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WO2014082110A1 - Procédé de production chimique par plasma de chlorosilanes - Google Patents

Procédé de production chimique par plasma de chlorosilanes Download PDF

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Publication number
WO2014082110A1
WO2014082110A1 PCT/AT2013/050228 AT2013050228W WO2014082110A1 WO 2014082110 A1 WO2014082110 A1 WO 2014082110A1 AT 2013050228 W AT2013050228 W AT 2013050228W WO 2014082110 A1 WO2014082110 A1 WO 2014082110A1
Authority
WO
WIPO (PCT)
Prior art keywords
plasma
reaction
plasma source
reactants
plasma torch
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/AT2013/050228
Other languages
German (de)
English (en)
Inventor
Gerd Lippold
Rolf MERKER
Johann Harter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ACTIV SOLAR GmbH
Original Assignee
ACTIV SOLAR GmbH
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 ACTIV SOLAR GmbH filed Critical ACTIV SOLAR GmbH
Publication of WO2014082110A1 publication Critical patent/WO2014082110A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
    • 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

Definitions

  • the present invention relates to a process for the plasma-chemical production of chlorosilanes, in particular of silicon tetrachloride.
  • the chlorosilanes silicon tetrachloride and trichlorosilane are currently produced in a large-scale process consisting of at least two process stages.
  • elemental silicon is first generated from silicon dioxide with excess carbon in an electric arc furnace.
  • This silicon is converted in a second process stage with hydrogen chloride or chlorine to the target product chlorosilane.
  • this two-stage process is to be replaced by a single process step, wherein the energy input takes place in an efficient manner at high temperatures by a thermal plasma.
  • the chlorination of Si0 2 in the presence of carbon is called carbochlorination.
  • Carbochlorination using the chlorine source hydrogen chloride is described for element oxides including SiO 2, for example in DE 102005024104 A1 and WO 2006/53675 A1.
  • the reaction temperatures are generally more than 800 ° C.
  • the main claim is limited to heating by means of an alternating electromagnetic field ("microwave heating"), in which the microwave energy is coupled into a component, namely the carbon content of a reaction mixture present as a bed in a reaction vessel, and first heats these particles and thus Secondary, the mixture and the thus directly in contact reactor vessel walls thermally.
  • microwave heating alternating electromagnetic field
  • WO 2006/053675 A1 does not specify the method of heating for the production of an elemental halide by contact of a charged mixture of a material containing the element and a carbon-containing material by contact with a gas stream containing hydrogen halide.
  • the application DE 102007009709 A1 describes a special embodiment of a carbochlorination process in which submitted reactants are heated by concentrated solar radiation (solar thermal) to the required high reaction temperature.
  • All said processes have the commonality, beds or Wrbel Anlagenbetten of consisting of gaseous and / or solid reactants and in contact with the reactor walls reaction mixture by direct or Indirect thermal heating to the required temperature of at least 800 ° C and to keep until the completion of the implementation at this temperature level.
  • the object of the present invention is to avoid the abovementioned disadvantages and to provide a process with which chlorosilanes can be prepared simply, effectively and inexpensively.
  • This object is achieved in that in a process for the preparation of chlorosilanes, in particular of silicon tetrachloride and / or trichlorosilane, by means of Carbochlorierung from Si0 2 , C, Cl and / or HCl as a reactant, the reaction to form a product mixture in a reaction zone within a takes place from a plasma source originating thermal plasma torch.
  • the process according to the invention for the plasma-chemical preparation of chlorosilanes, in particular for the production of silicon tetrachloride is distinguished from the prior art in that the physical conditions in a thermal plasma torch are used for the particularly efficient reaction of the reactants in the free gas space without high-temperature interaction with reactor walls and the desired composition of the reaction products is fixed by rapid relaxation and cooling of the reaction gases to avoid re-reactions. Several reactions take place in parallel and sequentially in the reactor.
  • the thermal plasma torch is generated by a plasma source of the types arc discharge source, inductively coupled plasma source or microwave plasma source.
  • a thermal atmospheric pressure plasma torch gas temperatures of well above 5000 ° C can be achieved, locally in the center of the plasma torch.
  • the plasma torch is available after its exit from the plasma source as a freely located in the gas space high temperature heat source with very high power density.
  • the plasma torch is generated by plasma excitation of a supporting gas. This gas may either be an additional inert or non-inert component introduced into the reaction mixture or one of the gaseous or vaporous reactants.
  • a specific type of plasma sources is referred to, in which for generating plasma microwave energy is radiated into the excitation space of a plasma source.
  • the result is a dense, thermal plasma that leaves the plasma source as a plasma torch through a nozzle opening.
  • the plasma is generated by electron impact, the energetic electrons receive their energy from the high-frequency electromagnetic field.
  • such a source has still other components, e.g. strong permanent magnets for the appropriate deflection of the electron orbits.
  • the microwave energy is used to generate plasma in the excitation space of a plasma source.
  • the arrangement for the plasma-thermal production of chlorosilanes consists of a reaction chamber (also referred to as a reactor), to which one or more plasma sources are mounted.
  • the reaction chamber is designed so that the hot plasma torches do not come into direct contact with the chamber walls.
  • the reaction chamber may include metering devices proximate to the exit nozzles of the plasma sources that allow injection of powdered solid, liquid or gaseous reactants into the hot center of the plasma torch.
  • One embodiment of the metering devices are annularly arranged gap nozzles.
  • the reaction chamber can also have one or more Have gas discharge openings.
  • cooling devices Downstream of these are one or more cooling devices, which allow by rapid relaxation and / or by injection of a cooling medium, a very rapid cooling of the gaseous product mixture to prevent a reverse reaction of CO with H 2 and subsequent hydrolysis of the chlorosilane product mixture.
  • the cooling medium used may preferably be the product mixture itself or silicon tetrachloride as its main component in liquid or gaseous form.
  • a gas pressure of 0.05 to 0.2 MPa prevails in the interior of the plasma source, particularly preferably 0.09 to 0.15 MPa.
  • Such a low pressure is favorable because at much higher pressures due to the ever shorter free path lengths of the electrons effective plasma ignition is becoming increasingly difficult, which is why pressures to normal pressure or slightly more preferred.
  • the inventive method does not work because no plasma torch can be generated and extracted from the source.
  • the gas pressure should also be as high as possible, because it achieves high gas phase mass throughput and the gas expansion necessary for rapid cooling after the reaction zone is easier to implement in terms of process technology. Generally speaking, pressure is as high as possible, but in the safe functional area of the plasma source. On the downside, pressure is initially limited mainly by productivity considerations and procedural reasons.
  • the temperature in the heating zone in the plasma torch is between 1500 ° C and 10000 ° C, preferably between 2000 ° C and 5000 ° C.
  • the temperature in the reaction zone of the plasma torch is between 1000 ° C and 2000 ° C, preferably between 1400 ° C and 2000 ° C.
  • Another embodiment of the present invention provides that at least one of the reactants is introduced into the plasma torch.
  • the plasma torch is used to heat the reactants quickly and to bring them to react in a homogeneous as possible gas phase.
  • a second function of the plasma torch is to transport the gaseous reaction products rapidly and directionally along the longitudinal axis of the plasma torch from the reaction zone to the following zone for rapid cooling to minimize their undirected diffusion into colder, wall-proximate areas and associated undesirable reverse reactions.
  • further gaseous substances which serve to operate the plasma torch. So can hydrogen individually or be used as a mixture with another, carbon-containing gas or vaporous material as a supporting gas of the plasma torch.
  • the dissociation of the molecular hydrogen due to the plasma excitation leads to an entry of recombination heat in the plasma torch and thus to advantageous conditions for a longer available reaction time of the registered reactants in the high temperature zone.
  • the further gaseous substances are preferably hydrogen or noble gases.
  • reaction mixture contains hydrogen chloride gas.
  • reaction mixture contains one or more members of the group comprising quartz powder, glass powder, fine sands, silicates, silicic acid, kieselguhr and / or mixtures thereof. These are available at low cost, eg. Directly by mining recoverable materials that have a high silicon content and can be easily bring as solids in very fine particle distribution.
  • the reaction mixture contain one or more members of the group comprising carbon in elemental form, carbon powder, carbonaceous suspensions, carbon in bound form as solid, liquid or gaseous carbon compounds and / or mixtures thereof. These are readily available in sufficiently pure accessible and finely distributable high carbon materials.
  • the reactants are fed into the plasma torch in a form which enables their as fast and spatially homogeneous availability as possible for the desired gas phase reactions.
  • the reaction partners are preferably in a solid or gaseous state when introduced into the plasma torch or the excitation space of the plasma source.
  • the reactants containing silicon and carbon are used as powders, in which the particles in each case contain both reactants as a mixture or are used together in the form of coated particles.
  • the silicon oxide-containing reactant in the form of powder of suitable particle size distribution is fed into the plasma torch or already into the discharge space of the plasma source by a gas stream containing the carbon-containing reactants individually or together with an additional support gas.
  • the carbonaceous reactant is fed as gas or vapor of a carbonaceous compound in the plasma torch or already in the excitation space of the plasma source.
  • the hydrogen chloride is as a steam individually or together with another Reactant fed into the plasma torch after its exit from the plasma source.
  • the silicon oxide-containing reactant in the form of a suspension of suitable particle size distribution can be fed into the plasma torch or already into the discharge space of the plasma source by a liquid stream containing the carbon-containing reactant.
  • the hydrogen chloride is fed as a vapor individually or together with another reactant into the plasma torch after its exit from the plasma source. It is also conceivable if both the silicon oxide-containing reactant and the carbonaceous reactant as a powder of suitable particle size distribution by a gas stream containing a support gas individually or in admixture with a chlorine-containing gas or vapor, are fed into the plasma torch or already in the discharge space of the plasma source.
  • the carbonaceous and the silicon oxide-containing reactant is introduced in the form of powder particles which contain the respective reactants either individually or as a mixture or as particles in a binder matrix or as coated particles.
  • the hydrogen chloride is fed as vapor into the plasma torch after it exits the plasma source.
  • Impurities in the reactants may also lead to the formation of metal chlorides which, together with possibly unreacted starting materials and any products of undesired back reactions outside the hot reaction zone, appear as dusty solid particles or liquid droplets. Therefore, it is preferably provided that the product mixture after leaving the reaction zone in a dust separator, preferably a cyclone, is separated from any remaining solids.
  • a dust separator preferably a cyclone

Landscapes

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

Abstract

L'invention concerne un procédé de production de chlorosilanes, en particulier de tétrachlorure de silicium et/ou de trichlorosilane, par carbochloration à partir de SiO2, C, Cl et/ou HCl en tant que partenaires réactionnels, la réaction de formation d'un mélange de produits se déroulant dans une zone réactionnelle à l'intérieur d'un jet de plasma thermique provenant d'une source de plasma.
PCT/AT2013/050228 2012-11-27 2013-11-27 Procédé de production chimique par plasma de chlorosilanes Ceased WO2014082110A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT505452012A AT513735B1 (de) 2012-11-27 2012-11-27 Verfahren zur plasmachemischen Herstellung von Chlorsilanen
ATA50545/2012 2012-11-27

Publications (1)

Publication Number Publication Date
WO2014082110A1 true WO2014082110A1 (fr) 2014-06-05

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT2013/050228 Ceased WO2014082110A1 (fr) 2012-11-27 2013-11-27 Procédé de production chimique par plasma de chlorosilanes

Country Status (2)

Country Link
AT (1) AT513735B1 (fr)
WO (1) WO2014082110A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106185950A (zh) * 2016-07-06 2016-12-07 成都蜀菱科技发展有限公司 生产四氯化硅的方法
CN113912066A (zh) * 2021-09-09 2022-01-11 全椒亚格泰电子新材料科技有限公司 一种制备氯代硅烷的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006053675A1 (fr) 2004-11-18 2006-05-26 Wacker Chemie Ag Procede de production d'halogenures elementaires
DE102005024104A1 (de) 2005-05-25 2006-11-30 Wacker Chemie Ag Verfahren zur Herstellung von Elementhalogeniden
DE102007009709A1 (de) 2007-02-28 2008-09-04 Rev Renewable Energy Ventures Ag Solarthermische Prozesschemie insbesondere zur Herstellung von SiCI4
CN101254921B (zh) * 2008-03-19 2010-10-06 四川金谷多晶硅有限公司 一种转化四氯化硅制取三氯氢硅和多晶硅的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101475175B (zh) * 2009-01-21 2011-05-04 东方电气集团东方汽轮机有限公司 等离子氢化四氯化硅制备三氯氢硅的方法
CN101734666B (zh) * 2009-11-24 2012-09-26 中国科学院过程工程研究所 用微波等离子氢化四氯化硅制三氯氢硅和二氯氢硅的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006053675A1 (fr) 2004-11-18 2006-05-26 Wacker Chemie Ag Procede de production d'halogenures elementaires
DE102005024104A1 (de) 2005-05-25 2006-11-30 Wacker Chemie Ag Verfahren zur Herstellung von Elementhalogeniden
DE102007009709A1 (de) 2007-02-28 2008-09-04 Rev Renewable Energy Ventures Ag Solarthermische Prozesschemie insbesondere zur Herstellung von SiCI4
CN101254921B (zh) * 2008-03-19 2010-10-06 四川金谷多晶硅有限公司 一种转化四氯化硅制取三氯氢硅和多晶硅的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106185950A (zh) * 2016-07-06 2016-12-07 成都蜀菱科技发展有限公司 生产四氯化硅的方法
CN113912066A (zh) * 2021-09-09 2022-01-11 全椒亚格泰电子新材料科技有限公司 一种制备氯代硅烷的方法

Also Published As

Publication number Publication date
AT513735A1 (de) 2014-06-15
AT513735B1 (de) 2015-02-15

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