CN115849384A - Cracking treatment method for polycrystalline silicon high-boiling residues - Google Patents
Cracking treatment method for polycrystalline silicon high-boiling residues Download PDFInfo
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- CN115849384A CN115849384A CN202211521364.5A CN202211521364A CN115849384A CN 115849384 A CN115849384 A CN 115849384A CN 202211521364 A CN202211521364 A CN 202211521364A CN 115849384 A CN115849384 A CN 115849384A
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- 238000009835 boiling Methods 0.000 title claims abstract description 80
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 75
- 238000005336 cracking Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000012535 impurity Substances 0.000 claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 75
- 229920005591 polysilicon Polymers 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 chlorosilane compound Chemical class 0.000 claims abstract description 10
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 5
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims abstract description 5
- 229910021381 transition metal chloride Inorganic materials 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 14
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000012856 packing Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- CBEFDCMSEZEGCX-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n,n-bis(1,1,2,2,2-pentafluoroethyl)ethanamine Chemical compound FC(F)(F)C(F)(F)N(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F CBEFDCMSEZEGCX-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- RTTCFFTVCUNXLX-UHFFFAOYSA-N n,n-di(octan-2-yl)acetamide Chemical compound CCCCCCC(C)N(C(C)=O)C(C)CCCCCC RTTCFFTVCUNXLX-UHFFFAOYSA-N 0.000 claims description 2
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 53
- 230000000694 effects Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- 229910021485 fumed silica Inorganic materials 0.000 description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 11
- 239000012798 spherical particle Substances 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000012216 screening Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 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 description 5
- 239000005049 silicon tetrachloride Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- UBQYURCVBFRUQT-UHFFFAOYSA-N N-benzoyl-Ferrioxamine B Chemical compound CC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCN UBQYURCVBFRUQT-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TZXKOCQBRNJULO-UHFFFAOYSA-N Ferriprox Chemical compound CC1=C(O)C(=O)C=CN1C TZXKOCQBRNJULO-UHFFFAOYSA-N 0.000 description 2
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229960003266 deferiprone Drugs 0.000 description 2
- 229960000958 deferoxamine Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical group CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
The invention provides a cracking treatment method of a polycrystalline silicon high-boiling residue, which comprises the following steps: 1) Distilling the polysilicon high-boiling residue in a pretreatment unit; the pretreatment unit comprises a heating and stirring device and a packed tower filled with a metal impurity treating agent which are sequentially communicated; the metal impurity treating agent comprises the following components in parts by weight: 900 to 1000 parts of alkali metal chloride, 2 to 10 parts of alkaline earth metal chloride and 1 to 5 parts of transition metal chloride; 2) And introducing the distilled polysilicon high-boiling residue and HCl into a catalytic cracking reaction unit together for catalytic cracking reaction to obtain a chlorosilane compound under the action of an organic amine catalyst. The method of the invention utilizes the metal impurity treating agent in the packed tower to reduce the separation difficulty of aluminum chloride impurities and high-boiling residues, and efficiently removes the aluminum chloride impurities which are easy to lose the organic amine catalyst by a distillation treatment mode, thereby having better cracking effect and lower cracking cost.
Description
Technical Field
The invention belongs to the technical field of polycrystalline silicon production, and relates to a cracking treatment method of a polycrystalline silicon high-boiling residue.
Background
Polycrystalline silicon is a basic raw material of the photovoltaic industry, and a part of high boiling point compounds (commonly called high boiling point substances) with the boiling point of over 70 ℃ can be generated as byproducts in the preparation process, wherein the mass of the high boiling point compounds accounts for 7.0-8.0% of that of a monomer crude product. These high boiling point compounds are 99% polychlorosilanes, the components are very complex and the boiling points of the components are relatively close, and it is difficult to separate the components by the usual separation methods, and therefore they cannot be used effectively. In the actual production process, the treatment method mainly comprises the steps of concentrating, separating and recovering a part of residual low-boiling-point substances such as silicon tetrachloride, and then carrying out hydrolysis treatment on the residual low-boiling-point substances and other solid impurities brought out in the polysilicon processing process, such as metal chloride, so that a large amount of valuable Si and Cl elements are consumed, and the sustainable development of polysilicon production is not facilitated. In addition, if the high boiling point materials are not properly treated, the production cost of enterprises is increased, and the problems of safety and environmental protection are caused.
In order to solve the above problems, organic amines such as tributylamine, tri-N-octylamine, N-diethylaniline, N-diethylbutylamine, etc. have been developed as catalysts to convert high boiling substances into monosilicon compounds for recycling. However, the high boiling substance contains some metal chloride impurities, mainly aluminum trichloride impurities, and the mass content of aluminum element is thousands ppm, the boiling point of aluminum trichloride is 182.7 ℃, but sublimation occurs at 177.8 ℃, the sublimation temperature is close to the distillation range (120-180 ℃) of the high boiling substance, and therefore the high boiling substance is difficult to be removed by a common separation means. Aluminum trichloride metal impurities in the high-boiling-point substances can be subjected to a complex reaction with organic amine in the catalyst in the subsequent catalytic cracking step, so that a large amount of cracking catalyst is lost, in order to ensure the catalytic effect, the lost catalyst needs to be continuously supplemented, the operation cost is improved, and the stability of the production process is seriously influenced.
Some methods for avoiding the loss of the aluminum chloride impurities to the catalyst have been studied, for example, in patent CN108658082A, a method for removing aluminum chloride by pretreating high-boiling substances is disclosed, which comprises feeding the high-boiling substances into a cooling stirring tank, stirring at a low temperature for 1-5 hours, feeding the high-boiling substances into a settling tank, and settling the high-boiling substances in a nitrogen environment for 1-20 hours, thereby separating a slurry containing solid impurities and metal halides, however, the method has a long treatment flow and the effect of removing aluminum chloride is not ideal; patent CN113149017A discloses a complexing agent for removing aluminum from polysilicon high-boiling residues and application thereof, wherein the complexing agent has a complex structure and is difficult to apply in actual production; patent CN105271246A discloses a method for removing aluminum chloride from high boiling residues, which comprises adding an auxiliary agent and aluminum-containing impurities into the high boiling residues to form a mixed system containing non-volatile aluminum compounds, and then separating the rest components in the high boiling residues from the mixed system by distillation to remove the aluminum chloride impurities, wherein the auxiliary agent used in the method is prepared by mixing "deferoxamine", "deferiprone" and "troxite" according to a certain ratio, and has the advantages of high iron removal effect, undesirable aluminum removal effect and high cost.
Therefore, the development of a high-efficiency, stable and low-cost method for cracking polysilicon high-boiling residues is an urgent technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a cracking treatment method for polysilicon high-boiling residues, which can reduce the separation difficulty of aluminum chloride impurities and the high-boiling residues in the polysilicon high-boiling residues by using a metal impurity treating agent filled in a packed tower, and efficiently remove the aluminum chloride impurities through distillation treatment, thereby avoiding the consumption of the aluminum chloride impurities on a cracking catalyst, and enabling the cracking reaction to have better cracking effect and lower cracking cost.
The invention provides a cracking treatment method of a polycrystalline silicon high-boiling residue, which comprises the following steps:
1) Distilling the polysilicon high-boiling residue in a pretreatment unit;
the pretreatment unit comprises a heating and stirring device and a packed tower filled with a metal impurity treating agent which are sequentially communicated;
the metal impurity treating agent comprises the following components in parts by weight: 900 to 1000 parts of alkali metal chloride, 2 to 10 parts of alkaline earth metal chloride and 1 to 5 parts of transition metal chloride;
2) And introducing the distilled polysilicon high-boiling residue and HCl into a catalytic cracking reaction unit together, and carrying out catalytic cracking reaction under the action of organic amine to obtain a chlorosilane compound.
In the step 1), the polysilicon high-boiling-point substance can be firstly introduced into a heating and stirring device to provide the temperature and pressure required by distillation, and then the distillate generated in the heating and stirring device is continuously introduced into a packed tower filled with a metal impurity treating agent to remove the metal impurities in the high-boiling-point substance.
The inventor researches and discovers that the metal impurity treating agent obtained by compounding different types of metal chlorides according to specific mass parts can form a multi-molten salt system with metal aluminum chloride impurities in polycrystalline silicon after contacting with the polycrystalline silicon high-boiling-point substance, different from single aluminum chloride, the metal aluminum chloride treating agent is easy to sublimate in the distillation range of the high-boiling-point substance, the phase change conditions of the aluminum chloride in the multi-molten salt system are changed, and the aluminum chloride is difficult to sublimate in the distillation range of the high-boiling-point substance, so that the main metal impurity aluminum trichloride in the high-boiling-point substance can be efficiently removed by utilizing the boiling point difference of the aluminum chloride and the high-boiling-point substance through simple distillation treatment, and in addition, the rest metal impurities (such as iron and the like) can be removed together with the rest metal impurities in the distillation treatment.
The polycrystalline silicon high-boiling-point substance distilled in the step 1) has metal impurities, especially aluminum trichloride, effectively removed, so that the loss of metal impurities such as aluminum chloride to organic amine serving as a cracking catalyst is effectively avoided, and the polycrystalline silicon high-boiling-point substance can be cracked more efficiently and economically to obtain a chlorosilane compound.
It should be noted that the chlorosilane compounds as cracking products of the present invention mainly include silicon tetrachloride and trichlorosilane.
The metal chloride in the metal impurity treating agent can be selected from inorganic metal salts which are cheap and easy to obtain in the field, so that the metal impurity treating agent also has the advantages of low cost and high economic benefit compared with organic complexing agents used in the prior art.
Further, when the metal impurity treating agent also comprises 1-3 parts by mass of alkaline earth metal sulfate, the aluminum removing effect is more prominent.
The alkali metal chloride of the present invention is selected from one or more of lithium chloride, sodium chloride and potassium chloride, and more preferably is sodium chloride and/or potassium chloride which is relatively inexpensive and readily available.
The alkaline earth metal chloride of the present invention is selected from one or more of calcium chloride, magnesium chloride, strontium chloride and barium chloride, more preferably calcium chloride and/or magnesium chloride.
The transition metal element in the transition metal element chloride is selected from one or more of iron, manganese, chromium, nickel, molybdenum, titanium, zinc and cobalt.
The alkaline earth metal sulfate of the present invention is selected from one or more of calcium sulfate, magnesium sulfate, strontium sulfate, and barium sulfate, and more preferably calcium sulfate and/or magnesium sulfate.
Further, according to the difference of the boiling points of the aluminum chloride, the rest metal impurities and the polysilicon high-boiling-point substance, the temperature of the distillation treatment can be controlled to be 140-180 ℃, preferably 152-177 ℃, and/or the pressure of the distillation treatment is controlled to be 0.1-1.0 MPa, preferably 0.1-0.4 MPa.
Further, since the high-boiling-point polysilicon product may contain some solid impurities such as silicon powder, the high-boiling-point polysilicon product may be subjected to a filtration treatment to remove the solid impurities before the distillation treatment. In a specific embodiment, a filter may be connected in series before the stirring device is heated, and the filtering process may be performed in the filter.
Further, the metal impurity treating agent of the present invention is filled in the packed tower by coupling with the packing member in the packed tower. Preferably, structured packing is used in the packed column. The coupling means that particles of the metal impurity treating agent are relatively fixed on the packing member, so that the metal impurities can be treated and separated while the high-boiling-point substances transfer mass. The invention has no special requirement on the coupling filling form, as long as enough filling space can be provided for the metal impurity treating agent, and the filled metal impurity treating agent has enough free space in the filler, so that two gas-liquid flow channels are provided, and the metal impurity treatment and the gas-liquid two-phase mass transfer are realized simultaneously.
The coupling filling mode of the metal impurity treating agent and the packing member can refer to the filling mode of catalytic rectification in the prior art, for example, the metal impurity treating agent can be covered by a metal wire mesh and then rolled into a cylinder to form a member structure for bundling packages; or the packing member is composed of corrugated plates, and the metal impurity treating agent is filled between every two staggered corrugated plates, and the filling amount can be adjusted by changing the distance.
In order to place the metal impurity treating agent in the filler member, the metal impurity treating agent needs to be formed into particles with a certain size, the size and the property of the particles are not particularly limited, and the metal impurity treating agent can be determined according to the structure and the placement scheme of the filler, and basically, the formed particles only need to be ensured to be stably combined with the filler and not to fall off easily in the operation process. In order to facilitate the molding of the metal impurity treating agent, the metal impurity treating agent can be used as an active component, and on the basis, a certain amount of inert molding aids are added, wherein the inert molding aids include but are not limited to spherical silica, flaky silica, massive silica, fumed silica, silica sol and other silicon-containing substances.
It can be understood that the treatment effect of the metal impurity treating agent is reduced along with the increase of the operation time of the packed tower, the treatment effect can be maintained for a period of time which is mainly related to the accumulated amount of the treated metal impurities and the loading amount of the metal impurity treating agent, the accumulated amount of the metal impurities is related to the difference of the metal impurities at the inlet and the outlet of the packed tower and the total processing amount of high boiling substances of polycrystalline silicon, and for the convenience of production, the loading amount of the metal impurity treating agent is at least required to be continuously operated for one year, and the loading amount is preferably required to be continuously operated for 1 to 3 years. In order to meet the operation time, the loading amount of the metal impurity treating agent can be controlled to be 1-5 tons/(ten thousand tons of polysilicon high-boiling substance x year).
The catalytic cracking reaction unit used in the step 1) is not particularly limited, and only needs to ensure that the distilled polysilicon high-boiling residue can be fully contacted with an organic amine catalyst to promote the catalytic cracking reaction, and specifically, a tank reactor, a fixed bed reactor, a fluidized bed reactor, a catalytic rectification reactor and the like can be used as the catalytic cracking reaction unit, and preferably, the tank reactor and the fixed bed reactor with stirring are used.
The organic amine catalyst of the present invention may be selected from the group consisting of tri-N-butylamine, dodecyldimethylamine, triethylamine, trimethylamine, N-dimethylaniline, N-diethylaniline, N-diethylaniline, dioctadecylsecondary amine, perfluorotriethylamine, N, N-bis (1-methylheptyl) acetamide, triphenylamine, tribenzylamine, N-dimethylaniline, N-dimethylbenzylamine, N-methylmorpholine, pyridine, quinoline, N-ethylpiperidine and N-methylpiperidine, isoquinoline and pyridine.
In the catalytic cracking reaction, the mass ratio of the organic amine catalyst to the polysilicon high boiling substance is (1-10): 100, preferably (2-4): 100.
In the catalytic cracking reaction, the molar ratio of HCl to the high-boiling components in the polycrystalline silicon is (1-5): 1, and preferably (1-3): 1. When the molar ratio of HCl to the polysilicon high-boiling-point substance is more than 1, the gas-phase material after the reaction contains a certain amount of unreacted HCl, and after the material is separated, the unreacted HCl is returned to the catalytic cracking reaction unit to continue to participate in the reaction.
The temperature of the catalytic cracking reaction is 60-150 ℃, and is preferably controlled to be 65-120 ℃; and/or the pressure of the catalytic cracking reaction is 0.1MPa to 1.0MPa, preferably 0.1MPa to 0.4MPa.
The implementation of the invention has at least the following beneficial effects:
the invention relates to a cracking treatment method of a polysilicon high-boiling residue, which comprises the steps of distilling the polysilicon high-boiling residue by utilizing a pretreatment unit comprising a heating and stirring device and a filler tower filled with a metal impurity treating agent before cracking treatment, wherein the metal impurity treating agent obtained by compounding alkali metal chloride, alkaline earth metal chloride and transition metal chloride according to specific mass parts can form a multi-molten salt system with main metal impurity aluminum chloride in the polysilicon high-boiling residue, so that the phase change condition of the aluminum chloride is changed, the aluminum chloride is difficult to sublimate in the distillation range of the high-boiling residue, and further the aluminum chloride and the rest metal impurities can be removed from the polysilicon high-boiling residue by utilizing the boiling point difference of the aluminum chloride and the rest metal impurities and the high-boiling residue through simple distillation, thereby avoiding the loss of an organic amine catalyst in the subsequent cracking reaction of the metal impurities and further efficiently and economically cracking the polysilicon high-boiling residue to obtain a chlorosilane compound.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a diagram of a cracking apparatus for high boiling components of polysilicon according to an embodiment of the present invention.
Description of the reference numerals:
1-a filter; 2-heating the stirred tank; 3-a packed column; 4-a cooler; 5-a buffer tank; 6-a kettle type reactor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The method for cracking a polysilicon high boiling substance provided by the present invention will be described in further detail with reference to specific examples.
In the following examples, all starting materials were prepared by either commercially available or conventional methods, unless otherwise specified.
Example 1
The embodiment provides a cracking treatment method of a polysilicon high boiling substance, fig. 1 is a diagram of a cracking treatment device of a polysilicon high boiling substance according to an embodiment of the present invention, as shown in fig. 1, the cracking treatment device includes a filter 1, a heating stirring tank 2, a packed tower 3, a cooler 4, a buffer tank 5, and a tank reactor 6, which are connected in sequence, and the embodiment adopts the cracking treatment device shown in fig. 1 to perform cracking treatment on the polysilicon high boiling substance, which specifically includes the following steps:
1) The polysilicon high boiling substance is filtered by a filter 1 to remove the solid impurities.
2) Introducing the polysilicon high-boiling residue filtered in the step 1) into a heating and stirring kettle 2, raising the temperature of the heating and stirring kettle 2 to 155 ℃ at the speed of 5 ℃/min, controlling the pressure to be 0.2MPa for distillation, and continuously feeding the distillate generated by distillation into a packed tower filled with a metal impurity treating agent A to remove metal impurities in the distillate;
the metal impurity treating agent A and a packing member in the packed tower are filled in a coupling mode, and the specific filling mode is as follows: the packing adopts BX500 wire mesh corrugated plate structured packing, the metallic impurity treating agent is filled in the gap between the corrugated plates, and the bottom of the corrugated plates is provided with a supporting grid plate for preventing the treating agentDropping, wherein the aperture of the grid plate is smaller than the particle diameter of the metal impurity treating agent; the total loading of the metal impurity treating agent A is 2 tons/(ten thousand tons of polysilicon high-boiling residue treatment amount x year); the preparation method of the metal impurity treating agent A comprises the following steps: 960 parts by mass of NaCl, 2 parts by mass of KCl and 3 parts by mass of CaCl 2 1 part by mass of FeCl 3 And 2 parts by mass of CaSO 4 Mixing, adding the mixture into a ball mill, carrying out ball milling for 3 hours, placing the mixture into a vibrating screen, screening the mixture through a 120-mesh stainless steel screen to obtain powder, and mixing the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol to form spherical particles with the diameter of 1.5 mm.
3) Cooling the distillate extracted from the packed tower 3 by a cooler 4 until the temperature of a material outlet is lower than 69 ℃, introducing the cooled material into a buffer tank 5, after the material is buffered and stabilized by the buffer tank 5, continuously introducing the material into a kettle-type reactor 6, simultaneously introducing HCl into the kettle-type reactor 6 according to the molar ratio of HCl to the polysilicon high-boiling substance being 1.5, introducing N, N-dimethylaniline into the kettle-type reactor 6 according to the mass ratio of the N, N-dimethylaniline to the polysilicon high-boiling substance being 3;
the catalytic cracking reaction adopts a batch reaction mode, and the reaction time is 2h each time.
4) After the catalytic cracking reaction is finished, the residual materials in the heating stirring kettle 2 and the kettle reactor 6 are discharged out of the device.
Example 2
The method for cracking the polysilicon high-boiling residue in this example is substantially the same as that in example 1, except that the metal impurity treating agent B is filled in the packed tower 3 in this example, and the preparation method is to add 900 parts by mass of NaCl, 15 parts by mass of KCl, and 4 parts by mass of CaCl 2 And 4 parts by mass of MgCl 2 3 parts by mass of FeCl 3 1 part by mass of MnCl 2 And 2 parts by mass of CaSO 4 Mixing, ball milling in a ball mill for 3 hr, sieving with a 120-mesh stainless steel sieve to obtain powder, mixing with the powder5 parts by mass of fumed silica and 1 part by mass of silica sol were mixed and molded into spherical particles having a diameter of 1.5 mm.
Example 3
The method for cracking a high boiling residue of polycrystalline silicon in this example was substantially the same as in example 1, except that the packed column 3 of this example was filled with the metal impurity treating agent C prepared by mixing 800 parts by mass of NaCl, 150 parts by mass of KCl, and 8 parts by mass of MgCl 2 3 parts by mass of FeCl 3 2 parts by mass of MnCl 2 And 3 parts by mass of MgSO 4 Mixing, adding the mixture into a ball mill, carrying out ball milling for 3 hours, placing the mixture into a vibrating screen, screening the mixture through a 120-mesh stainless steel screen to obtain powder, and mixing the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol to form spherical particles with the diameter of 1.5 mm.
Example 4
The cracking treatment method of the polysilicon high-boiling residue in this example is substantially the same as that in example 1, except that the metal impurity treating agent D is filled in the packed tower 3 in this example, and the preparation method is to add 970 parts by mass of NaCl, 5 parts by mass of KCl, and 5 parts by mass of CaCl 2 5 parts by mass of MgCl 2 5 parts by mass of FeCl 3 And 3 parts by mass of CaSO 4 Mixing, adding the mixture into a ball mill, performing ball milling for 3 hours, placing the mixture into a vibrating screen, screening the mixture through a 120-mesh stainless steel screen to obtain powder, and mixing the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol to form spherical particles with the diameter of 1.5 mm.
Example 5
The method for cracking a polysilicon high boiler in this example is substantially the same as that in example 1, except that the catalyst used in the catalytic cracking reaction in this example is N, N-diethylaniline.
Example 6
The method for cracking and treating the high boiling residue of polysilicon in this example is substantially the same as that of example 1, except that the catalyst used in the catalytic cracking reaction of this example is dodecyldimethylamine.
Example 7
The method for cracking and treating the polysilicon high boiling point substance in this example is substantially the same as that in example 1, except that the catalyst used in the catalytic cracking reaction in this example is a mixture of N, N-dimethylaniline and dodecyldimethylamine in a mass ratio of 5.
Example 8
The cracking treatment method of the polysilicon high boiling point substance in this example is substantially the same as that in example 1, except that the catalyst used in the catalytic cracking reaction in this example is a mixture of N, N-dimethylaniline and tri-N-butylamine in a mass ratio of 10.
Example 9
The cracking treatment method of the polysilicon high boiling residue in this embodiment is substantially the same as that in embodiment 1, except that the filler member in the packed tower 3 in this embodiment is a metal wire mesh, the mesh size of the wire mesh is 40 meshes, and the metal impurity treating agent a is wrapped in a single layer and filled between the layers of the metal wire mesh.
Example 10
The method for treating the high boiling residue of polycrystalline silicon by cracking in this example was substantially the same as in example 1, except that the metal impurity treating agent A in this example was formed into spherical particles having a diameter of 2.5 mm.
Example 11
The method for treating the high boiling residue of polycrystalline silicon by cracking in this example was substantially the same as in example 1, except that the metal impurity treating agent A in this example was formed into cylindrical pellets having a diameter of 1.5mm and a length of 1.5 mm.
Example 12
The method for cracking and treating the polysilicon high-boiling residue in this example is substantially the same as that in example 1, except that the metal impurity treating agent E is filled in the packed tower 3 in this example, and the method for preparing the metal impurity treating agent E comprises 960 parts by mass of NaCl, 2 parts by mass of KCl, and 3 parts by mass of CaCl 2 And 1 part by mass of FeCl 3 Mixing, adding the mixture into a ball mill, performing ball milling for 3 hours, placing the mixture into a vibrating screen, screening the mixture by a 120-mesh stainless steel screen to obtain powder, mixing the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol, and molding the mixture into a product with the diameter of1.5mm spherical particles.
Comparative example 1
The method for cracking treatment of a polysilicon high boiling substance of this comparative example is substantially the same as that of example 1 except that the metal impurity treating agent A is not filled in the packed tower 3 of this comparative example.
Comparative example 2
The cracking treatment method of the polysilicon high-boiling residue of the comparative example is basically the same as that of example 1, except that a metal impurity treating agent F is filled in a packed tower 3 of the comparative example, the preparation method comprises the steps of adding 900 parts by mass of zinc chloride into a ball mill, carrying out ball milling for 3 hours, then placing the zinc chloride into a vibrating screen, screening out the zinc chloride through a 120-mesh stainless steel screen to obtain powder, and then mixing the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol to form spherical particles with the diameter of 1.5 mm.
Comparative example 3
The cracking treatment method of the polysilicon high-boiling residue in the comparative example is basically the same as that in example 1, except that a metallic impurity treating agent G is filled in a packed tower 3 in the comparative example, the preparation method comprises the steps of adding 900 parts by mass of copper chloride into a ball mill for ball milling for 3 hours, then placing the mixture into a vibrating screen, screening the mixture through a 120-mesh stainless steel screen to obtain powder, and then mixing the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol to form spherical particles with the diameter of 1.5 mm.
Comparative example 4
The method for cracking a polysilicon high boiler of the present comparative example is substantially the same as that of example 1, except that a mixture of deferoxamine (CAS No. 70-51-9) and deferiprone (CAS No. 30621-11-0) in a mass ratio of 1 is added simultaneously to the heating and stirring tank 2, and the total addition amount satisfies 2 tons/(ten thousand tons of polysilicon high boilers × year); this comparative example does not fill the packed tower 3 with the metal impurity treating agent A.
Comparative example 5
The cracking treatment method of the polysilicon high-boiling residue in the comparative example is basically the same as that in example 1, except that a metal impurity treating agent H is filled in a packed tower 3 in the comparative example, 968 parts by mass of sodium chloride is added into a ball mill to be ball-milled for 3 hours, then the ball mill is put into a vibrating screen, a 120-mesh stainless steel screen is used for screening to obtain powder, and then the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol are mixed and molded into spherical particles with the diameter of 1.5 mm.
Comparative example 6
The cracking treatment method of the polysilicon high-boiling residue of the comparative example is basically the same as that of example 1, except that a metal impurity treating agent I is filled in a packed tower 3 of the comparative example, and the preparation method comprises the steps of adding 968 parts by mass of calcium chloride into a ball mill for ball milling for 3 hours, then placing the mixture into a vibrating screen, screening the mixture through a 120-mesh stainless steel screen to obtain powder, and then mixing the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol to form spherical particles with the diameter of 1.5 mm.
Comparative example 7
The cracking treatment method of the polysilicon high-boiling residue in the comparative example is basically the same as that in example 1, except that a metal impurity treating agent J is filled in a packed tower 3 in the comparative example, 968 parts by mass of ferric chloride is added into a ball mill to be ball-milled for 3 hours, then the ball mill is put into a vibrating screen, a 120-mesh stainless steel screen is used for screening to obtain powder, and then the powder, 5 parts by mass of fumed silica and 1 part by mass of silica sol are mixed and molded into spherical particles with the diameter of 1.5 mm.
Test example
1. Al content test is carried out on a polycrystalline silicon high-boiling-point material to be processed and a cracking reaction material introduced into the kettle type reactor 6, the test method refers to a method given in the section 5.5 'determination of contents of iron, aluminum, chromium, titanium, copper, manganese, nickel, boron and phosphorus' in the standard HG/T5745-2020 of the Chinese chemical industry, and the aluminum removal rate is calculated according to the aluminum removal rate = 1-Al content in the cracking reaction material/Al content in the polycrystalline silicon high-boiling-point material to be processed multiplied by 100%.
Wherein the unit wppm of the Al content means one part per million by mass. The results of the Al content test and the calculation of the aluminum removal rate are shown in table 1.
2. Performing component analysis on the polycrystalline silicon high-boiling-point substance raw material and the cracked product (namely the gas-phase component generated in the step 3) by adopting a gas chromatography, and specifically comprising the following steps:
taking about 1mL of sample, subpackaging into 2mL of sodium-calcium reagent bottles, sealing with a cover, and refrigerating for 30min before analysis; starting the gas chromatography, and starting analysis after the baseline is stable; placing a sodium-calcium reagent bottle containing a sample under a fume hood, rapidly extracting 5 mu L of sample by using a 25 mu L micro-injector, and calculating peak areas of the components by using a chromatographic workstation after gasification and separation; three sets of experiments were performed in parallel, and the data from two of the close sets were averaged.
The content of each component in chlorosilane in the cracking product is p by mass fraction i Calculating according to the formula (1):
in formula (1): p is a radical of formula i The mass fraction of each component is shown; a. The i Is the peak area of each component; sigma A i Is the sum of the peak areas of the components.
Chromatographic analysis conditions are that a capillary column of DB-1 30m multiplied by 0.32mm multiplied by 1.0 mu m is selected, and the injection port temperature is 180 ℃; column box, heating to 60 deg.C for 2min, heating to 180 deg.C at 5 deg.C/min, and maintaining for 3min; a FID detector; carrier gas of 99.999 percent high-purity H2 with the concentration of 130mL/min, and molecular sieve drying and purification are applied. Peak assignments were determined from standard sample peak-out times using absolute retention time legislative analysis.
According to the gas chromatography result, the cracking conversion rate X of the high-boiling-point substance and the selectivity Y of chlorosilane (silicon tetrachloride and trichlorosilane) in the catalytic cracking reaction are calculated by combining the following calculation formula, and the calculation method comprises the following steps:
X＝(m r0 -m r1 )/m r0 ×100％ (2)
in the formula (2): m is r0 For the mass of the high boilers to be cracked, which is introduced into the tank reactor 6, m r1 The mass of catalyst added was subtracted from the mass of residual material in the catalytic cracking reactor after the reaction.
Y＝(p TET +p TCS )×100％ (3)
In formula (2): p is a radical of TET And p TCS Respectively the mass fractions of the components of silicon tetrachloride and trichlorosilane in the cracking product.
The catalytic cracking reactions of the above examples and comparative examples were repeated 3 times (wherein, the 2 nd catalytic cracking reaction used the organic amine catalyst recovered after the 1 st catalytic cracking reaction, and the 3 rd catalytic cracking reaction used the organic amine catalyst recovered after the 2 nd catalytic cracking reaction), and the cracking conversion rates of the high boiling point compounds of the 1 st, 2 nd and 3 rd catalytic cracking reactions were respectively marked as X 1 、X 2 、X 3 The selectivities of chlorosilane (silicon tetrachloride and trichlorosilane) are respectively marked as Y 1 、Y 2 、Y 3 Calculating X 1 Subtract X 3 Difference of (a) X and (Y) 1 Minus Y 3 The difference Δ Y of (d).
X 1 、Y 1 And the results of Δ X and Δ Y calculations are shown in table 1.
TABLE 1
As can be seen from table 1, in the cracking treatment method of the embodiment of the present invention, the aluminum chloride impurities in the polysilicon high-boiling-point substance raw material are efficiently removed, so that the influence of the impurities on the catalytic cracking reaction can be avoided, the catalytic cracking reaction has high cracking rate and selectivity of the chlorosilane compound, and the cracking rate and the selectivity of the chlorosilane compound are not significantly reduced after the catalyst is repeatedly used three times.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A cracking treatment method of a polysilicon high-boiling residue is characterized by comprising the following steps:
1) Distilling the polysilicon high-boiling residue in a pretreatment unit;
the pretreatment unit comprises a heating and stirring device and a packed tower filled with a metal impurity treating agent which are sequentially communicated;
the metal impurity treating agent comprises the following components in parts by weight: 900 to 1000 parts of alkali metal chloride, 2 to 10 parts of alkaline earth metal chloride and 1 to 5 parts of transition metal chloride;
2) And introducing the distilled polysilicon high-boiling residue and HCl into a catalytic cracking reaction unit together, and carrying out catalytic cracking reaction under the action of an organic amine catalyst to obtain a chlorosilane compound.
2. The cracking treatment method according to claim 1, wherein the metal impurity treating agent further comprises 1 to 3 parts by mass of an alkaline earth metal sulfate.
3. The cracking treatment method according to claim 1 or 2, wherein the transition metal element in the transition metal element chloride is selected from one or more of iron, manganese, chromium, nickel, molybdenum, titanium, zinc, and cobalt.
4. The cracking treatment method according to any one of claims 1 to 3, wherein the temperature of the distillation treatment is 140 ℃ to 180 ℃;
and/or the pressure of the distillation treatment is 0.1MPa to 1.0MPa.
5. The cracking treatment method according to any one of claims 1 to 4, wherein the metallic impurity treating agent and the packing member in the packed column are packed in the packed column by coupling.
6. The cracking treatment method according to claim 1 or 5, wherein the loading amount of the metal impurity treatment agent is 1 to 5 tons/(ten thousand tons of polysilicon high boiler x year).
7. The cleavage treatment method according to any one of claims 1 to 6, wherein the organic amine is selected from the group consisting of tri-N-butylamine, dodecyldimethylamine, triethylamine, trimethylamine, N-dimethylaniline, N-diethylaniline, N-diethylbutylamine, dioctadecylsecondary amine, perfluorotriethylamine, N, N-bis (1-methylheptyl) acetamide, triphenylamine, tribenzylamine, N-dimethylaniline, N-dimethylbenzylamine, N-methylmorpholine, pyridine, quinoline, N-ethylpiperidine and N-methylpiperidine, isoquinoline and pyridine.
8. The cracking treatment method according to any one of claims 1 to 7, wherein the mass ratio of the organic amine catalyst to the polysilicon high-boiling material is (1-10): 100.
9. the cracking treatment method according to any one of claims 1 to 8, wherein the molar ratio of HCl to the polysilicon high boilers is (1-5): 1.
10. The cracking treatment method according to any one of claims 1 to 9, wherein the temperature of the catalytic cracking reaction is 60 ℃ to 150 ℃;
and/or the pressure of the catalytic cracking reaction is 0.1MPa to 1.0MPa.
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