WO2009029794A1 - Procédé servant à produire du trichlorosilane - Google Patents

Procédé servant à produire du trichlorosilane Download PDF

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Publication number
WO2009029794A1
WO2009029794A1 PCT/US2008/074791 US2008074791W WO2009029794A1 WO 2009029794 A1 WO2009029794 A1 WO 2009029794A1 US 2008074791 W US2008074791 W US 2008074791W WO 2009029794 A1 WO2009029794 A1 WO 2009029794A1
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WO
WIPO (PCT)
Prior art keywords
tcs
stc
dirty
process according
produce
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/US2008/074791
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English (en)
Inventor
Jon M. Bill, Jr.
Carl W. Merkh
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.)
Dynamic Engineering Inc
Original Assignee
Dynamic Engineering Inc
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
Priority claimed from US12/200,115 external-priority patent/US20090060819A1/en
Application filed by Dynamic Engineering Inc filed Critical Dynamic Engineering Inc
Priority to DE112008002299T priority Critical patent/DE112008002299T5/de
Priority to CN200880108523A priority patent/CN101808938A/zh
Publication of WO2009029794A1 publication Critical patent/WO2009029794A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C01B33/10778—Purification
    • 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
    • C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
    • C01B33/10757—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane
    • C01B33/10763—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane from silicon

Definitions

  • the present invention relates to processes for preparing trichlorosilane, and, more particularly, to a process for preparing high purity trichlorosilane from by-products of a primary reaction utilizing metallurgical or chemical-grade silicon stock, by-products of the Improved Siemens Process, or a combination thereof.
  • the present invention relates to the field of preparing high purity trichlorosilane
  • TCS formula HSiCl 3
  • TCS is a valuable intermediate product used to produce various silanes, for electronics and adhesives.
  • TCS especially the high purity grade, is used in the electronics industry including, for example, use in the preparation of solar and electronics grade polycrystalline silicon, which produces silicon tetrachloride as a by-product.
  • Powdered copper catalysts have been used in industry for similar reactions for some time.
  • the use of powdered copper or mixtures of copper metal, metal halides and bromides or iodides of iron, aluminum or vanadium is reported to react silicon with silicon tetrachloride, hydrogen and, if necessary, hydrogen chloride. See, for example, Chemical Abstracts CA 101, no. 9576d, 1984 and Chemical Abstracts CA 109, no. 57621b, 1988.
  • trichlorosilane is usually produced in a fluidized bed.
  • the raw material used in these reactions is often metallurgical or chemical grade silicon, other impurities are often present, such as, for example, carbon, boron, and phosphorus containing compounds.
  • a reactor for producing TCS in addition to producing DCS and STC as byproducts, also produces a variety of other impurities such as, for example, BCl 3 , PCl 3 , Iso- pentane, methyl trichlorosilane, and various other combinations of chlorine, oxygen, silane, methyl, chlorinated silane, and chlorinated methyl groups.
  • impurities such as, for example, BCl 3 , PCl 3 , Iso- pentane, methyl trichlorosilane, and various other combinations of chlorine, oxygen, silane, methyl, chlorinated silane, and chlorinated methyl groups.
  • An exit stream from the reactor for producing TCS from metallurgical grade silicon and hydrogen chloride is defined as "raw" TCS.
  • This stream, along with TCS, also contains DCS, STC, hydrogen, and a variety of impurities is often purified in a couple of steps to separate "raw" TCS, from "dirty" TCS and STC which are processed in waste streams and the "raw” TCS afterwards is sent on to further purification. This often yields only about 30% to 90% “raw” TCS (as a percentage of silicon molecules entering the reactor leaving in the
  • TCS is the name given to a by-product stream having mostly TCS and various other low boiling point compounds that may be present, including DCS.
  • these "dirty" by-product streams are either treated as waste or are used to produce compounds of lower value than TCS.
  • Exemplary embodiments of the present invention provide a means for reacting some portion of by-product streams containing STC and DCS with each other to produce more TCS after "dirty" STC has first been purified.
  • "Dirty" STC is purified, but not limited to, using methods of distillation and adsorption to remove high boiling point reaction byproducts to produce purified STC defined as "HP" STC known as "high purity” STC. Then the process simulates previous art in that the "HP" STC is hydrogenated back to TCS, also producing hydrogen chloride.
  • the TCS thus produced is reintroduced to the "raw" TCS stream from the initial separation, and is further purified to electronics grade.
  • the hydrogen chloride is reintroduced to the reactor utilizing the metallurgical or chemical grade silicon as a raw material.
  • the various exemplary embodiments herein drastically reduce kilograms of waste that are produced per kilogram of TCS.
  • the various exemplary embodiments herein reduce the overall requirement for use of chlorine, and the amount of chlorine exiting the process in the waste streams is calculated on a mass basis to be less than about 25% of that in the waste streams of traditional prior art methods.
  • Fig. 1 is a flow diagram of a process known as the "Improved Siemens Process” that is used for producing trichlorosilane.
  • the process modifications of the present invention can be used in the "Improved Siemens Process” shown in Fig. 1.
  • Fig. 2 is a flow diagram showing the modification in accordance with the present invention applied to the process shown in Fig. 1, for producing trichlorosilane at higher net yield efficiency.
  • the process of the present invention begins with "dirty" TCS being produced as a by-product from any number of existing purification methods such as, for example, a distillation scheme.
  • the "Improved Siemens Process” shown in Fig. 1 is one such process for which the present invention can be used.
  • other processes also can benefit from the application of modifications in accordance with the present invention.
  • Contaminated by-products from the "TCS Purification” stage include both “dirty” TCS and "dirty” STC.
  • the "dirty" TCS containing dichlorosilane abbreviated DCS, formula H 2 SiCl 2
  • purified STC known as "HP" STC
  • the new TCS product produced is recycled back to the TCS purification stage.
  • the selection of a reactor for the reaction according to the invention is not believed to be critical. A typical example is the introduction of the "dirty" TCS" containing DCS into the bottom or top of a stirred tank filled with STC and catalyst.
  • the reaction can take place at temperatures between about 4 0 C to about 7O 0 C, depending on the temperature stability of the catalyst in use.
  • the mole ratio of silicon tetrachloride molecules in the feed stock to dichlorosilane molecules in the reaction according to the invention can be for example about 1:4 to about 5:1.
  • a mole ratio of about 2: 1 to about 5: 1 is preferred.
  • STC Purification the silicon tetrachloride separated from the “dirty” TCS in the TCS purification stage, known as “dirty” STC, is separated from higher boiling impurities by a suitable separation process, such as, for example, distillation.
  • the purified STC obtained is then converted to TCS in accordance with known steps of the "Improved Siemens Process” such as, for example, STC hydrogenation.
  • the separation of TCS reactor by-products in the TCS Purification stage can include a reflux ratio of one to two hundred for the separation by distillation of "dirty" TCS from "raw” TCS.
  • the purification of "raw” TCS can include pressure and temperature swing adsorption.
  • the separation of STC hydrogenation reactor products can include the distillation of TCS from STC prior to mixing with unpurified TCS streams.
  • "Dirty" TCS containing DCS can be reacted with "HP" STC, chlorine, and/or hydrogen chloride in a liquid phase reactor.
  • TCS containing DCS is reacted using only purified STC, known as "HP" STC, in a liquid and/or vapor phase reactor in presence of a suitable catalyst to produce TCS for additional feedstock to the TCS purification process.
  • HP STC purified STC
  • the high purity trichlorosilane produced by the various exemplary embodiments of the present invention can be used, for example, for the manufacture of silane, and/or directly for solar-grade or electronics grade poly-silicon crystals. Therefore the invention also relates to a method for producing silane and/or poly-silicon crystals on the basis of high purity trichlorosilane obtained according to the above exemplary embodiments.
  • the various exemplary embodiments herein are integrated into a general method for manufacture of solar or electronics grade poly-silicon crystals.
  • an exemplary embodiments of the present invention can be integrated into a multistage general method for producing poly-silicon crystals, as specified, for example, in "Economics of Polysilicon Process, Osaka Titanium Co., DOE/JPL 1012122 (1985), 57-78" and comprising the steps of: producing TCS; disproportioning TCS to yield silane; purifying silane to obtain high-purity silane; and thermally decomposing silane in a fluidized-bed reactor and depositing hyper-pure silicon on the silicon particles which form the fluidized bed.
  • an exemplary embodiments of the present invention may be integrated into a method for producing silane and/or solar or electronics grade poly-silicon crystals comprising the steps of: synthesizing and isolating TCS via distillation from "raw” TCS, and recycling "dirty" TCS and silicon tetrachloride; additional purifying of the "raw” TCS by purification techniques, including, but not limited to, distillation and/or adsorption; additional purifying of silicon tetrachloride to remove high boiling impurities by purification techniques, including, but not limited to, distillation and/or adsorption; hydrogenating purified STC to produce additional TCS feed to the TCS purification process; chlorinating DCS by-product by reaction with purified STC to produce additional TCS feed to the TCS purification process; disproportioning high purity TCS to silane or poly-silicon crystals utilizing an deposition technique, including, but not limited to, a Siemens reactor.

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

Abstract

L'invention concerne un procédé servant à préparer du trichlorosilane (TCS) de pureté élevée utilisant des sous- produits contaminés issus d'une réaction primaire, du chlorure d'hydrogène, une matière première comprenant un silicium de qualité métallurgique ou chimique et/ou des sous-produits du procédé Siemens amélioré, dont des impuretés à faible point d'ébullition contenant du TCS « sale » telles que des impuretés à faible point d'ébullition contenant du dichlorosilane (DCS) et du STC « sale ». Le procédé consiste d'abord à purifier le STC « sale » et à en faire réagir une partie avec le DCS contenant du TCS « sale » pour produire une charge d'alimentation de TCS supplémentaire pour le procédé de purification du TCS; et hydrogéner une autre partie du STC purifié et reconvertir celui-ci en TCS pour produire une autre charge d'alimentation pour le procédé de purification du TCS. Le rendement de production net global du TCS de pureté élevée produit est accru par rapport à la pratique établie.
PCT/US2008/074791 2007-08-29 2008-08-29 Procédé servant à produire du trichlorosilane Ceased WO2009029794A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE112008002299T DE112008002299T5 (de) 2007-08-29 2008-08-29 Verfahren zur Herstellung von Trichlorsilan
CN200880108523A CN101808938A (zh) 2007-08-29 2008-08-29 生产三氯硅烷的方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US96870307P 2007-08-29 2007-08-29
US60/968,703 2007-08-29
US12/200,115 US20090060819A1 (en) 2007-08-29 2008-08-28 Process for producing trichlorosilane
US12/200,115 2008-08-29

Publications (1)

Publication Number Publication Date
WO2009029794A1 true WO2009029794A1 (fr) 2009-03-05

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PCT/US2008/074791 Ceased WO2009029794A1 (fr) 2007-08-29 2008-08-29 Procédé servant à produire du trichlorosilane

Country Status (2)

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DE (1) DE112008002299T5 (fr)
WO (1) WO2009029794A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817528A (zh) * 2010-03-26 2010-09-01 成都鸿宝新能源科技有限公司 SiCl4氢化生产SiHCl3的节能降耗循环工艺及系统
DE102011082662A1 (de) 2011-09-14 2013-03-14 Evonik Degussa Gmbh Verwertung niedrigsiedender Verbindungen in Chlorsilan-Prozessen
EP2537803A4 (fr) * 2010-02-18 2016-10-19 Tokuyama Corp Procédé de production de trichlorosilane
EP3206990A4 (fr) * 2014-10-14 2018-10-10 SiTec GmbH Procédé de distillation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011002749A1 (de) 2011-01-17 2012-07-19 Wacker Chemie Ag Verfahren und Vorrichtung zur Konvertierung von Siliciumtetrachlorid in Trichlorsilan

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4676967A (en) * 1978-08-23 1987-06-30 Union Carbide Corporation High purity silane and silicon production
US6670543B2 (en) * 1999-07-26 2003-12-30 Schott Glas Thin-film solar cells and method of making
US20060086247A1 (en) * 2004-10-25 2006-04-27 Vininski Joseph V Fluid purification system with low temperature purifier

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1073460B (de) 1958-01-11 1960-01-21 LICENTIA Patent-Verwaltungs-G.m.b.H., Frankfurt/M Verfahren zum Reinigen von Silan oder chlorierten Silanen
US3540861A (en) 1968-02-07 1970-11-17 Union Carbide Corp Purification of silicon compounds
DE2546957C3 (de) 1975-10-20 1980-10-23 Wacker-Chemitronic Gesellschaft Fuer Elektronik-Grundstoffe Mbh, 8263 Burghausen Verfahren zur Reinigung von Halogensilanen
DE10057482A1 (de) 2000-11-20 2002-05-23 Solarworld Ag Verfahren zur Reinigung von Trichlorsilan

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4676967A (en) * 1978-08-23 1987-06-30 Union Carbide Corporation High purity silane and silicon production
US6670543B2 (en) * 1999-07-26 2003-12-30 Schott Glas Thin-film solar cells and method of making
US20060086247A1 (en) * 2004-10-25 2006-04-27 Vininski Joseph V Fluid purification system with low temperature purifier

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2537803A4 (fr) * 2010-02-18 2016-10-19 Tokuyama Corp Procédé de production de trichlorosilane
CN101817528A (zh) * 2010-03-26 2010-09-01 成都鸿宝新能源科技有限公司 SiCl4氢化生产SiHCl3的节能降耗循环工艺及系统
DE102011082662A1 (de) 2011-09-14 2013-03-14 Evonik Degussa Gmbh Verwertung niedrigsiedender Verbindungen in Chlorsilan-Prozessen
WO2013037639A1 (fr) 2011-09-14 2013-03-21 Evonik Degussa Gmbh Valorisation de composés à bas point d'ébullition dans des processus pour chlorosilane
EP3206990A4 (fr) * 2014-10-14 2018-10-10 SiTec GmbH Procédé de distillation

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Publication number Publication date
DE112008002299T5 (de) 2010-07-22

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