CN102234117B - A kind of method for hydrolysis of the material containing hydrolyzable halogen atom - Google Patents
A kind of method for hydrolysis of the material containing hydrolyzable halogen atom Download PDFInfo
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- CN102234117B CN102234117B CN201010162174.XA CN201010162174A CN102234117B CN 102234117 B CN102234117 B CN 102234117B CN 201010162174 A CN201010162174 A CN 201010162174A CN 102234117 B CN102234117 B CN 102234117B
- Authority
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- China
- Prior art keywords
- halogen atom
- hydrolyzable halogen
- reaction
- hydrolysis
- gas
- Prior art date
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Links
- 238000000034 method Methods 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 106
- 125000005843 halogen group Chemical group 0.000 title claims abstract description 100
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 55
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 239000007789 gas Substances 0.000 claims abstract description 85
- 239000000047 product Substances 0.000 claims abstract description 69
- 238000002156 mixing Methods 0.000 claims abstract description 51
- 239000000376 reactant Substances 0.000 claims abstract description 46
- 239000007787 solid Substances 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 238000000746 purification Methods 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- 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 description 40
- 239000005049 silicon tetrachloride Substances 0.000 claims description 40
- 239000012265 solid product Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000003860 storage Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 229920005591 polysilicon Polymers 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 23
- 239000005052 trichlorosilane Substances 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 19
- 239000005046 Chlorosilane Substances 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 18
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 18
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 18
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 229960001866 silicon dioxide Drugs 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 239000002912 waste gas Substances 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 9
- 230000009102 absorption Effects 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 7
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000002910 solid waste Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims 1
- 230000006835 compression Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract description 16
- 239000012433 hydrogen halide Substances 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 150000004820 halides Chemical class 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 description 27
- 150000002431 hydrogen Chemical class 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 3
- 229960000359 chromic chloride Drugs 0.000 description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 235000011147 magnesium chloride Nutrition 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 208000011117 substance-related disease Diseases 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910008045 Si-Si Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 229910006411 Si—Si Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- APFVFJFRJDLVQX-AHCXROLUSA-N indium-111 Chemical compound [111In] APFVFJFRJDLVQX-AHCXROLUSA-N 0.000 description 2
- 229940055742 indium-111 Drugs 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 waste gas Chemical compound 0.000 description 2
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 102100024304 Protachykinin-1 Human genes 0.000 description 1
- 101800003906 Substance P Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HICCMIMHFYBSJX-UHFFFAOYSA-N [SiH4].[Cl] Chemical compound [SiH4].[Cl] HICCMIMHFYBSJX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 239000003637 basic solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SAUMVKNLVQDHMJ-UHFFFAOYSA-N dichlorine trioxide Inorganic materials ClOCl(=O)=O SAUMVKNLVQDHMJ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a kind of flow process short, less investment, the method for hydrolysis of the material containing hydrolyzable halogen atom easy and simple to handle, is carry out mixing, reacting with reaction member mixing containing material and the moisture material of hydrolyzable halogen atom; Control reaction conditions and make at least one reactant complete reaction as far as possible, especially crucially making to obtain reaction product is dry soild oxide and gas hydrogen halide, soild oxide product shifts out from gas solid separation and purification unit, and gas halides hydrogen product is via the process of gaseous product clean unit.The soild oxide that the method obtains and hydrogen halide are valuable commodity, and hydrogen halide also can be used for halid synthesis procedure.The method may be used for the process of the trade waste containing hydrolyzable halogen atom, also may be used for the compound containing hydrolyzable halogen atom for raw material production soild oxide and hydrogen halide product.
Description
Technical field
The present invention relates to a kind of method for hydrolysis of the material containing hydrolyzable halogen atom, especially the method for hydrolysis containing the tail gas of hydrolyzable halogen atom, waste liquid or solid waste and their mixtures produced in Industrial processes, also can be with containing the compound of hydrolyzable halogen atom and water for the method for soild oxide and hydrogen halide product to be produced by raw material by hydrolysis reaction.
Technical background
Organosilicon industry and polysilicon industry based on technical grade Pure Silicon Metal and chlorine or muriatic reaction, also can be normally the reactions of technical grade Pure Silicon Metal and other halogens (as fluorine, bromine, iodine or their compound).These reactions can produce a large amount of halogenide wastes.
Methyl chlorosilane is the important monomer of organosilicon industry.At present, generally adopt methyl chloride and silica flour both at home and abroad under the existence of copper catalyst, directly synthesize chlorosilane monomer.In the process, except target product dimethyldichlorosilane(DMCS), also have some by products.Its mid-boiling point is called high boiling material more than the part of 70 DEG C, accounts for 7 ~ 8% of crude monomer total amount; Boiling point is called low-boiling-point substance lower than the part of 40 DEG C, accounts for 1 ~ 2% of crude monomer total amount.Wherein said high boiling material is a kind of dark reddish brown, has a mixing liquid of aggressive with irritating smell, and normal temperature and pressure lower density is at about 1.139g/mL, and boiling range 80 ~ 215 DEG C, wherein main ingredient about has 30 multiple compounds.The composition of high boiling material and organosilane monomer produce in silica flour, the purity of methyl chloride, the character of catalyzer and reaction conditions etc. closely related, in the different batches of the even same production technique of various processes the composition of high boiling material and content all different.Therefore, the report of relevant high boiling material composition is also not quite similar both at home and abroad, but substantially thinks that it mainly consists of the compound containing Si-Si, Si-O-Si, Si-CH2-Si, and wherein hydrolyzable C1 atomicity is 1.2 ~ 2.8 with the ratio of Si atomicity.Said low-boiling-point substance refers to that the boiling point that produces in synthesizing methyl-chloro-silane monomer is lower than the material of 40 DEG C.Identical with high boiling material, the composition of low-boiling-point substance is subject to the impact of the purity of silica flour, the character of catalyzer and reaction conditions etc. equally, and in the different batches of the even same production line of different production line, the composition of low-boiling-point substance and content are not quite similar.It is generally acknowledged that the main component of low-boiling-point substance is methyl chlorosilane and a small amount of hydrocarbon polymer.And wherein topmost composition is (CH
3)
4si and (CH
3)
2hSiCl.
Industrial polysilicon is obtained through chemical method or Physical purification by technical grade Pure Silicon Metal.Polysilicon can be divided into solar-grade polysilicon (SG) (silicone content is (4N ~ 6N) between 99.99% ~ 99.9999%) and electronic-grade polycrystalline silicon (EG) (silicone content general requirement is greater than 99.9999% (6N), between ultra-high purity reaches 99.9999999% ~ 99.999999999% (9N ~ 11N)).The polysilicon of more than 80% is produced by Siemens process or improvement Siemens process in the world at present, adopt technical grade Pure Silicon Metal and hydrogen halide to react and generate halosilanes or silane, halosilanes or silane are after purifying, at high temperature there is deposition reaction and generate highly purified polysilicon, mainly comprise following process:
1) technical grade metallic silicon power and hydrogenchloride react and generate hydrogen, a chlorine three hydrogen silicon, dichlorosilane, trichlorosilane, silicon tetrachloride and high boiling point polychlorostyrene silane etc. in fluidized-bed reactor.Wherein primary product is that trichlorosilane accounts for 80 ~ 85%, and silicon tetrachloride accounts for 10 ~ 15%.High boiling point polychlorostyrene silane refers to the compound that silicon, chlorine and possible hydrogen, oxygen, carbon etc. be made up of of boiling point higher than silicon tetrachloride boiling point, mainly containing oligomeric (chlorine) silane, oligosiloxane etc. of 2 ~ 4 Siliciumatoms.In addition, in metallic silicon power, some impurity also can generate the impurity chlorides such as aluminum chloride, titanium tetrachloride, boron trichloride, magnesium dichloride, dichloride copper, iron trichloride, chromium trichloride, Nickel Chloride, Indium-111 chloride, gallium trichloride, phosphorus trichloride and phosphorus pentachloride with hcl reaction.
2) gaseous product generated in chlorosilane synthesis reactor is separated with unreacted metallic silicon power, enter trichlorosilane rectifying tower after condensation, obtains highly purified trichlorosilane.Wherein, the lower boiling muriate that the material that boiling point is lower generates as hydrogen, a chlorine three hydrogen silicon and dichlorosilane, impurity etc. are discharged from fractionation tower top becomes tail gas, enters exhaust treatment system.Silicon tetrachloride Yield compari@is large needs individual curing, and the high boiling point muriate that high boiling point polychlorostyrene silane and impurity generate and the metallic silicon power carried secretly into from fluidized-bed reactor are discharged from Fractionator Bottom to be become vinasse and enter liquid waste treatment system.
3) trichlorosilane hydrogen is under the high temperature of about 1000 DEG C, and hydrogenolysis reducing generates polysilicon, produces a large amount of tail gas simultaneously.Tail gas comprises hydrogen, trichlorosilane, a chlorine three hydrogen silicon, dichlorosilane, silicon tetrachloride, high boiling point polychlorostyrene silane etc.Wherein hydrogen and trichlorosilane can reclaim the production for polysilicon; The amount of one chlorine three hydrogen silicon, dichlorosilane is little, generally enters exhaust treatment system; High boiling point polychlorostyrene silane enters liquid waste treatment system; Wherein 1t polysilicon can by-product 10 ~ 15t silicon tetrachloride, and output is very large needs individual curing.
4) improve in Siemens process, it is trichlorosilane that silicon tetrachloride as by-product passes through hydroconverted, and have cold hydrogenation and hot hydrogenation two kinds of techniques, its per pass conversion is all very low, only has about 20%.The modern technique of these techniques is the monopolization of external major company, because strategic concerns is not to domestic enterprise's transferring technology.These two kinds of techniques of domestic research and development are also very immature, can not steady running, and energy consumption is very large, and the cost producing trichlorosilane with it is higher than the cost of Pure Silicon Metal and hcl reaction.
In addition, in the industrial production of metal halide, also often adopt metal simple-substance and halogen reacts or metal oxide, carbon and halogen react and produce, the waste that these reactions also can produce containing hydrolyzable halide.
The production of industrial titanium tetrachloride is normally by TiO
2the rutile ore of content 80%, artificial rutile or titanium slag, coke and chlorine are in ebullated bed chlorination furnace, and 950 ~ 1000 DEG C of reactions are obtained.At TiO
2while chlorination, the impurity in ore deposit also participates in chlorination reaction and generates the muriate containing hydrolyzable chlorine such as iron trichloride, silicon tetrachloride, aluminum chloride, vanadium oxytrichloride, manganous chloride, tin tetrachloride, magnesium dichloride.After being cooled to about 200 DEG C from chlorination furnace reactant gases out, the impurity chlorides that major part boiling point is high can be condensate on ashes and precipitate, the impurity chlorides that low-boiling impurity chlorides is high with small part boiling point can be got off with titanium tetrachloride condensation, is separated in follow-up titanium tetrachloride rectifying.This process can produce the solid waste such as a large amount of ashes containing hydrolyzable chlorine and a large amount of tail gas and vinasse containing hydrolyzable chlorine.
Industrial boron trichloride is normally produced by the chlorination reaction of the sinter of chlorine and boron simple substance or chlorine and boron trioxide and carbon dust.Can produce the muriate containing hydrolyzable chlorine such as silicon tetrachloride, tin tetrachloride, titanium tetrachloride, dichloride copper, iron trichloride, chromium trichloride, vanadium oxytrichloride in this reaction process, these muriates are usually separated at the chlorination furnace of boron trichloride production or rectifying tower and are used as byproduct or waste.
Produce in above-mentioned Industrial processes a large amount of tail gas containing hydrolyzable halogen atom, waste liquid, solid waste and or their mixture.These materials containing hydrolyzable halogen atom very easily produce hydrogen halide with the reaction of moisture in air, in discharge, storage process, all can cause huge pollution to ecotope.Along with China's expanding economy, the further expansion of commercial production scale, the absolute quantity of these by products is also come more.
For polysilicon industry, due to the fast development of solar photovoltaic industry, drive increasing sharply of China's polysilicon production capacity in recent years.Estimate 2010, Chinese polysilicon output will reach 40,000 tons, and only this kind of by product output of silicon tetrachloride will reach 400,000 tons ~ 600,000 tons, and quantity is very huge.Silicon tetrachloride is high toxic material, has intense stimulus to the eyes of people, skin, respiratory tract; Run into damp atmosphere to decompose immediately, generate silicic acid and hydrogenchloride.Just discharge if not treated or bury silicon tetrachloride, by serious environment pollution, even bringing eco-catastrophe, make discharge ground or bury ground animals and plants become extinct completely.On March 9th, 2008, U.S.'s Washington Post is to be entitled as the article of " Sunpower Corp. leaves China for rubbish ", and the silicon tetrachloride pollution problem of domestic polysilicon enterprise of report China, this section of article is once occurring becoming rapidly network focus.Can not rant out, for numerous domestic production of polysilicon enterprise, silicon tetrachloride pollution problem is just as being suspended on the sharp sword on their head, and the moment determines the destiny of these enterprises.Therefore, to silicon tetrachloride be representative containing the tail gas of hydrolyzable halogen atom, waste liquid, solid waste and or they mixture harmless treatment and recycle and become the task of top priority!
In order to process produce in above-mentioned Industrial processes containing the tail gas of hydrolyzable halogen atom, waste liquid, solid waste and or their mixture.The waste gas containing chlorosilane such as waste gas, reduction furnace start-stop car, accidental discharge waste gas, chlorosilane storage procedure storage tank safety relief gas, polysilicon reducing furnace tail gas process absorption waste gas of technique of trichlorosilane synthetic tail gas, the discharge of Trichlorosilane purification operation rectifying tower in current production of polysilicon factory, all sends into the washing of waste gas eluting column with pipeline.Waste gas after eluting column continuous washing, go out washings at the bottom of tower through in alkali lye and after, with being pumped into process residue treatment process, tail gas through 15m height aiutage discharge.The waste liquid that the chlorine-containing silanes such as clean chlorosilane raffinate are put in that Trichlorosilane purification operation rectifying tower is discharged, mainly containing silicon tetrachloride, polychlorostyrene silane compound and a small amount of metallic silicon power cauldron bottom residue and device parking is all admitted to raffinate receiving tank.Then with nitrogen, liquid is extruded, send into the washing of raffinate eluting column, then carry out neutralization disposal with alkali lye.Chlorosilane in waste liquid and alkali lye react and are converted to harmless material.These treatment processs consume a large amount of alkali and water, only achieve the harmless treatment of waste gas, waste liquid, consume ample resources, also bring the discharge of a large amount of waste water and waste residue, very uneconomical, not environmentally.
US4,597,983 production methods disclosing a kind of fumed silica, silicon tetrachloride gas and steam reaction directly generate fumed silica.US4,610,892 production methods disclosing a kind of fumed silica, the method is at 500 ~ 1000 DEG C, and silicon tetrachloride gas, fluorochemicals gas and steam reaction generate fluorine-containing fumed silica.US4,738,839 disclose a kind of silicon tetrachloride liquid-phase hydrolysis in fluorine-containing system produces the method for crystalline silica.US4,976,943 disclose a kind of mol ratio 2: 1 ~ 8: 1 water vapour and gas phase silicon tetrachloride 300 ~ 400 DEG C of mixing, and produce the method for spherical hydrophilic silicon dioxides 600 ~ 1200 DEG C of reactions.US4,826,521 production methods disclosing a kind of pole pure silicon dioxide, the method is by silicon tetrachloride and water mixed hydrolysis, control the mol ratio of silicon tetrachloride and water 0.031 ~ 0.012: 1, make reaction product generate gel, then by distillation, the HCl in gel is driven away, drier at 100 ~ 1000 DEG C.US4,572,729 disclose a kind of liquid silicon tetrachloride as polysilicon by-product and substoichiometric water reacts the method producing silica glass silicon-dioxide.
CN101,172,610 disclose a kind of basic solution and hydrogeneous halosilanes or alkyl halosilanes or silicon tetrachloride or their mixture is hydrolyzed, precipitates the method producing silicon-dioxide powdery.CN100,369,811 method of comprehensive utilization disclosing the by product in a kind of polysilicon production process are vaporized by by product, with the mixed firing such as oxygen, hydrogen, the nano silicon of high-temperature hydrolysis high-purity low chlorine content.CN1,222,472 to disclose a kind of be raw material and the mixed firing such as oxygen, hydrogen with halosilanes, and high-temperature hydrolysis produces the method for high-dispersion nano silicon-dioxide.CN1,282,603 disclose a kind of with halosilanes mixture be raw material and air, hydrogen mixed firing, the method for high-temperature hydrolysis production of silica white.CN1,803,603 disclose a kind of with silicon tetrachloride and the second silicon source and air, hydrogen mixed firing, and control flame temperature 1670 ~ 1730 DEG C, produces the method for silicon-dioxide.CN1,803,604 and US7,491,375 disclose a kind of with silicon tetrachloride and the second silicon source and air, hydrogen mixed firing, and control flame temperature 1570 ~ 1630 DEG C, produces the method for silicon-dioxide.CN1,803,605 and US7,351,388 disclose a kind of with silicon tetrachloride and the second silicon source and air, hydrogen mixed firing, and control flame temperature 1390 ~ 1450 DEG C, produces the method for silicon-dioxide.CN1,803,606 and US2006/0,154,994 disclose a kind of with silicon tetrachloride and the second silicon source and air, hydrogen mixed firing, and control flame temperature 1810 ~ 1890 DEG C, produces the method for silicon-dioxide.
CN101,337,674 disclose a kind of method that production of polysilicon waste and metal reaction generate silicon and metal chloride, and silicon can through purifying as polysilicon commodity, and metal chloride is through electrolysis production chlorine and metal simple-substance.US5,597,540 disclose the method that one is the waste gas of sorbent treatment chloride (as silicon tetrachloride etc.) with zinc oxide, alumina load alkaline matter.US4,690,810 to disclose a kind of take milk of lime as the method for neutralizing agent process chlorosilane by product, and this chlorosilane by product comprises metal (silicon) fine powder being no more than 20%, the aluminum chloride of 0.1 ~ 5%, iron(ic) chloride and titanium chloride.US5,080,804 disclose a kind of method that waste produced by calcium carbonate process chlorosilane with at least excessive 15%.US2006/0,183,958 disclose the treatment process that a kind of muriate produces waste, first lower boiling muriate are passed through Distillation recovery, and neutral solid matter in the waste urao of Distillation recovery and can not be generated, go soil-burial process or carry out metal recovery.
CN101,378,991 vinasses disclosing a kind of production of polysilicon tail gas condensing liquid, with air, hydrogen mixed firing, prepare the method for silicon-dioxide.US5,066,472 disclose the method that steam reaction that a kind of chlorosilane produces raffinate and 100 ~ 300 DEG C reclaims hydrochloric acid.US5,252,307 disclose the method that steam reaction that a kind of chlorosilane produces raffinate and 130 ~ 170 DEG C reclaims hydrochloric acid.
US5,246,682 treatment processs disclosing a kind of chlorosilane vinasse, comprise the steps: that a) chlorosilane vinasse and hydrochloric acid soln react generates hydrogen chloride gas; B) the reaction mixture precipitation in making step a); C) removed by solid matter, liquid gets back to step a); D) by step c) in produce solid matter be heated at least 140 DEG C; E) cooling step d) in produce gas, be recycled to step a) in.Hydrolyzable chlorine in chlorosilane vinasse can reclaim with the form of hydrogenchloride by the method, for the production stage of chlorosilane.The problem of the method is in step b) reaction mixture solid content about 10% be just easy to formed Silica hydrogel, and do not produce precipitation, cause step c) in do not have liquid to separate, thus make steps d) need the amount of the water of evaporation very large, energy consumption is also very large; In addition, the HCl that the method reclaims contains a large amount of water, is prepared into the dry HCl gas of chlorosilane production, and energy consumption is large, and yield is low.
US2010/0,061,912 disclose a kind of pyrohydrolysis halosilanes or halid method, comprise halosilanes and halogenide collection, be stored in the hold-up vessel of a band heating and stirring; Fluidized-bed reactor containing microgranular fluidizing medium is heated at least 300 DEG C, passes into water vapour, then pass into the above-mentioned halosilanes that exceedes stoichiometric ratio and halogenide reacts under fluidized state; The solid waste that reaction is generated continuously or interval shift out fluidized-bed reactor; The gas that reaction generates, first through cleaning apparatus, after removing solid particulate wherein, carry out condensation, the halosilanes of at least part of halosilanes and halogenide or partial reaction and halide condensation are got off, returns hold-up vessel with pump, uncooled gas delivers to gas concentration unit.The advantage of the method to prepare dry HCl gas, produces for chlorosilane.The shortcoming of the method is the Silica dehydration that temperature of reaction low (compared with the temperature of reaction of thermal silica 1000 ~ 2000 DEG C) is unfavorable for generating, silicon-dioxide containing great amount of hydroxy group is easily bonded on fluidized-bed reactor wall, cause reactor plugs, make reaction be not easy to carry out continuously; Adopt fluidized bed process, equipment is complicated, and running cost is higher.
Summary of the invention
Main purpose of the present invention is to provide that a kind of flow process is short, the method for hydrolysis of less investment, the material containing hydrolyzable halogen atom easy and simple to handle.An object of the present invention is to provide a kind of high-level efficiency, low cost reclaims the method for halogen atom in the compound or mixture containing hydrolyzable halogen atom, and halogen atom reclaims with the form of hydrogen halide usually.Another object of the present invention is to provide a kind of high-level efficiency, and low cost reclaims the method for other element in the compound or mixture containing hydrolyzable halogen atom, and other element reclaims with the form of soild oxide usually.A further object of the invention be to provide a kind of with containing the compound of hydrolyzable halogen atom and water for the method for soild oxide and hydrogen halide product to be produced by raw material by hydrolysis reaction.
The method for hydrolysis of the said material containing hydrolyzable halogen atom of the present invention, the material comprised containing hydrolyzable halogen atom mixes and reaction member with moisture material, gas solid separation and purification unit and gas product cleanup unit three major portions.
The said material containing hydrolyzable halogen atom of the present invention mixes with moisture material mainly provides the material containing hydrolyzable halogen atom to mix and reacting environment with moisture material with reaction member, should following features be had: containing material and the moisture material Homogeneous phase mixing of hydrolyzable halogen atom, with ensure react quick, carry out completely; Ensure that the solid materials generated can shift out reactor by continuous print, and sticky wall and latch up phenomenon do not occur; There is no dead volume, because this reaction is the reaction having solid to generate, if there is dead volume, finally can be filled up by solid product, and cause device normally not run; Also should be able to provide certain temperature of reaction, reaction pressure and certain reactant residence time for this reaction, to ensure carrying out completely of hydrolysis reaction.According to existing mixing effects such as above-mentioned requirements venturi mixer, static mixer, various dynamic mixer, pneumatic conveyor, tubular type chain handling machinery, drag conveyer, spiral conveyer and/or Screw Extrusion devices, there is again the fluid chemical field e Foerderanlage of conveying function all can use as mixing of the present invention and reactor, those skilled in the art can select flexibly according to practical situation, and the present invention does not do special restriction.
The said material containing hydrolyzable halogen atom of the present invention mixes with reaction member with moisture material, the equipment of the mixing of materials excellent performances such as venturi mixer, static mixer and/or various dynamic mixers is mainly used as mixing and mixing portion in reaction member usually.Wherein, said venturi mixer, be jet mixer, ejector etc. again, be rely on highly pressurised liquid to produce through the high speed flow that nozzle is formed negative pressure to suck the equipment of another kind of lowpressure stream, may also be the assisted venturi mixer of two kinds of high pressure fluid chargings, venturi mixer has mixing and conveying function simultaneously.Wherein, said static mixer is a kind of high-efficiency mixing device not having moving parts, and its mixing process is undertaken by the mixed cell of the different size of series installation in hollow pipe.Due to the effect of mixed cell, left-handed when making fluid, time and turn right and revolve, constantly change flow direction, not only core flow pushed to periphery, and peripheral fluid is pushed to center, thus cause good radial mixed effect.Meanwhile, the turning effort of fluid self also can occur on the interface of adjacent component junction, this perfect radial circular flow mixing effect, make material obtain the object mixed, static mixer may be used for liquid-liquid, liquid-gas, liquid-solid, the mixing between the different fluid such as gas-gas.Said dynamic mixer can be the various mixing devices having motion parts such as centrifugal mixer, spiral mixer, disk mixer, such as: CN9,1230,323.9 and CN1, dynamic mixer disclosed in 541,758.These equipment above-mentioned only need a small amount of change, even directly just may be used for the said material containing hydrolyzable halogen atom of the present invention and mix and reaction member with moisture material.
The said material containing hydrolyzable halogen atom of the present invention mixes with reaction member with moisture material, the equipment of the transportation performance excellences such as pneumatic conveyor, chain handling machinery, drag conveyer, spiral conveyer and/or Screw Extrusion device is mainly used as the reactive moieties of mixing and reaction member usually, especially inner chain handling machinery, drag conveyer, helical feed and the Screw Extrusion devices etc. with motion parts can ensure that solid product is continuously removed, and can ensure that again reactant exceeds the equipment being bonded at handling machinery inwall.Wherein said worm conveyor, also auger etc. is, be utilize spirochetally to rotate a kind of solid material conveying device forced to promote material and advance, have axle and shaftless two kinds of forms, also can stir material in course of conveying, mix, the operation such as heating and cooling.Wherein said Screw Extrusion device principle of work and worm conveyor just the same, it can be divided into the broad varietys such as Single screw extrusion device, twin screw extruder and multiscrew extruder.These equipment above-mentioned only need a small amount of change, even directly just may be used for the said material containing hydrolyzable halogen atom of the present invention and mix and reaction member with moisture material.
The said material containing hydrolyzable halogen atom of the present invention has an opening for feed at least in mixing with reactor, also can have multiple opening for feed.The said reaction product of the present invention has a discharge port at least in mixing with reactor, also can have multiple discharge port.The said reaction product of the present invention at its mixing portion, also in its reactive moieties, also can can have at its mixing portion and its reactive moieties at the opening for feed of device.The said reaction product of the present invention at the discharge port of device usually in its reactive moieties, and usually after opening for feed.
The said mixing of the present invention and reaction member include the material of hydrolyzable halogen atom and the reaction of moisture material, in order to ensure at least one reactant complete reaction as far as possible, especially crucially ensure that obtaining reaction product is dry soild oxide and gas hydrogen halide, mixing just seems particularly important with the control of hydrolysis reaction condition in reaction member.The said reaction conditions of the present invention is mainly as follows:
Hydrolysising reacting temperature in the said mixing of the present invention and reactor can be-50 ~ 2000 DEG C, preferably-20 ~ 1500 DEG C.Hydrolysis reaction containing the material of hydrolyzable halogen atom (as the reaction mechanism of hydrolyzing silicon tetrachloride, is shown in " Theoreticalstudyofthereactionmechanismandroleofwaterclus tersinthegas-phasehydrolysisosSiCl
4" Ignatovetal, J.Phys.Chem.A, 2003,107, p8705 ~ 8713), with the change of temperature of reaction, reaction mechanism is different.The hydrolysis reaction of silicon tetrachloride and other halosilanes, speed of response is very fast at a lower temperature, temperature of reaction more than 100 DEG C after, hydrolysis reaction speed declines, about 300 DEG C speed of response close to 0.After temperature of reaction is more than 300 DEG C, then improve temperature of reaction, hydrolysis reaction carries out according to other mechanism, and speed of response improves with temperature, and constantly accelerates, 500 DEG C time, close with speed of response when 100 DEG C.Therefore, the hydrolysising reacting temperature containing the material of hydrolyzable halogen atom has two optimum intervals ,-20 ~ 200 DEG C and 400 ~ 1200 DEG C.The advantage of reacting under low temperature is that energy consumption is low, and plant investment is little; The advantage of pyroreaction is that the solid product obtained is drier, and the halogen-containing compound of absorption is few.In addition, due to containing the material of hydrolyzable halogen atom, kind is very many, and hydrolytic activity is also not quite similar, some compound as: aluminum chloride, titanium tetrachloride, vanadium oxytrichloride, iron trichloride etc., hydrolysis reaction can not carry out completely at low temperatures.The active low compound of this kind of low temperature hydrolysis, preferably at high temperature carries out.
Hydrolysis reaction pressure in the said mixing of the present invention and reactor can be 0 ~ 20MPa, preferably 0.1 ~ 10MPa.Document " Theoreticalstudyofthereactionmechanismandroleofwaterclus tersinthegas-phasehydrolysisosSiCl
4" Ignatovetal, J.Phys.Chem.A, 2003; report in 107, p8705 ~ 8713, the hydrolysis reaction containing the compound of hydrolyzable halogen atom is the thermopositive reaction that thermodynamics can carry out completely; being second order reaction for reactants water at low temperatures, is first order reaction under high temperature; In investigated temperature range, compound reactant being contained to hydrolyzable halogen atom is first order reaction, boiling point in addition containing the compound of hydrolyzable halogen atom and water is all lower, be easy to vaporization, therefore certain pressure is kept in reactor, increase reactant concn, hydrolysis reaction speed can be accelerated, and do not bring disadvantageous effect.Higher reaction pressure makes the chance of the solid product primary particle particle collision generated in gas phase strengthen, and is conducive to forming larger offspring, thus contributes to the separation of gas-solid product.
The residence time of the hydrolysis reaction in the said mixing of the present invention and reactor can be 0 ~ 3600s, preferably 1 ~ 2000s.Although contain the hydrolysis reaction speed of the compound of hydrolyzable halogen atom quickly, but in order to ensure that hydrolysis reaction carries out completely, especially ensure the compound containing hydrolysis halogen atom and water, the one among these two kinds of both reactants reacts completely, and the residence time keeping certain is favourable.
The reactant ratio of the hydrolysis reaction in the said mixing of the present invention and reactor refers to the mol ratio containing the hydrolyzable halogen atom in the material of hydrolyzable halogen atom and the water in moisture material, usually can be 1: 0.1 ~ 10, be preferably 1: 0.2 ~ 5, be more preferably 1: 0.3 ~ 2.
The said reactant reacted in mixing with reactor of the present invention mainly contains the material containing hydrolyzable halogen atom, and moisture material.Wherein the said material containing hydrolyzable halogen atom of the present invention can be that the content wherein containing the compound of hydrolyzable halogen atom is greater than 1% usually, is preferably greater than 10% containing the compound of hydrolyzable halogen atom and its mixture with inert substance.Compound containing hydrolyzable halogen atom can be: the inorganic halides such as a chlorine three hydrogen silicon, dichlorosilane, trichlorosilane, silicon tetrachloride, high boiling point polychlorostyrene silane, tin tetrachloride, titanium tetrachloride, iron trichloride, chromium trichloride, vanadium oxytrichloride, magnesium dichloride, dichloride copper, Nickel Chloride, Indium-111 chloride, boron trichloride, gallium trichloride, phosphorus trichloride and phosphorus pentachloride, and (CH
3)
2hSiCl, (CH
3) HSiCl
2, (CH
3)
2siCl
2, (CH
3)
3one or more materials in the organohalosilanes such as SiCl, high boiling point organohalosilanes (wherein containing Si-Si, Si-O-Si, Si-CH2-Si group, hydrolyzable C1 atomicity is 1.2 ~ 2.8 with the ratio of Si atomicity).The present invention is said to be referred to not containing hydrolyzable halogen atom and the material (metallic silicon power etc. as in the hydrogen in tail gas from trichlorosilane production, silicon tetrachloride distillation residual liquid) do not reacted with hydrolyzable halogen atom containing the inert substance in the material of hydrolyzable halogen atom.The said material containing hydrolyzable halogen atom of the present invention can be muriate, bromide, iodide and their mixture, the said material containing hydrolyzable halogen atom of the present invention can with gas, liquid, solid and or any two or three the state of mixture exist.
Its water content of material such as the said moisture material of the present invention can be water, moisture solution, colloidal sol, gel, solid are greater than 20% usually, are preferably greater than 40%.The said water of the present invention is dissolved with the foreign gas such as oxygen, carbonic acid gas usually, if do not processed the purity that can affect gaseous product.Therefore the water that the present invention is used usually will through degassed process, to remove the rare gas element of dissolving.
The said gas solid separation of the present invention and purification unit mainly provide being separated and respective purifying place of reactant gases product and solid product, and this can carry out also can carrying out in different reactors respectively in a reactor.The separation of the present invention's said gas-solid product can be realized by the form well-known to those skilled in the art such as gravity separation, centrifugation.
After gas-solid product separation, in solid product, still can adsorb a large amount of gaseous products and a small amount of unreacted halogenide.The purifying of the said solid product of the present invention instigates the gaseous product desorption adsorbed in solid product, and make a small amount of unreacted halogenide in solid product continue reaction and desorption, to realize the purifying of solid product.This process can be realized by the form well-known to those skilled in the art such as elevated temperature desorption, inert gas purge.The temperature of the said elevated temperature desorption process of the present invention is usually at 200 ~ 1000 DEG C, and preferably 300 ~ 700 DEG C, the content of the soild oxide water in products obtained like this is less than 10%, the content of halogen atom is less than 0.1%.The said rare gas element of the present invention can be the rare gas elementes such as water vapour, nitrogen, hydrogen, in order to dusty gas product, preferably uses steam purging.
After gas-solid product separation, in gaseous product, possibly incorporating also a small amount of unreacted reactant.The purifying of the said gaseous product of the present invention refers to a kind of process in a small amount of unreacted water and these two kinds of materials of halogenide removing as far as possible and may comprise in gaseous product.With ensure gaseous product from gas solid separation and purifier out until the pipeline of gaseous product clean unit entrance and device not by water and halogenide continue to react the solid product that generates block, and alleviate the processing pressure of gaseous product clean unit.
The said gas solid separation of the present invention and purification unit must not comprise the purification part of gaseous product.Wherein, reactant residual in gaseous product is avoided to continue the problem of the solid product blocking gaseous product passage that reaction generates, can adopt and two cover gaseous products are set from gas solid separation and purifier out until the pipeline of gaseous product clean unit entrance and device alternate run, wherein a set of operation, another set of carry out cleaning tamper after for subsequent use; Also the methods well known to those skilled in the art such as the equipment that the continuous cleaning tampers such as scraper are set can be adopted.Alleviating the processing pressure of gaseous product clean unit, by improving the efficiency of mixing and reaction member and/or gaseous product clean unit, can be realized by reaction condition optimization etc.
The said gaseous product such as hydrogen halide, hydrogen (reactant differential responses gaseous product different) of gaseous product mainly containing hydrolysis reaction generation entering gaseous product clean unit of the present invention, a kind of residual reactants gas, and a small amount of solid product fine particle etc. carried secretly.The said gaseous product clean unit of the present invention mainly provides the place of the dedusting of reactant gases product and residual reactants.The dedusting of the present invention's said reactant gases product can pass through the dry dedusting technologies such as gravity separation, centrifugation, bag-type dust, also can pass through the wet dedusting techniques etc. such as shaped Venturi dedusting, spraying and dedusting, injection absorption, form well-known to those skilled in the art realizes.The said residual reactants of removing of the present invention can be realized by forms well-known to those skilled in the art such as condensation, pressurization, absorption and/or absorption.This can carry out also can carrying out in different reactors respectively in a reactor.
Accompanying drawing explanation
Accompanying drawing is a kind of possible schematic flow sheet of a kind of Substance P hydrolysis method containing hydrolyzable halogen atom provided by the invention.
Be further described below in conjunction with the method for hydrolysis of accompanying drawing to a kind of material containing hydrolyzable halogen atom provided by the invention.Accompanying drawing is a particular embodiment of inventive concept, not thereby limiting the invention.
In the present invention the said material containing hydrolyzable halogen atom mix with moisture material and reaction member by 1,2,3,4,5,6,7,8 and 10 forming in accompanying drawing.Wherein 1 is the material storage tank containing hydrolyzable halogen atom, 2 is moisture material storage tank, 3 for containing the material of hydrolyzable halogen atom and mixing and reactor of moisture material, 4 for containing the source handling equipment of the material of hydrolyzable halogen atom, the source handling equipment, 6 of 5 moisture materials be liquid and or the substance use equipment containing hydrolyzable halogen atom of solid state, 7 is moisture substance use equipment, 8 be gaseous phase containing the substance use equipment of hydrolyzable halogen atom, 10 is the handling equipment of solid circle oxide compound.
In the present invention, said gas solid separation and purification unit are by 9,11,12,13,14,15 and 16 forming in accompanying drawing.Wherein 9 is gas solid separation and purifier, 11 is the handling equipment of stripping gas, 12 is the handling equipment of solid product, 13 is solid product storage tank, 14 is solid product recycle stock handling equipment, 15 is the handling equipment of gaseous product purification media (material containing hydrolyzable halogen atom), and 16 is the handling equipment of gaseous product purification media (moisture material).
In the present invention, said gaseous product clean unit is by 17,18,19 and 20 forming in accompanying drawing.Wherein 17 is gaseous product handling equipment, and 18 is gaseous product dedusting and residual reactants reactor, and 19 is hydrogen halide recovery system, and 20 is the handling equipment of unreacted reactant reclaimed.
In the accompanying drawings, the said material containing hydrolyzable halogen atom of the present invention is transported in storage tank 1 by 4, and storage tank 1 can with stirring, heating or refrigerating unit, and to prevent the precipitation of solid in the material containing hydrolyzable halogen atom, the crystallization of liquid, or gaseous tension is too high.The liquid stored in storage tank 1 and or the material containing hydrolyzable halogen atom of solid state be transported to mixing and reactor 3 (material containing hydrolyzable halogen atom of the gaseous phase stored in storage tank 1 be transported to mix and reactor 3 through 8) through 6 and mix with the hydrous matter from storage tank 2 being delivered to 3 by 7 hydrolysis reaction occurs, control reactant conditions, make reaction generate soild oxide and hydrogen halide, and at least make wherein a kind of reactant complete reaction as far as possible; Through 3 primitive reactions completely after, product mixtures enters the middle part of gas solid separation and purifier 9, and the inside of 9 arranges the agitator of a slow stirring, and its profile is similar to 9, with being bonded on the inwall of 9 of ensureing that solid product exceeds.
Said solid product moves down more greatly because of density, the bottom of 9 arranges heating unit, keep comparatively high temps, under high temperature and/or the rare gas element effect next from 11, the complete desorb of hydrogen halide of soild oxide absorption, the soild oxide of purifying is discharged by the bottom of 9, and wherein a part as recycle stock 10, can enter 3 to ensure carrying out completely of hydrolysis reaction; Some through 14, after mixing, can also can enter the top of 9 with the gaseous product purification media from 15 or 16, make in gaseous product different from gaseous product purification media, another unreacted completely reactant reacts further.
Said gaseous product because of density less to 9 top diffusion, get off with the top from 9, from 14 containing a kind of reactant solid circulation material counter current contact after, enter gaseous product gaseous product clean unit 18 through 17.Gaseous product is removed wherein after entrained solid product fine particle and residual reactant in 18, through 19 gas recovery products.Through the unreacted reactant that 18 reclaim, inject corresponding reactant storage tank by 20.
The hydrogen halide obtained in the said reaction of the present invention can reclaim with the form of gas, for the synthesis procedure of halosilanes; Also can reclaim, for other purposes with the form of different concns haloid acid.The hydrogen halide reclaimed in the present invention, its rate of recovery is greater than 98% (gauge with hydrolyzable halogen atom) usually.The solid product obtained in the said reaction of the present invention, can sell as product, can obtain the different solid phase prod of physicochemical property by controlling reaction conditions of the present invention.In order to obtain the solid product that purity is high, physicochemical property are good, the compound containing hydrolyzable halogen atom that the raw material of the said method of the present invention can adopt purity high.
Embodiment
The method for hydrolysis of embodiment below to a kind of material containing hydrolyzable halogen atom provided by the invention is further described, not thereby limiting the invention.
Embodiment 1
According to the flow process in accompanying drawing of the present invention, but do not have in accompanying drawing 10 solid materials cyclic part, in accompanying drawing 14,15 and 16 purification for gas part and accompanying drawing in 11 rare gas element stripper section.Reaction is static mixer with the mixing portion of mixed cell 3, reactive moieties is spiral conveyer, gas purification units 18 is made up of cyclonic separator and condensing works and (adopts three grades of condensations, first use water-cooled,-20 DEG C are chilled to again with chilled brine, finally use refrigerant (can R507 or R404 be adopted) to be refrigerated to-40 DEG C, the silicon tetrachloride condensation of more than 99% can be got off).
The said material containing hydrolyzable halogen atom of this enforcement experiment is silicon tetrachloride, and its purity is 99.4%.
Before experiment starts, first open gas solid separation and the stirring of purifier 9 and the heating unit of bottom, the Wall Temperature of 9 bottoms is controlled at 700 DEG C.Open the spiral conveyer of mixing and reactor 3, adjusting rotary speed is 15r/min.Open the condensing works of 18.After experiment starts, silicon tetrachloride in storage tank 1, pump through 6, by after boost in pressure to 1MPa, is transported to mixing with the static mixer of reactor 3 with the flow of 90L/h, mixes with the water from storage tank 2 of the pressure 1MPa be delivered to by 7 in the static mixer of 3, flow 35L/h; Spiral conveyer outer wall, with the chuck being full of water coolant, makes temperature of reaction remain on 80 DEG C.The silicon tetrachloride that 18 condensations are got off is delivered to storage tank 1 by 20.
After the volume that solid product amount reaches 9 2/3, open the discharge valve of 12, start discharging.After plant running is stable, the output of hydrogen chloride gas is about 70Nm
3/ h.The solid silica output of butt 95% is about 50kg/h.
The HCl gas that this experiment is reclaimed can be directly used in trichlorosilane synthesis procedure.The solid silica reclaimed can be sold as high-quality white carbon black.
Embodiment 2
This enforcement experiment according to the flow process in accompanying drawing, but do not have in accompanying drawing 14,15 and 16 purification for gas part and accompanying drawing in 11 rare gas element stripper section.Reactant gases product from 17 directly passes into the bottom of storage tank 2, using storage tank 2 as bubbling reactor, reaches the object of gaseous product dedusting and residual reactants, namely stores up 2 simultaneously as gas purification units 18.Reaction and mixed cell 3 are spiral conveyer.
The said material containing hydrolyzable halogen atom of the present embodiment is technique of trichlorosilane synthetic tail gas, and its volume consists of hydrogen 60 ~ 70%, hydrogenchloride 25 ~ 35%, trichlorosilane 4 ~ 6%, other (as dichlorosilane etc.) 0.1 ~ 0.6%.
Before experiment starts, first loaded in gas solid separation and purifier 9 and accounted for its volume 2/3, the powdered silica that embodiment 1 is produced, open the heating unit of stirring and bottom, the Wall Temperature of 9 bottoms controlled at 300 DEG C.After experiment starts, first open mixing and reactor 3, adjusting rotary speed is after 10r/min, open the solid materials cyclic part of 10, make the silicon-dioxide in 9 enter mixing and reactor 3, after being full of solid materials in 3, the water pressure from storage tank 2 is promoted to 0.1MPa, inject 3 with the flow of 10L/h through 7, mix with the solid silica from 10; From the waste gas of storage tank 1, after pressure is adjusted to 0.1Mpa, with 100Nm
3the flow of/h injects another entrance of 3.The outer wall belt heating unit of 3, makes temperature of reaction remain on 400 DEG C.Have gas from storage tank 2 out after, open 12 discharge valve, start to draw off solid product.
When this experiment starts, only have hydrogen from storage tank 2 out in gaseous product, after the hydrochloric acid of storage tank 2 reaches finite concentration, in gaseous product, have hydrogen chloride gas and hydrogen.After plant running is stable, be about 120Nm from storage tank 2 gaseous product flow out
3/ h.In gaseous product, hydrogenchloride obtains highly purified hydrochloric acid after water absorbs, and can sell as product, and remaining hydrogen, after purifying, may be used for the reduction operation of polysilicon.The yield of solid silica is about 20kg/h, can sell as high-quality white carbon black.
Embodiment 3
The flow process of this enforcement experiment is with embodiment 1, and being to react with the mixing portion of mixed cell 3 with the difference of embodiment 1 is assisted venturi mixer, and reactive moieties is pneumatic conveyor.
The said material containing hydrolyzable halogen atom of this enforcement experiment is the waste liquid of the raffinate receiving tank of production of polysilicon factory.Its composition is with the difference in source, change greatly, be generally trichlorosilane 1 ~ 5%, silicon tetrachloride 10 ~ 30%, polychlorostyrene silane 40 ~ 60%, the solid impurities such as metallic silicon power 5 ~ 20%, other (containing titanium tetrachloride, aluminum chloride, boron trichlorides etc.) 1 ~ 5%.
Before experiment starts, first open the stirring of gas solid separation and purifier 9.Open the condensing works of 18.After experiment starts, waste liquid in storage tank 1 after 6 by boost in pressure to 5MPa, with the flow of 140L/h be transported to mixing with in the assisted venturi mixer of reactor 3 be delivered in the assisted venturi mixer of 3, pressure 5MPa, flow 80L/h water from storage tank 2 by 7 and mix; The pneumatic conveyor outer wall of 3, with heating unit, makes temperature of reaction remain on 800 DEG C.The concentrated hydrochloric acid that 18 condensations are got off is delivered to storage tank 2 by 20.
After the volume that solid product amount reaches 9 2/3, open the discharge valve of 12, start discharging.After device steady running, the output of hydrogen chloride gas is about 60Nm
3/ h.The solid product output of butt 98% is about 60kg/h.
The HCl gas that this experiment is reclaimed contains a small amount of hydrogen, and can be directly used in trichlorosilane synthesis procedure, the solid silica of recovery can be sold as white carbon black.
Claims (19)
1. the method for hydrolysis containing the material of hydrolyzable halogen atom, it is characterized in that: collect in a reactant storage tank, store the material containing hydrolyzable halogen atom, the described content containing the compound containing hydrolyzable halogen atom in the material of hydrolyzable halogen atom is greater than 1%, the described material containing hydrolyzable halogen atom is muriate, the described compound containing hydrolyzable halogen atom is selected from a chlorine three hydrogen silicon, dichlorosilane, one or more of trichlorosilane and silicon tetrachloride, wherein, the described mol ratio containing the water in hydrolyzable halogen atom in the material of hydrolyzable halogen atom and hydrous matter is 1:0.1 ~ 10, collect in another reactant storage tank, store moisture material, material containing hydrolyzable halogen atom is delivered to mix with moisture material simultaneously and carries out mixing, reacting with reaction member, controlling reaction conditions makes reaction product be dry soild oxide silicon-dioxide and gas hydrogenchloride, wherein, temperature of reaction is-20 ~ 200 DEG C or 400 ~ 800 DEG C, and reaction pressure is 0 ~ 20MPa, soild oxide continuously or interval shift out as solid product from gas-solid product separation and purification unit, hydrogen chloride gas enters gaseous product clean unit from gas-solid product separation and purification unit continuously, after removing fine solid particle wherein and at least part of unreacted reactant, as gaseous product, the unreacted reactant that conveying is reclaimed removes corresponding reactant storage tank.
2. method for hydrolysis as claimed in claim 1, wherein, described reaction pressure is 0.1 ~ 10MPa.
3. method for hydrolysis as claimed in claim 1, wherein, the described material containing hydrolyzable halogen atom be containing the compound of hydrolyzable halogen atom or its with not containing the mixture of the inert substance of hydrolyzable halogen atom, the described content containing the compound containing hydrolyzable halogen atom in the material of hydrolyzable halogen atom is greater than 10%; The described material containing hydrolyzable halogen atom with gas, liquid, solid and or the state of mixing exist.
4. method for hydrolysis as claimed in claim 3, wherein, the described material containing hydrolyzable halogen atom is: the tail gas containing hydrolyzable halogen atom produced in Industrial processes, waste liquid, solid waste and or their mixture, or contains the trichlorosilane rectifying cauldron bottom residue of a small amount of metallic silicon power.
5. method for hydrolysis as claimed in claim 4, wherein, described waste gas, the polycrystalline silicon reducing furnace start-stop car discharged from technique of trichlorosilane synthetic tail gas, trichlorosilane rectifying tower containing the material of hydrolyzable halogen atom, accidental discharge waste gas, chlorosilane storage tank safety relief gas or polysilicon reducing furnace tail gas process absorption waste gas.
6. method for hydrolysis as claimed in claim 3, wherein, the described material containing hydrolyzable halogen atom is silicon tetrachloride.
7. method for hydrolysis as claimed in claim 1, wherein, described moisture material is water, moisture solution, colloidal sol, gel or solid matter, and its water content is greater than 20%.
8. method for hydrolysis as claimed in claim 7, wherein, the water content of described moisture material is greater than 40%.
9. method for hydrolysis as claimed in claim 1, wherein, described mixing with reaction member is: provide the material containing hydrolyzable halogen atom to mix and reacting environment with moisture material, have and can make reaction mass Homogeneous phase mixing, the solid product of generation and gaseous product can be made to be continuously removed, also should be able to provide the reaction unit of the functions such as certain temperature of reaction, reaction pressure and certain reactant residence time for this reaction.
10. method for hydrolysis as claimed in claim 9, wherein, described mixing and reacton are venturi mixer, static mixer, dynamic mixer, pneumatic conveyor, chain handling machinery, drag conveyer, spiral conveyer and/or Screw Extrusion device, and the device combined between them.
11. method for hydrolysis as claimed in claim 10, wherein, described mixing and reaction member are venturi mixer, static mixer and/or various dynamic mixer are used as mix and mixing portion in reaction member, pneumatic conveyor, chain handling machinery, drag conveyer, spiral conveyer and/or Screw Extrusion device are used as the reactive moieties of mixing and reaction member, said mixing and reaction member have one or more opening for feed and at least one discharge port, and reactive moieties also has opening for feed.
12. method for hydrolysis as claimed in claim 1, wherein, material and moisture material containing hydrolyzable halogen atom are controlled to make at least one reactant complete reaction as far as possible mixing the reaction conditions with reaction member, and obtaining oxides silicon dioxide that reaction product is solid and hydrogenchloride, described reaction conditions is as follows: the residence time of reaction is at 0.1 ~ 3600s; The described mol ratio containing the hydrolyzable halogen atom in the material of hydrolyzable halogen atom and the water in moisture material is 1: 0.2 ~ 5.
13. method for hydrolysis as claimed in claim 1, wherein, the described mol ratio containing the hydrolyzable halogen atom in the material of hydrolyzable halogen atom and the water in moisture material is 1: 0.3 ~ 2.
14. method for hydrolysis as claimed in claim 1, wherein, reactant, containing when hydrolyzable halogen atom content is lower in the material of hydrolyzable halogen atom, has fraction solids material to circulate in mixing with reaction member, carries out to ensure to react completely.
15. method for hydrolysis as claimed in claim 1, wherein, described gas-solid product separation with purification unit is: provide being separated and respective purifying place of reactant gases product and solid product, the separation of described gas-solid product is by gravity separation or centrifugation; The purifying of solid product adopts rare gas element air lift and/or elevated temperature desorption method, described rare gas element be nitrogen, air and or water vapour; Described elevated temperature desorption temperature is at least not less than 200 DEG C; Gas-solid product separation and purifying carry out in a reactor, or carry out in different reactors respectively.
16. method for hydrolysis as claimed in claim 15, wherein, described elevated temperature desorption temperature is 300 ~ 1000 DEG C.
17. method for hydrolysis as described in claim 1 or 16, wherein, described gas-solid product separation and the gaseous product purification part of purification unit are: containing any one of the material of hydrolyzable halogen atom and these two kinds of reactants of moisture material, after gaseous product purification media and solid product mixing, again with gaseous product counter current contact, to ensure another reactant complete reaction.
18. method for hydrolysis as claimed in claim 1, wherein, described gaseous product clean unit is: provide the dedusting of reactant gases product and the place except Residual reactants, described reactant gases product dedusting is by dry dedusting technology or by wet dedusting technique, and described residual reactants of removing is realized by condensation, compression, absorption; Gaseous product purification is carried out in a reactor, or carries out in different reactors respectively.
19. method for hydrolysis as claimed in claim 18, wherein, described dry dedusting technology is gravity separation, centrifugation or bag-type dust, and described wet dedusting technique is shaped Venturi dedusting, spraying and dedusting or injection absorption.
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| CN103420381B (en) * | 2012-05-15 | 2015-03-25 | 天华化工机械及自动化研究设计院有限公司 | Method for recycling disposal of silicon tetrachloride slag slurry produced in polycrystalline silicon production and device thereof |
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| CN105984899B (en) | 2015-01-30 | 2017-05-17 | 中国科学院过程工程研究所 | System and method for purifying vanadium pentoxide |
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| CN113697841B (en) * | 2020-05-21 | 2023-06-02 | 江西理工大学 | Method for preparing rare earth oxide by low-temperature decomposition method |
| CN111672346A (en) * | 2020-07-10 | 2020-09-18 | 广西七色珠光材料股份有限公司 | Device and process for continuously preparing titanium oxychloride solution |
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