JPS6395108A - Production of trichlorosilane - Google Patents
Production of trichlorosilaneInfo
- Publication number
- JPS6395108A JPS6395108A JP24020086A JP24020086A JPS6395108A JP S6395108 A JPS6395108 A JP S6395108A JP 24020086 A JP24020086 A JP 24020086A JP 24020086 A JP24020086 A JP 24020086A JP S6395108 A JPS6395108 A JP S6395108A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- trichlorosilane
- silicon tetrachloride
- hydrogen
- silicon
- 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.)
- Granted
Links
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- 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 74
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- -1 aluminum halide Chemical class 0.000 claims abstract description 20
- 239000007790 solid phase Substances 0.000 claims abstract description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 26
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 claims description 4
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 claims description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical group FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims 1
- 238000003746 solid phase reaction Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 150000001649 bromium compounds Chemical class 0.000 abstract 1
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 150000004694 iodide salts Chemical class 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 29
- 239000007789 gas Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000007323 disproportionation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
皮ｌ上皇剋朋光互
本発明は四塩化ケイ素と水素からトリクロロシランを製
造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing trichlorosilane from silicon tetrachloride and hydrogen.
皿米皇狡亙
近年のエレクトロニクス産業の発展に伴ない多結晶シリ
コン、単結晶シリコン、モノシランガス等の需要は急激
に増大しており今後ますますその需要は増加の一途をた
どることが見込まれている、ここにおいてトリクロロシ
ランは上記シリコン物質の原料として最も大量に利用さ
れているものである０例えば高純度多結晶シリコンはト
リクロロシランの熱分解によって製造されており、現在
全世界での高純度多結晶シリコンの殆どがこの方法で製
造されている。また最近トリクロロシランの不均化反応
によってモノシランが製造される方法が実用化されつつ
あり極めてトリクロロシランの需要は今後その重要性が
増大する。しかしながら、これらの方法においては、ト
リクロロシランが消費されるとともに大量の四塩化ケイ
素が副生ずる。たとえばトリクロロシランの熱分解によ
る高純度多結晶シリコンの製造においては、トリクロロ
シランの約６０％が四塩化ケイ素として副生じ、また、
トリクロロシランの不均化によるモノシランの製造にお
いては実質的にモノシランの３倍モルの四塩化ケイ素が
副生ずる事になる。従ってこの副生した四塩化ケイ素は
例えばアエロジル等の原料として利用することでトリク
ロロシランの生産コストを低減する方法等が知られてい
るが。With the development of the electronics industry in recent years, demand for polycrystalline silicon, single crystal silicon, monosilane gas, etc. has increased rapidly, and demand is expected to continue to increase in the future. Here, trichlorosilane is used in the largest quantity as a raw material for the silicon material mentioned above. For example, high-purity polycrystalline silicon is produced by thermal decomposition of trichlorosilane, and currently high-purity polycrystalline silicon is produced throughout the world. Most silicon is manufactured using this method. Furthermore, recently, a method for producing monosilane by disproportionation reaction of trichlorosilane has been put into practical use, and the demand for trichlorosilane will become extremely important in the future. However, in these methods, trichlorosilane is consumed and a large amount of silicon tetrachloride is produced as a by-product. For example, in the production of high-purity polycrystalline silicon by thermal decomposition of trichlorosilane, approximately 60% of trichlorosilane is produced as silicon tetrachloride, and
In the production of monosilane by disproportionation of trichlorosilane, substantially three times the mole of silicon tetrachloride as monosilane is produced as a by-product. Therefore, it is known that this by-produced silicon tetrachloride is used as a raw material for, for example, Aerosil, thereby reducing the production cost of trichlorosilane.
実質上置も優れた四塩化ケイ素の利用方法はこれを再び
トリクロロシランに変換し、上記方法の原料として再利
用することである０例えば四塩化ケイ素をトリクロロシ
ランに変換することによって、トリクロロシランの不均
化によるモノシランの製造は実質的には金属ケイ素と水
素によってモノシランを製造するプロセスに帰着し、こ
のプロセスは最近実用化されつつある。A virtually superior way to utilize silicon tetrachloride is to convert it back into trichlorosilane and reuse it as a raw material in the above method. For example, by converting silicon tetrachloride into trichlorosilane, trichlorosilane can be The production of monosilane by disproportionation essentially results in a process of producing monosilane with metallic silicon and hydrogen, and this process has recently been put into practical use.
従って四塩化ケイ素をトリクロロシランに変換する技術
はきわめて有用であり、特にこれを安価、簡便かつ効率
よく行うことはプロセスの経済上極めて重要である。Therefore, the technology for converting silicon tetrachloride into trichlorosilane is extremely useful, and in particular, it is extremely important from the economic point of view of the process to be able to do this at low cost, simply, and efficiently.
従来、四塩化ケイ素をトリクロロシランに変換する方法
としては次の方法が知られている。Conventionally, the following method is known as a method for converting silicon tetrachloride into trichlorosilane.
（１）四塩化ケイ素と水素を１０００℃前後またそれ以
上の温度で反応させトリクロロシランを製造する方法。(1) A method of producing trichlorosilane by reacting silicon tetrachloride and hydrogen at a temperature of around 1000°C or higher.
（２）四塩化ケイ素、水素および金属ケイ素を５００″
Ｃ付近で反応させトリクロロシランを製造する方法（３
）四塩化ケイ素、水素、金属ケイ素及び塩化水素を５０
０℃付近で反応させトリクロワシランを製造する方法。(2) Silicon tetrachloride, hydrogen and metallic silicon at 500"
Method for producing trichlorosilane by reacting near C (3)
) Silicon tetrachloride, hydrogen, metallic silicon and hydrogen chloride 50
A method for producing tricloasilan by reacting at around 0°C.
（１）の方法に関してはたとえば特開昭５７−３７１１
号においては１１００−１６００℃で水素および四塩化
ケイ素を上記温度の発熱体に吹き付ける方法でトリクロ
ロシランが６０％の収率で得られている。また特開昭５
７−１５６３１８号では第一段目で９００ ’Ｃの温度
において水素と四塩化ケイ素をモル比Ｈｚ／５ｉＣ１４
・２で反応させ２５％の収率でトリクロロシランを得て
いる。また特開昭５９−４５９２０号においてはプラズ
マ中で四塩化ケイ素と水素を反応させてトリクロロシラ
ンを得ている。また特開昭６０−８１０１０号において
は１２００−１４００℃の温度範囲で四塩化ケイ素と水
素を反応させて約３０％の収率でトリクロロシランを得
ている。Regarding the method (1), for example, Japanese Patent Application Laid-Open No. 57-3711
In No. 1, trichlorosilane was obtained in a yield of 60% by spraying hydrogen and silicon tetrachloride onto a heating element at 1100-1600°C. Also, JP-A-5
No. 7-156318, in the first stage, hydrogen and silicon tetrachloride were mixed at a molar ratio of Hz/5iC14 at a temperature of 900'C.
・Trichlorosilane was obtained in 25% yield by the reaction in step 2. Furthermore, in JP-A-59-45920, trichlorosilane is obtained by reacting silicon tetrachloride with hydrogen in plasma. Furthermore, in JP-A-60-81010, trichlorosilane is obtained in a yield of about 30% by reacting silicon tetrachloride with hydrogen in a temperature range of 1200-1400°C.
（２）の方法は（１）の方法に比較して比較的低温で反
応が進行し、エネルギー的に有利な方法であると云える
。また（２）の方法でさらに有効に反応を進行させるた
めに塩化水素ガスを使用する（３）の方法も当然のこと
ながら同様な特長を有している。（２）及び（３）の方
法に関しては触媒を用いることが有効であり銅化合物ま
たは金属銅を触媒としている０例えば特開昭５６−７３
６１７号においては銅粉を触媒として３５０−６００°
Ｃで流動床反応を行いトリクロロシランを得ている。又
特開昭５８−１１０４２号においては銅担持又は銅及び
ニッケルを担持した触媒を用いて反応を行いトリクロロ
シランを得ている。Method (2) can be said to be an energetically advantageous method since the reaction proceeds at a relatively low temperature compared to method (1). Naturally, method (3) in which hydrogen chloride gas is used to advance the reaction more effectively than method (2) also has similar features. Regarding methods (2) and (3), it is effective to use a catalyst, and a method using a copper compound or metallic copper as a catalyst is effective, for example, in JP-A-56-73.
In No. 617, 350-600° using copper powder as a catalyst.
A fluidized bed reaction was carried out at C to obtain trichlorosilane. Furthermore, in JP-A-58-11042, trichlorosilane is obtained by conducting a reaction using a catalyst supported with copper or with copper and nickel supported.
これらの方法において１例えば（１）の方法では。One of these methods is, for example, method (1).
かなり高い四塩化ケイ素の転化率でトリクロロシランが
得られているが、とりわけ３０％以上の収率でトリクロ
ロシランを得るためには１０００°Ｃ以上の高温で反応
を行わねばならずこれに費やすエネルギーは莫大なもの
である。加えて、高温反応であるため、塩素化ケイ素に
よる反応器等の腐食が激しくさらに、望ましくない高分
子量のクロロシラン類が不可避的に副生ずる等の欠点を
有しており未だ実用化には程遠いものである。Trichlorosilane has been obtained with a fairly high conversion rate of silicon tetrachloride, but in order to obtain trichlorosilane with a yield of 30% or more, the reaction must be carried out at a high temperature of 1000°C or more, which requires energy consumption. is huge. In addition, since it is a high-temperature reaction, the reactor is severely corroded by silicon chloride, and undesirable high-molecular-weight chlorosilanes are inevitably produced as by-products. It is.
これに対し、（２）及び（３）の方法は熱力学的見地か
らも、トリクロロシランの製造に有用な方法であり、前
記した様にトリクロロシランの不均化によるモノシラン
を製造する方法で副生する四塩化ケイ素を変換しトリク
ロロシランを製造することは特に（２）の方法では実質
的にはケイ素と水素からモノシランを製造することとな
るため、非常に有用な方法であると云える。なお、（３
）の方法に於いては、トリクロロシランの収量は多いが
、塩化水素は四塩化ケイ素のトリクロロシランへの変換
には関与せず、実質的には金属シリコンからトリクロロ
シランを合成することに過ぎない、従って、四塩化ケイ
素の再利用という観点からすれば（２）の方法よりは幾
分有用性は劣るが、一方、トリクロロシランの収量が多
いと云う利点も有しており、塩化水素の使用量を少量に
して行うことにより、その特徴を発揮させることが望ま
しい。On the other hand, methods (2) and (3) are useful methods for producing trichlorosilane from a thermodynamic point of view, and as mentioned above, they are secondary to the method for producing monosilane by disproportionation of trichlorosilane. It can be said that converting the silicon tetrachloride produced to produce trichlorosilane is a very useful method, especially since method (2) essentially produces monosilane from silicon and hydrogen. In addition, (3
), the yield of trichlorosilane is high, but hydrogen chloride does not participate in the conversion of silicon tetrachloride to trichlorosilane, and the method essentially only synthesizes trichlorosilane from metallic silicon. Therefore, from the point of view of reusing silicon tetrachloride, it is somewhat less useful than method (2), but on the other hand, it has the advantage of increasing the yield of trichlorosilane, and the use of hydrogen chloride is It is desirable to bring out its characteristics by using a small amount.
さらに、これら（２）及び（３）の方法を組合せたプロ
セスも知られている（特開昭６０−３６３１８号）。Furthermore, a process that combines methods (2) and (3) is also known (Japanese Patent Application Laid-open No. 36318/1983).
以上の方法において、四塩化ケイ素の有効再利用という
観点からすれば（２）の方法が最も優れており、またト
リクロロシランの生成という観点からすれば（３）の方
法も優れた方法であり捨てがたい。Among the above methods, method (2) is the best from the viewpoint of effective reuse of silicon tetrachloride, and method (3) is also excellent from the viewpoint of producing trichlorosilane. It's tough.
すなわち、（２）または（３）の方法は経済性も高（特
に（２）の方法は現在本命の方法として実用化されつつ
ある。That is, method (2) or (3) is highly economical (method (2) in particular is currently being put into practical use as the preferred method).
しかしながら、（２）の方法においては９反応温度が通
常５００−６００℃で行われており、３００℃以下の反
応温度においては実質上トリクロロシランが生成した例
はない、従って当然のことながら２本発明におけるが如
（、四塩化ケイ素の臨界温度以下で四塩化ケイ素を液体
状として気休−液体−固体相の不均一反応によるトリク
ロロシランを製造した例は従来全く知られていない。However, in method (2), the reaction temperature is usually 500-600°C, and there is no example of trichlorosilane being substantially produced at a reaction temperature of 300°C or lower. As in the present invention, there has been no known example of producing trichlorosilane by a heterogeneous reaction of gas phase-liquid-solid phase using silicon tetrachloride as a liquid at a temperature below the critical temperature of silicon tetrachloride.
またこの（２）の方法においては、従来大量かつ連続的
にトリクロロシランを製造する場合には、気体一固体相
流動床装置が用いられている。しかしながら、その場合
、流動床を用いるため９反応により粒度の小さくなった
ケイ素金属や触媒成分の揮散等による有効成分の損失、
高温反応による触媒成分の揮散、装置の腐食、更には高
分子量のクロロシラン類の生成によるトリクロロシラン
の選択率の低下、高温であるためエネルギーの大量使用
等といった。工業化するためにはさらに解決さるべき多
（の欠点を有している。Furthermore, in the method (2), a gas-solid phase fluidized bed apparatus has conventionally been used when trichlorosilane is produced continuously in large quantities. However, in this case, since a fluidized bed is used, there is a loss of active ingredients due to volatilization of silicon metal and catalyst components whose particle size has become smaller due to the 9 reactions.
These include volatilization of catalyst components due to high-temperature reactions, corrosion of equipment, reduction in trichlorosilane selectivity due to the production of high-molecular-weight chlorosilanes, and use of a large amount of energy due to high temperatures. It has many drawbacks that need to be resolved in order to be industrialized.
本発明者らはこれらを鑑み鋭意検討した結果驚くべきこ
とに四塩化ケイ素の臨界温度以下に於いて四塩化ケイ素
を液体状態で反応させしかも高収率でかつ四塩化ケイ素
の単位体積当たりの処理量を増大させてトリクロロシラ
ンを製造する極めて経済的利点の高い方法を見出し本発
明を完成するにいたった。The inventors of the present invention have conducted extensive studies in view of the above, and have surprisingly found that silicon tetrachloride can be reacted in a liquid state below the critical temperature of silicon tetrachloride, with a high yield and a treatment rate per unit volume of silicon tetrachloride. The inventors discovered a highly economically advantageous method for producing trichlorosilane by increasing the amount thereof, and completed the present invention.
３浬廊ロシ亘
すなわち１本発明の目的は、上記トリクロロシランの熱
分解による多結晶シリコンの製造またはトリクロロシラ
ンの不均化反応によるモノシランの製造に於いて、副生
ずる四塩化ケイ素をトリクロロシランへ変換し、四塩化
ケイ素を有効に利用する極めて経済性の高い方法を提供
することにある。3. An object of the present invention is to convert by-produced silicon tetrachloride into trichlorosilane in the production of polycrystalline silicon by thermal decomposition of trichlorosilane or in the production of monosilane by disproportionation reaction of trichlorosilane. The object of the present invention is to provide an extremely economical method for converting and effectively utilizing silicon tetrachloride.
本発明に従えば、四塩化ケイ素と金属ケイ素を、水素若
しくは水素及び塩化水素と反応せしめてトリクロロシラ
ンを製造する方法において、該四塩化ケイ素をその臨界
温度以下の液体状態として、該反応系を気−液−固相の
不均一反応とすると共に、該気−液−固相の不均一反応
を、金属銅及びハロゲン化アルミニウムの存在下に行う
ことを特徴とするトリクロロシランの製造方法が提供さ
れる。According to the present invention, in the method for producing trichlorosilane by reacting silicon tetrachloride and metallic silicon with hydrogen or hydrogen and hydrogen chloride, the silicon tetrachloride is brought into a liquid state at a temperature below its critical temperature, and the reaction system is Provided is a method for producing trichlorosilane, characterized in that the heterogeneous reaction of gas-liquid-solid phase is carried out, and the heterogeneous reaction of gas-liquid-solid phase is carried out in the presence of metallic copper and aluminum halide. be done.
溌」Ｉ目！丞 以下本発明の詳細な説明する。溌”I eye! Jo The present invention will be explained in detail below.
本発明で行う四塩化ケイ素のトリクロロシランへの変換
は基本的に次式
％式％（）
で表わされる。この反応は平衡反応であり、温度が高い
ほど、圧力が高いほど、さらにｎｔ／５ｉｃ１ａモル比
が高いほど反応が右方向へ進行する。また、後述するよ
うに、四塩化ケイ素の臨界温度である２３３．６°Ｃ（
現実的には２３０°Ｃ以下）以下の温度で四塩化ケイ素
を液体状態としての低温気相−液相一固体相反窓でトリ
クロロシランを製造した例は今まで知られていなかった
が１本発明においては上記反応を金属銅及びハロゲン化
アルミニウムと云う特定の添加物の存在下に行うことで
、四塩化ケイ素を液体状態としてまたは反応状態におい
て不活性な溶媒に溶解させて液体状態で反応させ゛てト
リクロロシランを収率よ（製造することを可能ならしめ
たものである。また当然のことであるが塩化水素ガスを
本発明反応系内に加えることによって明らかにトリクロ
ロシランの収量を増大させる結果をもたらす手段を採用
しても良い。The conversion of silicon tetrachloride into trichlorosilane carried out in the present invention is basically expressed by the following formula % (%). This reaction is an equilibrium reaction, and the higher the temperature, the higher the pressure, and the higher the nt/5ic1a molar ratio, the more the reaction proceeds in the right direction. In addition, as described later, the critical temperature of silicon tetrachloride is 233.6°C (
Until now, there has been no known example of producing trichlorosilane using a low-temperature gas phase-liquid phase-solid phase window in which silicon tetrachloride is in a liquid state at a temperature below 230°C (actually 230°C or below), but the present invention. By carrying out the above reaction in the presence of specific additives such as metallic copper and aluminum halide, silicon tetrachloride can be reacted in a liquid state or in a liquid state by being dissolved in an inert solvent in the reaction state. This makes it possible to produce trichlorosilane in a higher yield.It goes without saying that adding hydrogen chloride gas to the reaction system of the present invention clearly increases the yield of trichlorosilane. You may adopt means that bring about this.
本発明に使用する金属ケイ素の純度等はとくに限定する
ものではなく、冶金ケイ素の低純度品でも高純度ケイ素
でもいずれであっても構わない。The purity of the metal silicon used in the present invention is not particularly limited, and it may be either low purity metallurgical silicon or high purity silicon.
経済的な観点からすれば前者を使用することが好ましい
、これら金属ケイ素の形態は問わないが好ましくは反応
速度の観点から表面積の大きい粉末状で使用することが
推奨される。勿論１粒状等他の形態で使用することも可
能である。From an economic point of view, it is preferable to use the former.Although the form of these metal silicons does not matter, from the viewpoint of reaction rate, it is recommended that they be used in the form of a powder with a large surface area. Of course, it is also possible to use it in other forms such as a single grain.
本発明においては、上記反応を金属銅及びハロゲン化ア
ルミニウムの存在下に行うが１本発明で使用する金属銅
は特に限定するものではな（１通常市販の電解銅が用い
られるがその他還元銅も使用可能である。純度に関して
はそれほど問題にする必要はない。金属銅の形態は問わ
ないが好ましくは反応速度の観点から表面積の大きい粉
末状で使用することが推奨される。勿論９粒状等他の形
態で使用することも可能である。In the present invention, the above reaction is carried out in the presence of metallic copper and aluminum halide, but the metallic copper used in the present invention is not particularly limited (1) Commercially available electrolytic copper is usually used, but other reduced copper may also be used. It can be used.There is no need to worry too much about purity.The form of metallic copper does not matter, but from the viewpoint of reaction rate, it is recommended to use it in the form of a powder with a large surface area.Of course, it is recommended to use it in the form of a powder with a large surface area.Of course, there are other forms such as 9 grains. It is also possible to use it in the form of
本発明で使用するハロゲン化アルミニウムとは塩化アル
ミニウム、臭化アルミニウム及びヨウ化アルミニウムで
あり、これらの１種または２種以上の混合物で使用する
。The aluminum halides used in the present invention include aluminum chloride, aluminum bromide, and aluminum iodide, and these are used alone or as a mixture of two or more thereof.
次に本発明に於ける四塩化ケイ素のトリクロロシランへ
の変換方法について述べる。Next, a method for converting silicon tetrachloride into trichlorosilane in the present invention will be described.
変換反応は基本的には上記（１）式に従って行われるが
１本発明においては１反応は、気体相−液体相−個体相
の所謂気−液−固相の不均一系で行う０通常四塩化ケイ
素を液体状とし、かつ加熱反応を行うため加圧する。当
然のことであるが反応圧力は設定した反応温度に於ける
四塩化ケイ素の蒸気圧以上の圧力とする。また反応に使
用する水素はあらかじめ反応に不活性な媒体（気体）た
とえばアルゴン、ヘリウム及び／又は窒素等で稀釈して
用いても構わないが１反応平衡９反応速度及び経済的な
観点から水素単独で使用することが好ましい、又通常予
期される程度の不純物を含んでいても差し支えなくい、
また反応条件に於いて原料、生成物、および金属銅、ハ
ロゲン化アルミニウム等の添加物等にたいして不活性な
溶媒２例えばｎ−へキサン、ｎ−へブタンに代表される
脂肪族炭化水素、シクロヘキサン、シクロオクタンに代
表される脂環式炭化水素及びベンゼン、トルエンに代表
される芳香族炭化水素等を使用することも可能である。The conversion reaction is basically carried out according to the above formula (1), but in the present invention, one reaction is carried out in a heterogeneous system of gas phase - liquid phase - solid phase, which is the so-called gas-liquid-solid phase. Silicon chloride is made into a liquid state and pressurized to carry out a heating reaction. As a matter of course, the reaction pressure is set to be higher than the vapor pressure of silicon tetrachloride at the set reaction temperature. Hydrogen used in the reaction may be diluted in advance with a medium (gas) inert to the reaction, such as argon, helium, and/or nitrogen, but from the viewpoint of reaction rate and economy, hydrogen is used alone. It is preferable to use it in
In addition, under the reaction conditions, solvents 2 that are inert to raw materials, products, and additives such as metallic copper and aluminum halides, etc., such as aliphatic hydrocarbons such as n-hexane and n-hebutane, cyclohexane, It is also possible to use alicyclic hydrocarbons such as cyclooctane and aromatic hydrocarbons such as benzene and toluene.
次に本発明における最も特筆すべき点である四塩化ケイ
素を液体状態として反応させる意義について述べる。Next, the significance of reacting silicon tetrachloride in a liquid state, which is the most noteworthy point in the present invention, will be described.
四塩化ケイ素を液体状態に保持したまま反応させること
は、液体状の四塩化ケイ素と固体金属ケイ素と、および
該液体状四塩化ケイ素中に溶解等によってまたは気液接
触によって取り込まれた水素と、が反応することを意味
するものであり、従って反応場は殆ど実質的に液体−固
体相である。Reacting silicon tetrachloride while keeping it in a liquid state means that liquid silicon tetrachloride and solid metal silicon, and hydrogen incorporated into the liquid silicon tetrachloride by dissolution or the like or by gas-liquid contact, reacts, and therefore the reaction field is almost essentially a liquid-solid phase.
そこで生成したトリクロロシランはまず液体相で生成し
液体に溶存するが更に気体相に移行する。The trichlorosilane produced there is first produced in the liquid phase and dissolved in the liquid, but then moves to the gas phase.
この際当然のことであるが四塩化ケイ素も同様に気体相
へ移行する。トリクロロシラン逅四塩化ケイ素の同一温
度に於ける蒸気圧はトリクロロシランの方がより高いた
め液体相に於ける ５ｉＨＣ１ｚ／ＳｉＣ１ｍ濃度比よ
りも気体相に於ける５ｉＨＣｈ／５ｉＣ１ａ濃度比の方
が高くなる。かくして該反応を連続的に行わしめれば常
に液相に於ける５ｉＨＣ１ｉ／ＳｉＣ１ｍ濃度比は減少
の方向に向かうがら１反応平衡の観点から該反応の反応
速度を高める事となり、トリクロロシランの製造に関し
てより有利な方向へ反応が進む事となる。従って１通常
の流動床反応の如く、生成ガス組成がそのままの組成で
排出されるのと比較して１反応平衡上常に生成物の組成
が生成物に有利になるように作用させる効果が期待出来
るのである。At this time, as a matter of course, silicon tetrachloride also transfers to the gas phase. Since the vapor pressure of trichlorosilane/silicon tetrachloride at the same temperature is higher, the 5iHCh/5iC1a concentration ratio in the gas phase is higher than the 5iHC1z/SiC1m concentration ratio in the liquid phase. . Thus, if the reaction is carried out continuously, the 5iHC1i/SiC1m concentration ratio in the liquid phase will always decrease, but from the viewpoint of one reaction equilibrium, the reaction rate will increase, and this will improve the production of trichlorosilane. The reaction will proceed in a more advantageous direction. Therefore, compared to a normal fluidized bed reaction where the composition of the product gas is discharged as it is, it is possible to expect the effect of making the composition of the product always work in favor of the product in terms of the reaction equilibrium. It is.
更に該反応に於いて無水塩化水素ガスを使用することで
トリクロロシランの生成量もより増大させる事ができる
。Furthermore, by using anhydrous hydrogen chloride gas in the reaction, the amount of trichlorosilane produced can be further increased.
以上の如くして１本発明においては１反応温度は四塩化
ケイ素の臨界温度以下で行い、好ましくは２３０°Ｃ以
下１００ ’Ｃ以上で行う、 １００ ”Ｃ未満の温度
ではトリクロロシランの実質的な生成は望めない。なお
本反応を行うに際して原料として仕込む四塩化ケイ素中
に反応平衡量以下のトリクロロシランが混在していても
構わなく、このことは反応によって生成したトリクロロ
シランを蒸留等により分離した際四塩化ケイ素中にトリ
クロロシランが残存しているものも使用可能であること
を意味するが、好ましくは反応平衡上なるべくトリクロ
ロシランを含まない若しくはトリクロロシラン含有量が
出来るだけ少ない四塩化ケイ素を使用することが実質的
にトリクロロシランの生成量が最も多くなる事となり望
ましい。As described above, in the present invention, the reaction temperature is below the critical temperature of silicon tetrachloride, preferably below 230°C and above 100'C. It is not expected that trichlorosilane will be produced.In addition, when carrying out this reaction, it does not matter if less than the reaction equilibrium amount of trichlorosilane is mixed in the silicon tetrachloride charged as a raw material. This means that silicon tetrachloride in which trichlorosilane remains can be used, but it is preferable to use silicon tetrachloride that does not contain trichlorosilane or has as little trichlorosilane content as possible in terms of reaction equilibrium. It is desirable to do so because the amount of trichlorosilane produced will be substantially the largest.
次に本発明における原料、金属銅、ハロゲン化アルミニ
ウム等の添加物の使用量について述べる、本発明に於け
る。金属ケイ素の使用量は特に限定はしないが、バッチ
式で行う場合は四塩化ケイ素に対して１重量％以上で行
うことが好ましくこの値未満であると反応とともに金属
ケイ素が消費され有効に反応が行いえなくなる恐れがあ
る。又金属銅及びハロゲン化アルミニウム等の添加物の
使用量は特に限定はしないが、金属ケイ素に対して金属
原子比で各々金属銅は０．５％以上、ハロゲン化アルミ
ニウムは０．１％以上で行うことが反応速度上好ましい
。Next, the amounts of additives such as raw materials, metallic copper, and aluminum halides used in the present invention will be described. The amount of silicon metal to be used is not particularly limited, but when conducting batchwise, it is preferably 1% by weight or more based on silicon tetrachloride, and if it is less than this value, silicon metal will be consumed along with the reaction and the reaction will not be effective. There is a possibility that you will not be able to do it. Furthermore, the amounts of additives such as metallic copper and aluminum halide are not particularly limited, but metallic copper should be at least 0.5% and aluminum halide should be at least 0.1% in terms of metal atomic ratio to metallic silicon. This is preferred from the viewpoint of reaction rate.
次に本発明を実際に実施するための具体的な態様につい
て述べる。前記した様に本発明における反応は１００°
Ｃ以上を必要とするため加圧（水素加圧が好ましい）状
態で行われ、また流通式反応法もしくはバッチ式反応の
いずれの方法で行うことも可能である。Next, specific embodiments for actually implementing the present invention will be described. As mentioned above, the reaction in the present invention is carried out at 100°.
C or more is required, so it is carried out under pressure (hydrogen pressure is preferred), and it is also possible to carry out by either a flow reaction method or a batch reaction method.
本発明に於ける実施方法に関しては特に規定はしないが
実施し易い方法として以下の方法が挙げられる。もちろ
んこれらの方法に本発明は限定されるものではない。Although the method of carrying out the present invention is not particularly specified, the following method may be mentioned as a method that is easy to carry out. Of course, the present invention is not limited to these methods.
（１）オートクレーブ中に所定量の四塩化ケイ素。(1) A predetermined amount of silicon tetrachloride in an autoclave.
金属ケイ素、金属銅及びハロゲン化アルミニウムを入れ
たのち所定の圧力に水素で加圧しその後加熱撹拌反応を
行う方法。A method in which metal silicon, metal copper, and aluminum halide are added, then pressurized with hydrogen to a predetermined pressure, and then heated and stirred.
（２）予め所定温、及び水素で所定圧に保たれた加圧反
応器中に所定量の四塩化ケイ素、銅及びハロゲン化アル
ミニウムを連続的に導入しかつ生成ガス及び／又は生成
液を連続的に抜出し反応を行う方法。(2) Continuously introduce a predetermined amount of silicon tetrachloride, copper, and aluminum halide into a pressurized reactor that has been maintained at a predetermined temperature and a predetermined pressure with hydrogen, and continuously feed the product gas and/or product liquid. A method of performing a selective extraction reaction.
（３）予め金属ケイ素１ｗ４及びハロゲン化アルミニウ
ムを反応器中に入れ所定温度に保ち乍ら水素加圧で四塩
化ケイ素及び水素を連続的に導入し且つ生成ガス及び／
又は生成液を連続的に抜出しながら反応を行い必要に応
じて金属ケイ素、金属銅及びハロゲン化アルミニウムを
間歇的に導入する方法。(3) Metallic silicon 1w4 and aluminum halide are placed in a reactor in advance, kept at a predetermined temperature, silicon tetrachloride and hydrogen are continuously introduced under hydrogen pressure, and the generated gas and/or
Or a method in which the reaction is carried out while the produced liquid is continuously extracted, and metallic silicon, metallic copper, and aluminum halide are intermittently introduced as necessary.
とりわけ大量にトリクロロシランを製造する方法として
（２）又は（３）の方法が望ましい、加えて連続反応を
行うことで２反応によって金属ケイ素は消費されるが、
ｆＩ及びハロゲン化アルミニウムは実質上消費されない
。従って反応を低温で行えばこれらの揮散を防ぐことが
できるので反応器中で金属ケイ素に対する銅及びハロゲ
ン化アルミニウムとの比率が高くても、更にこれらを継
足す必要はそれほどないため充分経済的に成立しうる方
法として行える。In particular, method (2) or (3) is preferable as a method for producing trichlorosilane in large quantities.In addition, by performing continuous reactions, metallic silicon is consumed by two reactions,
fI and aluminum halide are virtually not consumed. Therefore, if the reaction is carried out at a low temperature, volatilization of these substances can be prevented, so even if the ratio of copper and aluminum halide to metal silicon is high in the reactor, there is no need to add them further, so it is quite economical. This can be done as a viable method.
立里茨来
本発明は四塩化ケイ素をトリクロロシランへ経済的に変
換する極めて有効な方法である。従来不可能であった四
塩化ケイ素の臨界温度以下で操作することにより、四塩
化ケイ素を液体状態で反応器中に導入しかつ液体状態で
反応を行うことができる。従って反応容器を容易に小型
化することが可能となり経済的である。加えて当然のこ
とながら低温で反応を行うことを可能とした結果５反応
装置等の腐蝕を抑制することが可能となり、加えて低エ
ネルギーでトリクロロシランを製造することが可能とな
り経済的効果は非常に大きく工業的にきわめて有用であ
る。すなわち、従来高温反応のため多大のエネルギーを
要していたものが１ これにより大幅なエネルギーの削
減が可能となり。The present invention is an extremely effective method for economically converting silicon tetrachloride to trichlorosilane. By operating below the critical temperature of silicon tetrachloride, which was previously impossible, silicon tetrachloride can be introduced into the reactor in a liquid state and the reaction can be carried out in a liquid state. Therefore, it is possible to easily downsize the reaction container, which is economical. In addition, as a result of being able to carry out the reaction at low temperatures, it is possible to suppress corrosion of the reaction equipment, etc., and in addition, it is possible to produce trichlorosilane with low energy, which has a great economic effect. It is extremely useful industrially. In other words, the high-temperature reaction that conventionally required a large amount of energy has now become possible with a significant reduction in energy consumption.
低温下、液相（四塩化ケイ素）反応が可能となったため
１反応容器を小型化出来１反応装置の腐食を抑制し、か
つスチーム等の低温の熱媒体が使用出来るなど、大幅な
設備の削減が可能となるのである。Since liquid phase (silicon tetrachloride) reaction is now possible at low temperatures, the size of the reaction vessel can be reduced, corrosion of the reaction equipment can be suppressed, and low-temperature heat carriers such as steam can be used, resulting in a significant reduction in equipment. becomes possible.
２隻斑 以下本発明を実施例によって更に具体的に説明する。2 spots The present invention will be explained in more detail below using Examples.
実施例 １
耐圧３００Ｋｇ ７ｃｍ”Ｇ 、耐湿５００°Ｃ５ＵＳ
３１６製２００ｍ１オートクレーブに、金属ケイ素（２
００メツシユ。Example 1 Pressure resistance 300Kg 7cm"G, humidity resistance 500°C5US
Metallic silicon (2
00 metsushiyu.
純度９９．９％） ９．ＯＯｇ （３２０１１Ｉｇ−ａ
ｔｎ＋ ） 、塩化アルミニウム５．ＯＯｇ （３７，
５ｍｍｏｌ）市販の金属銅粉末８７゜００ｇ （１１０
ｍｇ−ａｔｍ ）及び四塩化ケイ素１３０ｇ （７６５
ｍｍｏｌ ）を入れた後室温で水素を圧入し圧力１１０
Ｋｇ／ｃ＋ａ’ Ｇとした後（ｌｌｚ／５ｉＣ１ａ〜０
．７５＋ｍｏｌ比） ３００ｒｐｍで撹拌し乍ら２３０
″Ｃに加熱しく昇温時間２０分）２３０ ’Ｃで５時間
反応を行った０反応終了後オートクレーブを５°Ｃに冷
却し、降圧後反応液をガスクロマトグラフ法により分析
した結果反応液組成はトリクロロシラン１８．１モル％
及び四塩化ケイ素８１．９モル％でありこれは四塩化ケ
イ素の転化率１４．１％に相当し低温度にかかわらず非
常に高収率でトリクロロシランを得ることが出来た。Purity 99.9%) 9. OOg (32011Ig-a
tn+), aluminum chloride5. OOg (37,
5 mmol) Commercially available metallic copper powder 87゜00g (110
mg-atm ) and silicon tetrachloride 130 g (765
mmol), then pressurized hydrogen at room temperature to a pressure of 110
After setting Kg/c+a' G (llz/5iC1a~0
．． 75 + mol ratio) while stirring at 300 rpm.
After the reaction was completed, the autoclave was cooled to 5°C, the pressure was lowered, and the reaction liquid was analyzed by gas chromatography. As a result, the composition of the reaction liquid was found to be Trichlorosilane 18.1 mol%
and 81.9 mol% of silicon tetrachloride, which corresponds to a conversion rate of 14.1% of silicon tetrachloride, and trichlorosilane could be obtained in a very high yield despite the low temperature.
実施例 ２
反応時間を２．５及び１時間とした以外は実施例１と全
く同一の反応条件で行い反応液をガスクロマトグラフ法
により分析した。結果は第１表に示した。Example 2 The reaction conditions were exactly the same as in Example 1 except that the reaction times were 2.5 hours and 1 hour, and the reaction solution was analyzed by gas chromatography. The results are shown in Table 1.
員上表
１ Ｂ、３ ９１．７
６．３宰Ｔｅｌトリクロロシラン、ＳＴＣ：四塩化ケイ
素を示す、以下同じ。Table 1 B, 3 91.7
6.3 Trichlorosilane, STC: Indicates silicon tetrachloride, the same applies hereinafter.
上記より、短時間で反応を行っても非常に高い四塩化ケ
イ素の転化率が得られることが分かった。From the above, it was found that a very high conversion rate of silicon tetrachloride can be obtained even if the reaction is carried out in a short time.
実施例３
実施例１と同一量の金属銅、金属ケイ素、塩化アルミニ
ウム及び四塩化ケイ素を実施例１と同一のオートクレー
ブに入れ水素仕込圧５５Ｋｇ／ｃｍ”Ｇ （仕込Ｈｚ
／５ｉＣ１４モル比〜０．３８）で水素を圧入した後２
３０℃で撹拌しながら加熱し当該温度で２．５時間反応
を行った後実施例１と同様に冷却後降圧し。Example 3 The same amounts of metallic copper, metallic silicon, aluminum chloride, and silicon tetrachloride as in Example 1 were placed in the same autoclave as in Example 1, and the hydrogen charging pressure was 55 Kg/cm"G (Preparing Hz)
/5iC14 molar ratio ~ 0.38) after injecting hydrogen 2
The mixture was heated at 30° C. with stirring and reacted at that temperature for 2.5 hours, then cooled and the pressure was lowered in the same manner as in Example 1.
反応液を分析した０反応液組成はトリクロロシラン７．
８％、四塩化ケイ素９２．２％であった。The reaction solution was analyzed and the composition of the reaction solution was trichlorosilane7.
8%, silicon tetrachloride 92.2%.
実施例 ４
実施例１と同一のオートクレーブに実施例１と同一量の
金Ｎ銅粉末り、塩化アルミニウム、四塩化ケイ素及び金
属ケイ素（純度９８χ、１５０メツシユに変更した）を
入れ水素仕込圧１１（１Ｋｇ／ｃｍ”Ｇで２３０”Ｃ２
，５時間（反応最高圧力１８０Ｋｇ／ｃ＋ｗ”Ｇ）で加
熱撹拌を行った後５°Ｃに冷却後反応液をガスクロマト
グラフ法によって分析を行った０反応液組成はトリクロ
ロシラン１５．１％、四塩化ケイ素８４．９％であった
。従って金属ケイ素の純度は９８％程度の市販のもので
充分であることが判明した。Example 4 The same amounts of gold-N copper powder, aluminum chloride, silicon tetrachloride, and metallic silicon (purity 98χ, changed to 150 mesh) as in Example 1 were placed in the same autoclave as in Example 1, and the hydrogen charging pressure was 11 ( 230”C2 at 1Kg/cm”G
After heating and stirring for 5 hours (maximum reaction pressure 180 Kg/c+w"G) and cooling to 5°C, the reaction solution was analyzed by gas chromatography. The composition of the reaction solution was 15.1% trichlorosilane, 4% The silicon chloride content was 84.9%.Therefore, it was found that commercially available silicon metal with a purity of about 98% was sufficient.
比較例 １（ブランク試験）
実施例４と同様の反応条件で塩化アルミニウムを加えな
いで金属ケイ素を９９．９χ純度のもの又は９８χ純度
のものを各々実施例１〜４と同一量使用し、実施例４と
同一の反応器、同一量の銅粉末。Comparative Example 1 (Blank Test) Conducted under the same reaction conditions as in Example 4 without adding aluminum chloride, using the same amounts of metallic silicon with a purity of 99.9χ or 98χ as in Examples 1 to 4, respectively. Same reactor as Example 4, same amount of copper powder.
四塩化ケイ素及び水素仕込圧及び同一の反応条件で反応
を行った。後実施例１〜４と同様に冷却降圧後反応液を
分析した。又同様に上記２種類の純度の金属ケイ素を同
一量用いて、金属銅を用いずに実施例４と同一の反応器
、同一量の塩化アルミニウム、金属系ケイ素及び四塩化
ケイ素、同−水素仕込圧及び同一反応条件で反応を行っ
た後同様に冷却、降圧して反応液を分析した。それぞれ
の結果を第２表に示す。The reaction was carried out using silicon tetrachloride and hydrogen charging pressure and the same reaction conditions. The reaction solution after cooling and pressure reduction was analyzed in the same manner as in Examples 1 to 4. Similarly, using the same amount of metallic silicon of the above two types of purity, but without using metallic copper, the same reactor as in Example 4, the same amount of aluminum chloride, metallic silicon and silicon tetrachloride, and the same amount of hydrogen were charged. After the reaction was carried out under the same pressure and reaction conditions, the reaction solution was similarly cooled, the pressure was lowered, and the reaction solution was analyzed. The results are shown in Table 2.
星！
以上実施例１〜４及び比較例１の結果から銅及び塩化ア
ルミニウムの相互作用によって極めて高い反応活性があ
られれることが判明した。加えて。Star! From the results of Examples 1 to 4 and Comparative Example 1, it was found that extremely high reaction activity could be achieved due to the interaction between copper and aluminum chloride. In addition.
比較例の結果からも明らかなように、トリクロロシラン
への従来の変換触媒である銅よりも極めて活性が高く、
従って銅触媒のみの様な高温反応を必要としなくても充
分低温液相でトリクロロシランへの高い転化率及び収率
が認められた。又原料金属ケイ素の純度は本発明におい
ては反応収率等に実質的に影響を及ぼさない、二とが明
らかになった。As is clear from the results of the comparative examples, it has significantly higher activity than copper, the conventional conversion catalyst for trichlorosilane.
Therefore, a high conversion rate and yield to trichlorosilane was observed in a sufficiently low temperature liquid phase without requiring a high-temperature reaction unlike when using only a copper catalyst. It has also been found that the purity of the raw material metal silicon does not substantially affect the reaction yield etc. in the present invention.
実施例 ５
実施例１〜４と同一のオートクレーブに、塩化アルミニ
ウム３７．５ｍｍｏｌ又は臭化アルミニウム３７．５１
ＩＩＩＩＩｏｌを金属’ｙイ素（純度９９．９％、２ｏ
ｏメツシユ）、金属銅粉末Ｂ７．Ｏｇ （１１０ｍｇ−
ａｔｍ ）及び四塩化ケイ素１７６．７ ｇ （１，０
４ｍｏｌ ）とともに入れ室温で水素を１１０Ｋｇ／ｃ
ｔａ” Ｇに圧入し、それぞれ２３０ ”Ｃで２．５時
間反応を行った後前記実施例１〜４と同様に冷却降圧後
反応液を分析した。結果は第３表に示した様に、ハロゲ
ン化アルミニウムを塩化アルミニウムないし臭化アルミ
ニウムに換えても活性は充分に認められることが判明し
た。更にこの方法に於いては低温かつ短時間に於いても
非常に高収率でトリクロロシランが得られ、また四塩化
ケイ素の量を増加させることによりトリクロロシランの
生成量が増加することが分がった。Example 5 In the same autoclave as Examples 1 to 4, 37.5 mmol of aluminum chloride or 37.51 aluminum bromide was added.
IIIol to metal 'y ion (purity 99.9%, 2o
o mesh), metallic copper powder B7. Og (110mg-
atm ) and silicon tetrachloride 176.7 g (1,0
4 mol) and hydrogen at room temperature at 110 kg/c.
ta" G and reacted at 230" C for 2.5 hours, and the reaction solution was cooled and depressurized and analyzed in the same manner as in Examples 1 to 4 above. As shown in Table 3, the results showed that sufficient activity was observed even when aluminum halide was replaced with aluminum chloride or aluminum bromide. Furthermore, it has been found that trichlorosilane can be obtained in a very high yield in this method even at low temperatures and in a short time, and that the amount of trichlorosilane produced can be increased by increasing the amount of silicon tetrachloride. It was.
３じＬ芝
実施例 ６
塩化アルミニウム５．０ｇ（３７，５ｍｍｏｌ）を実施
例５と同一の金属銅、金属ケイ素及び四塩化ケイ素とと
もに実施例１〜５と同一のオートクレーブに入れ反応温
度２１５及び２００℃としてそれぞれ５時間加熱撹拌反
応を行った後同様にしてオートクレーブを冷却、降圧後
反応液を分析した。結果を第４表に示した。低温度にか
かわらず各温度でトリクロロシランが良い収率で得られ
ることがわかった。3 L Sod Example 6 5.0 g (37.5 mmol) of aluminum chloride was placed in the same autoclave as Examples 1 to 5 with the same metal copper, metal silicon, and silicon tetrachloride as in Example 5, and the reaction temperature was 215 and 200. ℃ for 5 hours, the autoclave was similarly cooled, the pressure was lowered, and the reaction solution was analyzed. The results are shown in Table 4. It was found that trichlorosilane could be obtained in good yield at each temperature regardless of the low temperature.
Claims (2)
及び塩化水素と反応せしめてトリクロロシランを製造す
る方法において、該四塩化ケイ素をその臨界温度以下の
液体状態として、該反応系を気−液−固相の不均一反応
とすると共に、該気−液−固相の不均一反応を、金属銅
及びハロゲン化アルミニウムの存在下に行うことを特徴
とするトリクロロシランの製造方法。(1) In a method for producing trichlorosilane by reacting silicon tetrachloride and metallic silicon with hydrogen or hydrogen and hydrogen chloride, the silicon tetrachloride is brought into a liquid state below its critical temperature, and the reaction system is converted into a gas-liquid state. - A method for producing trichlorosilane, characterized in that the heterogeneous solid phase reaction is carried out, and the gas-liquid-solid phase heterogeneous reaction is carried out in the presence of metallic copper and aluminum halide.
塩化アルミニウム、臭化アルミニウムおよびヨウ化アル
ミニウムからなる群より選択されるハロゲン化アルミニ
ウムである特許請求の範囲第１項に記載の方法。(2) aluminum halide is aluminum fluoride,
The method of claim 1, wherein the aluminum halide is selected from the group consisting of aluminum chloride, aluminum bromide and aluminum iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24020086A JPH0788213B2 (en) | 1986-10-11 | 1986-10-11 | Method for producing trichlorosilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24020086A JPH0788213B2 (en) | 1986-10-11 | 1986-10-11 | Method for producing trichlorosilane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6395108A true JPS6395108A (en) | 1988-04-26 |
| JPH0788213B2 JPH0788213B2 (en) | 1995-09-27 |
Family
ID=17055945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24020086A Expired - Lifetime JPH0788213B2 (en) | 1986-10-11 | 1986-10-11 | Method for producing trichlorosilane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788213B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015536298A (en) * | 2013-09-30 | 2015-12-21 | エルジー・ケム・リミテッド | 卜 Lichlorosilane production method |
-
1986
- 1986-10-11 JP JP24020086A patent/JPH0788213B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015536298A (en) * | 2013-09-30 | 2015-12-21 | エルジー・ケム・リミテッド | 卜 Lichlorosilane production method |
| US9643851B2 (en) | 2013-09-30 | 2017-05-09 | Lg Chem, Ltd. | Method for producing trichlorosilane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0788213B2 (en) | 1995-09-27 |
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