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WO2011136517A2 - Procédé de préparation de tétrafluorure de silicium à l'aide de silice cristalline - Google Patents

Procédé de préparation de tétrafluorure de silicium à l'aide de silice cristalline Download PDF

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Publication number
WO2011136517A2
WO2011136517A2 PCT/KR2011/002981 KR2011002981W WO2011136517A2 WO 2011136517 A2 WO2011136517 A2 WO 2011136517A2 KR 2011002981 W KR2011002981 W KR 2011002981W WO 2011136517 A2 WO2011136517 A2 WO 2011136517A2
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WO
WIPO (PCT)
Prior art keywords
sulfuric acid
silicon tetrafluoride
crystalline silica
reactor
hydrogen fluoride
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
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PCT/KR2011/002981
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English (en)
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WO2011136517A3 (fr
Inventor
Kyoung Hoon Kang
Yeon Seok Cho
Se Jong Kim
Young Shin Yoo
Moon Gue Jun
Jeong Mo Shim
Hyun Dong Lee
Ji Hye Kim
Min Wook Song
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KCC Corp
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KCC Corp
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Publication date
Application filed by KCC Corp filed Critical KCC Corp
Publication of WO2011136517A2 publication Critical patent/WO2011136517A2/fr
Publication of WO2011136517A3 publication Critical patent/WO2011136517A3/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
    • C01B9/00—General methods of preparing halides
    • C01B9/08—Fluorides
    • 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 method of preparing silicon tetrafluoride (STF, SiF 4 ) by using crystalline silica (SiO 2 ). More specifically, the present invention relates to a method of preparing silicon tetrafluoride by reacting finely divided crystalline silica and hydrogen fluoride (HF) in the presence of concentrated sulfuric acid in a continuous manner. According to the present invention, silicon tetrafluoride can be economically prepared with high yield from crystalline silica which exists abundantly in the natural world, and the process productivity, workability and controllability can be improved remarkably.
  • the amount of unreacted hydrogen fluoride can be reduced significantly, and the difficulty in filtering the product by finely divided particles can be avoided since the crystalline silica reactant is consumed completely. Furthermore, since the used sulfuric acid can be isolated and recycled, the generation of discarded sulfuric acid can be minimized.
  • Silicon tetrafluoride (STF, SiF 4 ) gas is used in a dry etching process in manufacturing semiconductors and as a raw material for the preparation of wiring for optical fibers and the preparation of amorphous silicon thin films. It is also used as a precursor of monosilane (SiH 4 ) gas for manufacturing silicon wafers for solar cells.
  • the process of preparing SiF 4 by thermally decomposing hexafluorosilicic acid generated as a byproduct in phosphate fertilizer production requires use of a large amount of sulfuric acid to remove water which exists together with the hexafluorosilicic acid, and thus has a difficulty that the excessive diluted sulfuric acid generated thereby should be further treated for its recovery.
  • the precursor hexafluorosilicic acid is a byproduct generated in the production of phosphate fertilizer
  • the process of preparing SiF 4 depends on the phosphate fertilizer production process, and thus in order to enable the scale-up of SiF 4 production, the scale-up of the phosphate fertilizer production process must accompany it.
  • US Patent No. 6,770,253 suggests a method of preparing SiF 4 by reacting elemental silicon (Si) with HF at a high temperature condition of 300°C or more.
  • US Patent No. 4,382,071 suggests a method of preparing SiF 4 by reacting HF dissolved in sulfuric acid with amorphous silica.
  • this method has a demerit in that expensive amorphous silica with high purity should be used in order to obtain SiF 4 with a high yield of 70% or more.
  • the reaction becomes too vigorous and so its control is difficult.
  • the present invention has an object of providing a method of preparing silicon tetrafluoride, according to which silicon tetrafluoride can be economically prepared with high yield from crystalline silica which exists abundantly in the natural world, and the process productivity, workability and controllability can be improved remarkably, the amount of unreacted hydrogen fluoride can be reduced significantly, and the difficulty in filtering the product by finely divided particles can be avoided since the crystalline silica reactant is consumed completely, and since the used sulfuric acid can be isolated and recycled, the generation of discarded sulfuric acid can be minimized.
  • the present invention provides a method of preparing silicon tetrafluoride (SiF 4 ) comprising: reacting crystalline silica having an average particle size of 60 micrometers or less and hydrogen fluoride (HF) in the presence of concentrated sulfuric acid at 80 ⁇ 140°C to obtain silicon tetrafluoride.
  • SiF 4 silicon tetrafluoride
  • silicon tetrafluoride can be economically prepared with high yield from crystalline silica which exists abundantly in the natural world, instead of expensive amorphous silica material, and the process productivity, workability and controllability can be improved remarkably.
  • the amount of unreacted hydrogen fluoride can be reduced significantly, and the difficulty in filtering the product by finely divided particles can be avoided since the crystalline silica reactant is consumed completely.
  • the used sulfuric acid can be isolated and recycled, the generation of discarded sulfuric acid can be minimized.
  • Figure 1 schematically represents an embodiment of the reaction device for performing the method of preparing silicon tetrafluoride according to the present invention in a continuous manner.
  • crystalline silica existing abundantly in the natural world is used.
  • source materials of such crystalline silica include sand, quartzite and the like. Such source materials are pulverized and sorted to be used in the method of preparing silicon tetrafluoride of the present invention.
  • the average particle size of the crystalline silica used in the method of preparing silicon tetrafluoride of the present invention is 60 micrometers or less (for example, from 5 to 60 micrometers), and preferably 50 micrometers or less (for example, from 5 to 50 micrometers). If the average particle size of the crystalline silica is greater than 60 micrometers, the reactivity is insufficient and thus the intended yield (for example, a total yield of 70% or more) cannot be obtained. There is no particular limitation in the lower limit of the average particle size of the crystalline silica.
  • the reactivity can be controlled through adjustment of various process parameters such as the reactant feeding rate and the like.
  • the preparation process is designed in a continuous manner as in the embodiment of the present invention, even though the reaction rate in the first reactor is somewhat low, the further reaction in the subsequent reactor can increase the total yield to 70% or more, and preferably 90% or more.
  • the crystalline silica used in the present invention is a cheap material obtainable from sand or quartzite existing abundantly in the natural world, whereas most amorphous silica materials used in conventional processes except for diatomite are artificial products rather than those existing in the natural world and thus are expensive.
  • crystalline silica reacts with hydrogen fluoride (HF) in the presence of concentrated sulfuric acid.
  • HF hydrogen fluoride
  • the use amount ratio of crystalline silica and hydrogen fluoride there is no particular limitation to the use amount ratio of crystalline silica and hydrogen fluoride, and thus the use amount ratio may be selected appropriately according to need.
  • the reaction may be conducted with the equivalent amount ratio as shown in the above reaction scheme.
  • crystalline silica may be used in an amount less than the theoretical equivalent amount of the above reaction scheme ⁇ for example, 85 ⁇ 95% of the theoretical equivalent amount of the above reaction scheme.
  • hydrogen fluoride may be used in an amount less than the theoretical equivalent amount of the above reaction scheme ⁇ for example, 85 ⁇ 95% of the theoretical equivalent amount of the above reaction scheme.
  • crystalline silica is used in an amount corresponding to 85 ⁇ 95% of the theoretical equivalent amount of the hydrogen fluoride, it is possible that no solid silica remains in the reactor after the reaction, and in this case a filtering procedure may be omitted in a process of distilling and recycling diluted sulfuric acid after the reaction.
  • a difficulty in filtering of product due to fine particles may be avoided by using crystalline silica in an amount of 90% of the theoretical equivalent amount of the above reaction scheme.
  • the feeding amounts of silica and hydrogen fluoride as such the diluted sulfuric acid finally generated may not contain the solid silica component or hydrogen fluoride, and thus the process of re-treating sulfuric acid may be performed conveniently.
  • sulfuric acid is used to take up water generated as a result of the reaction between crystalline silica and hydrogen fluoride.
  • a concentrated sulfuric acid having a concentration of 95% or more (for example, 98%) is used.
  • the concentrated sulfuric acid is used in an amount that makes the concentration of diluted sulfuric acid discharged after the reaction become preferably 60% or more, and more preferably 75% or more.
  • the reaction of crystalline silica and hydrogen fluoride is conducted at a temperature of 80 ⁇ 140°C, preferably 90 ⁇ 130°C and more preferably 100 ⁇ 120°C. If the reaction temperature is lower than 80°C, the reaction becomes slow and thus the productivity decreases. If the reaction temperature is higher than 140°C, anhydrous hydrogen fluoride is not dissolved in sulfuric acid but is changed in gas phase and the reaction becomes difficult, resulting in the lowering of SiF 4 yield or the problem of escape from the reactor.
  • the method of preparing silicon tetrafluoride of the present invention may preferably be performed in a continuous manner by using plural reactors connected in series, by which a higher yield may be obtained.
  • crystalline silica having an average particle size of 60 micrometers or less is introduced into the first reactor A via line 1 , and at the same time anhydrous hydrogen fluoride and concentrated sulfuric acid are introduced into the reactor via lines 2 and 3 , respectively.
  • Reactor A is maintained at 80 ⁇ 140°C, and the reactants are agitated by a mechanical stirrer. After a given time (for example, 20 minutes ⁇ 1 hour), SiF 4 gas generation begins and the generated SiF 4 gas is then collected via line 4 .
  • the unreacted slurry mixture is transferred to the second reactor B in which further reaction is conducted to complete the reaction of the unreacted mixture.
  • a third reactor, a fourth reactor and the like may be further connected in series.
  • the time for the further reaction in the second reactor may be set to the time for re-filling the reactants in the first reactor to a predetermined level (i.e., the time for the reaction mixture level in the first reactor to rise from L LA to L HA ), and the time for the further reaction in the second reactor may be adjusted by controlling the feeding rate of reactants into the first reactor A .
  • SiF 4 gas generated in the second reactor B is discharged out of the second reactor via line 6 and then collected via line 4 .
  • the feeding rate of the reactants 60 to 70 mole% of the total yield of silicon tetrafluoride (STF) was prepared in the first reactor and the further reaction was conducted in the second reactor, by which the total yield could be increased to 95 mole% or more.
  • Silicon tetrafluoride was prepared by using the continuous-type reaction device as shown in Figure 1.
  • crystalline silica having an average particle size of 20 micrometers (SiO 2 ) was incorporated via line 1 at a feeding rate of 15g per hour (0.25mol/hr).
  • anhydrous hydrogen fluoride (HF) liquid was incorporated via line 2 at a feeding rate of 20g per hour (1mol/hr) and 38g of 98%-concentrated, cold sulfuric acid ( ⁇ 10°C) was incorporated via line 3 into reactor A , respectively.
  • the temperature inside reactor A was maintained at 120°C by heating wire and the incorporated reactants were agitated by a mechanical stirrer. After 30 minutes from the start of the reactant feeding, SiF 4 gas began to generate and the generated SiF 4 gas was collected via line 4 . Cold sulfuric acid was introduced through SiF 4 gas outlet line 4 in order to prevent unreacted hydrogen fluoride from escaping from the reactor along with the generated SiF 4 gas.
  • the gas discharged via line 4 was quenched for ingredient analysis by subsequently passing it through a trap containing sulfuric acid and a trap containing 5% aqueous solution of hydrogen fluoride.
  • a trap containing sulfuric acid and a trap containing 5% aqueous solution of hydrogen fluoride Through the sulfuric acid trap, the generation of water and unreacted HF escaping outside were checked.
  • the hydrogen fluoride trap the generated SiF 4 was converted to hexafluorosilicic acid which was then titrated to check the amount of generated SiF 4 .
  • the transfer pump was operated to transfer the reaction mixture in reactor A to reactor B .
  • the reaction was further conducted to be completion.
  • the further reaction in reactor B was conducted at 120°C for 15 hours in order that the unreacted hydrogen fluoride could be consumed completely.
  • the SiF 4 gas generated at that time was discharged out of the second reactor via line 6 and was then analyzed via line 4 as explained above.
  • Table 1 shows the generated amounts of SiF 4 when anhydrous hydrogen fluoride and silica were used in the equivalent amount ratio (Example 1) and when the use amount of silica was reduced to 90% of that of anhydrous hydrogen fluoride (Example 2), and the analysis result of the diluted sulfuric acid discharged out of the second reactor B finally.

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

Abstract

La présente invention porte sur un procédé de préparation de tétrafluorure de silicium (STF, SiF4) à l'aide de silice cristalline (SiO2). De façon plus spécifique, la présente invention porte sur un procédé de préparation de tétrafluorure de silicium par la réaction de silice cristalline finement divisée et de fluorure d'hydrogène (HF) en présence d'acide sulfurique concentré d'une manière continue. Selon la présente invention, du tétrafluorure de silicium peut être économiquement préparé avec un rendement élevé à partir de silice cristalline qui est présente en abondance dans la nature et la productivité, l'exploitabilité et la facilité de réglage du procédé peuvent être remarquablement améliorées. De plus, le problème de corrosion dans le procédé de recyclage par concentration d'acide sulfurique dilué peut être résolu par le réglage du rapport entre les réactifs de façon à ce qu'il ne reste pas de fluorure d'hydrogène incorporé après la réaction ou, par ailleurs, la difficulté de filtration du produit due aux particules finement divisées peut être évitée par réglage du rapport entre les réactifs de façon à ce que le réactif silice cristalline soit totalement consommé. En outre, dans la mesure où l'acide sulfurique usé peut être isolé et recyclé, la production d'acide sulfurique rejeté peut être réduite au minimum.
PCT/KR2011/002981 2010-04-27 2011-04-25 Procédé de préparation de tétrafluorure de silicium à l'aide de silice cristalline Ceased WO2011136517A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20100038878A KR101168942B1 (ko) 2010-04-27 2010-04-27 결정성 규사를 사용한 사불화규소의 제조방법
KR10-2010-0038878 2010-04-27

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WO2011136517A2 true WO2011136517A2 (fr) 2011-11-03
WO2011136517A3 WO2011136517A3 (fr) 2012-03-08

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CN103091271B (zh) * 2012-11-28 2016-05-18 贵州瓮福蓝天氟化工股份有限公司 测定四氟化硅气体中杂质碘含量的方法

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JPS604125B2 (ja) * 1981-02-16 1985-02-01 セントラル硝子株式会社 高純度四弗化珪素の製造法
UA73847C2 (en) * 2003-09-02 2005-09-15 A method for preparing silicon tetrafluoride, a method for isolation of the silicon tetrafluoride from oxygen and highly volatile admixtures, a method for preparing silicon powder from the silicon tetrafluoride
JP4576312B2 (ja) * 2005-10-03 2010-11-04 東北電力株式会社 四フッ化ケイ素の製造方法、及びそれに用いる製造装置
CN101795964B (zh) * 2007-08-23 2013-01-02 "索拉斯"有限公司 生产多晶硅的方法

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KR20110119267A (ko) 2011-11-02
WO2011136517A3 (fr) 2012-03-08
TW201204632A (en) 2012-02-01
KR101168942B1 (ko) 2012-08-02

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