JPS6395109A - Production of trichlorosilane - Google Patents
Production of trichlorosilaneInfo
- Publication number
- JPS6395109A JPS6395109A JP24020186A JP24020186A JPS6395109A JP S6395109 A JPS6395109 A JP S6395109A JP 24020186 A JP24020186 A JP 24020186A JP 24020186 A JP24020186 A JP 24020186A JP S6395109 A JPS6395109 A JP S6395109A
- 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.)
- Pending
Links
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- 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 68
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007790 solid phase Substances 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 21
- 239000010703 silicon Substances 0.000 claims description 21
- 150000004820 halides Chemical class 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003746 solid phase reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 54
- -1 vanadium halides Chemical class 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 5
- 229920001296 polysiloxane Polymers 0.000 abstract description 3
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 2
- 150000001649 bromium compounds Chemical class 0.000 abstract 1
- 150000004694 iodide salts Chemical class 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 25
- 239000007789 gas Substances 0.000 description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 238000007323 disproportionation reaction Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005046 Chlorosilane Substances 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
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 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
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021553 Vanadium(V) chloride Inorganic materials 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
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000014987 copper Nutrition 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
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940076136 ferrous iodide Drugs 0.000 description 1
- 238000004817 gas chromatography 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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 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
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- ZOYIPGHJSALYPY-UHFFFAOYSA-K vanadium(iii) bromide Chemical compound [V+3].[Br-].[Br-].[Br-] ZOYIPGHJSALYPY-UHFFFAOYSA-K 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
皮栗上皇肌夙分互
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.
ｌ米五弦歪
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。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
素が副生する。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 recent development of the electronics industry, the demand for polycrystalline silicon, single crystal silicon, monosilane gas, etc. is increasing rapidly, and the demand is expected to continue to increase in the future. Here, trichlorosilane is used in the largest amount as a raw material for the silicone material. For example, high-purity polycrystalline silicon is produced by thermal decomposition of trichlorosilane, and most of the high-purity polycrystalline silicon in the world is currently produced by 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°Ｃ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℃付
近で反応させトリクロロシランを製造する方法。(2) A method of producing trichlorosilane by reacting silicon hydrogen tetrachloride and metal silicon at around 500°C.
（３）四塩化ケイ素、水素、金属ケイ素及び塩化水素を
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) A method of producing trichlorosilane by reacting silicon tetrachloride, hydrogen, metallic silicon, and hydrogen chloride at around 500°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″Ｃ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
５７−１５６３１８号では第一段目で９００℃の温度に
おいて水素と四塩化ケイ素をモル比Ｈｘ／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°Ｃ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 JP-A-57-156318, trichlorosilane was obtained with a yield of 60% by spraying hydrogen and silicon tetrachloride onto a heating element at the above temperature at 1100-1600"C. Visually, at a temperature of 900°C, hydrogen and silicon tetrachloride are mixed in a molar ratio Hx/5iC14.
2 to obtain trichlorosilane with a yield of 25%. 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 at 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真人なもの
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 genuine. 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ず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. The production of trichlorosilane by converting the resulting silicon tetrachloride can be said to be 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 perspective 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 reducing the amount of hydrogen chloride used. It is desirable to make the most of its characteristics by using a small amount of it.
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く特
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, and 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１本発明におけるが如
く、四塩化ケイ素の臨界温度以下で四塩化ケイ素を液体
状として気体−液体一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（知られていない。However, in method (2), the reaction temperature is usually 500-600°C, and there is no example in which trichlorosilane was 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-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
多くの欠点を有している。In the method (2), conventionally, when trichlorosilane is produced continuously in large quantities, a gas-solid phase fluidized bed apparatus is used. However, in this case, since a fluidized bed is used, there is a loss of active ingredients due to the volatilization of silicon metal and catalyst components whose particle size has become smaller due to the 9 reactions, volatilization of catalyst components due to high temperature reactions, corrosion of equipment, and even high molecular weight chlorosilanes. The selectivity of trichlorosilane decreases due to the formation of trichlorosilane, and a large amount of energy is used due to the high temperature. It has many drawbacks that need to be further resolved in order to be industrialized.
本発明者らはこれらに鑑み鋭意検討した結果驚（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 conducted extensive studies in view of the above, and were surprised to find that silicon tetrachloride was reacted in a liquid state below the critical temperature of silicon tetrachloride, with a high yield and a small amount per unit volume of silicon tetrachloride. The inventors discovered a highly economically advantageous method for producing trichlorosilane by increasing the throughput and completed the present invention.
又里坐亘血
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。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−液一固相の
不均一反応とすると共に、該気−液−固相の不均一反応
を、金属銅並びに鉄及び／又はバナジウムのハロゲン化
物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 A trichlorosilane characterized in that it is a gas-liquid-solid phase heterogeneous reaction, and the gas-liquid-solid phase heterogeneous reaction is carried out in the presence of metallic copper and a halide of iron and/or vanadium. A manufacturing method is provided.
１里重皿丞 以下本発明の詳細な説明する。1 Riju Sarajo 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Ｈｚ／５ｘＣ１４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℃（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−液相一固体相反応でトリ
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並びに鉄及び／
又はバナジウムのハロゲン化物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く製造すること
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 Hz/5xC14 molar ratio, the more the reaction proceeds in the right direction. In addition, as described later, silicon tetrachloride is made into a liquid state at a temperature below 233.6°C (actually 230'C or less), which is the critical temperature of silicon tetrachloride, and a low-temperature gas phase - liquid phase - solid phase is obtained. Until now, there has been no known example of producing trichlorosilane through a reaction, but in the present invention, the above reaction is carried out using metallic copper, iron and/or
Alternatively, by carrying out the reaction in the presence of a specific additive called a vanadium halide, silicon tetrachloride can be reacted in a liquid state or dissolved in an inert solvent in the reaction state to produce trichlorosilane in a high yield. This made it possible to manufacture it. Naturally, it is also possible to adopt a method that clearly increases the yield of trichlorosilane by adding hydrogen chloride gas into the reaction system of the present invention.
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（、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 (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９粒状等池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 the form of 9 grains.
本発明においては、上記反応を金属銅並びに鉄及び／又
はバナジウムのハロゲン化物の存在下に行うが１本発明
で使用する金属銅は特に限定するものではなく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。も
ちろん１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 a halide of iron and/or vanadium.1 The metallic copper used in the present invention is not particularly limited, and commercially available electrolytic copper is usually used. Other reduced coppers can also be used. There is no need to worry much about the purity, and the form of the metal 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 also possible to use it in other forms such as a single grain.
本発明で使用する鉄またはバナジウムのハロゲン化物と
は９分子式でＦｅＣｈ＋ＦｅＣ１５＋ＶＣｌ３＋ＶＣｌ
５＋ＶＯＣ１ｚ＋ＦｅＢｒｔ＋ＦｅＢｒ３＋ＶＢｒ３．
Ｆｅ１ｚ＋Ｆｅ１３等の塩化物。The iron or vanadium halide used in the present invention has a nine molecular formula: FeCh+FeC15+VCl3+VCl
5+VOC1z+FeBrt+FeBr3+VBr3.
Chlorides such as Fe1z+Fe13.
臭化物及びヨウ化物であり、これらの１種または２種以
上の混合物で使用する。These are bromide and iodide, and these are used alone or in a mixture of two or more.
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
９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９反応平衡２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い、ま
た反応条件に於いて原料、生成物、および金属銅、鉄ま
たはバナジウムのハロゲン化物等の添加物等に対して不
活性な溶媒１例えばｎ−ヘキサン、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); however, 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 the raw materials, products, and additives such as metal copper, iron, or vanadium halides under the reaction conditions. Inert solvent 1 For example, aliphatic hydrocarbons such as n-hexane and n-hebutane, alicyclic hydrocarbons such as cyclohexane and cyclooctane, and aromatic hydrocarbons such as benzene and toluene. It is also possible to use .
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−面
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, so the reaction field is almost essentially a liquid-hedral 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。トリクロロシランと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 ５ｉＨＣｈ／５ｉＣ１４濃度比より
も気体相に於ける５ｉｆｔ（：ｌｉ／５ｉＣ１＊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５ｉＨＣ１ｓ／Ｓｉ（：１ａｆ１１
度比は減少Φ方向に向かうから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反応平衡上京に生
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. The vapor pressure of trichlorosilane and silicon tetrachloride at the same temperature is higher for trichlorosilane. Thus, if the reaction is carried out continuously, 5iHC1s/Si(:1af11) in the liquid phase will always be higher.
Since the degree ratio tends to decrease in the Φ direction, the reaction rate of the reaction increases from the viewpoint of one reaction equilibrium, and the reaction progresses in a more advantageous direction for the production of trichlorosilane. Therefore, compared to a normal fluidized bed reaction in which the composition of the produced gas is discharged as it is, we can expect the effect of making the composition of the product more favorable to 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反応場度は四塩化
ケイ素の臨界温度以下で行い、好ましくは２３０°Ｃ以
下１００℃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（
、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陥凹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（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, one reaction field is carried out at a temperature below the critical temperature of silicon tetrachloride, preferably at a temperature below 230°C and above 100°C. However, it does not matter if less than the reaction equilibrium amount of trichlorosilane is mixed in the silicon tetrachloride charged as a raw material when carrying out this reaction (
This means that it is also possible to use recessed silicon chloride obtained by separating the trichlorosilane produced by the reaction by distillation or the like, but it is preferable that trichlorosilane remains in the reaction equilibrium. It is desirable to use silicon tetrachloride that does not contain chlorosilane or has as little trichlorosilane as possible because this will substantially increase the amount of trichlorosilane produced.
次に本発明における原料、金属銅、鉄またはバナジウム
のハロゲン化物等の添加物の使用量について述べる０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
る恐熟がある。又金属銅及び鉄またはバナジウムのハロ
ゲン化物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、鉄またはバナジウムのハロゲン化物は０．１％以上
で行うことが１反応器度上好ましい。Next, the amounts of additives such as raw materials, metallic copper, iron or vanadium halides 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 fear of not being able to do anything. There are no particular limitations on the amounts of additives such as metallic copper and iron or vanadium halides, but metallic copper must be 0.5% or more in terms of metal atomic ratio to metallic silicon, and iron or vanadium halides should be used at least 0.5%. It is preferable to use 0.1% or more per reactor.
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 there are no particular regulations regarding the implementation method of the present invention, the following method can be mentioned as an easy-to-implement method. 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、金属銅及び鉄またはバナジウムのハロゲン
化物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 a halide of iron or vanadium 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、銅及び鉄またはバナ
ジウムのハロゲン化物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 iron or vanadium halide into a pressurized reactor that has been maintained at a predetermined temperature and a predetermined pressure with hydrogen, and produce gas and/or A method in which the reaction is performed by continuously extracting the product liquid.
（３）予め金属ケイ素、＃ｒ４及び鉄またはバナジウム
のハロゲン化物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、金属銅及び鉄またはバナ
ジウムのハロゲン化物を間歇的に導入する方法。(3) Metallic silicon, #r4, and a halide of iron or vanadium 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 generated A method in which the reaction is carried out while the liquid is continuously withdrawn, and metallic silicon, metallic copper, and iron or vanadium halides 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９反応によって金属ケイ素は消費されるが９
ｗ４及び鉄またはバナジウムのハロゲン化物は実質上消
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
及び鉄またはバナジウムのハロゲン化物との比率が高く
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 carrying out continuous reactions, metallic silicon is consumed by the 9 reaction, but 9
W4 and iron or vanadium halides are not substantially consumed, therefore their volatilization can be prevented if the reaction is carried out at low temperatures, so the ratio of copper and iron or vanadium halides to metallic silicon is high in the reactor. However, since there is not much need to add these additionally, it can be carried out as an economically viable method.
立度羞来
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１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、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 a highly 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, what used to require a large amount of energy due to high-temperature reactions has now become possible to significantly reduce 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５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 made smaller, 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.
災旌斑 以下本発明を実施例によって更に具体的に説明する。disaster spots The present invention will be explained in more detail below using Examples.
実施例 １
耐圧３００Ｋｇ ／ｃｎ＋”Ｇ 、耐湿５００℃Ｓｔ！
５３１６製２００ｍ１オートクレーブに、金属ケイ素（
２００メソシユ。Example 1 Pressure resistance 300Kg/cn+"G, humidity resistance 500℃St!
Metallic silicon (
200 mesoyu.
純度９９．９％） ９．０Ｏｇ （３２０ｍｇ−ａｔｍ
） 、塩化第２鉄６．０８ｇ （３７，５ｍｍｏｌ）
市販の金属銅粉末ＢＴ、ＯＯｇ （１１０＋ｎｇ−ａｔ
＋ｗ ）及び四塩化ケイ素１３０ｇ （７６５ｍｍｏｌ
）を入れた後室温で水素を圧入し圧力１１０Ｋｇ／ｃ
ｍ２Ｇとしだ後（Ｈｚ／５ｉＣ１４〜０．７５ｍｏｌ比
） ３００ｒｐ＠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℃に冷却し、さらに大気圧に
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１６．１モル％及び四
塩化ケイ素８３．９モル％であり、これは四塩化ケイ素
の転化率１２．６％に相当し四塩化ケイ素の臨界温度以
下の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%) 9.0Og (320mg-atm
), ferric chloride 6.08g (37.5mmol)
Commercially available metallic copper powder BT, OOg (110+ng-at
+w ) and silicon tetrachloride 130g (765mmol
), then pressurized hydrogen at room temperature to a pressure of 110 kg/c.
m2G (Hz/5iC14-0.75 mol ratio) Stir at 300 rpm and heat to 230"C for 20 minutes) React at 230"C for 5 hours. After cooling to ℃ and further lowering the pressure to atmospheric pressure, the reaction solution was analyzed by gas chromatography, and the composition of the reaction solution was 16.1 mol% of trichlorosilane and 83.9 mol% of silicon tetrachloride. This corresponded to a conversion rate of 12.6%, and trichlorosilane could be obtained in a very high yield despite the low temperature below the critical temperature of silicon tetrachloride.
実施例 ２
四塩化ケイ素の量を７６．７ｇ （１，０４ｍｏｌ）と
した以外は総て実施例１と同一の仕込条件及び同一の水
素仕込圧で実施例１と同一のオートクレーブを用いてそ
れぞれ１．２．５及び５時間２３０℃で加熱撹拌反応を
行った。後冷却及び降圧して反応液を分析した。結果を
第１表に示した。意外なことに。Example 2 Using the same autoclave as in Example 1 under the same charging conditions and the same hydrogen charging pressure as in Example 1 except that the amount of silicon tetrachloride was changed to 76.7 g (1.04 mol), A heating stirring reaction was carried out at 230° C. for 2.5 and 5 hours. After cooling and reducing the pressure, the reaction solution was analyzed. The results are shown in Table 1. Surprisingly.
Ｈｚ／５ｉＣ１ｎモル比が下がったにもかかわらず四塩
化ケイ素の量を増加させたことによって反応速度は高ま
り実施例１よりも同一反応時間で高い転化率が得られた
。Although the Hz/5iC1n molar ratio was lowered, the reaction rate was increased by increasing the amount of silicon tetrachloride, and a higher conversion rate than in Example 1 was obtained at the same reaction time.
第１表
５ ２１．３ ７８．７
ｄＣ３： ）リクロロシラン；ＳＴＣ：四塩化ケイ素実
施例 ３
実施例１〜２と同一のオートクレーブに実施例２と同一
の仕込量および同一の水素仕込圧で反応温度を２１５℃
及び２００″Ｃとして５時間反応を行った後同様にして
冷却、降圧後反応液を分析した。Table 1 5 21.3 78.7 dC3: ) Lichlorosilane; STC: Silicon tetrachloride Example 3 Reacted in the same autoclave as Examples 1 to 2 with the same charge amount and the same hydrogen charge pressure as Example 2. Temperature 215℃
After the reaction was carried out at 200''C for 5 hours, the reaction solution was similarly cooled and the pressure was lowered, and the reaction solution was analyzed.
結果は第２表に示したように２１５及び２００″Ｃとい
う低温でもよい収率でトリクロロシランが得られること
が判明した。As shown in Table 2, it was found that trichlorosilane could be obtained in good yield even at temperatures as low as 215 and 200''C.
第２表
実施例 ４
実施例１〜３と同一のオートクレーブを使用し、金属ケ
イ素を市販の純度９８％、１５０メツシュ品９、ＯＯｇ
に代えた以外は総て実施例２と同一の仕込量及び同一の
水素仕込圧で２３０°Ｃ２，５時間反応を行った。後同
様にして冷却、降圧し反応液を分析した０反応液組成は
トリクロロシラン１７．０モル％、四塩化ケイ素８３．
０モル％であり、原料の金属ケイ素は純度９９，９％の
ものに代えて純度９８％の市販の金属ケイ素を使用して
も実質的になんら差し支えないことが判明した。Table 2 Example 4 Using the same autoclave as in Examples 1 to 3, metallic silicon was commercially available with a purity of 98%, 150 mesh product 9, OOg
The reaction was carried out at 230° C. for 2.5 hours using the same amount of hydrogen and the same pressure of hydrogen as in Example 2, except that . Afterwards, the reaction solution was similarly cooled and depressurized, and the reaction solution was analyzed.The composition of the reaction solution was 17.0 mol% of trichlorosilane and 83.0% of silicon tetrachloride.
0 mol %, and it was found that there is virtually no problem in using commercially available silicon metal with a purity of 98% instead of silicon metal with a purity of 99.9% as the raw material.
比較例（ブランク試験）
塩化第２鉄を加えない以外は実施例４と全く同一の反応
条件で反応を行った。その後同様にして冷却、降圧後反
応液を分析した。反応液組成はトリクロロシラン３．４
モル％、四塩化ケイ素９６．６モル％となり塩化第２鉄
を加えないことにより、極端に反応は抑制されることが
分かった。塩化第２鉄が極めて有効な添加物であること
が判明した。Comparative Example (Blank Test) A reaction was carried out under exactly the same reaction conditions as in Example 4, except that ferric chloride was not added. Thereafter, the reaction solution was cooled and depressurized in the same manner, and the reaction solution was analyzed. The reaction solution composition is trichlorosilane 3.4
It was found that the reaction was extremely suppressed by not adding ferric chloride, which was 96.6 mol% of silicon tetrachloride. Ferric chloride has been found to be a very effective additive.
実施例 ５
実施例１〜４と同一のオートクレーブに、実施例４と同
一量の金属ケイ素（純度９８％）、金属銅粉末Ｂおよび
四塩化ケイ素と塩化第２鉄の代わりに各々塩化第１鉄（
ＦｅＣ１ｔ） 、五塩化バナジウム（ＶＣＩＳ） 、
三塩化バナジウム（ＶＣＩＳ） 、三塩化バナジル（
ＶＯＣＩｓ） 、臭化第２鉄（ＦｅＢｒｓ） 、三臭化
バナジウム（Ｖｌｒ３） ＋ ヨウ化第１鉄（ＦｅＴ
ｔ） をそれぞれ３７．５ｍｓ＋ｏｌ加え、２３０℃
で２．５時間反応を行った後同様に冷却降圧し反応液を
分析した。結果は第３表に示したようにいずれの鉄もし
くはバナジウムのハロゲン化物の添加物によっても好収
率が得られることがわかった。Example 5 Into the same autoclave as Examples 1 to 4, the same amounts of metallic silicon (purity 98%) as in Example 4, metallic copper powder B, and ferrous chloride in place of silicon tetrachloride and ferric chloride, respectively. (
FeClt), vanadium pentachloride (VCIS),
Vanadium trichloride (VCIS), vanadyl trichloride (
VOCIs), ferric bromide (FeBrs), vanadium tribromide (Vlr3) + ferrous iodide (FeT
t) for 37.5ms+ol each, and 230℃
After the reaction was carried out for 2.5 hours, the reaction solution was cooled and the pressure was lowered in the same manner, and the reaction solution was analyzed. As shown in Table 3, it was found that a good yield could be obtained with any iron or vanadium halide additive.
添加物 ＦｅＣ１゜ ＣＩｓ ｃｔｓ ＶＯＣｌ２ ｅＢｒ３ Ｂｒ２ ｅ１ｇAdditive FeC1゜ CIs cts VOCl2 eBr3 Br2 e1g
Claims (1)
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
並びに鉄及び／又はバナジウムのハロゲン化物の存在下
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 it is a heterogeneous solid phase reaction, and the gas-liquid-solid phase heterogeneous reaction is carried out in the presence of metallic copper and a halide of iron and/or vanadium. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24020186A JPS6395109A (en) | 1986-10-11 | 1986-10-11 | Production of trichlorosilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24020186A JPS6395109A (en) | 1986-10-11 | 1986-10-11 | Production of trichlorosilane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6395109A true JPS6395109A (en) | 1988-04-26 |
Family
ID=17055961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24020186A Pending JPS6395109A (en) | 1986-10-11 | 1986-10-11 | Production of trichlorosilane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6395109A (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 JP24020186A patent/JPS6395109A/en active Pending
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 |
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