JPH02172811A - Production of trichlorosilane - Google Patents
Production of trichlorosilaneInfo
- Publication number
- JPH02172811A JPH02172811A JP32829888A JP32829888A JPH02172811A JP H02172811 A JPH02172811 A JP H02172811A JP 32829888 A JP32829888 A JP 32829888A JP 32829888 A JP32829888 A JP 32829888A JP H02172811 A JPH02172811 A JP H02172811A
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- reaction
- trichlorosilane
- silicon tetrachloride
- gas
- 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.)
- Pending
Links
- 239000005052 trichlorosilane Substances 0.000 title abstract description 32
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title description 30
- 238000004519 manufacturing process Methods 0.000 title description 17
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 47
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011863 silicon-based powder Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 238000004821 distillation Methods 0.000 description 12
- 239000005046 Chlorosilane Substances 0.000 description 8
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 8
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、トリクロロシランの製造方法に関し、さらに
詳細には四塩化ケイ素を原料として多結晶シリコンおよ
びアモルファスシリコンの製造に好適なトリクロロシラ
ンの製造方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing trichlorosilane, and more particularly to a method for producing trichlorosilane suitable for producing polycrystalline silicon and amorphous silicon using silicon tetrachloride as a raw material. Regarding the method.
トリクロロシラン（Ｓ ｉ ＨＣｌ１ｓ ） 、ジクロ
ロシラン（Ｓ ｉ Ｈｚ Ｃｆｚ ）などのクロロシラ
ンは、半導体用の高純度シリコン製造の原料として、あ
るいは太陽電池に利用されるアモルファスシリコン製造
の原料として非常に有用である。Chlorosilanes such as trichlorosilane (S i HCl1s ) and dichlorosilane (S i Hz Cfz ) are extremely useful as raw materials for producing high-purity silicon for semiconductors or for producing amorphous silicon used in solar cells. .
半導体用高純度シリコンの製造には、クロロシランと水
素の混合ガスを通電加熱したシリコン棒上に接触させ、
還元によりシリコンの結晶を析出させるのであるが、こ
の際、四塩化ケイ素が３０〜７０重量％と多量に副生ず
る。To produce high-purity silicon for semiconductors, a mixed gas of chlorosilane and hydrogen is brought into contact with a silicon rod heated by electricity.
Silicon crystals are precipitated by reduction, and at this time, a large amount of silicon tetrachloride (30 to 70% by weight) is produced as a by-product.
また、後者のアモルファスシリコンの製造には、クロロ
シランから次の不均化反応、すなわち４ Ｓ ｉ ＨＣ
ｌ ３→Ｓ ｉ Ｈ４＋３ Ｓ ｉ Ｃ１ｍ２ＳｉＨｚ
Ｃｆｚ→Ｓ ｉ Ｈ４＋ Ｓ ｉ Ｃｌ ａによりシ
ラン（ＳｉＨ，）を生成し、これをグロー放電によりア
モルファスシリコンに転換している。この不均化反応に
おいても、前記のごとく四塩化ケイ素がシランの数倍モ
ル量生成することが分かる。この副生ずる四塩化ケイ素
は、原料として再利用するため、反応塔に循環供給し水
素化反応によりクロロシランに転換している。この四塩
化ケイ素を水素化反応によりクロロシランに転換する方
法については、現在までいくつかの方法が提案されてい
るが、特開昭５８−２１７４２２号公報で開示されてい
る方法が特に有名である。In addition, for the production of the latter amorphous silicon, the following disproportionation reaction is performed from chlorosilane, that is, 4 Si HC
l 3→S i H4+3 S i C1m2SiHz
Silane (SiH,) is produced by Cfz→S i H4+ S i Cla, and this is converted into amorphous silicon by glow discharge. It can be seen that in this disproportionation reaction, as described above, silicon tetrachloride is produced in an amount several times the molar amount of silane. This by-produced silicon tetrachloride is recycled to the reaction tower and converted into chlorosilane through a hydrogenation reaction in order to be reused as a raw material. Several methods have been proposed to date for converting silicon tetrachloride into chlorosilane through a hydrogenation reaction, but the method disclosed in JP-A-58-217422 is particularly famous.
この方法は、水素化反応器の頂部より金属シリコンの粉
体を投入し、底部より水素と四塩化ケイ素の混合ガスを
供給し１、温度−４５０〜５５０°Ｃ１圧力＝４００〜
６００ｐｓｉの条件下で流動層状態で次の反応によりク
ロロシランを生成させるものである。In this method, metallic silicon powder is introduced from the top of the hydrogenation reactor, and a mixed gas of hydrogen and silicon tetrachloride is supplied from the bottom.
Chlorosilane is produced by the following reaction in a fluidized bed under conditions of 600 psi.
３ Ｓ ｉＣｆ２ａ ＋ ２ Ｈｚ ＋ Ｓ Ｉ→４Ｓ
ｉＨＣｆｆｉ。3 S iCf2a + 2 Hz + S I→4S
iHCffi.
Ｓ ｉ ＣＬ ＋２ Ｈｚ ＋Ｓ ｔ−＋２
３ ｉ Ｈｚ Ｃ１ｚ前記反応では、主として
トリクロロシランを生成するが、同時にジクロロシラン
も副生ずる。S i CL +2 Hz +S t-+2
3 i Hz C1z In the above reaction, trichlorosilane is mainly produced, but dichlorosilane is also produced as a by-product.
反応器を出たトリクロロシラン、ジクロロシラン、四塩
化ケイ素および水素ガスの混合体は、冷却されて水素ガ
ス以外は凝縮液化し、次いで蒸留によりクロロシランと
未反応の四塩化ケイ素は分離され、四塩化ケイ素は、前
記水素化反応器に原料として循環再利用される。また、
クロロシランは、アモルファスシリコン製造のために利
用されるときは、前記の不均化反応によりモノシランに
転換され、アモルファスシリコンの原料となる。The mixture of trichlorosilane, dichlorosilane, silicon tetrachloride, and hydrogen gas that exits the reactor is cooled, and everything except hydrogen gas is condensed and liquefied.Then, chlorosilane and unreacted silicon tetrachloride are separated by distillation, and the mixture is converted into tetrachloride. Silicon is recycled and reused as a raw material in the hydrogenation reactor. Also,
When chlorosilane is used for producing amorphous silicon, it is converted to monosilane by the above-mentioned disproportionation reaction and becomes a raw material for amorphous silicon.
不均化反応の際に副生ずる四塩化ケイ素は、蒸留操作に
より分離され、前記と同様に水素化反応器に循環供給さ
れ、原料として再利用される。Silicon tetrachloride, which is produced as a by-product during the disproportionation reaction, is separated by a distillation operation, and is circulated and supplied to the hydrogenation reactor in the same manner as described above to be reused as a raw material.
以上の従来技術においては、水素化反応器の操業条件が
、温度が４５０〜５５０°Ｃであるとともに、圧力も４
００〜６００ｐｓｉと高く過酷であるため、水素化反応
器の運転管理が容易でないこと、四塩化ケイ素のトリク
ロロシランおよびジクロロシランへの変換効率が１５〜
２０％と低く、多量の四塩化ケイ素および水素をｗｌｇ
、するため、装置容量が大きくなり、同時に運転用役費
も増加するという問題がある。In the above conventional technology, the operating conditions of the hydrogenation reactor are a temperature of 450 to 550°C and a pressure of 4.
Since the pressure is high and harsh at 00 to 600 psi, it is difficult to manage the operation of the hydrogenation reactor, and the conversion efficiency of silicon tetrachloride to trichlorosilane and dichlorosilane is 15 to 600 psi.
Low as 20%, containing large amounts of silicon tetrachloride and hydrogen
Therefore, there is a problem in that the capacity of the equipment increases and at the same time, the operating costs also increase.
［発明が解決しようとする課題］
本発明は、前記従来技術の課題を背景になされたもので
、四塩化ケイ素を有効に１−ジクロロシランへ変換する
とともに、変換効率も５０〜６０％と高く、コンパクト
な設備となすことが可能なトリクロロシランの製造方法
を提供することを目的とする。[Problems to be Solved by the Invention] The present invention has been made against the background of the above-mentioned problems of the prior art, and it effectively converts silicon tetrachloride into 1-dichlorosilane and has a high conversion efficiency of 50 to 60%. The purpose of the present invention is to provide a method for producing trichlorosilane that can be implemented using compact equipment.
本発明は、四塩化ケイ素と金属シリコンとを１．１００
〜１，３００°Ｃの温度で反応させ、次いで得られた反
応生成物を塩化水素と反応させることを特徴とするトリ
クロロシランの製造方法を提供するものである。In the present invention, silicon tetrachloride and metal silicon are combined at a concentration of 1.100
The present invention provides a method for producing trichlorosilane, which is characterized by carrying out the reaction at a temperature of -1,300°C, and then reacting the obtained reaction product with hydrogen chloride.
本発明では、まず四塩化ケイ素と金属シリコンとを、１
，１００〜１，３００’Ｃの高い反応温度で反応させる
（以下「−次反応」ということがある）。すなわち、四
塩化ケイ素を１，１００〜１．３００の高い温度範囲で
金属シリコンの粉末と接触させると、次の反応式により
二塩化ケイ素および三塩化ケイ素をかなり高濃度で生成
さセることかできる。In the present invention, silicon tetrachloride and metallic silicon are first
, 100 to 1,300'C (hereinafter sometimes referred to as "-order reaction"). In other words, when silicon tetrachloride is brought into contact with metallic silicon powder at a high temperature range of 1,100 to 1,300 ℃, silicon dichloride and silicon trichloride are produced at a fairly high concentration according to the following reaction equation. can.
５ｉＣｆｆ、＋Ｓｉ−→２ＳｉＣｆｆｉ２３ Ｓ ｉ
Ｃｅ４＋Ｓ ｉ−＋４ Ｓ ｉ （、Ｌ＋前記反応温度
が１，１００°Ｃより低いと、二塩化ケイ素、三塩化ケ
イ素−・の転換効率が低くなり、一方１．３００°Ｃを
越えると反応器材質および熱経済的に〒利となる。なお
、この−次反応において、原料の金属シリコンとしては
、冶金工業的に得られるシリコンでよく、粉末粒子の大
きさとしては１５０〜３００μｍが好ましい。5iCff, +Si−→2SiCffi23 S i
Ce4+S i-+4 S i (, L+ When the reaction temperature is lower than 1,100°C, the conversion efficiency of silicon dichloride, silicon trichloride -. It is advantageous in terms of thermoeconomics.In this second reaction, the metal silicon used as a raw material may be silicon obtained in the metallurgical industry, and the size of the powder particles is preferably 150 to 300 μm.
この−次反応で得られる反応生成物（二塩化ケイ素およ
び三塩化ケイ素）は不安定であるが、さらに塩化水素と
反応させることにより（以下「二次反応」ということあ
る）、下記反応式に示すとおり、トリクロロシラン（Ｓ
ＩＦＩＣｌ、３）の形で得られる。The reaction products (silicon dichloride and silicon trichloride) obtained in this secondary reaction are unstable, but by further reacting with hydrogen chloride (hereinafter sometimes referred to as "secondary reaction"), the following reaction formula can be obtained. As shown, trichlorosilane (S
It is obtained in the form of IFICl, 3).
Ｓ ｉ ＣｊＥｚ ＋ＨＣｆｆ→Ｓ ｉ ＨＣｅｚＳ
ｒ Ｃｌｖ ＋ＨＣｉ！→Ｓ ｉ ＨＣ，ｅ、 ＋１／
２Ｃｆｆｉｚこの反応〆温度は、通常、２５０〜１，０
００“Ｃ１好ましくは３００〜７００°Ｃであり、２５
０“Ｃ未満では反応性に乏しく、一方１．ＯＯＯ”Ｃを
超えると反応子ｉ新上好ましくない。なお、この二次反
応において、適当量の水素ガスを塩化水素ガス中ｔこ混
入させることにより５．副生ずる塩素ガスを塩化水素ガ
スに変換させることができ、この塩化水素ガスをさらに
反応に寄与させることかできる。S i CjEz +HCff→S i HCezS
rClv+HCi! →S i HC, e, +1/
2Cffiz This reaction termination temperature is usually 250 to 1,0
00"C1 preferably 300-700°C, 25
If it is less than 0"C, the reactivity is poor, while if it exceeds 1.00"C, it is unfavorable in terms of reactant i. In addition, in this secondary reaction, by mixing an appropriate amount of hydrogen gas into the hydrogen chloride gas, 5. Chlorine gas produced as a by-product can be converted into hydrogen chloride gas, and this hydrogen chloride gas can further contribute to the reaction.
以下、本発明をＶ面を用いてさらに具体的に説明する。Hereinafter, the present invention will be explained in more detail using a V-plane.
第１図は、本発明のトリクロロシランの製造装置を含む
フローシートである。FIG. 1 is a flow sheet including an apparatus for producing trichlorosilane according to the present invention.
まず、その構成を説明する。First, its configuration will be explained.
本発明のトリクロロシランの製造装置は、第１図に示す
ように供給手段１０、反応塔２０、分離手段３０および
蒸留・精製工程４０のほかに、後工程として多結晶シリ
コン製造工程５０を備えている。As shown in FIG. 1, the trichlorosilane production apparatus of the present invention includes a supply means 10, a reaction column 20, a separation means 30, a distillation/purification process 40, and a polycrystalline silicon production process 50 as a subsequent process. There is.
供給手段１０は、反応に供される金属シリコン、塩化水
素ガスおよび水素ガスを供給するための手段であり、金
属シリコンを貯蔵するシリコンホッパー１１、四塩化ケ
イ素供給手段１２および塩化水素供給手段１３、さらに
塩化水素供給手段１３の上流に直結する水素ガス供給設
備１４とからなる。The supply means 10 is a means for supplying metal silicon, hydrogen chloride gas, and hydrogen gas to be subjected to the reaction, and includes a silicon hopper 11 for storing metal silicon, a silicon tetrachloride supply means 12, a hydrogen chloride supply means 13, It further includes a hydrogen gas supply facility 14 directly connected upstream of the hydrogen chloride supply means 13.
反応塔２０は、金属シリコンを充填し、この金属シリコ
ンと四塩化ケイ素とを反応させる反応塔内筒２１とこの
反応によって生成する反応生成物を塩化水素ガスと反応
させる反応塔外筒２２および反応塔２０全体を外部から
加熱する加熱器２３とからなる。The reaction column 20 is filled with metallic silicon, and includes a reaction column inner column 21 for reacting the metallic silicon with silicon tetrachloride, a reaction column outer column 22 for reacting a reaction product produced by this reaction with hydrogen chloride gas, and a reaction column outer column 22 for reacting the reaction product produced by this reaction with hydrogen chloride gas. It consists of a heater 23 that heats the entire column 20 from the outside.
なお、前記シリコンホッパー１１および四塩化ケイ素供
給手段１２は、反応塔内筒２１の頂部に直結しており、
また塩化水素ガス供給手段１３は、反応塔外筒２２の頂
部に直結している。また、反応塔内筒２１の形式として
は、棚段式または空塔式などの移動層が好適である。Note that the silicon hopper 11 and the silicon tetrachloride supply means 12 are directly connected to the top of the reaction column inner cylinder 21,
Further, the hydrogen chloride gas supply means 13 is directly connected to the top of the reaction column outer cylinder 22. Further, as the type of the reaction column inner cylinder 21, a moving bed type such as a tray type or an empty column type is suitable.
分離手段３０は、反応によって得られる反応生成ガスと
このガス中に含まれる微細な金属シリコン粉末とを分離
するためのサイクロン３１、反応ガスを凝縮する冷却器
３２、塩化水素ガスとトリクロロシラン、四塩化ケイ素
などとを分離する分離器３３、分離器３３で分離された
トリクロロシランなどを蒸留・分離工程に送るための送
液ポンプ３４、さらに塩化水素供給設備３５とからなる
。The separation means 30 includes a cyclone 31 for separating the reaction product gas obtained by the reaction and the fine metal silicon powder contained in this gas, a cooler 32 for condensing the reaction gas, hydrogen chloride gas, trichlorosilane, and hydrogen chloride gas. It consists of a separator 33 for separating silicon chloride and the like, a liquid feed pump 34 for sending trichlorosilane and the like separated by the separator 33 to a distillation/separation process, and hydrogen chloride supply equipment 35.
蒸留・精製工程４０は、トリクロロシランと四塩化ケイ
素とを蒸留により分離する蒸留・精製装置４１、該装置
４１の底部より取り出される四塩化ケイ素を貯蔵する四
塩化ケイ素貯槽４２、四塩化ケイ素の送液ポンプ４３、
この四塩化ケイ素をガス化させる四塩化ケイ素蒸発器４
４、ガス化された四塩化ケイ素を反応に供するために所
定温度に予熱する四塩化ケイ素子熱器４５とからなる。The distillation/purification process 40 includes a distillation/purification device 41 that separates trichlorosilane and silicon tetrachloride by distillation, a silicon tetrachloride storage tank 42 that stores silicon tetrachloride taken out from the bottom of the device 41, and a silicon tetrachloride feeder. liquid pump 43,
Silicon tetrachloride evaporator 4 that gasifies this silicon tetrachloride
4. A silicon tetrachloride heater 45 for preheating gasified silicon tetrachloride to a predetermined temperature for use in a reaction.
多結晶シリコン製造工程５０は、蒸留・精製装置４１か
ら送られてきたトリクロロシランを不均化する多結晶シ
リコン製造装置５１、この装置にトリクロロシランを還
元してシリコンとするための水素ガスを供給する水素ガ
ス供給手段５２、前記装置５１で副生ずるトリクロロシ
ラン、四塩化ケイ素などを蒸留・精製装置４１にフィー
ドバックするためのリサイクル手段５３とからなる。The polycrystalline silicon manufacturing process 50 includes a polycrystalline silicon manufacturing device 51 that disproportionates trichlorosilane sent from a distillation/refining device 41, and hydrogen gas for reducing trichlorosilane to silicon to this device. and a recycling means 53 for feeding back trichlorosilane, silicon tetrachloride, etc. produced as by-products in the device 51 to the distillation/refining device 41.
次に、本発明のトリクロロシランの製造方法を使用した
製造装置の作用を説明する。Next, the operation of the manufacturing apparatus using the method for manufacturing trichlorosilane of the present invention will be explained.
シリコンホッパー１１に貯槽された金属シリコン粉末は
、連続的に反応塔内筒２１へ供給され、塔内を下降しな
がら、ここで四塩化ケイ素供給手段１２より供給された
四塩化ケイ素と反応し、二塩化ケイ素および三塩化ケイ
素が生成する。The metal silicon powder stored in the silicon hopper 11 is continuously supplied to the reaction column inner tube 21, and as it descends inside the column, it reacts with silicon tetrachloride supplied from the silicon tetrachloride supply means 12, Silicon dichloride and silicon trichloride are formed.
この反応塔２０は、反応塔外筒２２の外部にある加熱器
２３により電気ヒータなどで加熱されるか、あるいは高
周波加熱装置を用いて反応塔内筒２１のみを加熱しても
よいが、いずれにせよ反応塔内筒２１内の温度は１，１
００〜１，３００°Ｃに保持される。This reaction tower 20 may be heated by an electric heater or the like using a heater 23 located outside the reaction tower outer cylinder 22, or only the reaction tower inner cylinder 21 may be heated using a high frequency heating device. In any case, the temperature inside the reaction column inner cylinder 21 is 1.1
The temperature is maintained between 00 and 1,300°C.
得られる反応生成物（二塩化ケイ素、三塩化ケイ素）は
、低級塩化物であり不安定であるので、反応塔内筒２１
の下部から高速で噴射されると、反応塔外筒２２の頂部
から塩化水素供給手段１３を経て送られてきた水素ガス
を含む塩化水素ガスと槻めて短時間に反応し、トリクロ
ロシランのほか、副生ずる塩素ガスが水素ガスと反応し
、塩化水素ガスが生成する。反応後のガスは、微細なシ
リコンの粉末を含むので、サイクロン３１により未反応
シリコン粉末を除去する。The reaction products (silicon dichloride, silicon trichloride) obtained are lower chlorides and are unstable, so
When injected at high speed from the lower part of the reaction column, it reacts in a short time with hydrogen chloride gas containing hydrogen gas sent from the top of the reaction tower outer cylinder 22 via the hydrogen chloride supply means 13, and produces trichlorosilane and other substances. , the by-product chlorine gas reacts with hydrogen gas to generate hydrogen chloride gas. Since the gas after the reaction contains fine silicon powder, the cyclone 31 removes the unreacted silicon powder.
次に、冷却器３２により反応生成物であるトリクロロシ
ラン、および副反応により生成した微量のジクロロシラ
ン、未反応の四塩化ケイ素を凝縮し、分離器３３で水素
ガス、塩化水素ガスと気液分離する。ここで、気液分離
された水素ガスおよび塩化水素ガスは、塩化水素供給設
備３５および水素ガス供給設備１４により供給された塩
化水素ガスおよび水素ガスとともに反応塔２０ヘリサイ
クルされる。Next, the reaction product trichlorosilane, a trace amount of dichlorosilane produced by a side reaction, and unreacted silicon tetrachloride are condensed in the cooler 32, and separated into gas and liquid into hydrogen gas and hydrogen chloride gas in the separator 33. do. Here, the gas-liquid separated hydrogen gas and hydrogen chloride gas are recycled to the reaction tower 20 together with the hydrogen chloride gas and hydrogen gas supplied by the hydrogen chloride supply equipment 35 and the hydrogen gas supply equipment 14.
一方、分離器３３で分離された凝縮液は、送液ポンプ３
４により蒸留・精製装置４１へ送られ、トリクロロシラ
ン、四塩化ケイ素、ジクロロシランなどに分離・精製さ
れ、トリクロロシランは多結晶シリコン製造装置５１へ
原料ガスとして水素ガスと混合後送られる。On the other hand, the condensate separated by the separator 33 is transferred to the liquid sending pump 3
4 is sent to a distillation/purification device 41 where it is separated and purified into trichlorosilane, silicon tetrachloride, dichlorosilane, etc. Trichlorosilane is sent to a polycrystalline silicon production device 51 after being mixed with hydrogen gas as a raw material gas.
また、四塩化ケイ素は、四塩化ケイ素貯槽４２で一旦貯
蔵されたのち、送液ポンプ４３を経て、四塩化ケイ素蒸
発器４４でガス化されたのち、四塩化ケイ素子熱器４５
で所定温度に加熱され、再び反応塔内￥１２１へ送られ
る。Furthermore, silicon tetrachloride is once stored in a silicon tetrachloride storage tank 42, passed through a liquid feed pump 43, and then gasified in a silicon tetrachloride evaporator 44.
It is heated to a predetermined temperature and sent to the reaction tower again for ¥121.
多結晶シリコン製造装置５１で生成した排出ガス中のシ
リコン化合物（トリクロロシラン、四塩化ケイ素など）
は、リサイクル手段５３を経て薄留・精製装置４１ヘリ
サイクルされ、成分分離される。Silicon compounds (trichlorosilane, silicon tetrachloride, etc.) in the exhaust gas generated by the polycrystalline silicon manufacturing equipment 51
is recycled to the thin distillation/purification device 41 via the recycling means 53 and separated into components.
本発明では、まず四塩化ケイ素と金属シリコンとをｌ、
１００〜１，３００°Ｃの高温で反応させることにより
、二塩化ケイ素、三塩化ケイ素などの低級塩素化合物へ
高率で転換させる。In the present invention, first, silicon tetrachloride and metallic silicon are
By reacting at a high temperature of 100 to 1,300°C, it is converted to lower chlorine compounds such as silicon dichloride and silicon trichloride at a high rate.
次いで、この低級塩素化合物を塩化水素と反応させるこ
とにより高率でトリクロロシランへ転換させることがで
きる。Next, this lower chlorine compound can be converted into trichlorosilane at a high rate by reacting with hydrogen chloride.
［実施例］
以下、実施例を挙げて本発明をさらに具体的に説明する
。[Example] Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例１
第１図に準じた製造装置を用い、四塩化ケイ素と金属シ
リコンとより低級塩素化合物を生成し、次いでこの低級
塩素化合物を塩化水素と反応させてトリクロロシランを
製造した。Example 1 Using a manufacturing apparatus similar to that shown in FIG. 1, a lower chlorine compound was produced from silicon tetrachloride and metal silicon, and then this lower chlorine compound was reacted with hydrogen chloride to produce trichlorosilane.
すなわち、内径２５ ＋ｎｍの反応塔内筒２１・に純度
９８．２％の金属シリコン（平均粒径−２００μｍ）を
連続的に充填し、反応塔外筒２２の外部を電気ヒータか
らなる加熱器２３により１．２８０°Ｃに加熱した。That is, a reaction column inner tube 21 with an inner diameter of 25 + nm is continuously filled with metal silicon of 98.2% purity (average particle size -200 μm), and the outside of the reaction column outer tube 22 is filled with a heater 23 consisting of an electric heater. The mixture was heated to 1.280°C.
反応塔内筒２１が所定の温度になったところで反応塔内
筒２１の頂部から四塩化ケイ素蒸発器４４で蒸発され、
四塩化ケイ素子熱器４５で３００°Ｃに予熱された四塩
化ケイ素ガスを一定量（１〜５Ｉ！／分）供給し、高温
の金属シリコン充填層を通過させ反応させた。When the reaction column inner cylinder 21 reaches a predetermined temperature, silicon tetrachloride is evaporated from the top of the reaction column inner cylinder 21 in the silicon tetrachloride evaporator 44,
A constant amount (1 to 5 I!/min) of silicon tetrachloride gas preheated to 300° C. by a silicon tetrachloride heater 45 was supplied, and the gas was passed through a high-temperature metal silicon packed bed to cause a reaction.
反応塔内筒２１の底部から噴出した反応生成ガスに常温
の水素ガスを含む塩化水素ガスを、四塩化ケイ素ガス量
のほぼ３倍量（３〜１５Ａ／分）供給した。Hydrogen chloride gas containing hydrogen gas at room temperature was supplied to the reaction product gas ejected from the bottom of the reaction column inner cylinder 21 in an amount approximately three times the amount of silicon tetrachloride gas (3 to 15 A/min).
このガスをサイクロン３１を経て冷却器３２で冷却し、
分離器３３で凝縮液を回収するとともに重量を測定し、
分析試料とした。This gas passes through a cyclone 31 and is cooled by a cooler 32,
Collecting the condensate in the separator 33 and measuring its weight,
This was used as an analysis sample.
この実験結果の一例を次に示す。An example of the experimental results is shown below.
実験時間；６０分
四塩化ケイ素供給流量；１．３ｆｆｉ／分塩化水素ガス
供給流量；４．ＯＲ１分
水素ガス供給流量；０．５ｆｆｉ／分
金属シリコン充１ａＮ温度；１．２８０°ｂ凝縮液重量
；７３０ｇ
凝縮液の分析結果；
トリクロロシラン−６１，４重量％
ジクロロシラン−４，８重量％
四塩化ケイ素＝３３．８重量％
〔発明の効果〕
本発明によれば１．四塩化ケイ素を有効にトリクロロシ
ランへ変換するとともに、変換効率も５０〜６０％ト高
く、コンパクトな設備となすことが可能なトリクロロシ
ランの製造方法を提供することができる。Experiment time; 60 minutes Silicon tetrachloride supply flow rate; 1.3ffi/min Hydrogen chloride gas supply flow rate; 4. OR 1 minute hydrogen gas supply flow rate: 0.5ffi/min Metal silicon filling 1aN temperature: 1.280°b Condensate weight: 730g Condensate analysis results: Trichlorosilane - 61.4% by weight Dichlorosilane - 4.8% by weight Silicon tetrachloride = 33.8% by weight [Effects of the invention] According to the present invention: 1. It is possible to provide a method for producing trichlorosilane that effectively converts silicon tetrachloride into trichlorosilane, has a conversion efficiency of 50 to 60%, and can be constructed using compact equipment.
第１図は、本発明のトリクロロシランの製造装置を含む
フローシートである。
１０；供給手段
２０；反応塔
３０；分離手段
４０ｉ蒸留・精製工程
５０；多結晶シリコン製造工程
特許出願人 三菱化工機株式会社
代理人 弁理士 白 井 重 隆FIG. 1 is a flow sheet including an apparatus for producing trichlorosilane according to the present invention. 10; Supply means 20; Reaction column 30; Separation means 40i Distillation/purification process 50; Polycrystalline silicon manufacturing process Patent applicant Mitsubishi Kakoki Co., Ltd. Agent Patent attorney Shige Takashi Shirai
Claims (1)
，３００℃の温度で反応させ、次いで得られた反応生成
物を塩化水素と反応させることを特徴とするトリクロロ
シランの製造方法。(1) Silicon tetrachloride and metal silicon at 1,100 to 1
, 300°C, and then reacting the obtained reaction product with hydrogen chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32829888A JPH02172811A (en) | 1988-12-26 | 1988-12-26 | Production of trichlorosilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32829888A JPH02172811A (en) | 1988-12-26 | 1988-12-26 | Production of trichlorosilane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02172811A true JPH02172811A (en) | 1990-07-04 |
Family
ID=18208664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32829888A Pending JPH02172811A (en) | 1988-12-26 | 1988-12-26 | Production of trichlorosilane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02172811A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5422088A (en) * | 1994-01-28 | 1995-06-06 | Hemlock Semiconductor Corporation | Process for hydrogenation of tetrachlorosilane |
| DE102010044755A1 (en) | 2010-09-08 | 2012-03-08 | Spawnt Private S.À.R.L. | Process for producing high purity silicon |
| CN102381712A (en) * | 2011-10-20 | 2012-03-21 | 中国恩菲工程技术有限公司 | Equipment for treating solution containing silicon tetrachloride |
| WO2012062526A1 (en) * | 2010-11-09 | 2012-05-18 | Evonik Degussa Gmbh | Process for preparing trichlorosilane |
| KR101309600B1 (en) * | 2010-08-04 | 2013-09-23 | 주식회사 엘지화학 | Method for producing trichlorosilane |
| CN103820852A (en) * | 2014-03-05 | 2014-05-28 | 重庆高策科技发展有限公司 | System and method for preparation of polycrystalline silicon by utilizing hydrochloric acid and silicon tetrachloride |
| JP2015221936A (en) * | 2014-05-01 | 2015-12-10 | 株式会社フィルテック | Solid vaporizer |
-
1988
- 1988-12-26 JP JP32829888A patent/JPH02172811A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5422088A (en) * | 1994-01-28 | 1995-06-06 | Hemlock Semiconductor Corporation | Process for hydrogenation of tetrachlorosilane |
| KR101309600B1 (en) * | 2010-08-04 | 2013-09-23 | 주식회사 엘지화학 | Method for producing trichlorosilane |
| DE102010044755A1 (en) | 2010-09-08 | 2012-03-08 | Spawnt Private S.À.R.L. | Process for producing high purity silicon |
| WO2012032129A1 (en) | 2010-09-08 | 2012-03-15 | Spawnt Private S.À.R.L. | Method for the production of high-purity silicon |
| WO2012062526A1 (en) * | 2010-11-09 | 2012-05-18 | Evonik Degussa Gmbh | Process for preparing trichlorosilane |
| JP2013542167A (en) * | 2010-11-09 | 2013-11-21 | エボニック デグサ ゲーエムベーハー | Production method of trichlorosilane |
| CN102381712A (en) * | 2011-10-20 | 2012-03-21 | 中国恩菲工程技术有限公司 | Equipment for treating solution containing silicon tetrachloride |
| CN103820852A (en) * | 2014-03-05 | 2014-05-28 | 重庆高策科技发展有限公司 | System and method for preparation of polycrystalline silicon by utilizing hydrochloric acid and silicon tetrachloride |
| JP2015221936A (en) * | 2014-05-01 | 2015-12-10 | 株式会社フィルテック | Solid vaporizer |
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