WO2006019334A1 - Procede de production de silicium, procede de separation du silicium et d'une masse de sels en fusion et procede de fabrication du tetrafluorure de silicium - Google Patents
Procede de production de silicium, procede de separation du silicium et d'une masse de sels en fusion et procede de fabrication du tetrafluorure de silicium Download PDFInfo
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- WO2006019334A1 WO2006019334A1 PCT/RU2005/000400 RU2005000400W WO2006019334A1 WO 2006019334 A1 WO2006019334 A1 WO 2006019334A1 RU 2005000400 W RU2005000400 W RU 2005000400W WO 2006019334 A1 WO2006019334 A1 WO 2006019334A1
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- WO
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- Prior art keywords
- silicon
- melt
- carried out
- tetrafluoride
- powder
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 116
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 90
- 239000010703 silicon Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 150000003839 salts Chemical class 0.000 title claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 54
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 47
- 239000011737 fluorine Substances 0.000 claims abstract description 47
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000005496 eutectics Effects 0.000 claims abstract description 29
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000155 melt Substances 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 12
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 7
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000003792 electrolyte Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 24
- 238000005868 electrolysis reaction Methods 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- -1 alkali metal salts Chemical class 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 31
- 239000004065 semiconductor Substances 0.000 abstract description 23
- 238000009738 saturating Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 11
- 229910020640 KF—NaF Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 0.000 description 2
- 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 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical group [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 1
- 229910021338 magnesium silicide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004576 sand Substances 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
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- IEPMHPLKKUKRSX-UHFFFAOYSA-J silicon(4+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Si+4] IEPMHPLKKUKRSX-UHFFFAOYSA-J 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation 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
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/20—Fluorine
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
Definitions
- the invention relates to technologies for the production of rare metals and non-metals, namely: to the production of electrolytically pure, suitable for use in solar energy and in semiconductor technology, silicon powder, more specifically, to methods for reducing silicon from gaseous silicon tetrafluoride, as well as to a technology for producing tetrafluoride silicon.
- Semiconductor silicon is obtained from a technical (metallurgical) material by chlorinating finely ground silicon powder with anhydrous hydrogen chloride, followed by purification of chlorosilanes formed during chlorination by rectification to the required purity (see the book by E. Falkevich, et al. Semiconductor silicon technology., M. : Metallurgy, 1992). In some countries, semiconductor silicon is obtained by fusion of industrial silicon with magnesium, decomposition of magnesium silicide, subsequent low-temperature distillation purification of monosilane and its thermal decomposition (see the book Belov I.P. et al. Monosilane in the technology of semiconductor materials.
- a known method of producing a fine silicon powder from gaseous silicon tetrafluoride see RU 2066296, IPC C01BZZ / 03, publ.
- SHEET 09/10/96 isolated from waste products of uranium hexafluoride, which is Na 2 SiF 6 .
- the basis of this method is the decomposition of gaseous silicon tetrafluoride under the action of laser radiation.
- powerful continuous radiation of a CO 2 laser (2-10 kW) was introduced into the reaction chamber (closed volume), in which gaseous silicon tetrafluoride and hydrogen circulating fluorine during the decay of SiF 4 are simultaneously circulated.
- the method of producing silicon from silicon tetrafluoride by laser technology using waste production of uranium hexafluoride allows you to get pure silicon at a relatively low cost.
- the purity of such silicon is approximately 99%, which is insufficient for its use in solar energy or in semiconductor technology.
- a known technology for producing semiconductor silicon, in particular silicon for solar cells (see RU 2035397, IPC C01B ⁇ / 02, publ. 05.20.1995), including a series of gas transport reactions using silicon tetrafluoride, from which, as a result of its interaction with deionized water, hydrofluoric acid. Silicon is obtained by reducing it at room temperature from fluorosilicic acid with atomic hydrogen.
- Replacement sheet low melting cathode which is used as a molten metal, in particular zinc.
- a mixture of fluorine and chlorine on the anode, a mixture of fluorine and chlorine, and the cathode, i.e. Zinc melt absorbs metallic silicon released from the aforementioned silicon-containing compounds and, as a solution of metallic silicon, is further processed to produce silicon as a commercial product.
- Another disadvantage of the prototype is the frequency of the process. In order to separate silicon from a liquid cathode melt, it is necessary at a certain stage characterized by sufficient saturation of the cathode melt with silicon particles, stop the electrolysis, direct the silicon melt to the silicon precipitation stage, and fill the electrolytic apparatus with a new zinc melt, and only after all these procedures to continue the process.
- the disadvantage of this method is that in addition to fluorine, chlorine gas is released on the anode.
- both of the elements released on the anode are transported to release silicon from a silicon-containing raw material, i.e. these elements are negotiable, the need to separate one element from another complicates the technology, increases its hardware support and, as a result, leads to an increase in the cost of the final product.
- a known method of producing silicon tetrafluoride from a solution of hydrofluoric acid see patent RU 2046095, IPC COl B 33/10, publ. 20.10.95, including the interaction of a solution of this acid with a solution of an organic base with the formation of salts of hydrofluoric acid.
- the resulting salt is washed, dried and decomposed by treatment with concentrated mineral acid, and after the decomposition step, the obtained silicon terrafluoride is separated from hydrogen fluoride.
- the main disadvantage of the prototype is the environmental insecurity of the technology, as well as the fact that the silicon tetrafluoride obtained is characterized by a high content of impurities, which makes it unsuitable for use in semiconductor silicon production technology.
- the problem to which the claimed group of inventions is directed is to develop an effective and environmentally safer technology for producing electrolytically pure and relatively inexpensive semiconductor silicon with the simultaneous production of high-purity silicon tetrafluoride and elemental fluorine, which can be used as in the inventive method for producing semiconductor silicon as a reverse chemical compounds and chemical elements, and can be commercial products with high quality tween characteristics.
- the problem is solved in that in the method for producing silicon from silicon tetrafluoride with the simultaneous production of elemental fluorine by electrolysis and with the release of elemental fluorine at the anode, according to the claimed invention, electrolysis of the eutectic melt of ternary alkali metal fluoride salts systems saturated with silicon tetrafluoride is electrolytically decomposed. Silicon released in the form of a suspension of silicon powder and electrolyte, which is the above-mentioned eutectic melt of ternary systems of alkali metal fluoride salts, is removed from the electrolyzer. After withdrawal of said suspension, i.e. outside the electrolyzer, silicon powder is separated from the eutectic melt of the ternary systems of alkali metal fluoride salts.
- the technical result of the claimed method is the ability to realize the production of silicon in a continuous mode, with a high yield of finished products and its high quality. This result is due to the following distinctive features.
- a distinctive feature of the proposed method is that in the process of producing high-purity silicon, the eutectic melt of ternary systems of fluoride salts of certain alkali metals is used, i.e. chemical compounds containing fluorine, and the saturation of this melt is carried out with silicon tetrafluoride, i.e. a chemical compound that also contains fluorine. This allows one stage to obtain high quality electrolytically pure semiconductor
- Another distinctive feature of the proposed method for producing silicon is that for the selection of the product does not need to stop the electrolysis process, the withdrawal of silicon powder in a mixture with molten electrolyte can be continuous.
- the method in which the eutectic melt of the ternary systems of alkali metal fluoride salts after separation of the silicon powder is sent for reuse in the electrolysis process, thereby closing the process and ensuring waste-free production.
- the withdrawal of electrolytically obtained silicon is accompanied by a drain of the electrolyte and its constant replenishment, i.e. the electrolyte is essentially flowing, but due to the fact that the suspension is taken in the inter-pole gap of the electrolyte, the electrolyte is not subject to “flow” in full, but to the “chosen” part, i.e. the volume (that part) that represents the suspension with the highest concentration of the released powder is constantly withdrawn from the process.
- the continuity of the withdrawal of the suspension by silicon and electrolyte powders is also facilitated by the fact that the density of the electrolyte with the released silicon powder is less than the density of the electrolyte without powder, i.e. the suspension is extruded by a column of electrolyte.
- the inventive method is the most technologically advanced if the eutectic melt of the following composition is used as a melt eutectic of ternary systems of alkali metal fluoride salts: LiF-KF-NaF, and electrolysis is carried out at a temperature of 450 ° C-600 ° C.
- a salt melt is preferable on the basis that the melting temperature of the initial components of the melt is lower than the melting temperature of silicon, while the temperature regime is most optimal for electrolysis and the process of separation of silicon powder.
- the melt of the eutectic of fluoride salts LiF-KF-NaF is saturated with silicon tetrafluoride in the range of 2-35% of May. according to SiF 4.
- a parameter below 2% requires a very high voltage, which is not economically feasible, and a parameter above 35% will increase the melting point of the eutectic of fluoride salts, which is also undesirable.
- the electrolysis efficiency increases if the saturation of the eutectic melt of ternary systems of alkali metal fluoride salts is carried out by bubbling silicon tetrafluoride into the melt. This is because bubbling ensures uniform saturation of the molten electrolyte with higher fluoride of the starting element in the gas phase.
- the inventive method for separating silicon from molten salts solves the same problem as the method described above for producing high-purity semiconductor silicon and elemental fluorine, i.e. the task of obtaining high-purity semiconductor silicon of low cost.
- Replacement sheet NaF in the form of a liquid phase and from silicon particles, which are a solid phase, is filtered to separate the solid phase in the form of silicon powder, and the liquid phase is directed to the distillation of hydrogen fluoride, which is used in the dissolution stage.
- the solidified melt with silicon particles is crushed before dissolution, and the dissolution process is carried out at a temperature of from -5 ° C to +12 0 C, with the preferred result of the dissolution process being the resulting composition with a solid phase to liquid phase ratio of 1 : 23, i.e. 23 parts of HF + (Li-KF-NaF) contain one part of solid silicon particles.
- This ratio predetermined by the supply of an appropriate amount of anhydrous hydrogen fluoride to a certain amount of melt with silicon particles, is most optimal for further filtering the composition and separating the silicon powder.
- the filtration is carried out by centrifugation using centrifuges produced by the industry, or the same centrifuges, structurally modified based on specific production conditions.
- the proposed method it is applicable to purify silicon powder from metal impurities by washing it with a solution of a mixture of inorganic acids, in particular of the following composition: 2-3 MH 2 SO 4 + OD-0.2 M HF at a temperature of 5 ° C-75 ° C, followed by drying of silicon powder in an inert medium and at 80 0 C - 120 ° ⁇ .
- a solution of a mixture of inorganic acids in particular of the following composition: 2-3 MH 2 SO 4 + OD-0.2 M HF at a temperature of 5 ° C-75 ° C, followed by drying of silicon powder in an inert medium and at 80 0 C - 120 ° ⁇ .
- the melt of the eutectic of fluoride salts LiF-KF-NaF is used in the method of producing high-purity silicon powder from silicon tetrafluoride with the simultaneous production of elemental fluorine, i.e. in the first of the claimed group of the invention set forth in claim l of the formula.
- electrolytically pure silicon which is characterized by the content of the following components: silicon with a weight content of C 1 , metal impurities with a weight content of C 2 and non-metal impurities with a weight content of C 3 .
- electrolytically pure silicon is obtained by fluoride technology according to the method according to claim 1, i.e. during electrolytic decomposition of the eutectic melt of ternary systems of alkali metal fluoride salts saturated with silicon tetrafluoride, it is removed from the electrolyzer in the form of a suspension with an electrolyte, isolated from the electrolyte melt according to the method of claim 8, and is characterized by the above composition provided that:
- the claimed solutions provide highly pure elemental fluorine, including fluorine with a mass content of C 4 and impurities with their mass content of C 5 , which is obtained by fluoride technology according to the method according to claim 1 of the formula, i.e. isolated on the anode during electrolytic decomposition of the eutectic melt of ternary systems of alkali metal fluoride salts saturated with silicon tetrafluoride, and is characterized by the above composition under the condition:
- the problem of obtaining high-purity silicon powder is also solved by a method for producing silicon tetrafluoride used in the above technology, which includes the use of silicon dioxide as the starting compound, and which differs from the known solutions for the production of silicon tetrafluoride in that silicon dioxide is fluorinated by exposure to elemental fluorine, the fluorination process lead in two stages, of which: at the first stage, silicon dioxide is treated with elemental fluorine at a temperature of HOO 0 C - 1200 0 C, while the supply of elemental fluorine is carried out from May 20-30%. excess relatively stoichiometrically necessary amount and the gas phase is sent to the 2nd stage of the process, at the 2nd stage carry out the fluorination of silicon dioxide when it is supplied with 70-
- Replacement sheet May 80th. excess, while using an excess of elemental fluorine of the 1st stage with its complete absorption.
- fluorination is carried out in a flame of a flame reactor.
- fluorine obtained by the method for producing high-purity silicon powder by electrolysis of a melt eutectic of ternary systems of alkali metal fluoride salts saturated with silicon tetrafluoride i.e. fluorine obtained by the method described in paragraph l of the formula of the claimed group of inventions.
- the proposed methods serve one purpose and provide the possibility of recirculation of the chemical elements and compounds obtained during the process, thereby causing the closure of the technological cycle for producing high-purity silicon, which, along with solving the problem by means of a set of characteristics set forth in independent clauses, is also aimed at reducing the cost of the final product - high purity semiconductor silicon.
- the possibility of returning the spent substance back to the process solves the problem of waste of harmful substances, eliminates their release into the atmosphere, eliminates the need for their disposal and cleaning, etc.
- the claimed group of inventions is so interconnected that these inventions form a single common inventive concept, and there is a technical relationship between the inventions.
- FIG. 1 is a flowchart showing a process (part I) for producing high-purity silicon powder and elemental fluorine, including a set of process steps (part II) for separating silicon powder from molten salts;
- FIG. 2 is a flowchart illustrating a method for producing silicon tetrafluoride;
- equipment and hardware complexes used at the enterprises of the chemical industry and in metallurgy are used, namely: electrolyzers or similar reactors, flare (flame) reactors; bubbling plants, equipment for flotation, flushing, etc., drying units, transport systems designed to supply gas, liquid or solid reagents, known control equipment, etc.
- the electrolyte saturated with silicon tetrafluoride is continuously supplied to electrolyzer 2, either with a liquid metal cathode or with a solid cathode (stainless steel, silicon) and with inert anodes (carbide, silicon nitride, graphite).
- electrolyzer 2 either with a liquid metal cathode or with a solid cathode (stainless steel, silicon) and with inert anodes (carbide, silicon nitride, graphite).
- the design of the electrolyzer should be carried out taking into account the continuous withdrawal of the suspension of the released silicon powder and electrolyte from the pole gap of the electrolyzer.
- Si F 6 2 " dissociates into ions: positive Si 4+ ions and negative fluorine ions (6F " ), which are reduced: positive silicon ions on the cathode are reduced to metal silicon powder (Si), negative fluorine ions - on the anode to elemental fluorine ( ⁇ F ⁇ )
- silicon is obtained in the form of a suspension of Si powder in the electrolyte melt in a ratio of 2: 8 parts, i.e. 2 parts of silicon powder and 8 parts of electrolyte.
- Silicon powder mixed with an electrolyte melt i.e., a suspension including silicon powder and LiF-KF-NaF eutectic melt) is discharged from the cell.
- the silicon powder is separated from the molten electrolyte. This can be done by any known methods, or by the claimed method of separating silicon from molten salts (see Fig. 1, part II).
- the process is carried out in accordance with the claimed method of separating silicon from a salt melt, namely from a melt of the eutectic of fluoride salts LiF-KF-NaF.
- the solidified molten electrolyte with silicon powder is crushed in a known manner using a crusher 3.
- the crushed composition in the reactor 4 is dissolved with hydrogen fluoride HF, dissolve with stirring and at a temperature of from -5 0 C to + 12 ° C.
- a suspension is obtained from the electrolyte and silicon powder dissolved in hydrogen fluoride and the suspension is filtered to separate the Si powder using a centrifuge 5.
- the silicon powder separated by centrifugation is sent to flotation machine b, and
- the silicon powder is washed first in a solution of inorganic acids of the composition 2-3 MH 2 SO 4 + 0.1-0.2 M HF, and in the washing installation 8 with condensate (demineralized water).
- the silicon powder washed with demineralized water on the unit 9 is filtered off from water and dried in a dryer 10 in an inert medium at a temperature of 80 ° C-120 ° C. Ready high-purity, suitable for use in solar energy and in semiconductor technology, silicon powder is packaged.
- the electrolytically pure silicon powder obtained by the above method is characterized by a composition comprising silicon with a weight content of C 1 , metal impurities with a weight content of C 2 and non-metal impurities with a weight content of C 3 , under the condition:
- silicon tetrafluoride is used, which is obtained using a complex of equipment 13 and the claimed method for producing silicon tetrafluoride, an example of which is given below (see Fig. 2).
- the starting material for producing silicon tetrafluoride is natural quartzite, silica sand or other raw materials containing a large amount of silicon dioxide.
- this raw material is characterized by the following composition: SiO 2 ⁇ 97%, macroimpurity: Fe 2 O 3 , CaO, Al 2 O 3
- silicon dioxide SiO 2 is treated with elemental fluorine F 2 (obtained by the method according to claim 1) at a temperature of HOO 0 C - 1200 ° C, while the treatment is carried out in a flame of a flame reactor 14.
- the elemental fluorine is fed into the reactor 14 with excess (20-30%) relative to the stoichiometrically necessary amount.
- the gaseous phase including gaseous silicon tetrafluoride SiF 4 , and also including the oxygen obtained in the reaction process and the excess fluorine (02 + F2) not involved in the reaction process.
- a slurry containing macroimpurity fluorides is removed from reactor 14: aluminum trifluoride (AlF 3 ), calcium difluoride (CaF 2 ), iron trifluoride (FeF 3 ).
- AlF 3 aluminum trifluoride
- CaF 2 calcium difluoride
- FeF 3 iron trifluoride
- silicon dioxide is simultaneously fed into it, which is supplied from May 70-80%. in excess.
- the excess of elementary fluorine of the 1st stage is completely absorbed, the silicon tetrafluoride obtained is used as a reagent to saturate the electrolyte in the method for producing high-purity silicon powder and elemental fluorine, or it is removed from the process as a finished product, and the excess of silicon dioxide is sent into the first reactor 14, thus closing the process.
- the inventive method for producing silicon tetrafluoride ensures the full use of elemental fluorine in the technological process, including it may be fluorine obtained by electrolytic production of silicon powder.
- the inventive inventions forming a fluoride technology for producing high-purity semiconductor silicon are energy and
- SHEET resource-saving while the technology is characterized by environmental friendliness due to the fact that the process is conducted in a closed cycle using fluorine obtained during electrolysis to obtain silicon tetrafluoride, and also due to the fact that the spent electrolyte is returned completely to the process.
- the resulting products (silicon, fluorine, silicon tetrafluoride) are characterized by a very small amount of impurities, and the cost of silicon as a finished product is much lower than by other known technologies.
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
UAA200700624A UA80662C2 (en) | 2004-08-12 | 2005-01-08 | Method for preparation of silicium, method for separation of silicium from fusion of salts and method for preparation of silicium tetrafluoride |
DE112005001969T DE112005001969T5 (de) | 2004-08-12 | 2005-08-01 | Verfahren zur Herstellung von Silicium, Verfahren zur Abtrennung von Silicium aus einer Salzschmelze und Verfahren zur Herstellung von Siliciumtetrafluorid |
CN2005800271905A CN101090862B (zh) | 2004-08-12 | 2005-08-01 | 生产硅的方法、从熔融的盐中分离硅的方法和生产四氟化硅的方法 |
US11/673,788 US20070209945A1 (en) | 2004-08-12 | 2007-02-12 | Method for producing silicon, method for separating silicon from molten salt and method for producing tetrafluoride |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2004124626/15A RU2272785C1 (ru) | 2004-08-12 | 2004-08-12 | Способ получения высокочистого порошка кремния из тетрафторида кремния с одновременным получением элементного фтора, способ отделения кремния от расплава солей, полученные вышеуказанным способом порошок кремния и элементный фтор и способ получения тетрафторида кремния |
RU2004124626 | 2004-08-12 |
Related Child Applications (1)
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US11/673,788 Continuation US20070209945A1 (en) | 2004-08-12 | 2007-02-12 | Method for producing silicon, method for separating silicon from molten salt and method for producing tetrafluoride |
Publications (1)
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WO2006019334A1 true WO2006019334A1 (fr) | 2006-02-23 |
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PCT/RU2005/000400 WO2006019334A1 (fr) | 2004-08-12 | 2005-08-01 | Procede de production de silicium, procede de separation du silicium et d'une masse de sels en fusion et procede de fabrication du tetrafluorure de silicium |
Country Status (7)
Country | Link |
---|---|
US (1) | US20070209945A1 (fr) |
CN (1) | CN101090862B (fr) |
DE (1) | DE112005001969T5 (fr) |
ES (1) | ES2319072B1 (fr) |
RU (1) | RU2272785C1 (fr) |
UA (1) | UA80662C2 (fr) |
WO (1) | WO2006019334A1 (fr) |
Families Citing this family (9)
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EP1880042B1 (fr) * | 2005-05-13 | 2010-10-20 | Wulf Nägel | Electrolyse du quartz en bain de sels fondus, à basse température |
CH703236B1 (fr) * | 2007-12-19 | 2011-12-15 | Ecole Polytech | Procédé de récupération de silicium dans des déchets de sciage. |
CN101736354B (zh) * | 2008-11-06 | 2011-11-16 | 北京有色金属研究总院 | 电化学法制备硅纳米粉、硅纳米线和硅纳米管中的一种或几种的方法 |
US9101896B2 (en) * | 2010-07-09 | 2015-08-11 | Sri International | High temperature decomposition of complex precursor salts in a molten salt |
RU2486290C1 (ru) * | 2012-05-10 | 2013-06-27 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Способ получения нано- и микроструктурных порошков и/или волокон кристаллического и/или рентгеноаморфного кремния |
CN106145127A (zh) * | 2015-04-21 | 2016-11-23 | 广州凌玮科技股份有限公司 | 一种中空微球二氧化硅的制备方法 |
CN105019015A (zh) * | 2015-07-09 | 2015-11-04 | 上海大学 | 一种无定型硅材料的电化学制备方法 |
US10106902B1 (en) | 2016-03-22 | 2018-10-23 | Plasma Processes, Llc | Zirconium coating of a substrate |
CN109037028B (zh) * | 2018-06-22 | 2021-03-02 | 江苏京尚圆电气集团有限公司 | 一种硅料清洗方法 |
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SU460326A1 (ru) * | 1973-06-19 | 1975-02-15 | Институт общей и неорганической химии | Электролит дл получени металлического кремни электролизом из расплавов |
RU2156220C1 (ru) * | 1999-05-26 | 2000-09-20 | Карелин Александр Иванович | Способ получения раствора металлического кремния, способ получения металлического кремния из раствора и металлический кремний, полученный на основе этих способов, способ получения керамических материалов и керамический материал, полученный на основе этого способа |
US20040094428A1 (en) * | 2001-02-26 | 2004-05-20 | Stubergh Jan Reidar | Process for preparing silicon by electrolysis and crystallization and preparing low-alloyed and high-alloyed aluminum silicon alloys |
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US1080662A (en) * | 1912-01-23 | 1913-12-09 | Percy E Donner | Triple valve. |
US3022233A (en) * | 1959-11-18 | 1962-02-20 | Dow Chemical Co | Preparation of silicon |
US3983012A (en) * | 1975-10-08 | 1976-09-28 | The Board Of Trustees Of Leland Stanford Junior University | Epitaxial growth of silicon or germanium by electrodeposition from molten salts |
US4142947A (en) * | 1977-05-12 | 1979-03-06 | Uri Cohen | Electrodeposition of polycrystalline silicon from a molten fluoride bath and product |
FR2480796A1 (fr) * | 1980-04-21 | 1981-10-23 | Extramet Sarl | Procede de production de silicium de haute purete par voie electrochimique |
RU2046095C1 (ru) * | 1991-06-25 | 1995-10-20 | Всероссийский научно-исследовательский институт неорганических материалов им.акад. А.А.Бочвара | Способ получения тетрафторида кремния |
NO942121L (no) * | 1994-06-07 | 1995-12-08 | Jan Stubergh | Fremstilling og anordning for fremstilling av silisium-"metall", silumin og aluminium-metall |
UA73847C2 (en) * | 2003-09-02 | 2005-09-15 | A method for preparing silicon tetrafluoride, a method for isolation of the silicon tetrafluoride from oxygen and highly volatile admixtures, a method for preparing silicon powder from the silicon tetrafluoride |
-
2004
- 2004-08-12 RU RU2004124626/15A patent/RU2272785C1/ru not_active IP Right Cessation
-
2005
- 2005-01-08 UA UAA200700624A patent/UA80662C2/uk unknown
- 2005-08-01 WO PCT/RU2005/000400 patent/WO2006019334A1/fr active IP Right Grant
- 2005-08-01 ES ES200750013A patent/ES2319072B1/es not_active Expired - Fee Related
- 2005-08-01 DE DE112005001969T patent/DE112005001969T5/de not_active Withdrawn
- 2005-08-01 CN CN2005800271905A patent/CN101090862B/zh not_active Expired - Fee Related
-
2007
- 2007-02-12 US US11/673,788 patent/US20070209945A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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SU460326A1 (ru) * | 1973-06-19 | 1975-02-15 | Институт общей и неорганической химии | Электролит дл получени металлического кремни электролизом из расплавов |
RU2156220C1 (ru) * | 1999-05-26 | 2000-09-20 | Карелин Александр Иванович | Способ получения раствора металлического кремния, способ получения металлического кремния из раствора и металлический кремний, полученный на основе этих способов, способ получения керамических материалов и керамический материал, полученный на основе этого способа |
US20040094428A1 (en) * | 2001-02-26 | 2004-05-20 | Stubergh Jan Reidar | Process for preparing silicon by electrolysis and crystallization and preparing low-alloyed and high-alloyed aluminum silicon alloys |
Also Published As
Publication number | Publication date |
---|---|
DE112005001969T5 (de) | 2007-07-12 |
ES2319072B1 (es) | 2010-02-16 |
US20070209945A1 (en) | 2007-09-13 |
ES2319072A1 (es) | 2009-05-01 |
UA80662C2 (en) | 2007-10-10 |
CN101090862B (zh) | 2010-08-11 |
RU2272785C1 (ru) | 2006-03-27 |
CN101090862A (zh) | 2007-12-19 |
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