JPH0472764B2 - - Google Patents
Info
- Publication number
- JPH0472764B2 JPH0472764B2 JP27194084A JP27194084A JPH0472764B2 JP H0472764 B2 JPH0472764 B2 JP H0472764B2 JP 27194084 A JP27194084 A JP 27194084A JP 27194084 A JP27194084 A JP 27194084A JP H0472764 B2 JPH0472764 B2 JP H0472764B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- trichlorosilane
- column
- distillation
- silicon tetrachloride
- 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.)
- Expired
Links
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 81
- 239000005052 trichlorosilane Substances 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 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 description 40
- 239000003054 catalyst Substances 0.000 claims description 40
- 239000005049 silicon tetrachloride Substances 0.000 claims description 40
- 238000004821 distillation Methods 0.000 claims description 34
- 238000007323 disproportionation reaction Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 17
- -1 silane compound Chemical class 0.000 claims description 15
- 229910000077 silane Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Chemical class 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Chemical class Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 239000011863 silicon-based powder Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 13
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 10
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 1
- 229910003923 SiC 4 Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OAGOUCJGXNLJNL-UHFFFAOYSA-N dimethylcyanamide Chemical compound CN(C)C#N OAGOUCJGXNLJNL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001293 incoloy Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、金属硅素粉末を流動床反応塔によつ
てトリクロルシランを合成し、得られたトリクロ
ルシランから不均斉化反応によりジクロルシラ
ン、モノクロルシラン、モノシラン等のシラン化
合物を連続的に取得するシラン化合物の連続的製
造法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention involves synthesizing trichlorosilane from metal silicon powder using a fluidized bed reaction column, and producing dichlorosilane and monochlorosilane by a disproportionation reaction from the obtained trichlorosilane. , relates to a continuous production method for silane compounds such as monosilane.
例えば、本発明に係るモノシランを製造する反
応式は次のように表わすことができる。 For example, the reaction formula for producing monosilane according to the present invention can be expressed as follows.
トリクロルシランの不均斉化反応で副生する四塩
化硅素は、前工程のトリクロルシラン合成反応工
程で循環される。全工程で、リーク等によりジク
ロルシラン、トリクロルシランあるいは四塩化硅
素等の塩素化硅素のロス分に相当する塩素分は、
塩化水素あるいは四塩化硅素としてトリクロルシ
ラン合成反応工程に補給される。 Silicon tetrachloride produced as a by-product in the disproportionation reaction of trichlorosilane is recycled in the previous trichlorosilane synthesis reaction step. In the entire process, the chlorine content corresponding to the loss of dichlorosilane, trichlorosilane, or silicon chloride such as silicon tetrachloride due to leakage, etc. is
It is supplied to the trichlorosilane synthesis reaction process as hydrogen chloride or silicon tetrachloride.
ジクロルシラン、モノクロルシラン及びモノシ
ラン等は半導体や太陽電池等の素子に使用される
高純度シリコンの原料として益々需要の増加が見
込まれており、特にジクロルシラン及びモノシラ
ンを大量に効率よく製造することが要望されてい
る。 Demand for dichlorosilane, monochlorosilane, monosilane, etc. is expected to increase as raw materials for high-purity silicon used in devices such as semiconductors and solar cells, and there is a particular demand for efficient production of dichlorosilane and monosilane in large quantities. ing.
（従来の技術）
従来から、クロルシラン類の不均斉化反応は公
知であり、その触媒については種々提案されてい
る。例えば、第３級アミン又は第４級アンモニウ
ムを含む網目状陰イオン交換樹脂、Ｎメチル２ピ
ロリドン、メチルイミダゾール、テトラメチエル
尿素、ジメチルシアナミド、テトラメチルグアニ
ジン、トリメチルシリルイミダゾール、ベンゾチ
アゾール、NNジメチルアセトアミド等があげら
れる。これらの触媒とトリクロルシランとを接触
させると、次の(1)式、(2)式及び(3)式の不均斉化反
応式に従つてジクロルシラン、モノクロルシラン
及びモノシランが生成する。(Prior Art) The disproportionation reaction of chlorosilanes has been known, and various catalysts have been proposed. Examples include network anion exchange resins containing tertiary amines or quaternary ammonium, N-methyl pyrrolidone, methylimidazole, tetramethylurea, dimethyl cyanamide, tetramethylguanidine, trimethylsilylimidazole, benzothiazole, N-dimethylacetamide, etc. It will be done. When these catalysts are brought into contact with trichlorosilane, dichlorosilane, monochlorosilane, and monosilane are produced according to the following disproportionation reaction formulas (1), (2), and (3).
2SiHC3→SiH2Ｃ2＋SiC4 (1)
2SiH2Ｃ2→SiH3Ｃ＋SiHC3 (2)
2SiH3Ｃ→SiH4＋SiH2Ｃ2 (3)
このようにして塩素原子の多い原料水素化塩化
硅素から塩素原子の少ないシラン化合物を取得す
ることができる。 2SiHC 3 →SiH 2 C 2 +SiC 4 (1) 2SiH 2 C 2 →SiH 3 C+SiHC 3 (2) 2SiH 3 C→SiH 4 +SiH 2 C 2 (3) In this way, the raw material containing many chlorine atoms is hydrogenated silicon chloride. A silane compound with few chlorine atoms can be obtained from.
さらに詳しく説明すると、例えば、触媒として
第３級アミンを含む陰イオン交換樹脂を充填した
固定床式の反応塔において、反応温度30〜200℃、
圧力１〜30気圧の条件下で一方の供給口より原料
トリクロルシランを供給すると、他方の排出口よ
りモノシラン、モノクロルシラン、ジクロルシラ
ン、トリクロルシラン及び四塩化硅素からなる反
応生成物が得られる。しかし前記不均斉化反応式
(1)、(2)及び(3)式は平衡反応であるので、例え反応
時間を大きくとつたとしても原料トリクロルシラ
ンの反応率は約10％、モノシラン生成率は約１％
と極めて小さい。従つて、工業的に製造するには
反応生成物を蒸留分離し、それを循環使用する際
に、反応塔および蒸留塔の運転に多大なエネルギ
ーを必要とする欠点があつた。 To explain in more detail, for example, in a fixed bed reaction tower packed with an anion exchange resin containing a tertiary amine as a catalyst, the reaction temperature is 30 to 200°C,
When the raw material trichlorosilane is supplied from one supply port under a pressure of 1 to 30 atmospheres, a reaction product consisting of monosilane, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride is obtained from the other outlet. However, the disproportionation reaction formula
Equations (1), (2), and (3) are equilibrium reactions, so even if the reaction time is increased, the reaction rate of the raw material trichlorosilane is about 10%, and the monosilane production rate is about 1%.
and extremely small. Therefore, for industrial production, when the reaction product is separated by distillation and recycled, there is a drawback that a large amount of energy is required to operate the reaction column and the distillation column.
（発明が解決しようとする問題点）
本発明は、以上の欠点を解決し、トリクロルシ
ランの原料生産からトリクロルシランよりも水素
原子の多い高純度シラン化合物の取得までの工程
を連続化したプロセスを開発したものである。(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks and provides a continuous process from the production of raw materials for trichlorosilane to the acquisition of a high-purity silane compound that has more hydrogen atoms than trichlorosilane. It was developed.
（問題点を解決するための手段）
すなわち、本発明は、次の第１〜３工程からな
るシラン化合物の連続的製造法である。(Means for Solving the Problems) That is, the present invention is a continuous method for producing a silane compound comprising the following first to third steps.
第１工程；
金属硅素粉末を充填してなる流動床反応塔に四
塩化硅素と水素の混合ガスを供給してトリクロル
シランを合成する工程。 First step: A step of synthesizing trichlorosilane by supplying a mixed gas of silicon tetrachloride and hydrogen to a fluidized bed reaction tower filled with metal silicon powder.
第２工程；
下記一般式で示される第３級脂肪族炭化水素置
換アミンと塩化水素との混合物又は反応生成物か
らなる不均斉化触媒を存在させてなり蒸留機能を
有する第１反応塔に、第１工程で得られたトリク
ロルシランを供給し、不均斉化反応と蒸留を行わ
せながら塔頂成分を取得する工程。 Second step: A first reaction column having a distillation function in which a disproportionation catalyst consisting of a mixture or reaction product of a tertiary aliphatic hydrocarbon-substituted amine and hydrogen chloride represented by the following general formula is present, A step of supplying the trichlorosilane obtained in the first step and obtaining a column top component while performing a disproportionation reaction and distillation.
第３工程；
下記一般式で示される第３級脂肪族炭化水素置
換アミンと塩化水素との混合物又は反応生成物か
らなる不均斉化触媒を存在させてなり蒸留機能を
有する第２反応塔に、第１反応塔で取得された塔
頂成分を供給し、不均斉化反応と蒸留を行わせな
がら塔頂成分を取得する工程。 Third step: A second reaction column having a distillation function in which a disproportionation catalyst consisting of a mixture or reaction product of a tertiary aliphatic hydrocarbon-substituted amine and hydrogen chloride represented by the following general formula is present, A step of supplying the top component obtained in the first reaction column and obtaining the top component while performing a disproportionation reaction and distillation.
（第３級脂肪族炭化水素置換アミンの一般式）
（但し、式中R1、R2、R3は脂肪族炭化水素基、
そのR1、R2及びR3の炭素数の和が10以上であり、
しかもそのR1、R2、R3はそれぞれ同種又は異種
のものである。）
以下さらに本発明を詳しく説明する。(General formula of tertiary aliphatic hydrocarbon-substituted amine) (However, in the formula, R 1 , R 2 , R 3 are aliphatic hydrocarbon groups,
The sum of the carbon numbers of R 1 , R 2 and R 3 is 10 or more,
Furthermore, R 1 , R 2 , and R 3 are of the same type or different types. ) The present invention will be further explained in detail below.
本発明の反応工程は、トリクロルシラン合成反
応（第１工程）と生成したトリクロルシランの不
均斉化反応（第２工程）とジクロルシランの不均
斉化反応（第３工程）から成り立つている。この
反応式は、それぞれ、(4)、(5)、(6)式で表わせる。 The reaction process of the present invention consists of a trichlorosilane synthesis reaction (first step), a disproportionation reaction of the produced trichlorosilane (second step), and a disproportionation reaction of dichlorosilane (third step). This reaction formula can be expressed by equations (4), (5), and (6), respectively.
3SiC4＋2H2＋Si→4SiHC3 (4)
5SiHC3→3SiH2Ｃ2＋3SiC4 (5)
3SiH2Ｃ2→SiH4＋2SiHC3 (6)
ここで、トリクロルシランの不均斉化反応で副
生する四塩化硅素は、第１工程のトリクロルシラ
ン合成反応に循環し、ジクロルシランの不均斉化
反応で副生するトリクロルシランは第２工程のト
リクロルシランの不均斉化反応に循環するので、
全工程を表わす反応式は(7)で表わされる。 3SiC 4 +2H 2 +Si→4SiHC 3 (4) 5SiHC 3 →3SiH 2 C 2 +3SiC 4 (5) 3SiH 2 C 2 →SiH 4 +2SiHC 3 (6) Here, Silicon chloride is recycled to the trichlorosilane synthesis reaction in the first step, and trichlorosilane, which is a by-product in the disproportionation reaction of dichlorosilane, is recycled to the disproportionation reaction of trichlorosilane in the second step.
The reaction formula representing the entire process is expressed by (7).
Si＋2H2→SiH4 (7)
以下、第１工程、第２工程、第３工程の順に、
さらに詳しく説明する。 Si+2H 2 →SiH 4 (7) Below, in the order of the first step, second step, and third step,
I will explain in more detail.
第１工程のトリクロルシラン合成反応は、原料
の金属硅素粉末を充填した流動床反応塔に四塩化
硅素と水素の混合ガスを供給することによつて行
われる。 The trichlorosilane synthesis reaction in the first step is carried out by supplying a mixed gas of silicon tetrachloride and hydrogen to a fluidized bed reaction tower filled with metal silicon powder as a raw material.
さらに説明すると、流動床反応塔には、粒子径
10〜1000μの金属硅素粉末が充填されており、下
部に設けた多孔板あるいはバルブキヤツプ等のガ
ス分散装置を通して四塩化硅素と水素の混合ガス
を吹込み反応させる。触媒としては、銅又は塩化
銅を使用し、反応温度300〜800℃、圧力０〜100
Kg／cm2Ｇ、反応器内に充填された金属硅素粒と反
応原料ガスとの接触時間は10〜100秒で行われる。
反応で得られた生成ガスを冷却すれば、トリクロ
ルシラン20〜30モル％程度を含むトリクロルシラ
ンと未反応四塩化硅素の混合溶液が得られる。 To explain further, the fluidized bed reactor has particle size
It is filled with metal silicon powder of 10 to 1000 microns, and a mixed gas of silicon tetrachloride and hydrogen is blown into it through a gas dispersion device such as a perforated plate or a valve cap installed at the bottom to cause a reaction. Copper or copper chloride is used as a catalyst, reaction temperature is 300-800℃, pressure is 0-100℃.
Kg/cm 2 G, and the contact time between the metal silicon particles filled in the reactor and the reaction raw material gas is 10 to 100 seconds.
By cooling the product gas obtained in the reaction, a mixed solution of trichlorosilane and unreacted silicon tetrachloride containing about 20 to 30 mol % of trichlorosilane can be obtained.
トリクロルシランと未反応四塩化硅素の混合溶
液は、蒸留塔でトリクロルシランを分離して第２
工程に供給される。なお分離された四塩化硅素は
トリクロルシラン合成反応に再使用される。 The mixed solution of trichlorosilane and unreacted silicon tetrachloride is separated from trichlorosilane in a distillation column and
Supplied to the process. The separated silicon tetrachloride is reused in the trichlorosilane synthesis reaction.
第２工程は、第１反応塔にトリクロルシランを
供給し不均斉化反応と蒸留を同時に行わせ、塔頂
からはトリクロルシランよりも水素原子の多いジ
クロルシランを主成分とする水素化塩化硅素を取
得する一方、塔底からは未反応トリクロルシラ
ン、四塩化硅素及び触媒の混合物を抜き取る工程
である。 In the second step, trichlorosilane is supplied to the first reaction column and the disproportionation reaction and distillation are carried out simultaneously, and hydrogenated silicon chloride whose main component is dichlorosilane, which has more hydrogen atoms than trichlorosilane, is obtained from the top of the column. Meanwhile, a mixture of unreacted trichlorosilane, silicon tetrachloride, and catalyst is extracted from the bottom of the column.
触媒としては、前記一般式で表わせる第３級脂
肪族炭化水素置換アミンと塩化水素ととの混合物
又は反応生成物を使用する。このような触媒は、
シラン化合物の不均斉化反応速度を大とし、か
つ、従来の触媒のように、シラン化合物と反応し
て系内を詰らせることも少ない。前記一般式で示
される第３級脂肪族炭化水素置換アミンを塩化水
素の割合は、前者98〜20モル％に対し後者２〜80
モル％とするのが望ましい。使用量はシラン化合
物に対して２〜50モル％程度である。以上の触媒
については、特願昭59−67488号明細書に詳述さ
れている。 As the catalyst, a mixture or reaction product of a tertiary aliphatic hydrocarbon-substituted amine represented by the above general formula and hydrogen chloride is used. Such a catalyst is
It increases the disproportionation reaction rate of the silane compound, and unlike conventional catalysts, it is less likely to react with the silane compound and clog the system. The proportion of hydrogen chloride in the tertiary aliphatic hydrocarbon-substituted amine represented by the above general formula is 98 to 20 mol% for the former and 2 to 80 mol% for the latter.
It is desirable to set it as mol%. The amount used is about 2 to 50 mol% based on the silane compound. The above catalysts are described in detail in Japanese Patent Application No. 59-67488.
第１反応塔は、蒸留塔形式であり、例えば、シ
ーブトレイやバブルキヤツプトレイ等で仕切られ
た段等、あるいはラシヒリングやポールリング等
の充填物を充填した充填塔である。これら蒸留機
能を有する反応塔であればどんな構造のものでも
よいが、本発明に係わるシラン化合物の不均斉化
反応が液相反応であるので、液ホールドアツプの
大きい反応塔が好ましい。 The first reaction column is in the form of a distillation column, for example, stages partitioned by sieve trays, bubble cap trays, etc., or a packed column filled with a packing such as a Raschig ring or a Pall ring. Any structure may be used as long as the reaction column has a distillation function, but since the disproportionation reaction of the silane compound according to the present invention is a liquid phase reaction, a reaction column with a large liquid hold-up is preferred.
反応温度は20〜300℃の範囲で行われる。20℃
未満では反応速度が低く不均斉化反応が実質的に
進行せず、また300℃をこえると第３級脂肪族炭
化水素置換アミンの熱分解が生じ易くなり好まし
くない。なお、本反応は沸騰状態で操作されるの
で上記反応温度に保つためには加圧する必要があ
り、ゲージ圧力で０〜40Kg／cm2Ｇ程度となる。 The reaction temperature ranges from 20 to 300°C. 20℃
If it is less than 300°C, the reaction rate is low and the disproportionation reaction does not substantially proceed, and if it exceeds 300°C, thermal decomposition of the tertiary aliphatic hydrocarbon-substituted amine tends to occur, which is not preferable. In addition, since this reaction is operated in a boiling state, it is necessary to pressurize the reaction temperature in order to maintain the above reaction temperature, and the gauge pressure is about 0 to 40 kg/cm 2 G.
第１反応塔の塔頂からは、ジクロルシランを主
成分とする水素化塩化硅素が得られる。一方、塔
底からは、未反応トリクロルシラン、四塩化硅素
及び触媒を含む混合物が抜き取られ、蒸発器で触
媒が分離される。分離された触媒は、第１反応塔
頂部に循環される。未反応トリクロルシラン及び
四塩化硅素等のシラン化合物はトリクロルシラン
蒸留塔でトリクロルシランと四塩化硅素に分離さ
れ、トリクロルシランは第１反応塔に循環され、
四塩化硅素はトリクロルシラン合成反応に循環さ
れる。 Hydrogenated silicon chloride containing dichlorosilane as a main component is obtained from the top of the first reaction column. On the other hand, a mixture containing unreacted trichlorosilane, silicon tetrachloride, and a catalyst is extracted from the bottom of the column, and the catalyst is separated in an evaporator. The separated catalyst is recycled to the top of the first reaction column. Silane compounds such as unreacted trichlorosilane and silicon tetrachloride are separated into trichlorosilane and silicon tetrachloride in a trichlorosilane distillation column, and trichlorosilane is recycled to the first reaction column,
Silicon tetrachloride is recycled to the trichlorosilane synthesis reaction.
第３工程は、第１反応塔の塔頂より取得された
ジクロルシランを主成分とする水素化塩化硅素を
第２反応塔に供給し、不均斉化反応と蒸留を行わ
せ、塔頂成分として、モノシランを主成分とする
シラン化合物を取得する一方、塔底からは、未反
応ジクロルシラン、副生したトリクロルシラン等
の水素化塩化硅素と触媒を含む混合物を抜き取る
工程である。 In the third step, hydrogenated silicon chloride containing dichlorosilane as a main component obtained from the top of the first reaction tower is supplied to the second reaction tower, where a disproportionation reaction and distillation are performed, and as a top component, This is a step in which a silane compound containing monosilane as a main component is obtained, while a mixture containing hydrogenated silicon chloride and a catalyst, such as unreacted dichlorosilane and by-produced trichlorosilane, is extracted from the bottom of the column.
触媒と第２反応塔の形式については、前述した
ものが使用される。反応温度は20〜300℃の範囲
で行われる。 Regarding the format of the catalyst and the second reaction column, those described above are used. The reaction temperature ranges from 20 to 300°C.
第２反応塔の塔頂からはモノシランを主成分と
するシラン化合物が連続的に取得される。一方、
塔底からは、未反応ジクロルシラン及び副生した
トリクロルシラン、モノクロルシランを含む水素
化塩化硅素と触媒の混合物が抜き取られるが、そ
れらは蒸留塔で分離され、触媒は第２反応塔頂部
に、また、ジクロルシラン及びトリクロルシラン
等の水素化塩化硅素は第１反応塔にそれぞれ循環
される。 A silane compound containing monosilane as a main component is continuously obtained from the top of the second reaction column. on the other hand,
A mixture of unreacted dichlorosilane and by-produced trichlorosilane and monochlorosilane containing hydrogenated silicon chloride and catalyst is extracted from the bottom of the column, but they are separated in a distillation column, and the catalyst is placed at the top of the second reaction column and , dichlorosilane, and trichlorosilane are each recycled to the first reaction column.
なお、第１反応塔より得られたジクロルシラン
を主成分とする水素化塩化硅素を直接第２反応塔
に供給せず、中間に未反応トリクロルシランを分
離する蒸留塔を設置し、トリクロルシランを除去
してから供給することもできる。 Note that the hydrogenated silicon chloride containing dichlorosilane as a main component obtained from the first reaction column is not directly supplied to the second reaction column, but a distillation column is installed in the middle to separate unreacted trichlorosilane to remove trichlorosilane. It can also be supplied afterwards.
以下、図面に従つてさらに説明する。 Further explanation will be given below with reference to the drawings.
図面は、本発明の実施例の製造工程を説明する
ブロツク図である。 The drawings are block diagrams illustrating the manufacturing process of an embodiment of the present invention.
硅素含量98.5重量％の金属硅素を粉砕して粒子
径100〜1000μの粉末としそれを配管１０よりト
リクロルシラン合成塔１に供給する。トリクロル
シラン合成塔１は、内径305mm、高さ4000mm、材
質インコロイ800の流動床反応塔で下部にガス分
散板を付滞しており、また、外部ヒーターにより
加熱出来るようになつている。四塩化硅素と水素
の原料ガスは、配管１６よりトリクロルシラン合
成塔１の下部より分散板を通して金属硅素中に吹
き込まれ、反応温度300〜800℃、圧力０〜100
Kg／cm2Ｇ程度にして運転すると金属硅素と接触反
応してトリクロルシランガス等が生成する。 Metallic silicon having a silicon content of 98.5% by weight is pulverized into a powder having a particle size of 100 to 1000 μm, which is supplied to the trichlorosilane synthesis tower 1 through a pipe 10. The trichlorosilane synthesis tower 1 is a fluidized bed reaction tower having an inner diameter of 305 mm, a height of 4000 mm, and made of Incoloy 800, and is equipped with a gas distribution plate at the bottom, and can be heated by an external heater. Raw material gases of silicon tetrachloride and hydrogen are blown into metal silicon from the lower part of the trichlorosilane synthesis tower 1 through a pipe 16 through a dispersion plate, at a reaction temperature of 300 to 800°C and a pressure of 0 to 100°C.
When operated at around Kg/cm 2 G, trichlorosilane gas and the like are produced by contact reaction with metal silicon.
このトリクロルシラン及び未反応四塩化硅素と
水素を含む反応生成ガスは、反応塔上部の配管１
３より取り出され、トリクロルシラン回収器２に
送られる。トリクロルシラン回収器２は、伝熱面
積２m2のステンレス製コンデンサー２基から構成
されており、１段目は20℃の冷水、２段目は−20
℃のエチレングリコール冷媒で冷却出来るように
なつている。反応生成ガスに含まれるトリクロル
シラン及び未反応四塩化硅素は凝縮し、液状混合
物として配管１７より回収される。一方、未凝縮
ガスである水素は配管１４より四塩化硅素蒸発器
３に送られる。 This reaction product gas containing trichlorosilane, unreacted silicon tetrachloride, and hydrogen is transferred to the pipe 1 at the top of the reaction tower.
3 and sent to the trichlorosilane recovery vessel 2. The trichlorosilane recovery unit 2 consists of two stainless steel condensers with a heat transfer area of 2m2 , the first stage is cold water at 20°C, and the second stage is -20°C cold water.
It can be cooled with ethylene glycol refrigerant at ℃. Trichlorosilane and unreacted silicon tetrachloride contained in the reaction product gas are condensed and recovered from the pipe 17 as a liquid mixture. On the other hand, hydrogen, which is an uncondensed gas, is sent to the silicon tetrachloride evaporator 3 through the pipe 14.
四塩化硅素蒸発器３は、伝熱面積１m2のステン
レス製蒸発器からなり、そのジヤケツトには温水
が循環されており、加温出来るようになつてい
る。そして、下部より水素を吹き込むと、四塩化
硅素は蒸発し、四塩化硅素と水素の混合ガスが得
られるようになつている。この四塩化硅素と水素
との混合比は四塩化硅素蒸発器３のジヤケツト温
度を調節することにより変えることが出来る。こ
の混合ガスに、水素を配管１２より補給し、さら
に塩化水素ガスを配管１１より補給して配管１６
よりトリクロルシラン合成塔１に循環される。 The silicon tetrachloride evaporator 3 consists of a stainless steel evaporator with a heat transfer area of 1 m 2 , and hot water is circulated through its jacket so that it can be heated. When hydrogen is blown from the bottom, silicon tetrachloride evaporates and a mixed gas of silicon tetrachloride and hydrogen is obtained. This mixing ratio of silicon tetrachloride and hydrogen can be changed by adjusting the jacket temperature of the silicon tetrachloride evaporator 3. This mixed gas is replenished with hydrogen from the pipe 12, and hydrogen chloride gas is further replenished from the pipe 11, and then the pipe 16
It is then recycled to the trichlorosilane synthesis tower 1.
トリクロルシラン回収器２より回収されたトリ
クロルシランと四塩化硅素の混合溶液は配管１７
よりトリクロルシラン蒸留塔４に供給される。ト
リクロルシラン蒸留塔４は、段数40段のシーブト
レイ塔で、塔頂よりトリクロルシランが回収さ
れ、塔底より四塩化硅素が分離回収される。この
回収四塩化硅素は配管１９より四塩化硅素蒸発器
３に戻される。トリクロルシラン蒸留塔４の塔頂
から得られたトリクロルシランは配管１８より第
１反応塔５に供給される。 The mixed solution of trichlorosilane and silicon tetrachloride recovered from the trichlorosilane recovery device 2 is transferred to the pipe 17.
The trichlorosilane is then supplied to the trichlorosilane distillation column 4. The trichlorosilane distillation column 4 is a sieve tray column with 40 plates, and trichlorosilane is recovered from the top of the column, and silicon tetrachloride is separated and recovered from the bottom of the column. This recovered silicon tetrachloride is returned to the silicon tetrachloride evaporator 3 through a pipe 19. Trichlorosilane obtained from the top of the trichlorosilane distillation column 4 is supplied to the first reaction column 5 through a pipe 18.
第１反応塔５は、径５インチ、段数12段のシー
ブトレイ塔で、塔の中央部にトリクロルシランが
供給され、塔頂より触媒が配管２２により循環さ
れる。 The first reaction tower 5 is a sieve tray tower with a diameter of 5 inches and 12 stages. Trichlorosilane is supplied to the center of the tower, and the catalyst is circulated through a pipe 22 from the top of the tower.
第１反応塔５では、不均斉化反応と蒸留による
分離が同時に起こり、不均斉化反応で生じたジク
ロルシラン等の低沸点成分は、塔頂より取得さ
れ、配管２０により第２反応塔７に供給される。
一方、不均斉化反応で副生した四塩化硅素及び未
反応トリクロルシランは塔底に移行し、塔底に付
設されたリボイラーより触媒と共に配管２１より
触媒分離器６に抜き取られる。 In the first reaction column 5, a disproportionation reaction and separation by distillation occur simultaneously, and low-boiling components such as dichlorosilane produced in the disproportionation reaction are obtained from the top of the column and supplied to the second reaction column 7 through a pipe 20. be done.
On the other hand, silicon tetrachloride and unreacted trichlorosilane, which are by-produced in the disproportionation reaction, migrate to the bottom of the tower and are extracted from a reboiler attached to the bottom of the tower together with the catalyst through a pipe 21 to a catalyst separator 6.
触媒分離器６は、ジヤケツトを付滞した攪拌槽
であり、ジヤケツトはスチームで加温出来るよう
になつている。トリクロルシラン及び四塩化硅素
は蒸発し、配管２３よりトリクロルシラン蒸留塔
４に循環される。一方、分離された触媒は配管２
２より再び第１反応塔５の塔頂に循環される。 The catalyst separator 6 is a stirring tank in which a jacket is stagnated, and the jacket can be heated with steam. Trichlorosilane and silicon tetrachloride are evaporated and circulated to the trichlorosilane distillation column 4 via piping 23. On the other hand, the separated catalyst is transferred to pipe 2
2 to the top of the first reaction column 5 again.
第１反応塔５の塔頂からは、ジクロルシランを
主成分とするシラン化合物が取得され、配管２０
により第２反応塔７に供給される。 From the top of the first reaction tower 5, a silane compound containing dichlorosilane as a main component is obtained, and the pipe 20
is supplied to the second reaction tower 7.
第２反応塔７は、径４インチ、段数10段のシー
ブトレイ塔であり、配管２６より触媒が循環され
る。第２反応塔でも不均斉化反応と蒸留による分
離が同時に起こり、不均斉化反応で生じたモノシ
ランを主成分とするシラン化合物は塔頂より取得
され、副生したトリクロルシラン及び未反応ジク
ロルシランは塔底より触媒と共に配管２５より触
媒分離器８に抜き取られる。触媒分離器８でジク
ロルシラン及びトリクロルシランは蒸発し配管２
９より第１反応塔５に循環される。 The second reaction tower 7 is a sieve tray tower with a diameter of 4 inches and 10 stages, and the catalyst is circulated through a pipe 26. In the second reaction column, the disproportionation reaction and separation by distillation occur simultaneously, and the silane compound containing monosilane as the main component produced in the disproportionation reaction is obtained from the top of the column, and the by-produced trichlorosilane and unreacted dichlorosilane are removed from the column. The catalyst is extracted from the bottom along with the catalyst through the pipe 25 into the catalyst separator 8. Dichlorosilane and trichlorosilane are evaporated in the catalyst separator 8 and transferred to the pipe 2.
9 to the first reaction tower 5.
第２反応塔７の塔頂から得られたモノシラン等
の低沸点成分は配管２４よりモノシラン蒸留塔９
に供給される。モノシラン蒸留塔９は段数100段
のシーブトレイ塔であり、そこで第２反応塔より
同伴されるジクロルシラン、モノクロシラン及び
ジボラン、ホスフイン等の不純物質が蒸留除去さ
れる。これらは配管２８により第２反応等７に循
環される。 The low-boiling components such as monosilane obtained from the top of the second reaction column 7 are sent to the monosilane distillation column 9 through a pipe 24.
supplied to The monosilane distillation column 9 is a sieve tray column with 100 plates, in which impurities such as dichlorosilane, monochlorosilane, diborane, and phosphine entrained from the second reaction column are removed by distillation. These are circulated to the second reaction etc. 7 via piping 28.
（実施例）
金属銅粒５重量％を含有してなる粒子径100〜
800μの金属硅素粉末を400ｇ／hrの速度で流動床
トリクロルシラン合成塔１に供給する一方、四塩
化硅素蒸発器３より水素：四塩化硅素のモル比が
２：１である混合ガスを235／minの流量で吹
込み、圧力0.2Kg／cm2Ｇ、温度550℃に保ち、トリ
クロルシランを合成した。トリクロルシラン回収
器２からはトリクロルシラン20.2モル％、未反応
四塩化硅素79.8モル％の混合液が36Kg／hrの流量
で得られた。これをトリクロルシラン蒸留塔４に
供給した。(Example) Particle size 100~ containing 5% by weight of metallic copper particles
Metal silicon powder of 800 μm was fed to the fluidized bed trichlorosilane synthesis tower 1 at a rate of 400 g/hr, while a mixed gas with a hydrogen:silicon tetrachloride molar ratio of 2:1 was fed from the silicon tetrachloride evaporator 3 to 235/hr. Trichlorosilane was synthesized by blowing at a flow rate of min., maintaining the pressure at 0.2 Kg/cm 2 G and the temperature at 550°C. A mixed liquid containing 20.2 mol % of trichlorosilane and 79.8 mol % of unreacted silicon tetrachloride was obtained from the trichlorosilane recovery vessel 2 at a flow rate of 36 kg/hr. This was supplied to the trichlorosilane distillation column 4.
トリクロルシラン蒸留塔４は圧力１Kg／cm2Ｇ、
塔頂コンデンサーの還流比を３で運転した。塔頂
からは四塩化硅素0.4モル％を含むトリクロルシ
ランが10Kg／hrの速度で取得され、それを第１反
応塔５に供給した。一方、塔底からは、トリクロ
ルシラン0.5モル％を含む四塩化硅素を35.5Kg／
hrの速度で四塩化硅素蒸発器３に抜き取つた。 Trichlorosilane distillation column 4 has a pressure of 1 Kg/cm 2 G,
The overhead condenser was operated at a reflux ratio of 3. Trichlorosilane containing 0.4 mol% of silicon tetrachloride was obtained from the top of the column at a rate of 10 kg/hr, and was supplied to the first reaction column 5. On the other hand, from the bottom of the column, 35.5 kg/silicon tetrachloride containing 0.5 mol% of trichlorosilane was collected.
It was extracted into silicon tetrachloride evaporator 3 at a rate of hr.
第１反応塔５は、圧力５Kg／cm2Ｇとし、触媒と
して、トリｎオクチルアミン：塩化水素のモル比
80：20のものを2.5／hrの流量で供給し、還流
比５にして運転したところ、モル割合で、モノシ
ラン５％、モノクロルシラン16％、ジクロルシラ
ン48％、トリクロルシラン31％のシラン化合物が
取得され、それを第２反応塔７に供給した。一
方、塔底からは、トリクロルシラン、四塩化硅素
及び触媒の混合液が回収され、それを温度110℃
に保たれた触媒分離器６に抜き取り、トリクロル
シランと四塩化硅素を蒸発回収してトリクロルシ
ラン蒸留塔４に、循環した。触媒分離器６で分離
された触媒は第１反応塔５の塔頂に循環した。 The first reaction tower 5 has a pressure of 5 Kg/cm 2 G and a molar ratio of trin-octylamine:hydrogen chloride as a catalyst.
When 80:20 was supplied at a flow rate of 2.5/hr and operated at a reflux ratio of 5, silane compounds with a molar ratio of 5% monosilane, 16% monochlorosilane, 48% dichlorosilane, and 31% trichlorosilane were obtained. and supplied it to the second reaction column 7. On the other hand, a mixed solution of trichlorosilane, silicon tetrachloride, and catalyst was recovered from the bottom of the tower, and it was heated to 110°C.
The trichlorosilane and silicon tetrachloride were collected by evaporation and recycled to the trichlorosilane distillation column 4. The catalyst separated in the catalyst separator 6 was circulated to the top of the first reaction tower 5.
第２反応塔７は、圧力５Kg／cm2Ｇとし、触媒
は、第１反応塔で使用したものと同一なものを２
／hrの流量で循環し、還流比５で運転したとこ
ろ、モル割合で、モノシラン76％、モノクロルシ
ラン13％、ジクロルシラン11％のシラン化合物が
670ｇ／hrで取得され、それをモノシラン蒸留塔
９に供給した。一方、塔底からは、高沸点シラン
化合物と触媒の混合液が回収され、触媒分離器８
で触媒を分離して塔頂に戻すと共に、モノクロル
シラン、ジクロルシラン、トリクロルシランの高
沸点シラン化合物は、第１反応塔に循環した。 The second reaction tower 7 has a pressure of 5 kg/cm 2 G, and the catalyst is the same as that used in the first reaction tower.
When circulating at a flow rate of /hr and operating at a reflux ratio of 5, the molar ratio of silane compounds was 76% monosilane, 13% monochlorosilane, and 11% dichlorosilane.
670 g/hr was obtained and fed to the monosilane distillation column 9. On the other hand, a mixed liquid of a high-boiling silane compound and a catalyst is recovered from the bottom of the tower, and is collected in a catalyst separator 8.
The catalyst was separated and returned to the top of the column, and high-boiling silane compounds such as monochlorosilane, dichlorosilane, and trichlorosilane were circulated to the first reaction column.
モノシラン蒸留塔９は、圧力30Kg／cm2Ｇ、還流
比10で運転したところ、モノシラン100％の高純
度モノシランが370ｇ／hr（トリクロルシランに対
するモノシラン生成率は約15％である）の割合で
得られた。 When the monosilane distillation column 9 was operated at a pressure of 30 kg/cm 2 G and a reflux ratio of 10, high purity monosilane containing 100% monosilane was obtained at a rate of 370 g/hr (the monosilane production rate relative to trichlorosilane is approximately 15%). It was done.
なお、補給水素と補給塩化水素は、それぞれ
6.5／minと11／minの割合で、配管１２と１
１により供給した。 In addition, make-up hydrogen and make-up hydrogen chloride are each
Pipes 12 and 1 at a rate of 6.5/min and 11/min.
1.
（発明の効果）
本発明によれば、金属硅素からシラン化合物が
収率よく、しかもエネルギーの消費が少なく低コ
ストで連続的に製造することができる。(Effects of the Invention) According to the present invention, a silane compound can be continuously produced from metal silicon in good yield and at low cost with less energy consumption.
図面は本発明の実施例の製造工程を説明するブ
ロツク図である。
符号、１……トリクロルシラン合成塔、２……
トリクロルシラン回収器、３……四塩化硅素蒸発
器、４……トリクロルシラン蒸留塔、５……第１
反応塔、６……触媒分離器、７……第２反応塔、
８……触媒分離器、９……モノシラン蒸留塔。
The drawings are block diagrams illustrating the manufacturing process of an embodiment of the present invention. Code, 1...trichlorosilane synthesis tower, 2...
Trichlorosilane recovery device, 3... silicon tetrachloride evaporator, 4... trichlorosilane distillation column, 5... first
Reaction tower, 6... Catalyst separator, 7... Second reaction tower,
8... Catalyst separator, 9... Monosilane distillation column.
Claims (1)
続的製造法。 第１工程； 金属硅素粉末を充填してなる流動床反応塔に四
塩化硅素と水素の混合ガスを供給してトリクロル
シランを合成する工程。 第２工程； 下記一般式で示される第３級脂肪族炭化水素置
換アミンと塩化水素との混合物又は反応生成物か
らなる不均斉化触媒を存在させてなり蒸留機能を
有する第１反応塔に、第１工程で得られたトリク
ロルシランを供給し、不均斉化反応と蒸留を行わ
せながら塔頂成分を取得する工程。 第３工程； 下記一般式で示される第３級脂肪族炭化水素置
換アミンと塩化水素との混合物又は反応生成物か
らなる不均斉化触媒を存在させてなり蒸留機能を
有する第２反応塔に、第１反応塔で取得された塔
頂成分を供給し、不均斉化反応と蒸留を行わせな
がら塔頂成分を取得する工程。 （第３級脂肪族炭化水素置換アミンの一般式） （但し、式中R1、R2、R3は脂肪族炭化水素基、
そのR1、R2及びR3の炭素数の和が10以上であり、
しかもそのR1、R2、R3はそれぞれ同種又は異種
のものである。）[Scope of Claims] 1. A method for continuously producing a silane compound comprising the following 1st to 3rd steps. First step: A step of synthesizing trichlorosilane by supplying a mixed gas of silicon tetrachloride and hydrogen to a fluidized bed reaction tower filled with metal silicon powder. Second step: A first reaction column having a distillation function in which a disproportionation catalyst consisting of a mixture or reaction product of a tertiary aliphatic hydrocarbon-substituted amine and hydrogen chloride represented by the following general formula is present, A step of supplying the trichlorosilane obtained in the first step and obtaining a column top component while performing a disproportionation reaction and distillation. Third step: A second reaction column having a distillation function in which a disproportionation catalyst consisting of a mixture or reaction product of a tertiary aliphatic hydrocarbon-substituted amine and hydrogen chloride represented by the following general formula is present, A step of supplying the top component obtained in the first reaction column and obtaining the top component while performing a disproportionation reaction and distillation. (General formula of tertiary aliphatic hydrocarbon-substituted amine) (However, in the formula, R 1 , R 2 , R 3 are aliphatic hydrocarbon groups,
The sum of the carbon numbers of R 1 , R 2 and R 3 is 10 or more,
Furthermore, R 1 , R 2 , and R 3 are of the same type or different types. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27194084A JPS61151017A (en) | 1984-12-25 | 1984-12-25 | Continuous production of silane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27194084A JPS61151017A (en) | 1984-12-25 | 1984-12-25 | Continuous production of silane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61151017A JPS61151017A (en) | 1986-07-09 |
| JPH0472764B2 true JPH0472764B2 (en) | 1992-11-19 |
Family
ID=17506955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27194084A Granted JPS61151017A (en) | 1984-12-25 | 1984-12-25 | Continuous production of silane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61151017A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004045245B4 (en) * | 2004-09-17 | 2007-11-15 | Degussa Gmbh | Apparatus and process for the production of silanes |
| DE102007028254A1 (en) * | 2007-06-20 | 2008-12-24 | Wacker Chemie Ag | Process for the preparation of SiH-containing silanes |
| JP5444839B2 (en) * | 2008-05-28 | 2014-03-19 | 三菱マテリアル株式会社 | Trichlorosilane production apparatus and production method |
| CN102092720B (en) * | 2009-02-13 | 2013-03-27 | 李明成 | Continuous preparation device for high-purity silane gas |
| EP2426088A1 (en) | 2010-09-03 | 2012-03-07 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process for producing monosilane from dichlorosilane |
-
1984
- 1984-12-25 JP JP27194084A patent/JPS61151017A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61151017A (en) | 1986-07-09 |
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