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WO2008120996A1 - Procédé de fabrication du tétrachlorure de silicium par réaction de silicium métallique et de chlore avec un refroidissement interne - Google Patents

Procédé de fabrication du tétrachlorure de silicium par réaction de silicium métallique et de chlore avec un refroidissement interne Download PDF

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Publication number
WO2008120996A1
WO2008120996A1 PCT/NO2008/000107 NO2008000107W WO2008120996A1 WO 2008120996 A1 WO2008120996 A1 WO 2008120996A1 NO 2008000107 W NO2008000107 W NO 2008000107W WO 2008120996 A1 WO2008120996 A1 WO 2008120996A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
reaction
chlorine
cooling medium
sici
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/NO2008/000107
Other languages
English (en)
Inventor
Per Bakke
Terje Fuglerud
Patrick Müller
Christian Rosenkilde
Jorild Margrete Svalestuen
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.)
Norsk Hydro ASA
Original Assignee
Norsk Hydro ASA
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 Norsk Hydro ASA filed Critical Norsk Hydro ASA
Publication of WO2008120996A1 publication Critical patent/WO2008120996A1/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
    • C01B33/10715—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material
    • C01B33/10721—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material with the preferential formation of tetrachloride
    • C01B33/10726—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by reacting chlorine with silicon or a silicon-containing material with the preferential formation of tetrachloride from silicon

Definitions

  • the present invention relates to a process for producing silicon tetrachloride by reaction of silicon metal and chlorine.
  • reaction of silicon metal with chlorine gas is characterized by an extremely high positive reaction enthalpy; at room temperature 687kJ/mol SiCI 4 . This high release of energy causes major challenges.
  • the temperature can rise to 1200 0 C and above. Under these conditions it is possible that the silicon metal begins to melt leading to an uncontrolled reaction. It is a significant challenge to get rid of this generated energy (heat). Due to the restricted surface of a reactor and thereby small convection areas, an outside cooling wall-system may not be sufficient. Small size reactors (i.e. greater surface) may be used, but in such case the output will be small and hence this is not a commercially interesting option. An internal cooling of the reactor is, because of the corrosive chlorine atmosphere and the high reaction temperature, considered to be dangerous. Another problem is related to the requirements of the construction-materials. Due to the corrosive medium chlorine represents and the high temperature of the process there are hardly materials available which would meet the strong requirements of the reaction of silicon and chlorine.
  • the known SiCI 4 -production processes are based mainly on the reaction of HCI with silicon metal.
  • the reaction enthalpy is only less than one third (ca. 27%) of the direct chlorine process, 185 kJ/mol, and therefore less demanding in terms of temperature control and material selection.
  • This reaction can take place in a fluidized bed reactor or a solid bed reactor.
  • this process has the following disadvantages:
  • the present invention is represented by a novel process for direct chlorination of silicon metal with chlorine.
  • the basic and novel feature of the invention is the use of a cooling medium, preferably the end product of the process as an energy reduction and reaction modifying agent which enables full control of the reaction temperature and speed of the process.
  • the invention is characterized by injection of a liquid cooling medium, preferably SiCI 4 directly into the chlorination reaction, as defined in the attached independent claim 1.
  • the present invention relates as initially stated to a process for producing silicon tetrachloride by reaction of silicon metal and chlorine, and as further explained above, the invention is based on the use of a cooling medium, preferably the end product of the process, SiCI 4 , as an energy reduction and reaction modifying agent by injecting such medium directly into the reaction zone of the process.
  • a cooling medium preferably the end product of the process, SiCI 4
  • the injection can be done with liquid and/or with gaseous SiCI 4 .
  • the injection of gaseous SiCI 4 has the advantage of selecting an optimum mixture of the reactant (chlorine) with the cooling component (SiCI 4 ).
  • the components are preferably mixed before injection into the reactor.
  • the liquid silicon tetrachloride injection has a double-effect: thus the secondary heat obtained by evaporation of SiCI 4 comes in addition to the energy consumed to heat the SiCI 4 to the temperature in the reactor.
  • the liquid SiCI 4 -injection may preferably be sprayed with nozzles directly into the reaction zone of reactor in the vicinity of where the chlorine is injected.
  • the amount of SiCI 4 may, based on calculations, be in the range of one to twenty moles per produced mole of SiCI 4 , preferably in the range 4 - 12 depending on the reaction rate, the heat loss through the reactor walls and the outlet gas temperature.
  • the process according to the invention has two important and advantageous effects.
  • the evaporation energy (secondary heat) of the liquid SiCI 4 and the energy to heat the gaseous silicon tetrachloride are used to decrease and thereby enable adjustment of the reaction temperature, (heat of evaporation is 28 kJ/mol; specific heat capacity: 95 J/mol 0 K). Evaporation and heating to for example 500 0 C require approximately 70 kJ/mole.
  • inert gasses such as Ar and He may also be used.
  • the mixing of chlorine with inert gases like Ar and He in this process are, however, far less efficient since the specific heat capacity of Ar and He both are only 21 J/mol 0 K which is far lower than for SiCI 4 .
  • Cl 2 significantly larger volume flows of Ar or He must be used to provide the same effect. This can lead to entrapment of fine particles in the gas flow leading to deposition downstream of the reactor or contamination of the product as a result.
  • the secondary heat (heat of evaporation) effect cannot be easily utilized with Ar or He since the boiling temperatures for Ar and He are -186 0 C and -269 0 C, respectively.
  • Fig. 1 shows the volume flow ratio of SiCI 4 to CI 2 on the left vertical axis as a function of volume flow of SiCI 4 to achieve constant temperature 500 0 C in an industrial scale tube type reactor with 1.5m inner diameter and 6m height.
  • the corresponding output of SiCI 4 assuming 100% conversion of the injected Cl 2 gas is plotted.
  • Solid lines indicate a situation where liquid SiCI 4 is introduced to the reactor hence the heat of evaporation is utilized for cooling.
  • Dotted lines indicate a situation where SiCI 4 is introduced as a gas at 100 0 C. In both situations, a constant heat loss through the reactor walls of 1kW/m 2 is assumed.
  • the volume flow ratio of SiCI 4 to Cl 2 has to be increased if SiCI 4 is introduced as a vapour and not as a liquid. If the outlet gas temperature is chosen to be lower than 500 0 C, the volume flow ratio of SiCI 4 to Cl 2 has to be increased. Likewise, if the heat loss through the walls is lower than 1kW/m 2 the volume flow ratio of SiCI 4 to Cl 2 has to be increased.
  • Additional cooling of the reaction can be supplied by external cooling at the reactor walls. With this cooling the amount of SiCI 4 -injection can be reduced. With the injection procedure, keeping the reaction temperature low (e. g. ⁇ 40O 0 C), internal cooling with heat exchangers (pipe systems) can be an option.
  • the cooling medium that is a gas or liquid at the temperature of injection and a gas at the selected reactor temperature can be used.
  • An additional requirement is that the cooling medium cannot decompose to any product that is considered to contaminate the reactor or the reaction product.
  • the preferred cooling agent is SiCI 4 or similar compounds like Si 2 CI 6 or liquid silicone-organic polymers. The latter compounds have the advantage of higher boiling points. (SiCI 4 - boiling point: 57,6 0 C; Si2Cl6-boiling point: 146 0 C; Silicone-organic polymers about 22O 0 C).
  • the amount of SiCI 4 used for cooling can be directly recycled to the chlorination-reactor.
  • the produced SiCI 4 may be transferred to a distillation process for further purification.
  • the proposed process can take place in a solid-bed, as well as in a fluidized bed- reactor.
  • a fluid bed can offer higher production rates since the Si particles are relatively small and thus provide a large surface to volume ratio.
  • the reaction rate is largely governed by the available surface. With the high reaction rates the need for cooling increases.
  • a fixed bed larger particles are used, and the particle size can be selected so as to control the reaction rate and temperature.
  • a fixed bed reactor need to be of a significantly larger size.

Landscapes

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

Abstract

L'invention porte sur un procédé de fabrication du tétrachlorure de silicium, SiCl4, par réaction de silicium métallique, Si, et de chlore, Cl2, dans un réacteur. Les températures et la vitesse de réaction sont régulées par injection simultanée, directe, de chlore et d'un agent réfrigérant dans la zone de réaction du réacteur où l'agent réfrigérant est introduit sous forme liquide à une température inférieure à la température de réacteur et s'évapore à l'intérieur du réacteur en utilisant sa chaleur d'évaporation et sa capacité thermique spécifique pour le refroidissement. L'agent réfrigérant peut, de préférence, être du tétrachlorure de silicium ou un gaz inerte.
PCT/NO2008/000107 2007-04-02 2008-03-17 Procédé de fabrication du tétrachlorure de silicium par réaction de silicium métallique et de chlore avec un refroidissement interne Ceased WO2008120996A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20071765 2007-04-02
NO20071765A NO20071765L (no) 2007-04-02 2007-04-02 Prosess for fremstilling av silisium tetraklorid ved reaksjon mellom silisium metall og klor med intern kjoling

Publications (1)

Publication Number Publication Date
WO2008120996A1 true WO2008120996A1 (fr) 2008-10-09

Family

ID=39808494

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NO2008/000107 Ceased WO2008120996A1 (fr) 2007-04-02 2008-03-17 Procédé de fabrication du tétrachlorure de silicium par réaction de silicium métallique et de chlore avec un refroidissement interne

Country Status (3)

Country Link
NO (1) NO20071765L (fr)
TW (1) TW200902443A (fr)
WO (1) WO2008120996A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103101913A (zh) * 2013-01-31 2013-05-15 内蒙古盾安光伏科技有限公司 四氯化硅冷氢化生产三氯氢硅的系统及方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467091A (zh) * 2018-12-25 2019-03-15 天津中科拓新科技有限公司 一种四氯化硅合成的节能装置及方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8905023A (pt) * 1989-09-29 1991-04-02 Fundacao Centro Tecnologico De Processo e equipamento para sintese e purificacao de tetracloreto de silicio para fabricacao de fibras opticas
JP2002173313A (ja) * 2000-12-04 2002-06-21 Denki Kagaku Kogyo Kk 四塩化珪素の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8905023A (pt) * 1989-09-29 1991-04-02 Fundacao Centro Tecnologico De Processo e equipamento para sintese e purificacao de tetracloreto de silicio para fabricacao de fibras opticas
JP2002173313A (ja) * 2000-12-04 2002-06-21 Denki Kagaku Kogyo Kk 四塩化珪素の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103101913A (zh) * 2013-01-31 2013-05-15 内蒙古盾安光伏科技有限公司 四氯化硅冷氢化生产三氯氢硅的系统及方法

Also Published As

Publication number Publication date
TW200902443A (en) 2009-01-16
NO20071765L (no) 2008-10-03

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