WO2014177560A1 - Procédé de production de tétrafluorure de silicium - Google Patents

Procédé de production de tétrafluorure de silicium Download PDF

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Publication number
WO2014177560A1
WO2014177560A1 PCT/EP2014/058722 EP2014058722W WO2014177560A1 WO 2014177560 A1 WO2014177560 A1 WO 2014177560A1 EP 2014058722 W EP2014058722 W EP 2014058722W WO 2014177560 A1 WO2014177560 A1 WO 2014177560A1
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WO
WIPO (PCT)
Prior art keywords
mixture
sif
carbon
containing material
transfer
Prior art date
Application number
PCT/EP2014/058722
Other languages
German (de)
English (en)
Inventor
Norbert Auner
Christian Bauch
Rumen Deltschew
Sven Holl
Javad MOHSSENI
Original Assignee
Spawnt Private S.À.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Spawnt Private S.À.R.L. filed Critical Spawnt Private S.À.R.L.
Publication of WO2014177560A1 publication Critical patent/WO2014177560A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/10705—Tetrafluoride

Definitions

  • the present invention relates to a process for producing silicon tetrafluoride (SiF 4 ).
  • HF tetrafluoride
  • Both compounds are washed out in technical production with water from the reaction exhaust gas and are then as an aqueous solution of hexafluorosilicic acid H 2 SiF6
  • H 2 SiF 6 is not isolable in pure form, but decomposes upon dehydration of the solution in reversal of the formation reaction to HF and SiF 4 .
  • alkali metal hexafluorosilicates can be precipitated by addition of suitable alkali metal compounds.
  • alkali metal hexafluorosilicates can be decomposed by heating, for example, to about 650 ° C. for sodium hexafluorosilicate, to alkali metal fluorides and SiF 4 .
  • the object of at least one embodiment of the invention is to provide an improved method for the production of SiF 4 .
  • This object is achieved by a method according to claim 1.
  • Embodiments of the method are the subject of dependent claims.
  • the carbon-containing material may be water present and optionally HF present in excess ⁇ hands to in the mixture, based in accordance with a ⁇ For implementation of the method.
  • the mixture provided in the process can be, for example, an aqueous mixture or an aqueous solution of H 2 SiF 6 and / or HF. If the mixture is in the vapor state, the H 2 SiF 6 is at least partially decomposed in HF and SiF 4 .
  • production of SiF 4 should be understood here and below to mean the isolation of SiF 4 already present in the mixture.
  • passing over in this context is a mixture of bringing into contact with the carbon-containing material to be understood, where a chemical reaction Zvi ⁇ rule at least components of the mixture and at least Components of the carbon-containing material made ⁇ light.
  • the preposition "about” refers in this context to the surface of the carbon-containing material. It is also conceivable that the carbon-containing Mate ⁇ rial is formed porous, and the mixture through the pores is passed through it, again the mixture over the Surface is passed in the pores of the carbonaceous material.
  • the elevated temperature during the transfer leads to the mixture being converted into or being held in a vapor or gaseous state. After passing, the mixture containing the carbon-containing material is in the vapor state.
  • the carbon-containing material may include, for example, a carbon-containing bed.
  • the coal can lenstoff (2 0 H) to form CO and H 2 in accordance with the following reaction scheme reagie ⁇ ren with the water contained in the mixture:
  • the carbon is used for dehydration of the mixture.
  • the carbon-containing material which is suitable mixtures containing the reaction of H 2 O may contain a substance which is selected from the group consisting of coal, coke, active carbon, charcoal, rice ash, oil sands, insbeson ⁇ particular after the oil recovery from the Oil sands, or includes scraps of it.
  • carbon ent ⁇ holding materials may contain substances that analysis of the thermo-containing carbon starter materials from ⁇ essentially uniform oxygen or with limited oxygen supply, so with only limited access of oxygen, he will keep ⁇ .
  • Starter materials containing carbon may be selected from coal or biomass, such as wood and lignite ⁇ .
  • the preparation of the mixture can comprise the use of HF and / or H 2 SiF 6 , for example in the form of an aqueous solution, from the acid treatment of phosphate minerals in the production of phosphate fertilizers.
  • This can be used to prepare aqueous solutions which are soluble in the acidic digestion of minerals
  • Phosphates and the washing of the exhaust gas of acid treatment with water in the production of phosphate fertilizers incurred in the process are used. Purification of such an aqueous solution is usually not required because the process is insensitive to variations in the input materials as long as the basic reactions occur. Furthermore, only small amounts of impurities are contained in the solution by the manufacturing process of the hexafluorosilicate solution, since the natural phosphate sources contain only small amounts of other salts.
  • the mixture can be transferred to a gas- be ⁇ relationship as vapor state before being passed over the carbon-containing material at least partially.
  • the mixture which is, for example, an aqueous solution of H 2 S 1 F 6 and / or HF, are heated to boiling. This produces a vaporous mixture containing HF and H 2 O or HF, SiF 4 and H 2 O.
  • the mixture is not converted before being passed into a vapor-like state under a stream of the mixture is the A ⁇ drops or understand injecting the mixture to the material containing a carbon material, wherein a reaction of the mixture containing the carbonaceous material takes place , So at least components of the mixture with at least constituents of
  • Carbon containing material chemically react with each other. Since the passing at elevated temperature instead takes place, the mixture is transferred during the passing over the carbon-containing material in the vaporous state ⁇ stand. In the event that the mixture is at least partially converted to the vapor state before being passed over, the mixture in the vapor state can be passed over the carbon-containing material. Also, the passing of a mixture, which is present partly in dampfförmi- gene and partly in the aqueous state, brain ⁇ bar.
  • an Si-containing compound is additionally added to the carbon-containing material. Containing the carbon material may also be added to an Si-containing compound, when the Mi ⁇ research H 2 SiF 6 or H 2 and HF S1F 6 contains.
  • the Si-containing Ver ⁇ bond may be present on HF in excess based according to an embodiment.
  • the mixture may thus be passed over a carbon-containing material containing an Si compound in the process.
  • material in this context is meant a mixture of carbon-containing compounds and Si-containing compounds.
  • Si compounds can in particular be understood as meaning compounds containing SiO 2 and SiO 2 groups.
  • the Si compound can be selected from a group comprising silicas, silicates, silicas, rice ash and oil sands, especially after oil extraction from the oil sands, and mixtures thereof. These compounds may, for example, be added to the carbon-containing material in the form of quartz sand, normal sand, broken glass or rice ash.
  • the Si-containing compound can react with the HF of the mixture according to the following reaction scheme:
  • HF is converted to SiF 4 by means of an Si-containing compound, as exemplified by SiO 2 .
  • Si-containing compound as exemplified by SiO 2 .
  • the reaction of the mixture containing H 2 S1F 4 , in the presence of Si or S1O 2 -containing compounds in the carbon-containing material thus increases the yield of SiF 4 from this Ver ⁇ process step, since in addition to H 2 S1F 4 already present in the mixture and / or by the decomposition of the
  • By-produced HF ie, for example, unreacted HF after passing over, can be selectively removed by cooling the transferred mixture.
  • HF ie, for example, unreacted HF after passing over
  • arising as a by-product HF REUSE ⁇ turns are, for example, for the further production of SiF 4, when it for providing a new mixture is used. So that no or virtually no Ver ⁇ losses of HF in the process occur.
  • the H 2 SiF 6 -containing mixture can also be mixed with the carbon-containing material in the absence of
  • HF is not converted to SiF 4 .
  • the RF may then be selectively removed from the mixture which is present after passing in the vapor state by is contributed play cooled to temperatures below the condensation ⁇ point of HF (19.5 ° C) but above the condensation ⁇ point of SiF 4 ,
  • the temperature during the transfer can be kept at more than 700 ° C, in particular at more than 800 ° C. Due to the high temperatures, the reaction of the water contained in the mixture to H 2 O + CH 2 + CO can be made possible.
  • the tempera ⁇ turobergrenze is defined by the method used in the Si-containing compound or by the material of the Re ⁇ actuator, in which the process takes place. In ⁇ example, pure S1O 2 should not be heated above 1500 ° C to prevent melting, but other silicon sources melt even at lower temperatures. The melting of the silicon source can affect the Fully ⁇ ness of RF implementation or the reaction rate in consequence of the altered contact surface, the implementation works in principle but also with Si-containing melts in the reactor.
  • the mixture may be prior to passing over the carbon containing material diluted with an inert gas and / or with hydrogen.
  • inert gases are argon or helium.
  • the inert gas and / or hydrogen can be used as a carrier gas, which facilitates in particular the transport of the mixture to the carbonaceous material, when the Mi ⁇ research is converted before being passed to a vapor state.
  • incurred SiF 4 can be isolated.
  • the resulting SiF 4 can be separated from the mixture or product mixture which is in the vapor state.
  • the separation can ⁇ temperatures, for example, by cooling to below the condensation point Tempe of SiF 4 (- 95.2 ° C) take place.
  • the cooling of the transferred vaporous mixture to temperatures below 150 ° C after passing can be done quickly, for example within a second or shorter.
  • the cooling can be done after leaving the bed, so the carbonaceous material, and the reactor in which the process has taken place in a separate device, such as a venturi or a cooler or heat exchanger.
  • the Si-containing compounds are added, is passed over the mixture before the Kochlei ⁇ th and / or during which a vaporous mixture, H 2 O, HF, and optionally contains SiF 4, transferred, where ⁇ raufhin then run the following reactions:
  • Si0 2 is given here by way of example for Si-containing compounds with which HF can react.
  • the remaining gas mixture of H 2 and CO is known as Synthe ⁇ segas or "syngas" and may be used in a variety che ⁇ mixer processes from the prior art the advertising.
  • a portion of the synthesis gas may be at least ver ⁇ burnt be to heat for heating the mixture of carbon-containing material, optionally comprising Si-containing compounds, at elevated temperatures and / or for the evaporation of the aqueous solution of H 2 SiF 6 and / or to generate HF.
  • the synthesis gas may be separated by methods known in the art into CO and H 2 , such as membrane separation or pressure swing adsorption.
  • syngas may be reacted with additional water vapor in a catalytic process known in the art to obtain a mixture of CO 2 and H 2 .
  • CO 2 and H 2 can be separated by methods known in the art, such as by membrane separation or pressure swing adsorption.
  • the resulting purified hydrogen can be used for the white ⁇ direct processing of the SiF 4 produced.
  • This approach has the advantage that a separate electrochemical at ⁇ play as, the production of hydrogen is not required and can be found by-products of the manufacturing process itself for this purpose use instead.
  • the resulting SiF 4 can react by means of thermal or plasmachemic conversion to fluorinated polysilanes (PFS). If the reaction takes place plasmachemically, SiF 4 is reacted with hydrogen in the plasma.
  • PFS fluorinated polysilanes
  • a reduction with the formation of HF and PFS takes place approximately according to the following reaction equation: SiF 4 + H 2 -> S1F 2 + 2 HF.
  • the S1F 2 then polymerizes to PFS: nSiF 2 ->
  • the PFS can then be thermally converted to silicon and SiF 4 , for example, whereby the latter can be recycled back into the process.
  • the fluorinated polysilane produced can be used, for example, for the production of high purity silicon or for the production of hydrogenated polysilanes.
  • salt-like hydrides are used for the hydrogenation.
  • salzar hydrides are simple hydrides such as LiH, NaH, KH, MgH 2 , CaH 2 , AlH 3 or complex hydrides such as LiAlH 4 , NaAlH 4 ,
  • the salt-like fluorides which are by-produced during the hydrogenation step, can be used as starting materials or auxiliaries for the production of aluminum or for the fluoridation of water.
  • the fluorinated polysilane can be used to prepare fluorinated and / or partially fluorinated oligosilanes.
  • the fluorinated oligosilanes can be obtained by thermal decomposition of the fluorinated polysilane.
  • the partially fluorinated oligosilanes can be generated with HF by partial hydrogenation ⁇ tion of fluorinated oligosilanes or by reaction of fluorinated oligosilanes or fluorinated polysilane.
  • the RF for the preparation of partially fluorinated oligosilanes can at least partially derived from the polymerization ⁇ step, is recovered in the fluorinated polysilane of SiF 4 by reduction with hydrogen.
  • An H 2 SiF 6 solution from the fertilizer production is mixed with 10-15 mass% quartz sand. In the mixture, HF gas is passed until no more gas is absorbed. The concentrated H 2 SiF 6 solution is transferred to an acid-proof metal container. Connected to the metal container is also an acid-resistant metal tube, which is heated to 1200 ° C. The metal tube is filled with pellets ⁇ ge, which have been produced from quartz sand, silica gel and activated carbon powder. For this purpose, the starting materials are stirred with starch and water to a pulp, formed into pellets and calcined by slow heating to last 700 ° C for 30 min under a stream of weak nitrogen.
  • the concentrated H 2 SiF 6 solution is heated to boiling and the resulting gas is passed through the heated filling of carbon ⁇ containing pellets.
  • the escaping gas is passed through a cooled to -100 ° C cold trap and thereby condensed out SiF 4 .
  • the SiF 4 is recombined by careful thawing and stored in a ge ⁇ suitable compressed gas tank.
  • An H 2 SiF 6 solution from the fertilizer production is transferred to an acid-proof metal container.
  • An acid-resistant metal pipe which is heated to 1200 ° C, is connected to the metal tank.
  • the metal tube is filled with pellets which are made of quartz sand, silica gel and Ak ⁇ tivkohlepulver.
  • the starting substances are mixed with starch and water into a pulp, shaped into pellets and calcined by slow heating to 700 ° C. for 30 minutes under a slight stream of nitrogen.
  • the H2 SiF6 solution is heated to boiling and the resulting gas is passed through the heated filling material ⁇ coal-containing pellets.
  • the escaping gas is passed through a cooled to -100 ° C cold trap and thereby condensed out SiF 4 .
  • the SiF 4 is recombined by careful thawing and stored in a suitable compressed gas tank.
  • a hydrofluoric acid with 48% HF content is transferred to a kla ⁇ refesten metal container.
  • Connected to the metal container is also an acid-resistant metal ⁇ tube, which is heated to 1200 ° C.
  • the metal tube is filled with pellets made of quartz sand, silica gel and activated carbon powder.
  • the output ⁇ substances are mixed with starch and water to form a slurry, and formed into pellets by slowly heating to last 700 ° C calcined for 30 min under a stream of mild nitrogen.
  • the HF solution is heated to boiling and the ent ⁇ standing gas is passed through the heated filling of carbon ⁇ containing pellets.
  • the escaping gas is passed through a cooled to -100 ° C cold trap and thereby HF and SiF 4 condensed out.
  • the SiF 4 is recombined by careful thawing and stored in a suitable compressed gas tank. Not Abrea ⁇ gêts HF remains during thawing the cold trap in this.
  • An H 2 SiF 6 solution from the fertilizer production is transferred to an acid-proof metal container. Connected to the metal container is also an acid-resistant metal tube, which is heated to 1200 ° C. The metal tube is filled with granular activated carbon. The H2 SiF6 solution is heated to boiling and the resulting gas is passed through he ⁇ overheated filling of activated carbon. The escaping gas is passed through a cooled to -100 ° C cold trap and thereby HF and SiF 4 condensed out. After completion of the reaction, the SiF 4 is recombined by careful thawing and stored in a suitable compressed gas tank. HF remains during the thawing of the cold trap in this back ⁇ .
  • He ⁇ invention encompasses any new feature and any combination of features, which in particular includes any combination of features in the patent claims, even if this feature or this combination itself is not explicitly specified in the Pa ⁇ tentvarn or examples.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne un procédé de production de SiF4, selon lequel on prend un mélange contenant de l'eau, H2S1F6 et/ou HF, et le mélange est passé au-dessus d'un matériau carboné à une température élevée.
PCT/EP2014/058722 2013-04-30 2014-04-29 Procédé de production de tétrafluorure de silicium WO2014177560A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201310104398 DE102013104398A1 (de) 2013-04-30 2013-04-30 Verfahren zur Herstellung von Siliziumtetrafluorid
DE102013104398.4 2013-04-30

Publications (1)

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WO2014177560A1 true WO2014177560A1 (fr) 2014-11-06

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674431A (en) * 1970-07-01 1972-07-04 Cities Service Co Generation of silicon tetrafluoride
EP0173793A2 (fr) * 1984-09-05 1986-03-12 D. Swarovski & Co. Procédé de préparation de tétrafluorure de silicium
WO2005030642A1 (fr) * 2003-09-25 2005-04-07 Showa Denko K.K. Procede de production de tetrafluorosilane
US20100150789A1 (en) * 2008-12-17 2010-06-17 Memc Electronic Materials, Inc. Systems for producing silicon tetrafluoride from fluorosilicates in a fluidized bed reactor
US20120009116A1 (en) * 2010-07-09 2012-01-12 Angel Sanjurjo High temperature decomposition of complex precursor salts in a molten salt

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3273963A (en) * 1963-01-17 1966-09-20 Columbian Carbon Process for generating silicon tetrafluoride
US4590043A (en) * 1982-12-27 1986-05-20 Sri International Apparatus for obtaining silicon from fluosilicic acid
US8142549B2 (en) * 2008-03-26 2012-03-27 Matheson Tri-Gas, Inc. Purification of fluorine containing gases and systems and materials thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674431A (en) * 1970-07-01 1972-07-04 Cities Service Co Generation of silicon tetrafluoride
EP0173793A2 (fr) * 1984-09-05 1986-03-12 D. Swarovski & Co. Procédé de préparation de tétrafluorure de silicium
WO2005030642A1 (fr) * 2003-09-25 2005-04-07 Showa Denko K.K. Procede de production de tetrafluorosilane
US20100150789A1 (en) * 2008-12-17 2010-06-17 Memc Electronic Materials, Inc. Systems for producing silicon tetrafluoride from fluorosilicates in a fluidized bed reactor
US20120009116A1 (en) * 2010-07-09 2012-01-12 Angel Sanjurjo High temperature decomposition of complex precursor salts in a molten salt

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Ullmann's Encyclopedia of Industrial Chemistry", 15 June 2000, WILEY-VCH VERLAG GMBH & CO. KGAA, Weinheim, Germany, ISBN: 978-3-52-730673-2, article JEAN AIGUEPERSE ET AL: "Fluorine Compounds, Inorganic", XP055054753, DOI: 10.1002/14356007.a11_307 *

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