50-500 KPa, the top temperature is 70-130 ℃, the reflux feed ratio is 5-10: 1, the silicon tetrachloride is separated from the tower top, and the hexachlorodisilane is separated from the tower kettle.
In the step (6), hexachlorodisilane extracted from the tower kettle enters a two-stage rectifying tower, the two towers run at low pressure, the running pressure is 0-50 KPa, and the hexachlorodisilane sequentially enters a hexachlorodisilane lightness-removing tower 27 and a hexachlorodisilane weight-removing tower 26 to respectively carry out first-stage lightness removal and first-stage weight removal, the theoretical plates of the two towers are 50-150, the top temperature is 140-180 ℃, and the reflux feed ratio is 5-10: 1. The light component removal tower is used for separating trace low-component impurities such as silicon tetrachloride and trichlorosilane in materials, high-boiling-point impurities such as octachloropropane and the like are extracted from a tower kettle of the heavy component removal tower, electronic-grade hexachlorodisilane is extracted from a tower top, the product components are more than or equal to 99.99%, and the product indexes of the electronic-grade hexachlorodisilane are met. The low temperature chemical vapor deposition process is used for producing high quality silicon nitride, silicon oxide and silicon oxynitride film in advanced semiconductor memory and logic chip manufacture.
In the step (5), a part of the separated silicon tetrachloride is preheated along with hydrogen and silicon powder and then introduced into the hydrogenation reactor 22, the prepared chlorosilane returns to the dividing wall rectifying tower 7 for component separation, and the recovered hydrogen returns to the hydrogenation reactor 22 for continuous cyclic utilization; the other part of the silicon tetrachloride is sequentially led into a photocatalysis chlorination coupling rectifying tower 28, a silicon tetrachloride lightness-removing tower 29 and a silicon tetrachloride heaving-removing tower 30 to prepare the optical fiber silicon tetrachloride.
Wherein, a part of the silicon tetrachloride extracted from the top of the silicon tetrachloride separating tower 19 enters a hydrogenation fluidized bed for preparing the trichlorosilane. The method comprises the steps of preheating silicon tetrachloride, hydrogen and silicon powder, then introducing the preheated silicon tetrachloride, hydrogen and silicon powder into a hydrogenation reactor 22, preheating at the temperature of 200-300 ℃, introducing hot nitrogen at the temperature of 300 ℃ to heat the silicon powder for drying, removing water in the silicon powder, allowing the dried silicon powder to flow to a silicon powder dense-phase conveying device 20 through gravity, replacing the nitrogen in the silicon powder in the device by the hydrogen through the silicon powder dense-phase conveying device 20, blowing the silicon powder into the hydrogenation reactor 22 through high-pressure hydrogen after replacement is qualified, realizing closed conveying of the silicon powder, and reducing dust pollution.
Reacting silicon powder in a fluidized bed layer in a hydrogenation reactor 22 with superheated hydrogen and silicon tetrachloride mixed gas at the reaction temperature of 500-700 ℃ and the reaction pressure of 2000-5000 KPa, installing a cyclone dust collector at the top of the reactor, returning the recovered silicon powder to the reactor again through a central pipe of the dust collector for utilization, introducing the gas from the side surface of the cyclone dust collector, discharging the gas from the top of the reactor, introducing the gas into a hydrogenation quenching tower 23 for washing and dust removal, rapidly reducing the temperature after the gas enters the hydrogenation quenching tower 23, washing unreacted silicon powder and metal chloride carried in the mixed gas, and concentrating and enriching the unreacted silicon powder and metal chloride at the bottom of the quenching tower. The cooled gas rises in the hydrogenation quenching tower 23, and is subjected to gas-liquid exchange with the spray liquid from the top of the tower, and further washed and cooled.
The second step deep cooling heat exchange system 24 comprises a multi-stage heat exchanger, and chlorosilane and hydrogen are separated by utilizing refrigerants with different tastes and the cooling capacity in the system. The gas continuously enters a primary water cooler, a secondary water cooler, an intermediate heat exchanger and a terminal cooler, after-55 ℃ Freon is cooled in the terminal cooler, chlorosilane in the gas is basically cooled completely, and a liquid chlorosilane mixture condensed by a hydrogenation quenching tower 23 and the heat exchanger is sent to a partition wall rectifying tower 7 for component separation. The hydrogen recovered by the second-step cryogenic heat exchange system 24 returns to the preheater 21 and the hydrogenation reactor 22 again for continuous recycling.
And purifying the other part of the silicon tetrachloride extracted from the top of the silicon tetrachloride separating tower 19 to prepare the optical fiber silicon tetrachloride. The method is characterized in that a photocatalytic chlorination coupling rectifying tower 28 is adopted to remove hydrogen-containing impurities such as trace methyl chlorosilane and trichlorosilane in silicon tetrachloride, the photocatalytic chlorination coupling rectifying tower 28 comprises a stripping section, a reaction section and a rectifying section, wherein tower plates or fillers are arranged in the stripping section and the rectifying section, the reaction section is a bulk quartz filler, the fillers can be quartz rods, quartz rings, quartz tubes and the like, light can penetrate through the quartz filler to be refracted, scattered and the like, and the light can penetrate through the filler in the reaction section. The wall of the tower plate at the filling section is provided with a plurality of sight glasses which are arranged in a layered manner, the sight glasses are made of quartz, ultraviolet light can penetrate through the sight glasses and then irradiate the sight glasses into the tower, an ultraviolet light source is arranged at the sight glasses, the wavelength of the light source is preferably 300, 365, 405 and 450nm, the wavelength of the light source can be selected from one or a plurality of combinations, energy is provided to dissociate chlorine into chloride ions, the chloride ions and hydrogen-containing impurities in the silicon tetrachloride are subjected to chlorination reaction and converted into substances with high chlorine content, so that the boiling point difference between the chloride ions and the silicon tetrachloride is increased, and the separation is performed through rectification. The operating pressure of a photocatalytic chlorination coupling rectifying tower 28 is 50-200 KPa, the top temperature is 70-97 ℃, the reflux feed ratio is 8-15: 1, silicon tetrachloride extracted from the top of the tower enters a subsequent two-stage rectifying tower, the first-stage lightness removal and the first-stage weight removal are respectively carried out, 70-120 theoretical plates of the two towers have the operating pressure of 50-500 KPa, the top temperature is 70-130 ℃, the reflux feed ratio is 5-10: 1, silicon tetrachloride with low hydrogen-containing impurities is extracted from the top of the heavy-removing tower, the infrared transmittance of the product is greater than or equal to 99%, the content of methyltrichlorosilane is less than 0.01ppm, the content of total metal impurities is less than 1ppb, the indexes of OVD, VAD and PCVD-grade optical fiber silicon tetrachloride products are met, and the photocatalytic chlorination coupling rectifying tower is used for preparing optical fiber preforms.
The prepared high-purity optical fiber silicon tetrachloride is used as a raw material and reacts with high-purity ethanol to prepare electronic-grade ethyl orthosilicate, the silicon tetrachloride and the ethanol enter an ethyl orthosilicate reactor 31 according to a set proportion, the molar ratio of the silicon tetrachloride to the ethanol is 1: 4-6, and the reaction temperature is as follows: 20-100 ℃, reaction time: 1-5 h, stirring speed: 100 to 1000 r/min. The reacted materials enter an ethyl orthosilicate separating tower 32, excessive ethanol which is not fully reacted is extracted from the top of the tower, the ethanol returns to an ethyl orthosilicate reactor 31 to react with the optical fiber silicon tetrachloride again, the non-condensable gas discharged from the top of the tower is mainly hydrogen chloride, and the cooled non-condensable gas can be sent to a hydrogenation reactor 22 for trichlorosilane synthesis. The tetraethoxysilane separation tower 32 is a plate tower or a packed tower, the number of theoretical plates is 50-80, the operation pressure is 50-200 KPa, and the reflux feed ratio is 5-10: 1.
And enabling tetraethoxysilane extracted from the tower kettle to enter an tetraethoxysilane lightness-removing tower 33 and an tetraethoxysilane weight-removing tower 34, and respectively carrying out first-level lightness removal and first-level weight removal, wherein the two towers run under negative pressure, the running pressure is-98 to-60 KPa, 50 to 150 theoretical plates are adopted, and the reflux feed ratio is 5-20: 1. The light component removal tower is used for separating trace low-component impurities such as silicon tetrachloride, ethanol, hydrogen chloride and the like in materials, high-boiling-point impurities such as metal impurities and the like are extracted from a tower bottom of the heavy component removal tower, electronic-grade ethyl orthosilicate is extracted from a tower top, the product components are more than or equal to 99.99%, the total metal impurities are less than or equal to 1ppb, the content of chloride ions is less than 0.1ppm, the water content is less than 10ppm, and the product indexes of the electronic-grade ethyl orthosilicate are met.
In the step (4), the prepared electronic grade trichlorosilane is used as a raw material, and a catalytic disproportionation reaction method is used for preparing the electronic grade dichlorosilane. The disproportionation reactor 11 is provided with two or more than two parallel-connected heat exchange tubes inside the disproportionation reactor 11, a jacket is arranged outside the disproportionation reactor 11, high-temperature water is used as a heat source, temperature detection is arranged at different positions of the upper part, the middle part and the lower part, and the high-temperature water is interlocked with the flow of the heat source, so that the accurate control of the temperature inside the disproportionation reactor 11 is realized. The operation temperature of the disproportionation reactor 11 is 20-100 ℃, the operation pressure is 200-1000 KPa, the material retention time is 10-30 min, the length-diameter ratio of the disproportionation reactor 11 is 2-80: 1, the inside of the disproportionation reactor is filled with catalytic resin, the resin is loaded with tertiary amine groups, quaternary amine groups or a mixture of the tertiary amine groups and the quaternary amine groups, the volume exchange capacity is more than or equal to 1.5eq/L, and the particle size is 400-1000 mu m.
The material at the outlet of the disproportionation reactor 11 enters a dichlorosilane separation tower 12, a rectifying tower is a plate tower or a packed tower, the number of theoretical plates is 50-150, the operating pressure is 200-1000 KPa, and the reflux feed ratio is 8-12: 1. And (3) introducing the top product mainly containing dichlorosilane into a two-stage rectifying tower, namely sequentially introducing a dichlorosilane lightness-removing tower 13 and a dichlorosilane heavy-removing tower 14, wherein the operating pressure is 50-500 KPa, performing first-stage lightness removal and first-stage heavy removal respectively, wherein 50-100 theoretical plates of the two towers have the top temperature of 20-70 ℃, and the reflux feed ratio is 8-15: 1. The lightness-removing tower is used for separating trace low-component impurities such as monochlorosilane, silane and the like in materials, high-boiling-point impurities such as trichlorosilane, silicon tetrachloride and the like are extracted from the tower bottom of the weight-removing tower, electronic-grade dichlorosilane is extracted from the tower top, the product components are more than or equal to 99.99 percent, the content of total metal impurities in the product is less than 1ppb, and the product index of the electronic-grade dichlorosilane is met.
The material extracted from the tower bottom of the dichlorosilane separation tower 12 is a mixture of trichlorosilane and silicon tetrachloride, a dichlorosilane recovery tower 25 is arranged to separate the trichlorosilane from the silicon tetrachloride, the separated trichlorosilane returns to the system again to be used as a raw material for disproportionation reaction, and the separated silicon tetrachloride can be used as a raw material for a hydrogenation reactor 22 or optical fiber silicon tetrachloride for recycling. The dichlorosilane recovery tower 25 is a plate tower or a packed tower, the number of theoretical plates is 50-100, the operation pressure is 50-300 KPa, and the reflux feed ratio is 8-10: 1.
The system has openness and extensibility, related products and materials of the system are high-purity media, and corresponding intermediate products and byproducts have low impurity content.
For example: when the silicon tetrachloride is used for synthesizing the ethyl orthosilicate product, a byproduct hydrogen chloride can be generated, and the hydrogen chloride can be recovered and purified by adopting a separation acid-making method to prepare electronic-grade hydrogen chloride.
The prepared tetraethoxysilane or high-purity silicon tetrachloride is used as a raw material to react with high-purity water to synthesize high-purity dioxide which is used for synthesizing high-purity quartz sand or an additive for semiconductor chemical mechanical polishing.
By utilizing the electronic-grade dichlorosilane preparation system, the prepared electronic-grade dichlorosilane product is used as a raw material, silane can be prepared by a reactor, and the subsequent rectifying tower is utilized to realize purification.
The prepared electronic-grade hexachlorodisilane is used as a raw material and reacts with lithium aluminum hydride or sodium aluminum hydride to prepare disilane.
Another embodiment of the present application provides an ultra-high purity polysilicon and silicon derivative production system, which comprises a mixer 15, a reduction furnace 1, a tail gas recovery device, a hydrogen purification device, a dividing wall rectifying tower 7, a hydrogenation fluidized bed, an adsorption reactor 8, a photocatalytic chlorination coupling rectifying tower 28, an ethyl orthosilicate reactor 31 and a disproportionation reactor 11.
An outlet of the mixer 15 is connected with an inlet of the reduction furnace 1, an outlet of the reduction furnace 1 is connected with a tail gas recovery device, the tail gas recovery device is respectively connected with an inlet of the dividing wall rectifying tower 7 and an inlet of the hydrogen purification device, the top of the dividing wall rectifying tower 7 is connected with an inlet of the mixer 15, an adsorption reactor 8, a trichlorosilane lightness-removing tower 9 and a trichlorosilane heavy-removing tower 10 are sequentially connected in the dividing wall rectifying tower 7, and a tower kettle of the dividing wall rectifying tower 7 is connected with a silicon tetrachloride separation tower 19.
The hydrogen purification device is respectively connected with the inlet of the mixer 15 and the inlet of the hydrogenation fluidized bed, and the outlet of the hydrogenation fluidized bed is connected with the inlet of the dividing wall rectifying tower 7.
The top of the silicon tetrachloride separating tower 19 is connected with the inlet of a hydrogenation fluidized bed and the inlet of a photocatalytic chlorination coupling rectifying tower 28, the outlet of the photocatalytic chlorination coupling rectifying tower 28 is sequentially connected with a silicon tetrachloride lightness-removing tower 29 and a silicon tetrachloride heaving-removing tower 30, and the bottom of the silicon tetrachloride separating tower 19 is sequentially connected with a hexachlorodisilane lightness-removing tower 27 and a hexachlorodisilane heaving-removing tower 26.
An outlet of the silicon tetrachloride heavy removal tower 30 is sequentially connected with an ethyl orthosilicate reactor 31, an ethyl orthosilicate separation tower 32, an ethyl orthosilicate light removal tower 33 and an ethyl orthosilicate heavy removal tower 34.
The outlet of the trichlorosilane de-heavy tower 10 is sequentially connected with a disproportionation reactor 11 and a dichlorosilane separation tower 12, the tower top of the dichlorosilane separation tower 12 is sequentially connected with a dichlorosilane lightness-removing tower 13 and a dichlorosilane de-heavy tower 14, the tower bottom of the dichlorosilane separation tower 12 is connected with the inlet of a dichlorosilane recovery tower 25, the tower top of the dichlorosilane recovery tower 25 is connected with the inlet of the disproportionation reactor 11, and the tower bottom of the dichlorosilane recovery tower 25 is connected with the inlet of a photocatalytic chlorination coupling rectifying tower 28.
Example 1
1. Purification of trichlorosilane
An adsorbent loaded with 2 mass percent of adsorbent is filled into an adsorption reactor 8, the adsorbent carrier is styrene-polyethylene styrene resin, the reagent is a mixture of diphenyl thiocarbazone, triphenylchloromethane, phenyl acetate and diphenyl sulfide in equal proportion, and oxygen is introduced from the bottom of the adsorption reactor 8, wherein the addition amount of the oxygen is 1000 times of the molar content of impurities in the trichlorosilane. The operating pressure of the adsorption reactor 8 is 500KPa, the operating temperature is 100 ℃, trichlorosilane enters a trichlorosilane light component removal tower 9 in a gaseous state, and then enters a trichlorosilane heavy component removal tower 10, 80 theoretical plates of the two towers have the operating pressure of 200KPa, the reflux feed ratio is 10:1, the top temperature is 68 ℃, electronic-grade trichlorosilane is extracted from the top of the heavy component removal tower, the boron impurity content in the product is 0.02ppb, the phosphorus impurity content is 0.04ppb, and the total metal impurity content is 0.8 ppb.
2. Purification of hydrogen
Purifying the hydrogen recovered by reduction, firstly, primarily purifying by using an activated carbon adsorber 18, preferably selecting coconut shell activated carbon with larger area from the activated carbon, and performing high-temperature oxygen-deficient activation on the activated carbon at 1200 ℃ to form abundant micropores in the activated carbon, wherein the pore diameter is 2nm, and the specific surface area is 1000m2The activated carbon is spherical activated carbon with the particle size of 0.5-5 mm for reducing the fluid resistance, and HNO is adopted3、H2SO4、H2O2The mixed acid system carries out oxidation modification on the activated carbon, so that the contents of carboxyl and nitro are improved, and the impurity trapping capacity is improved. The proportion of each acid in the mixed acid system is not required, and the mixed acid system can be prepared according to any proportion, which is not the key point to be protected in the scheme. Effectively remove impurities such as trichlorosilane, silicon tetrachloride, hydrogen chloride and the like in the hydrogen. One part of the hydrogen adsorbed by the activated carbon is sent to a hydrogenation fluidized bed for preparing electronic-grade trichlorosilane, and the other part of the hydrogen is further purified deeply and returned to the reduction furnace 1 for preparing zone-melting silicon.
The hydrogen enters a built-in deoxygenation adsorbent of a primary purifier 17 after the activated carbon adsorption, and trace O in the gas is deeply removed2、H2O、CO、CO2When impurities exist, the operation temperature of the primary purifier 17 is 80 ℃, the pressure is 200KPa, the deoxidation adsorbent is a mixture of manganese oxide, nickel oxide and copper oxide (the mixture ratio of the substances is not required, the mixture ratio can be any ratio, and the key point is not protected in the scheme), the impurities enter the secondary purifier 16 after being preheated, the operation temperature is 500 ℃, the pressure is 500KPa, and the impurities are used for treating N in the gas2、CH4Deep removal is carried out, and the secondary purifier 16 is filled with metal alloy consisting of zinc, nickel, vanadium, iron, zirconium and platinum (the proportion of each substance is not required, and any proportion can be adopted, which is not the key point to be protected in the scheme). After purification, O2、H2O、CO、CO2、N2、CH4The content of the impurities is less than 0.5ppb, and the purity of the hydrogen reaches 99.99999 percent.
3. Reduction reaction
And (2) introducing the trichlorosilane and the hydrogen into a reduction furnace 1, wherein the molar ratio of the trichlorosilane to the hydrogen is 3:1, 12 pairs of silicon rods are arranged in the reduction furnace 1, the inner wall of the reduction furnace is subjected to silver plating treatment, the thickness of a plating layer is 2mm, and the surface deposition rate of the silicon rods is 1.0 mm/h. The internal temperature of the reducing furnace 1 is 1100 ℃, the pressure is 100KPa, the diameter of a silicon rod is 120mm, the N-type resistivity is 2200 omega cm, the total amount of metal impurities is 0.6ppb, and the product purity reaches 99.99999999999%.
4. Recovery of reduction tail gas by dry method
And arranging a double-effect heat exchanger 2 to exchange heat between the reduction tail gas and the hydrogen, trichlorosilane and dichlorosilane which are used as raw materials of the reduction furnace 1, on one hand, cooling the reduction tail gas, on the other hand, preheating the raw materials of the reduction furnace 1, and setting the temperature difference of 10 ℃ in the double-effect heat exchanger 2. And (3) feeding the heat-exchanged reduction tail gas into a bubbling leaching tower 3, bubbling the reduction tail gas in chlorosilane in a tower kettle of a bubbling rectifying tower, leaching the reduction tail gas by using the chlorosilane, collecting the separated chlorosilane from the bottom of the leaching tower, and feeding the chlorosilane into a dividing wall rectifying tower 7 for purification. The temperature of the leacheate is 5 ℃, and the operating pressure of the bubbling leaching tower 3 is 50 KPa. The method comprises the steps of pressurizing the washed reduction tail gas to 800KPa by using a tail gas compressor 4, arranging a first step deep cooling heat exchange system 5, continuously feeding the gas into a first-stage water cooler, a second-stage water cooler, an intermediate double-effect heat exchanger and a terminal cooler, cooling by Freon at the temperature of-55 ℃ in the terminal cooler, and exchanging heat between the gas subjected to deep cooling and the compressed gas by using the intermediate double-effect heat exchanger after almost all the chlorosilane in the gas is cooled.
5. Dry condensate separation
And (3) recovering tail gas extracted from the reduction furnace 1 by dry cryogenic cooling, wherein the recovered chlorosilane firstly enters a dividing wall rectifying tower 7, the operating pressure is 200KPa, and the reflux feed ratio is 15: 1. The feeding amount is controlled by controlling the temperature of the feeding measurement sensitive plate, the line extraction amount is controlled by controlling the temperature of the extraction measurement sensitive plate, the extraction of materials is carried out at the tower top and the tower kettle according to the temperature, the separation of dichlorosilane at the tower top is realized, trichlorosilane is extracted from the tower, and silicon tetrachloride and hexachlorodisilane are extracted from the tower kettle.
And (3) feeding the mixture of the silicon tetrachloride and the hexachlorodisilane extracted from the tower bottom into a silicon tetrachloride separation tower 19 for component separation, wherein 80 theoretical plates are adopted, the operating pressure is 100KPa, the top temperature is 80 ℃, the reflux feed ratio is 7:1, the silicon tetrachloride is separated from the tower top, and the hexachlorodisilane is separated from the tower bottom.
6. Hydrogenation of silicon tetrachloride
The method comprises the steps of preheating silicon tetrachloride and hydrogen, then introducing the preheated silicon tetrachloride and hydrogen into a hydrogenation fluidized bed reactor, introducing hot nitrogen at the temperature of 300 ℃ to heat silicon powder for drying, removing moisture in the silicon powder, allowing the dried silicon powder to flow to a silicon powder dense-phase conveying device 20 through gravity, replacing the nitrogen in the silicon powder in the device by using the hydrogen through the silicon powder dense-phase conveying device 20, and blowing the silicon powder into a hydrogenation reactor 22 through high-pressure hydrogen after the silicon powder is qualified in replacement.
The silicon powder, hydrogen and silicon tetrachloride in the fluidized bed reactor are subjected to hydrogenation reaction at the reaction temperature of 600 ℃ and the reaction pressure of 3000KPa, the reacted gas enters a hydrogenation quenching tower 23, the temperature is rapidly reduced, the unreacted silicon powder and metal chloride carried in the mixed gas are washed, and the silicon powder and the metal chloride are concentrated and enriched at the bottom of the quenching tower. The cooled gas rises in the hydrogenation quenching tower 23, and is subjected to gas-liquid exchange with the spray liquid from the top of the tower, and further washed and cooled.
And arranging a second step deep cooling heat exchange system 24, continuously feeding the gas into a first-stage water cooler, a second-stage water cooler, an intermediate heat exchanger and a terminal cooler, cooling by-55 ℃ Freon in the terminal cooler, and feeding the liquid chlorosilane mixture condensed by the hydrogenation quenching tower 23 and the heat exchanger into a partition wall rectifying tower 7 for component separation after the chlorosilane in the gas is basically completely cooled. The hydrogen recovered by the second-step cryogenic heat exchange system 24 returns to the hydrogenation reactor 22 again for continuous recycling.
7. Preparation of electronic-grade hexachlorodisilane
Introducing hexachlorodisilane extracted from the tower kettle into a two-stage rectifying tower, wherein the two towers are operated at low pressure and 50KPa, and are respectively subjected to primary light weight removal and primary heavy weight removal, the top temperature of 120 theoretical plates of the two towers is 180 ℃, and the reflux feed ratio is 10: 1. The electronic-grade hexachlorodisilane is extracted from the top of the de-weighting tower, the product components are 99.99 percent, and the product index of the electronic-grade hexachlorodisilane is met.
8. Preparation of optical fiber silicon tetrachloride
The silicon tetrachloride extracted from the top of the silicon tetrachloride separating tower 19 enters a photocatalytic chlorination coupled rectifying tower 28, the photocatalytic chlorination coupled rectifying tower 28 comprises a stripping section, a reaction section and a rectifying section, wherein tower plates or fillers are arranged in the stripping section and the rectifying section, the reaction section is a random quartz filler, the filler is a quartz ring, an ultraviolet light source is arranged at a sight glass, the wavelength of the light source is 405nm, the operating pressure of the tower is 100KPa, the top temperature is 80 ℃, the reflux feed ratio is 15:1, the silicon tetrachloride extracted from the top of the tower enters a subsequent two-stage rectifying tower, primary light removal and primary weight removal are respectively carried out, 100 theoretical plates of the two towers are 100, the operating pressure is 100KPa, the top temperature is 80 ℃, the reflux feed ratio is 10:1, the silicon tetrachloride with low hydrogen-containing impurities is extracted from the top of the heavy tower, the infrared transmittance of the product is more than or equal to 99%, the content of methyltrichlorosilane is less than 0.01ppm, and the content of total metal impurities is 0.9 ppb.
9. Preparation of electronic grade ethyl orthosilicate
High-purity silicon tetrachloride is used as a raw material, and the high-purity silicon tetrachloride and high-purity ethanol enter an ethyl orthosilicate reactor 31 according to a set proportion, wherein the molar ratio of the silicon tetrachloride to the ethanol is 1:5, and the reaction temperature is as follows: 50 ℃, reaction time: 4h, stirring speed: 600 r/min. The reacted materials enter an ethyl orthosilicate separating tower 32, excessive ethanol which is not fully reacted is extracted from the top of the tower, the ethanol returns to an ethyl orthosilicate reactor 31 to react with the silicon tetrachloride again, the ethyl orthosilicate separating tower 32 is a packed tower, the number of theoretical plates is 60, the operating pressure is 50KPa, and the reflux feed ratio is 6: 1.
The ethyl orthosilicate extracted from the tower kettle enters a two-stage rectifying tower, the two towers run at negative pressure of-90 KPa, and are respectively subjected to primary light weight removal and primary heavy weight removal, the theoretical plates of the two towers are 120, and the reflux feed ratio is 15: 1. The electronic-grade ethyl orthosilicate is extracted from the top of the de-weighting tower, the product component is 99.994%, the total metal impurities are 0.4ppb, the chloride ion content is 0.08ppm, and the water content is 7ppm, so that the product index of the electronic-grade ethyl orthosilicate is met.
10. Preparation of electronic-grade dichlorosilane
The prepared electronic grade trichlorosilane enters a disproportionation reactor 11, the water amount of a jacket and a tube array of the disproportionation reactor 11 is adjusted by hot water, the temperature of the reactor is controlled to be 50 ℃, the operating pressure is 500KPa, the material retention time is 20min, the length-diameter ratio of the reactor is 60:1, the catalytic resin in the reactor is loaded with tertiary amine groups, the volume exchange capacity is 1.5eq/L, and the particle size is 600-700 mu m.
The material at the outlet of the disproportionation reactor 11 enters a dichlorosilane separation tower 12, the rectifying tower is a plate tower, the number of theoretical plates is 70, the operating pressure is 450KPa, and the reflux feed ratio is 8: 1. The product extracted from the tower top is mainly dichlorosilane, enters a dichlorosilane light component removal tower 13 and a dichlorosilane heavy component removal tower 14, the operation pressure is 200KPa, the top temperature is 42 ℃, and the reflux feed ratio is 10:1, wherein the theoretical plate number is 60. Electronic-grade dichlorosilane is extracted from the top of the dichlorosilane de-weighting tower 14, the product components are 99.995%, and the total metal impurity content in the product is 0.6ppb, so that the indexes of electronic-grade dichlorosilane products are met.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; may be mechanically coupled, may be electrically coupled or may be in communication with each other; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (12)
1. A production process of ultra-pure polysilicon and silicon derivatives is characterized in that trichlorosilane, dichlorosilane and hydrogen are introduced into a reduction furnace to prepare polysilicon, and tail gas containing chlorosilane and hydrogen is recycled;
conveying one part of the recovered hydrogen after deep purification to a reduction furnace to participate in preparation of polysilicon, conveying the other part of the recovered hydrogen to a hydrogenation fluidized bed to participate in synthesis of trichlorosilane, introducing the recovered chlorosilane into a dividing wall rectifying tower, and extracting dichlorosilane, trichlorosilane, silicon tetrachloride and hexachlorodisilane;
conveying dichlorosilane extracted from the dividing wall rectifying tower to a reducing furnace to participate in preparing polycrystalline silicon;
preparing electronic-grade trichlorosilane from trichlorosilane extracted by a dividing wall rectifying tower, conveying one part of the prepared electronic-grade trichlorosilane to a reduction furnace to participate in preparation of polycrystalline silicon, and preparing electronic-grade dichlorosilane from the other part of the prepared electronic-grade trichlorosilane by a catalytic disproportionation reaction method;
conveying one part of silicon tetrachloride extracted from a dividing wall rectifying tower to a hydrogenation fluidized bed to participate in synthesizing electronic-grade trichlorosilane, purifying the other part of silicon tetrachloride to prepare optical fiber silicon tetrachloride, and reacting the prepared optical fiber silicon tetrachloride with ethanol to synthesize electronic-grade ethyl orthosilicate;
and (3) preparing electronic-grade hexachlorodisilane from the hexachlorodisilane extracted from the dividing wall rectifying tower.
2. The production process of ultra-high purity polysilicon and silicon derivatives according to claim 1, wherein the preparation method of the electronic grade trichlorosilane comprises the following steps: trichlorosilane extracted from the dividing wall rectifying tower is sequentially introduced into an adsorption reactor, a trichlorosilane lightness-removing tower and a trichlorosilane weight-removing tower, wherein the adsorption reactor is filled with an adsorbent loaded with a reagent, and oxygen, ozone or a mixture of the oxygen and the ozone are introduced into the adsorption reactor.
3. The process for producing ultra-high purity polysilicon and silicon derivatives as claimed in claim 2, wherein the reagent is one or more selected from diphenylthiocarbazone, triphenylchloromethane, phenyl acetate, diphenyl sulfide, aluminum chloride, benzaldehyde, cinnamaldehyde and their derivatives, the loading amount of the reagent is 0.5-10 wt%, and the water content is less than 0.5%.
4. The production process of ultra-high purity polysilicon and silicon derivatives according to claim 1, wherein the hydrogen is firstly introduced into an activated carbon adsorber for preliminary purification, part of the purified hydrogen is conveyed to a hydrogenation fluidized bed to participate in synthesis of trichlorosilane, and the other part of the purified hydrogen is firstly introduced into a first-stage purifier and a second-stage purifier for deep purification, then is introduced into a mixer to be mixed with dichlorosilane and trichlorosilane, and then is introduced into a reduction furnace for preparation of polysilicon.
5. The process for producing ultra-high purity polysilicon and silicon derivatives as claimed in claim 4, wherein the activated carbon adsorber is filled with spherical coconut shell activated carbon and HNO3、H2SO4、H2O2The mixed acid system is used for carrying out oxidation modification on the coconut shell activated carbon.
6. The process for producing ultra-high purity polysilicon and silicon derivatives as claimed in claim 4, wherein the first purifier is filled with a deoxidized adsorbent, the deoxidized adsorbent is metal oxide, and the second purifier is filled with metal alloy.
7. The process for producing ultra-high purity polysilicon and silicon derivatives as claimed in claim 1, wherein the number of pairs of silicon rods in the reduction furnace is 12, 24, 36, 48 or 64, the inner wall of the reduction furnace is treated by silver plating, and the molar ratio of hydrogen and trichlorosilane introduced into the reduction furnace is: 2-5: 1, wherein the addition amount of dichlorosilane is 2-10% of that of trichlorosilane, the internal temperature of the reducing furnace is 900-1200 ℃, and the pressure is 30-1000 Kpa.
8. The production process of the ultra-high purity polysilicon and the silicon derivatives according to claim 1, wherein the tail gas of the reduction furnace is recovered by a dry cryogenic process, a double-effect heat exchanger is arranged to exchange heat between the tail gas and the reduction furnace raw material hydrogen, trichlorosilane and dichlorosilane, the tail gas after heat exchange enters a bubbling leaching tower, the tail gas is leached by chlorosilane, the chlorosilane in the tail gas is liquefied and separated from the gas, the separated chlorosilane is leached and extracted from the bottom of the tower, and the separated chlorosilane enters a dividing wall rectifying tower for purification; and introducing unseparated tail gas into a tail gas compressor and a first step cryogenic heat exchange system in sequence to separate hydrogen from chlorosilane, introducing the separated hydrogen into an activated carbon adsorber for purification and recycling, and introducing the separated chlorosilane into a dividing wall rectifying tower.
9. The process for producing ultra-high purity polysilicon and silicon derivatives as claimed in any one of claims 1 to 8, wherein the silicon tetrachloride and hexachlorodisilane extracted from the column bottom of the dividing wall rectifying column are introduced into a silicon tetrachloride separating column, and the separated hexachlorodisilane sequentially enters a hexachlorodisilane lightness-removing column and a hexachlorodisilane weight-removing column to prepare electronic-grade hexachlorodisilane;
preheating a part of the separated silicon tetrachloride along with hydrogen and silicon powder, then introducing the preheated silicon tetrachloride into a hydrogenation reactor, returning the prepared chlorosilane to a dividing wall rectifying tower for component separation, and returning the recovered hydrogen to the hydrogenation reactor for continuous cyclic utilization;
and the other part of the separated silicon tetrachloride sequentially passes through a photocatalysis chlorination coupling rectifying tower, a silicon tetrachloride lightness-removing tower and a silicon tetrachloride heaving-removing tower to prepare the optical fiber silicon tetrachloride.
10. The process for producing ultra-high purity polysilicon and silicon derivatives as claimed in claim 9, wherein the preparation method of the electronic grade tetraethoxysilane comprises the following steps: and (2) introducing the prepared optical fiber silicon tetrachloride and ethanol into an ethyl orthosilicate reactor, introducing the reacted materials into an ethyl orthosilicate separation tower, returning the separated excessive ethanol to the ethyl orthosilicate reactor for recycling, and sequentially introducing the separated ethyl orthosilicate into an ethyl orthosilicate lightness-removing tower and an ethyl orthosilicate heaving-removing tower to prepare the electronic grade ethyl orthosilicate.
11. The production process of the ultra-high purity polysilicon and the silicon derivatives according to claim 4, wherein the preparation method of the electronic-grade dichlorosilane comprises the following steps: introducing the prepared electronic grade trichlorosilane into a disproportionation reactor, introducing the reacted materials into a dichlorosilane separation tower, separating dichlorosilane from the tower top of the dichlorosilane separation tower, and separating trichlorosilane and silicon tetrachloride from the tower kettle;
wherein, dichlorosilane is sequentially introduced into a dichlorosilane lightness-removing tower and a dichlorosilane heavy-removing tower to prepare electronic-grade dichlorosilane;
trichlorosilane and silicon tetrachloride are fed into a dichlorosilane recovery tower to separate trichlorosilane and silicon tetrachloride, the separated trichlorosilane returns to the disproportionation reactor again for cyclic utilization, and the separated silicon tetrachloride is fed into the hydrogenation reactor or the photocatalytic chlorination coupling rectifying tower for cyclic utilization.
12. A production system of ultra-pure polysilicon and silicon derivatives is characterized by comprising a mixer, a reduction furnace, a tail gas recovery device, a hydrogen purification device, a dividing wall rectifying tower, a hydrogenation fluidized bed, an adsorption reactor, a photocatalytic chlorination coupling rectifying tower, an ethyl orthosilicate reactor and a disproportionation reactor;
an outlet of the mixer is connected with an inlet of the reduction furnace, an outlet of the reduction furnace is connected with a tail gas recovery device, the tail gas recovery device is respectively connected with an inlet of the dividing wall rectifying tower and an inlet of the hydrogen purification device, the top of the dividing wall rectifying tower is connected with an inlet of the mixer, an adsorption reactor, a trichlorosilane lightness-removing tower and a trichlorosilane heavy-removing tower are sequentially connected in the dividing wall rectifying tower, and a tower kettle of the dividing wall rectifying tower is connected with a silicon tetrachloride separation tower;
the hydrogen purification device is respectively connected with the inlet of the mixer and the inlet of the hydrogenation fluidized bed, and the outlet of the hydrogenation fluidized bed is connected with the inlet of the dividing wall rectifying tower;
the top of the silicon tetrachloride separation tower is connected with an inlet of a hydrogenation fluidized bed and an inlet of a photocatalytic chlorination coupling rectifying tower, an outlet of the photocatalytic chlorination coupling rectifying tower is sequentially connected with a silicon tetrachloride lightness-removing tower and a silicon tetrachloride heavy-removing tower, and a tower kettle of the silicon tetrachloride separation tower is sequentially connected with a hexachlorodisilane lightness-removing tower and a hexachlorodisilane heavy-removing tower;
the outlet of the silicon tetrachloride heavy-duty removal tower is sequentially connected with an ethyl orthosilicate reactor, an ethyl orthosilicate separation tower, an ethyl orthosilicate light-duty removal tower and an ethyl orthosilicate heavy-duty removal tower;
the outlet of the trichlorosilane de-heavy tower is sequentially connected with a disproportionation reactor and a dichlorosilane separation tower, the tower top of the dichlorosilane separation tower is sequentially connected with a dichlorosilane light-ends removal tower and a dichlorosilane de-heavy tower, the tower kettle of the dichlorosilane separation tower is connected with the inlet of a dichlorosilane recovery tower, the tower top of the dichlorosilane recovery tower is connected with the inlet of the disproportionation reactor, and the tower kettle of the dichlorosilane recovery tower is connected with the inlet of a photocatalytic chlorination coupling rectifying tower.
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