WO2011112097A1 - Procédé de production de trichlorosilane à partir de silicium, d'hydrogène et de tétrachlorure de silicium - Google Patents

Procédé de production de trichlorosilane à partir de silicium, d'hydrogène et de tétrachlorure de silicium Download PDF

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Publication number
WO2011112097A1
WO2011112097A1 PCT/NO2011/000075 NO2011000075W WO2011112097A1 WO 2011112097 A1 WO2011112097 A1 WO 2011112097A1 NO 2011000075 W NO2011000075 W NO 2011000075W WO 2011112097 A1 WO2011112097 A1 WO 2011112097A1
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WIPO (PCT)
Prior art keywords
silicon
chromium
reactor
supplied
ppm
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Application number
PCT/NO2011/000075
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English (en)
Inventor
Harry Morten Rong
Torbjørn RØE
Jan-Otto Hoel
Henning KJØNLI
Bodil Eik-Nes
Original Assignee
Elkem As
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Publication date
Application filed by Elkem As filed Critical Elkem As
Publication of WO2011112097A1 publication Critical patent/WO2011112097A1/fr

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    • 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

Definitions

  • the present invention relates to a method for the production of trichlorosilane by reaction of silicon by a mixture of silicon tetrachloride gas and hydrogen gas, and to production of silicon for the use in production of trichlorosilane.
  • metallurgical grade silicon is reacted with silicon tetrachloride (STC) gas and hydrogen gas in a fluidized bed reactor, solid bed reactor or in a stirred bed reactor (US patent 4676967).
  • STC silicon tetrachloride
  • the process is generally carried out at a temperature between 400 and 600°C.
  • TCS can also be produced by reacting metallurgical grade with hydrogen chloride (HCI) gas in a fluidized bed reactor, solid bed reactor or in a stirred bed reactor. This process is generally carried out at a temperature between 250 and 1100°C. In the reaction, other volatile silanes than TCS are also formed, mainly STC. The amount of STC is typically about 10-85% depending on the reactor temperature, impurity content in the metallurgical silicon and any catalysts added to the reactor.
  • HCI hydrogen chloride
  • STC is also produced in large amounts during decomposition of TCS to pure silicon and in the redistribution reactions to produce silane (SiH 4 ) from TCS.
  • 4HSiCI 3 Si + 3SiCI 4 + 2H 2
  • STC is mainly used to produce silicon dioxide (fumed silica) by reacting STC with hydrogen and oxygen. Some STC is also used to produce optical fibres or sold to other applications. In general too much STC is available in the market and recycling is required to balance the production.
  • the advantage of reacting STC with metallurgical silicon and hydrogen is that the by-product from the decomposition or redistribution step is recycled to TCS. Recycling will reduce the amount of silicon required to produce polysilicon since the silicon that otherwise produces STC will be converted to polysilicon. Only part of the STC can be converted to TCS in one reactor pass and maximum conversion of STC is given by the equilibrium composition. Complete conversion of the STC requires multiple reactor passes and subsequent distillations to remove TCS. Normally, the conversion of STC in one reactor pass is lower than predicted from the equilibrium composition due to the fact that reaction kinetics are important at these temperatures.
  • catalysts to the reactor will increase the conversion (closer to the equilibrium composition), and well known catalysts for this process is copper (any copper source will work) and/or iron (any iron source will work). Iron is always present in metallurgical silicon and will act as a catalyst to increase conversion.
  • Metallurgical grade silicon contains a number of contaminating elements like Fe, Ca, Al, Mn, Ni, Zr, Cr, O, C, Zn, Ti, B, P and others. Some contaminants will either be inert to STC, or form solid, stable chlorides. The stable metal chlorides will, depending on their size, either be blown out of the reactor with the product gas or be accumulated in the reactor. Other contaminants like Al, Zn, Ti, B and P normally form volatile metal chlorides, which leave the reactor together with the silanes produced.
  • O and C are enriched in slag particles in the silicon that do not react or react very slowly with STC and tend to accumulate in the reactor.
  • the smallest slag particles can be blown out of the reactor and trapped in the filter systems. Species that accumulate will take up space in the reactor, leaving less space for silicon and thereby reducing the effective surface area of silicon. This gives a less effective reaction. In such a way, a chemically inert compound may actually influence the reaction.
  • the present invention relates to a method for the production of trichlorosilane by reaction of silicon with silicon tetrachloride gas and hydrogen gas at a temperature between 300° and 800°C and an absolute pressure of 0.5 - 40 atm in a fluidized bed reactor, in a stirred bed reactor or in a solid bed reactor, which method is characterised in that the silicon supplied to the reactor contains between 50 and 10 000 ppm of chromium.
  • the silicon supplied to the reactor contains between 75 and 1500 ppm chromium and more preferably between 100 and 1000 ppm.
  • the chromium is then alloyed with the silicon, is mechanically mixed with the silicon or is added to the reactor separately.
  • the chromium can be alloyed to the silicon in the furnace process for production of metallurgical grade silicon, in the refining ladle or in the casting step.
  • Adding chromium to the furnace can be done in several ways. For instance by addition of chromium containing raw materials to the furnace, using electrodes or electrode casing/ribs containing chromium or any other addition of chromium to the furnace.
  • Chromium can also be added to the silicon during tapping of the furnace for instance by using chromium containing tapping tools or chromium containing materials in the tapping of the silicon from the furnace into the refining ladle.
  • Chromium can also be added to the silicon in the refining ladle. Any chromium compound added will be reduced by silicon to metallic chromium that will form different intermetallic phases when the silicon solidifies. Different ratios of the main impurities like iron, aluminium, calcium and iron can form different intermetallic phases with chromium.
  • Chromium can also be added to the silicon in the casting step, for instance by adding a chromium compound to the molten silicon, by using chromium compounds or chromium containing silicon in the casting moulds or by casting the silicon on a surface of a material containing chromium.
  • Chromium can also be mechanically mixed with silicon.
  • One preferred way of mechanically mixing chromium with the silicon is to subject the silicon to grinding using chromium containing grinding bodies, such as for example chromium containing steel balls.
  • the silicon used according to the present invention is produced in conventional way in carbothermic reduction furnaces.
  • the chromium content in the silicon can either be regulated and controlled by selection of raw materials, adding chromium to the furnace, using electrodes or electrode casings containing chromium or chromium may be added to molten silicon in the ladle after the silicon has been tapped from the reduction furnace.
  • the present invention relates to a method for the producing of trichlorosilane by reaction of silicon with silicon tetrachloride gas and hydrogen gas at a temperature between 300° and 800° C and an absolute pressure of 0.5 - 40 atm in a fluidized bed reactor, in a stirred bed reactor or in a solid bed reactor, which method is characterised in that chromium or chromium containing species is added to the reactor in an amount necessary to control a chromium content in the reactor of between 100 and 50 000 ppm based on the weight of silicon in the reactor.
  • chromium is supplied to the reactor in an amount necessary to control the chromium content in the reactor to between 250 and 25 000 ppm.
  • Chromium can be supplied to the reactor in any suitable way .
  • the chromium can be supplied to the reactor alloyed with silicon, mechanically mixed with silicon or added separately to the reactor. According to one embodiment the chromium compounds are added to the reactor with reactant gases. Chromium can also be added to the reactor together with compounds having another or no effect on the trichlorosilane process.
  • Figure 3 shows a diagram for the conversion of STC to TCS in a quartz reactor at 550°C and 10 bar (absolute).
  • the silicon sample was mixed with 10 000 ppm (1% by weight) chromium (metallic) according to the present invention and compared with the STC conversion according to prior art.
  • Figure 4 shows a diagram for the conversion of STC to TCS in a quartz reactor at 550°C and 10 bar (absolute).
  • the silicon sample was pure silicon alloyed with 471 ppm Cr according to the present invention and compared with the STC conversion according to prior art.
  • the following example 1 was carried out in a laboratory fluid bed reactor made from quartz and embedded in a heated iron block.
  • the temperature of the heating block was kept at 550°C. Due to the low ⁇ of the reaction, the temperature of the reaction mass is assumed to also be 550°C.
  • the pressure of the reactor was kept at 10 bara.
  • 10 gram of commercially available silicon having a particle size of between 125 and 180 ⁇ » was mixed with copper chloride (0.16g) and chromium metal (0.1g) and added to the quartz reactor.
  • a mixture of silicon tetrachloride gas, hydrogen gas and argon gas (inert, reference for GC) in amounts of 252 Nl/min STC, 504 Nml/min H 2 and 84 Nl/min Ar was supplied to the reactor.
  • the composition of the product gas from the reactor was measured with a GC.
  • STC conversion was measured as % of the supplied STC being converted to TCS in the reactor.
  • the experiment was run continous, and silicon reacting was replaced by additions of fresh silicon, also containing 10 000 ppm (1% by weight) chromium, admixed.
  • the conversion of silicon tetrachloride of the sample was measured as first pass conversion. The experiment is compared to experiments with STC conversion according to prior art.
  • the following example 2 was carried out in a laboratory fluid bed reactor made from quartz and embedded in a heated iron block.
  • the temperature of the heating block was kept at 550°C. Due to the low ⁇ of the reaction, the temperature of the reaction mass is assumed to also be 550°C.
  • the pressure of the reactor was kept at 10 bar (absolute). 10 gram of pure silicon alloyed 471 ppm chromium, having a particle size of between 125 and 180 ⁇ was mixed with copper chloride (0.16g) and added to the quartz reactor.
  • a mixture of silicon tetrachloride gas, hydrogen gas and argon gas (inert, reference for GC) in amounts of 252 Nl/min STC, 504 Nl/min H 2 and 84 Nl/min Ar was supplied to the reactor.
  • the composition of the product gas from the reactor was measured with a GC.
  • STC conversion was measured as % of the supplied STC being converted to TCS in the reactor.
  • the experiment was run continous, and silicon reacting was replaced by additions of fresh silicon, also pure silicon alloyed 471 ppm chromium.
  • the conversion of silicon tetrachloride of the sample was measured as first pass conversion. The experiment is compared to experiments with STC conversion according to prior art.
  • Samples A according to the invention containing 10000 ppm chromium was made by mixing sample B with 10000 ppm chromium.
  • Sample B is Silgrain® silicon, produced by Elkem AS, screened to 125-180 microns. Samples A and B were used to produce trichlorosilane in a laboratory fluid-bed reactor described above. The amount of STC converted to TCS from sampleA and sample B are shown in Figure 3.
  • a high-purity silicon (polysilicon) was melted and alloyed with chromium in an induction furnace and cast in inert atmosphere. The sample was crushed and screened to a particle size between 125 and 180 ⁇ and named sample C.
  • Samples C according to the invention and sample B according to the prior art were used to produce trichlorosilane in a laboratory fluid-bed reactor described above.
  • the amount of STC converted to TCS from samples C and B are shown in Figure 4.

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

Abstract

La présente invention concerne un procédé de production de trichlorosilane en faisant réagir du silicium avec du tétrachlorure de silicium gazeux et de l'hydrogène gazeux à une température comprise entre 300 °C et 800 °C, et une pression absolue allant de 0,5 à 40 atm dans un réacteur à lit fluidisé, un réacteur à lit agité ou un réacteur à lit solide, le silicium alimenté dans le réacteur contenant entre 50 et 10 000 ppm de chrome. L'invention concerne en outre un procédé de production de trichlorosilane en faisant réagir du silicium avec du tétrachlorure de silicium gazeux et de l'hydrogène gazeux, la teneur en chrome dans le réacteur étant maintenue entre 100 et 50 000 ppm.
PCT/NO2011/000075 2010-03-12 2011-03-04 Procédé de production de trichlorosilane à partir de silicium, d'hydrogène et de tétrachlorure de silicium WO2011112097A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20100358A NO20100358A1 (no) 2010-03-12 2010-03-12 Fremgangsmate for fremstilling av triklorsilan fra silisium, hydrogen og silisiumtetraklorid
NO20100358 2010-03-12

Publications (1)

Publication Number Publication Date
WO2011112097A1 true WO2011112097A1 (fr) 2011-09-15

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NO (1) NO20100358A1 (fr)
WO (1) WO2011112097A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018172246A (ja) * 2017-03-31 2018-11-08 三菱マテリアル株式会社 水素混合ガスの製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005003030A1 (fr) * 2003-07-07 2005-01-13 Elkem Asa Procede de production de trichlorosilane et silicium destine a etre utilise dans la production de trichlorosilane
WO2007035108A1 (fr) * 2005-09-22 2007-03-29 Elkem As Procede de production de trichlorosilane et de silicium destine a etre utilise dans la production de trichlorosilane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005003030A1 (fr) * 2003-07-07 2005-01-13 Elkem Asa Procede de production de trichlorosilane et silicium destine a etre utilise dans la production de trichlorosilane
WO2007035108A1 (fr) * 2005-09-22 2007-03-29 Elkem As Procede de production de trichlorosilane et de silicium destine a etre utilise dans la production de trichlorosilane

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018172246A (ja) * 2017-03-31 2018-11-08 三菱マテリアル株式会社 水素混合ガスの製造方法

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