CN110606490A - Synthesis and purification method of high-purity silicon tetrafluoride - Google Patents
Synthesis and purification method of high-purity silicon tetrafluoride Download PDFInfo
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- CN110606490A CN110606490A CN201910536842.1A CN201910536842A CN110606490A CN 110606490 A CN110606490 A CN 110606490A CN 201910536842 A CN201910536842 A CN 201910536842A CN 110606490 A CN110606490 A CN 110606490A
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- fluoride
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- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000000746 purification Methods 0.000 title abstract description 7
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 238000005336 cracking Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 22
- 230000005764 inhibitory process Effects 0.000 claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000003795 desorption Methods 0.000 claims abstract description 8
- 229940104869 fluorosilicate Drugs 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 18
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 claims description 13
- 229940096017 silver fluoride Drugs 0.000 claims description 9
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims description 8
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 8
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 7
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 7
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 7
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 7
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims description 7
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 7
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 7
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 7
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 229920005990 polystyrene resin Polymers 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims 1
- 238000010977 unit operation Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 229910004016 SiF2 Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910004014 SiF4 Inorganic materials 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910007260 Si2F6 Inorganic materials 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- -1 sodium fluorosilicate Chemical compound 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- SYNPRNNJJLRHTI-UHFFFAOYSA-N 2-(hydroxymethyl)butane-1,4-diol Chemical compound OCCC(CO)CO SYNPRNNJJLRHTI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SDNBGJALFMSQER-UHFFFAOYSA-N trifluoro(trifluorosilyl)silane Chemical compound F[Si](F)(F)[Si](F)(F)F SDNBGJALFMSQER-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004883 Na2SiF6 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 229910008284 Si—F Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 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
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ATVLVRVBCRICNU-UHFFFAOYSA-N trifluorosilicon Chemical compound F[Si](F)F ATVLVRVBCRICNU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10705—Tetrafluoride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10778—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a method for synthesizing and purifying high-purity silicon tetrafluoride. A method for synthesizing and purifying high-purity silicon tetrafluoride comprises the following steps: pre-treating fluosilicate; carrying out cracking reaction on fluorosilicate to prepare a silicon tetrafluoride coarse material; removing trace moisture and acid gas in a first adsorption section; performing desorption and polymerization inhibition control on the fluorosilicone at a second adsorption section; separating light components and heavy components in a rectification section; and separating the azeotropic substance impurities through a complicated rectification working section. The synthesis and purification method of high-purity silicon tetrafluoride scientifically combines heating cracking, adsorption unit operation, rectification and complex rectification, adopts the adsorption unit to remove fluorosilicone, and adds a complex rectification process to remove azeotropic substances after the conventional rectification unit operation.
Description
Technical Field
The invention relates to the fields of chemical engineering, separation engineering and electronic special gases, in particular to a method for synthesizing and purifying high-purity silicon tetrafluoride.
Background
Silicon tetrafluoride (SiF)4) The compound of the tetrahalosilane family has the highest silicon atom proportion (about 27 percent), stable Si-F chemical bond energy (541.0 kJ/mol) and non-flammability and non-explosive characteristics. In the processing technology of high-depth wide-range and large-capacity silicon/silicon oxide and metal interlayer insulating layers in the new generation chip process, silicon tetrafluoride shows unique physical and chemical properties. Silicon tetrafluoride and N2O、O2、SiH4And H2The gases are used together to achieve the chemical deposition rate of 300-500 nm/min, and wide and thick SiO can be obtained within a limited time2An insulating layer. In addition, silicon tetrafluoride can also be used as a main raw material for preparing high-purity quartz glass by using various epitaxial precipitation diffusion silicon sources such as silicon carbide, silicon nitride and the like, and optical fibers, and is a key component of a silicon-based semiconductor ion injection process in the optical fiber industry.
In 1771 Scheele et al successfully synthesized silicon tetrafluoride for the first time, specifically obtained by the reaction of hydrofluoric acid and silicon dioxide, and the reaction equation is as follows: SiO 22 + 4 HF = SiF4 + 2 H2And O. However, silica is chemically stable, has a large Si — O bond energy, requires a large amount of hydrogen fluoride, and the reaction temperature is often high, and this method is gradually eliminated due to the high cost of hydrogen fluoride.
The widely applied silicon tetrafluoride preparation method at present is a silicon dioxide fluorite sulfuric acid method, and the reaction equation is as follows: 2CaF2+ 2H2SO4 + SiO2 = 2CaSO4 + SiF4 + 2H2And O. The method has the characteristics of easily available raw material sources, low cost and suitability for large-scale production, but mainly faces the problem that water is generated in a product, the water can react with silicon tetrafluoride to generate fluorosilicone ether impurities, and the reaction equation is as follows: 2SiF4 + H2O = (SiF3)2O + 2 HF. The fluorosilicone ether impurity has gel-like property, and is easy to flocculate and form polyfluorosilane- (SiF) with silicon tetrafluoride by continuous secondary growth2O) n-, which easily causes the pipe fitting to be blocked, and threatens the safety and stability of production. On the other hand, the raw material fluorite has more impurities, the reaction cracking control difficulty is high, and the components in the produced silicon tetrafluoride coarse material are very complex.
The other preparation method of the silicon tetrafluoride is a cracking technology: mixing Na2SiF6Thermally cracking at high temperature to produce silicon tetrafluoride and sodium fluoride. The reaction equation is: na (Na)2SiF6 = SiF4+ 2 NaF. The synthesis method has the characteristics of avoiding the use of concentrated sulfuric acid, not generating calcium sulfate slurry waste residue and further improving the safety and environmental protection. However, this method has some problems, such as numerous cracking reaction products, complex composition of different fluorine substituted silicide-forming azeotropes, low cracking conversion rate, and easy generation of fluorosilicones, polyfluorosilanes, and other impurities during the cracking process.
In the silicon tetrafluoride synthesis section, the former carries out partial improvement on the process on the basis of the methods. For example, patent CN 108658081 a adopts a method of producing hydrogen fluoride and silicon tetrafluoride to be prepared by reacting sodium fluorosilicate with sulfuric acid, and repeatedly utilizes and integrates the generated hydrogen fluoride gas in many aspects, so that the hydrogen fluoride reacts with silicon dioxide to further react to obtain silicon tetrafluoride, and the method effectively utilizes hydrogen fluoride corrosive gas. Patent CN 105502410A mixes silicon-containing substance and fluorine-containing substance to react to obtain silicon tetrafluoride. According to the method, acidic and corrosive liquid substances are avoided, silicon-containing substances and fluorine-containing substances, particularly gaseous fluorine-containing substances are used for reacting to prepare the silicon tetrafluoride, less impurities are introduced, the purity of the product silicon tetrafluoride is high, less waste acid and waste residue can be generated, and the environmental pollution is less. CN 102897769 discloses a process for producing silicon tetrafluoride, which comprises the steps of stirring and heating raw materials of sodium fluosilicate, silicon dioxide powder and concentrated sulfuric acid to react at a certain temperature. CN 104843713 discloses a device for preparing silicon tetrafluoride by pyrolyzing sodium fluosilicate, which comprises the steps of washing and purifying sodium fluosilicate, then loading the sodium fluosilicate into a decomposition reaction kettle, heating and decomposing the sodium fluosilicate in a thin-layer static manner, collecting the obtained silicon tetrafluoride gas, condensing the silicon tetrafluoride gas by a heat exchanger and collecting the silicon tetrafluoride gas. The method for producing high-purity silicon tetrafluoride in the process of wet processing of phosphate ore by CN 102001666 collects fluorine-containing gas generated in the process of wet processing of phosphate ore; introducing the fluorine-containing gas into a reactor added with sulfuric acid and silicon dioxide to obtain a high-purity silicon tetrafluoride product. CN 104445074 is a method for preparing anhydrous hydrogen fluoride and co-producing silicon tetrafluoride by treating dilute fluosilicic acid by a solvent extraction method.
In a silicon tetrafluoride purification section, the traditional method is a rectification process at present, but silicon tetrafluoride still contains fluorosilicone ether and azeotrope impurities, and trace removal is difficult to realize. CN101774588 removes light and heavy component impurities by a conventional rectification method. CN 105347348A introduces silicon tetrafluoride, diluent gas and carbonyl fluoride into a water removal tower filled with filler, and the carbonyl fluoride contacts with water in the silicon tetrafluoride to react and remove water in the silicon tetrafluoride.
In order to reduce the production cost and improve the yield of the silicon tetrafluoride, although a large amount of work is also carried out domestically, the work cannot be really realized all the time. In summary, there are still deficiencies: 1. the silicon tetrafluoride reaction conversion rate is low; 2. the reaction selectivity is low, and the number of byproducts is large; 3. fluorosilicone in silicon tetrafluoride, although removed by adsorption, does not further achieve polymerization inhibition; 4. the impurities in the complex system of the azeotrope cannot be effectively removed.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a method for synthesizing and purifying high-purity silicon tetrafluoride, which scientifically combines pyrolysis, adsorption unit operation, rectification and complex rectification, removes fluorosilicone by adopting an adsorption unit, and removes azeotropic substances by adding a complex rectification process after the conventional rectification unit operation.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a method for synthesizing and purifying high-purity silicon tetrafluoride, which comprises the following steps:
and step S1: pre-treating fluosilicate;
and step S2: carrying out cracking reaction on fluorosilicate to prepare a silicon tetrafluoride coarse material;
and step S3: removing trace moisture and acid gas in a first adsorption section;
and step S4: performing desorption and polymerization inhibition control on the fluorosilicone at a second adsorption section;
and step S5: separating light components and heavy components in a rectification section;
and step S6: and separating the azeotropic substance impurities through a complicated rectification working section.
Preferably, the cracking reaction conditions are that the pressure is 0.02 ~ 0.1.1 MPa, the temperature is 300 ~ 500 ℃, the operation flow of the outlet of the reactor is 10-30 kg/h, and the volume of the reactor is 500-1000L.
Preferably, the fluorosilicone is removed and polymerization inhibition is controlled in the second adsorption section by using a fluorinated resin, and the fluorinated resin is prepared by coating metal fluoride on the surface of the resin.
Preferably, the metal fluoride is one of silver fluoride, cobalt fluoride, manganese fluoride, lead fluoride, aluminum fluoride, copper fluoride or magnesium fluoride, and the metal fluoride loading rate is 1 ~ 5 mmol/g.
Preferably, the resin is porous polystyrene cross-linked resin with the specific surface area of 300 ~ 600m2/g。
Preferably, the rectification section comprises a heavy component removal tower and a light component removal tower, the feeding amount of the heavy component removal tower is 2 ~ 50kg/h, the tower pressure is 0.1 ~ 3.0.0 MPa, the tower top temperature is-80 ~ -10 ℃, the tower bottom temperature is-70 ~ -5 ℃, the feeding amount of the light component removal tower is 2 ~ 50kg/h, the tower pressure is 0.1 ~ 4.0.0 MPa, the tower top temperature is-80 ~ 5 ℃, and the tower bottom temperature is-70 ~ 15 ℃.
Preferably, the complex rectification section adopts a volume ratio of 4: 3: 3, extracting and rectifying the cyclohexane, the hexachlorobenzene and the m-phenylenediamine as extracting agents.
Preferably, the complex rectification section comprises three removal towers connected in series, wherein the feeding amount of the removal towers is 2 ~ 50kg/h, the tower pressure is 0.2 ~ 4.0.0 MPa, the tower top temperature is-80 ~ 5 ℃, and the tower bottom temperature is-70 ~ 15 ℃.
Preferably, the S1 step is to vacuumize the fluorosilicate while heating at 100 ~ 200 deg.C.
The method for synthesizing and purifying the high-purity silicon tetrafluoride has the beneficial effects that:
(1) a negative pressure process is adopted in the cracking reaction, when silicon tetrafluoride is produced, the silicon tetrafluoride can be pumped away quickly, and the conversion rate and selectivity of cracking are improved.
(2) The adsorption unit is adopted to remove the fluorosilicone ether, and the polymerization problem of the fluorosilicone ether is solved through the polymerization inhibitor.
(3) Aiming at the difficulty in removing the azeotrope, a complex rectification process system is added after the conventional rectification unit is adopted for operation.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The synthesis and purification method of high purity silicon tetrafluoride according to the embodiment of the present invention will be described in detail below.
The embodiment of the invention provides a method for synthesizing and purifying high-purity silicon tetrafluoride, which comprises the following steps:
and step S1: pre-treating fluosilicate;
further, in the preferred embodiment of the invention, the fluorosilicate is vacuumized and heated at 100 ~ 200 ℃, the moisture in the fluorosilicate can be effectively removed through the vacuumization and the heating, and the normal operation of the cracking reaction is ensured by removing the moisture and the oxygen in the air.
And step S2: carrying out cracking reaction on fluorosilicate to prepare a silicon tetrafluoride coarse material; the crude silicon tetrafluoride material with complex components, including light components and heavy component impurities, is obtained by cracking. Wherein the light component impurities comprise H2、CO、CO2、O2、SiF3H、SiF2H、SiFH3、SiH4And the like. Heavy component impurities including HF, Si2F6O、Si2F6、Si3F8、SiF3Cl、SiF2Cl2And the like.
Furthermore, in the preferred embodiment of the present invention, the cracking reaction conditions are 0.02 ~ 0.1.1 MPa, 300 ~ 500 ℃, 10-30 kg/h of reactor outlet operation flow rate, and 500-1000L of reactor volume, and the cracking reaction is a gap operation, under which better cracking can be achieved.
And step S3: removing trace moisture and acid gas in a first adsorption section; trace moisture and acid gas are removed through the first adsorption section, and pure products are obtained subsequently.
And step S4: performing desorption and polymerization inhibition control on the fluorosilicone at a second adsorption section;
further, in the preferred embodiment of the present invention, the fluorosilicone is removed and polymerization inhibition is controlled in the second adsorption section by using a fluorinated resin prepared by coating a metal fluoride on the surface of the resin. In the production and purification of high-purity electronic grade silicon tetrafluoride, fluorosilicone ether impurities are easily generated, and the impurities can be even repolymerized with silicon tetrafluoride to generate fluorosilicone ether high polymer. The fluorosilicone polymer can be rapidly aggregated into particles from the colloid, so that the pipeline and the adsorbent are easily blocked, and safety accidents occur, thereby having an important effect on the removal and polymerization inhibition control of the fluorosilicone.
Further, in the preferred embodiment of the present invention, the metal fluoride is one of silver fluoride, cobalt fluoride, manganese fluoride, lead fluoride, aluminum fluoride, copper fluoride or magnesium fluoride, and the loading rate of the metal fluoride is 1 ~ 5 mmol/g.
Further, in the preferred embodiment of the present invention, the resin is a porous cross-linked polystyrene resin with a specific surface area of 300 ~ 600m2(ii) in terms of/g. The adoption of a larger specific surface area can not only increase the loading capacity of the metal fluoride, but also improve the adsorption effect.
And step S5: separating light components and heavy components in a rectification section; the crude silicon tetrafluoride material prepared by the cracking, the first adsorption section and the second adsorption section comprises light components and heavy component impurities. Wherein the light component impurities comprise H2、CO、CO2、O2、SiF3H、SiF2H、SiFH3、SiH4And the like. Heavy component impurities including HF, Si2F6O、Si2F6、Si3F8、SiF3Cl、SiF2Cl2And the like. Light component impurities and heavy component impurities which can not form the azeotrope are respectively separated by using a common rectification method in a rectification section.
Further, in the preferred embodiment of the invention, the rectification section comprises a heavy component removal tower and a light component removal tower, the feeding amount of the heavy component removal tower is 2 ~ 50kg/h, the tower pressure is 0.1 ~ 3.0.0 MPa, the tower top temperature is-80 ~ -10 ℃, the tower bottom temperature is-70 ~ -5 ℃, the feeding amount of the light component removal tower is 2 ~ 50kg/h, the tower pressure is 0.1 ~ 4.0.0 MPa, the tower top temperature is-80 ~ 5 ℃, and the tower bottom temperature is-70 ~ 15 ℃, so that most of heavy component and light component impurities can be separated by the heavy component removal tower and the light component removal tower.
And step S6: and separating the azeotropic substance impurities through a complicated rectification working section. After the rectification working section, the composition of the azeotropic substance is SiF4、SiF3H、SiF2H2、SiFH3、SiF3Cl and SiF2Cl2. These substances have different boiling points but become azeotropic substances. The separation can not be carried out by adopting the conventional rectification, and the separation is carried out by adopting the complex rectification.
Further, in the preferred embodiment of the present invention, the complex rectification section employs a volume ratio of 4: 3: 3, extracting and rectifying the cyclohexane, the hexachlorobenzene and the m-phenylenediamine as extracting agents. The extractant can separate the azeotrope.
Further, in the preferred embodiment of the invention, the complex rectification section comprises three removal towers connected in series, the feeding amount of the removal towers is 2 ~ 50kg/h, the tower pressure is 0.2 ~ 4.0.0 MPa, the tower top temperature is-80 ~ 5 ℃, and the tower bottom temperature is-70 ~ 15 ℃, so that the purity of the product can be effectively improved through the series work of the three removal towers.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a method for synthesizing and purifying high-purity silicon tetrafluoride, which comprises the following steps:
and step S1: pretreating 1000 kg of sodium fluosilicate; specifically, the sodium fluosilicate is vacuumized and heated at 150 ℃.
And step S2: carrying out cracking reaction on the sodium fluosilicate in a reactor with the volume of 1000L to prepare silicon tetrafluoride coarse material; the specific cracking reaction conditions are as follows: the pressure was 0.06MPa, the temperature was 400 ℃ and the flow rate at the reactor product outlet was controlled to 25 kg/h.
And step S3: removing trace moisture and acid gas in a first adsorption section;
and step S4: performing desorption and polymerization inhibition control on the fluorosilicone at a second adsorption section; wherein, the fluorosilicone is removed and polymerization inhibition control is carried out at the second adsorption working section by adopting fluorinated resin, the fluorinated resin is prepared by coating silver fluoride on the surface of porous polystyrene cross-linked resin, the loading rate of the silver fluoride is 3mmol/g, and the specific surface area of the porous polystyrene cross-linked resin is 450m2(ii) in terms of/g. In this embodiment, the metal fluoride is silver fluoride, and in other embodiments, the metal fluoride may be one of cobalt fluoride, manganese fluoride, lead fluoride, aluminum fluoride, copper fluoride, or magnesium fluoride. In the present embodiment, the resin is a porous crosslinked polystyrene resin, and in other embodiments, may be other adsorbent resins, which can achieve the technical effects of the present embodiment and are also within the scope of the present embodiment.
And step S5: separating light components and heavy components in a rectification section; wherein the rectification working section comprises a heavy component removal tower for removing heavy component impurities and a light component removal tower for removing light component impurities, the feeding amount of the heavy component removal tower is 26kg/h, the tower pressure is 0.45 MPa, the tower top temperature is-60 ℃, and the tower bottom temperature is-55 ℃. The feeding amount of the light component removal tower is 26kg/h, the tower pressure is 0.35MPa, the tower top temperature is-65 ℃, and the tower bottom temperature is-61 ℃.
And step S6: and separating the azeotropic substance impurities through a complicated rectification working section. The complex rectification section adopts a volume ratio of 4: 3: 3, extracting and rectifying the cyclohexane, the hexachlorobenzene and the m-phenylenediamine as extracting agents. Will have the composition SiF4、SiF3H、SiF2H2、SiFH3、SiF3Cl and SiF2Cl2Constant boiling ofThe material was further isolated. Wherein the complex rectification working section comprises three removal towers connected in series, the feeding amount of the removal towers is 26kg/h, the tower pressure is 2.5MPa, the tower top temperature is-27 ℃, and the tower bottom temperature is-23 ℃.
Example 2
The embodiment provides a method for synthesizing and purifying high-purity silicon tetrafluoride, which comprises the following steps:
and step S1: pretreating 800 kg of barium fluosilicate; specifically, the barium fluosilicate is vacuumized and heated at 100 ℃.
And step S2: carrying out cracking reaction on the barium fluosilicate in a reactor with the volume of 800L to prepare silicon tetrafluoride coarse material; the specific cracking reaction conditions are as follows: the pressure is 0.1MPa, the temperature is 300 ℃, the operation flow of a product outlet of the reactor is 20kg/h, and the volume of the reactor is 800L.
And step S3: removing trace moisture and acid gas in a first adsorption section;
and step S4: performing desorption and polymerization inhibition control on the fluorosilicone at a second adsorption section; wherein, the fluorosilicone is removed and polymerization inhibition control is carried out at the second adsorption section by adopting fluorinated resin, the fluorinated resin is prepared by coating lead fluoride on the surface of porous polystyrene cross-linked resin, the load rate of the lead fluoride is 1mmol/g, and the specific surface area of the porous polystyrene cross-linked resin is 600m2(ii) in terms of/g. In this embodiment, the metal fluoride is lead fluoride, and in other embodiments, the metal fluoride may be one of cobalt fluoride, manganese fluoride, silver fluoride, aluminum fluoride, copper fluoride, or magnesium fluoride. In the present embodiment, the resin is a porous crosslinked polystyrene resin, and in other embodiments, may be other adsorbent resins, which can achieve the technical effects of the present embodiment and are also within the scope of the present embodiment.
And step S5: separating light components and heavy components in a rectification section; wherein the rectification working section comprises a heavy component removal tower for removing heavy component impurities and a light component removal tower for removing light component impurities, the feeding amount of the heavy component removal tower is 20kg/h, the tower pressure is 3.0 MPa, the tower top temperature is-10 ℃, and the tower bottom temperature is-4 ℃. The feeding amount of the light component removal tower is 20kg/h, the tower pressure is 4MPa, the tower top temperature is 7 ℃, and the tower bottom temperature is 12 ℃.
And step S6: and separating the azeotropic substance impurities through a complicated rectification working section. The complex rectification section adopts a volume ratio of 4: 3: 3, extracting and rectifying the cyclohexane, the hexachlorobenzene and the m-phenylenediamine as extracting agents. Will have the composition SiF4、SiF3H、SiF2H2、SiFH3、SiF3Cl and SiF2Cl2Further separating the azeotrope of (1). Wherein the complex rectification working section comprises three removal towers connected in series, the feeding amount of the removal towers is 50kg/h, the tower pressure is 4.0MPa, the tower top temperature is-80 ℃, and the tower bottom temperature is-70 ℃.
Example 3
The embodiment provides a method for synthesizing and purifying high-purity silicon tetrafluoride, which comprises the following steps:
and step S1: pretreating 400 kg of potassium fluosilicate; specifically, potassium fluosilicate is vacuumized and heated at 200 ℃.
And step S2: cracking the potassium fluosilicate in a reactor with the volume of 500L to prepare a silicon tetrafluoride coarse material; the specific cracking reaction conditions are as follows: pressure 0.02MPa, temperature 500 ℃, reactor product outlet operating flow: 10kg/h, reactor volume: 500L.
And step S3: removing trace moisture and acid gas in a first adsorption section;
and step S4: performing desorption and polymerization inhibition control on the fluorosilicone at a second adsorption section; wherein, the fluorosilicone is removed and polymerization inhibition control is carried out at the second adsorption section by adopting fluorinated resin, the fluorinated resin is prepared by coating lead fluoride on the surface of porous polystyrene cross-linked resin, the load rate of the lead fluoride is 5mmol/g, and the specific surface area of the porous polystyrene cross-linked resin is 300m2(ii) in terms of/g. In this embodiment, the metal fluoride is lead fluoride, and in other embodiments, the metal fluoride may be one of cobalt fluoride, manganese fluoride, silver fluoride, aluminum fluoride, copper fluoride, or magnesium fluoride. In the present embodiment, the resin is a porous crosslinked polystyrene resin, and in other embodiments, may be another adsorbent resin, and the technical effects of the present embodiment can be achieved, and the present embodiment is also appliedThe scope of protection of the examples.
And step S5: separating light components and heavy components in a rectification section; wherein the rectification working section comprises a heavy component removal tower for removing heavy component impurities and a light component removal tower for removing light component impurities, the feeding amount of the heavy component removal tower is 2kg/h, the tower pressure is 0.1MPa, the tower top temperature is-69 ℃, and the tower bottom temperature is-62 ℃. The feeding amount of the light component removal tower is 2kg/h, the tower pressure is 0.1MPa, the tower top temperature is-66 ℃, and the tower bottom temperature is-62 ℃.
And step S6: and separating the azeotropic substance impurities through a complicated rectification working section. The complex rectification section adopts a volume ratio of 4: 3: 3, extracting and rectifying the cyclohexane, the hexachlorobenzene and the m-phenylenediamine as extracting agents. Will have the composition SiF4、SiF3H、SiF2H2、SiFH3、SiF3Cl and SiF2Cl2Further separating the azeotrope of (1). Wherein the complex rectification working section comprises three removal towers connected in series, the feeding amount of the removal towers is 2kg/h, the tower pressure is 0.2 MPa, the tower top temperature is-60 ℃, and the tower bottom temperature is-57 ℃.
Example 4
The embodiment provides a method for synthesizing and purifying high-purity silicon tetrafluoride, which comprises the following steps:
and step S1: pretreating 1200 kg of copper fluosilicate; specifically, the copper fluosilicate is vacuumized and heated at 180 ℃.
And step S2: carrying out cracking reaction on the copper fluosilicate in a reactor with the volume of 1000L to prepare a silicon tetrafluoride coarse material; the specific cracking reaction conditions are as follows: the pressure is 0.08MPa, the temperature is 400 ℃, the operation flow of a product outlet of the reactor is 30 kg/h, and the volume of the reactor is 1000L.
And step S3: removing trace moisture and acid gas in a first adsorption section;
and step S4: performing desorption and polymerization inhibition control on the fluorosilicone at a second adsorption section; wherein, the fluorine-silicon ether is removed and polymerization inhibition is controlled at the second adsorption section by adopting fluorinated resin, the fluorinated resin is prepared by coating lead fluoride on the surface of porous polystyrene cross-linked resin, the load rate of the lead fluoride is 4mmol/g, and the porous polystyrene cross-linked resin is prepared by the way that the fluorine-silicon ether is removed and polymerization inhibition is carried out on the fluorine-silicon etherSpecific surface area of lipid is 400m2(ii) in terms of/g. In this embodiment, the metal fluoride is lead fluoride, and in other embodiments, the metal fluoride may be one of cobalt fluoride, manganese fluoride, silver fluoride, aluminum fluoride, copper fluoride, or magnesium fluoride. In the present embodiment, the resin is a porous crosslinked polystyrene resin, and in other embodiments, may be other adsorbent resins, which can achieve the technical effects of the present embodiment and are also within the scope of the present embodiment.
And step S5: separating light components and heavy components in a rectification section; wherein the rectification working section comprises a heavy component removal tower for removing heavy component impurities and a light component removal tower for removing light component impurities, the feeding amount of the heavy component removal tower is 30 kg/h, the tower pressure is 2.0MPa, the tower top temperature is-40 ℃, and the tower bottom temperature is-45 ℃. The feeding amount of the light component removal tower is 30 kg/h, the tower pressure is 2.5MPa, the tower top temperature is-35 ℃, and the tower bottom temperature is-28 ℃.
And step S6: and separating the azeotropic substance impurities through a complicated rectification working section. The complex rectification section adopts a volume ratio of 4: 3: 3, extracting and rectifying the cyclohexane, the hexachlorobenzene and the m-phenylenediamine as extracting agents. Will have the composition SiF4、SiF3H、SiF2H2、SiFH3、SiF3Cl and SiF2Cl2Further separating the azeotrope of (1). In this embodiment, a volume ratio of 4: 3: 3, extracting and rectifying the cyclohexane, hexachlorobenzene and m-phenylenediamine as an extracting agent to achieve the aim of complex rectification, and distilling by adopting a high-pressure distillation method to separate azeotropic substances. Wherein the complex rectification working section comprises three removal towers connected in series, the feeding amount of the removal towers is 30 kg/h, the tower pressure is 3.0 MPa, the tower top temperature is-28 ℃, and the tower bottom temperature is-25 ℃.
Comparative example 1
The main difference between this comparative example 1 and example 1 is that: comparative example 1 did not have the step of S4.
Comparative example 2
The main difference between this comparative example 2 and example 1 is that: the adsorption was performed using the untreated porous polystyrene crosslinked resin in the step S4 of comparative example 2.
Comparative example 3
The main difference between this comparative example 3 and example 1 is that: in comparative example 3 there was only one removal column.
Test example 1
The experimental example uses Agilent 7820 as equipment and adopts a cutting sample injection method specified in GB/T28726 to measure the contents of hydrogen, oxygen + argon, nitrogen, carbon monoxide, carbon dioxide and methane in the silicon tetrafluoride synthesized in example 1 ~ 4 and comparative example 1 ~ 3.
Pre-separation column, 316L stainless steel column with length of about 5m and inner diameter of 2mm, and Porapak Q (high molecular polymer) with particle size of 0.18mm ~ 0.25.25 mm.
The chromatographic column I is a 316L stainless steel column with the length of about 2m and the inner diameter of 2mm, and is filled with a 5A molecular sieve with the particle size of 0.18mm ~ 0.25mm and used for analyzing hydrogen, oxygen, argon and nitrogen.
Chromatographic column II, 316L stainless steel column with length of about 2m and inner diameter of 2mm, filled with HayeSep DB (high molecular polymer) with particle size of 0.18mm ~ 0.25mm for analyzing the content of carbon monoxide, methane and carbon dioxide.
Standard samples: the volume fraction of the component content is 2 x 10-6The balance gas is helium.
The content of hydrogen sulfide and sulfur dioxide in the silicon tetrafluoride synthesized in example 1 ~ 4 and comparative example 1 ~ 3 was determined by the method of cutting sample injection specified in GB/T28726.
The pre-separation column is a polytetrafluoroethylene tube with a length of about 5m and an inner diameter of 2mm, and is filled with Porapak Q (high molecular polymer) with a particle size of about 0.18mm ~ 0.25.25 mm.
Chromatographic column I is polytetrafluoroethylene tube with length of 3m and inner diameter of 2mm, and GDX-303 with particle size of 0.18mm ~ 0.25mm is filled in the tube.
Standard samples: the volume fraction of the component content is 2 x 10-6The balance gas is helium.
The silicon tetrafluoride purity is calculated by the formula:
A=100-（A1+ A2+ A3+ A4+ A5+ A6+ A7+ A8）*10-4
in the formula:
a: silicon tetrafluoride purity (volume fraction), 10-2；
A1: content of Hydrogen (volume fraction), 10-6；
A2: content of Nitrogen (volume fraction), 10-6；
A3: oxygen + argon content (volume fraction), 10-6；
A4: carbon monoxide content (volume fraction), 10-6；
A5: carbon dioxide content (volume fraction), 10-6；
A6: content of methane (volume fraction), 10-6；
A7: content of hydrogen sulfide (volume fraction), 10-6；
A8: sulfur dioxide content (volume fraction), 10-6；
The results of test example 1 are shown in Table 1 below
Table 1 purity of silicon tetrafluoride prepared in example 1 ~ 4 and comparative example 1 ~ 3
From example 1 ~ in table 1, the purity of the silicon tetrafluoride prepared by the present invention is as high as 99.99%, even though only one removal column is used in comparative example 4, the purity of the obtained silicon tetrafluoride is 95%, and when the removal and inhibition control is not performed on fluorosilicone, the purity of the silicon tetrafluoride is low and cannot reach the electronic grade.
In conclusion, the synthesis and purification method of high-purity silicon tetrafluoride provided by the invention adopts a negative pressure process in the cracking reaction, and when the silicon tetrafluoride is produced, the silicon tetrafluoride can be quickly pumped away, so that the conversion rate and selectivity of cracking are improved. The adsorption unit is adopted to remove the fluorosilicone ether, and the polymerization problem of the fluorosilicone ether is solved through the polymerization inhibitor. Aiming at the difficulty in removing the azeotrope, a complex rectification process system is added after the conventional rectification unit is adopted for operation. The synthetic method scientifically combines heating cracking, adsorption unit operation, rectification and complex rectification, adopts the adsorption unit to remove fluorosilicone, adopts the conventional rectification unit operation and adds a complex rectification process to remove azeotrope, and the purity of the synthesized high-purity silicon tetrafluoride can reach five 9, namely 5N5 electronic grade, and can be used in the fields of integrated circuits, flat panel display, photovoltaics, optical fibers and the like.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (9)
1. A method for synthesizing and purifying high-purity silicon tetrafluoride is characterized by comprising the following steps:
and step S1: pre-treating fluosilicate;
and step S2: carrying out cracking reaction on fluorosilicate to prepare a silicon tetrafluoride coarse material;
and step S3: removing trace moisture and acid gas in a first adsorption section;
and step S4: performing desorption and polymerization inhibition control on the fluorosilicone at a second adsorption section;
and step S5: separating light components and heavy components in a rectification section;
and step S6: and separating the azeotropic substance impurities through a complicated rectification working section.
2. The method as claimed in claim 1, wherein the cracking reaction is performed under the conditions of pressure 0.02 ~ 0.1.1 MPa, temperature 300 ~ 500 ℃, reactor outlet operation flow rate 10-30 kg/h, reactor type rotary kiln reactor and volume 500-1000L in the step S2.
3. The method for synthesizing and purifying high-purity silicon tetrafluoride according to claim 1, wherein in the step of S4, the fluorosilicone ether is removed and polymerization inhibition controlled at the second adsorption stage by using a fluorinated resin prepared by coating a metal fluoride on the surface of a resin.
4. The method for synthesizing and purifying high-purity silicon tetrafluoride according to claim 3, wherein the metal fluoride is one of silver fluoride, cobalt fluoride, manganese fluoride, lead fluoride, aluminum fluoride, copper fluoride or magnesium fluoride, and the metal fluoride loading rate is 1 ~ 5 mmol/g.
5. The method as claimed in claim 4, wherein the resin is a porous cross-linked polystyrene resin having a specific surface area of 300 ~ 600m2/g。
6. The method for synthesizing and purifying high-purity silicon tetrafluoride according to claim 1, wherein in the step of S5, the rectifying section comprises a de-weighting tower and a de-weighting tower, the feeding amount of the de-weighting tower is 2 ~ 50kg/h, the tower pressure is 0.1 ~ 3.0.0 MPa, the tower top temperature is-80 ~ -10 ℃, the tower bottom temperature is-70 ~ -5 ℃, the feeding amount of the de-weighting tower is 2 ~ 50kg/h, the tower pressure is 0.1 ~ 4.0.0 MPa, the tower top temperature is-80 ~ 5 ℃, and the tower bottom temperature is-70 ~ 15 ℃.
7. The method as claimed in claim 6, wherein in the step of S6, the complicated distillation section adopts a volume ratio of 4: 3: 3, extracting and rectifying the cyclohexane, the hexachlorobenzene and the m-phenylenediamine as extracting agents.
8. The method for synthesizing and purifying high-purity silicon tetrafluoride according to claim 6, wherein in the step of S6, the complicated distillation section comprises three removal columns connected in series, the feeding amount of the removal columns is 2 ~ 50kg/h, the column pressure is 0.2 ~ 4.0.0 MPa, the temperature at the top of the column is-80 ~ 5 ℃, and the temperature at the bottom of the column is-70 ~ 15 ℃.
9. The method for synthesizing and purifying high-purity silicon tetrafluoride according to claim 1, wherein the step S1 is carried out by vacuum-pumping fluorosilicate and heating at 100 ~ 200 ℃.
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