JPH0829928B2 - Continuous production method of silanes - Google Patents
Continuous production method of silanesInfo
- Publication number
- JPH0829928B2 JPH0829928B2 JP7968287A JP7968287A JPH0829928B2 JP H0829928 B2 JPH0829928 B2 JP H0829928B2 JP 7968287 A JP7968287 A JP 7968287A JP 7968287 A JP7968287 A JP 7968287A JP H0829928 B2 JPH0829928 B2 JP H0829928B2
- Authority
- JP
- Japan
- Prior art keywords
- silanes
- ammonia
- reaction
- reaction system
- reactor
- 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 - Lifetime
Links
- 150000004756 silanes Chemical class 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 12
- 238000010924 continuous production Methods 0.000 title claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 24
- -1 ammonium halide Chemical class 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021338 magnesium silicide Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 description 18
- 239000007789 gas Substances 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 206010010144 Completed suicide Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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、シラン類の連続的製造方法に関し、更に詳
しくは、半導体、太陽電池及び感光体ドラム等の原料と
して有用なモノシラン、ジシラン及びトリシラン等のシ
ラン類の経済的安価な製造方法に関するものである。TECHNICAL FIELD The present invention relates to a continuous production method of silanes, and more specifically, to monosilane, disilane, trisilane and the like which are useful as raw materials for semiconductors, solar cells, photosensitive drums and the like. The present invention relates to an economical and inexpensive method for producing silanes.
従来技術 ケイ化マグネシウムとハロゲン化アンモニウムの混合
物に液体アンモニアを添加してシランガスを発生せし
め、これをハロゲン化水素酸で洗浄してシランを得るこ
とは特公昭42−14708号に開示されている。2. Description of the Related Art It is disclosed in Japanese Patent Publication No. 42-14708 that liquid ammonia is added to a mixture of magnesium silicide and ammonium halide to generate silane gas, which is washed with hydrohalic acid to obtain silane.
又、アンモニアを含有するシランの蒸留精製法（特公
昭42−12061号）においては、アンモニアの融点が−77
℃であるため大気圧付近での蒸留ではアンモニアの固化
堆積が生じるので、蒸留圧力を３気圧以上に保つ方法が
行われている。Further, in the distillation purification method of silane containing ammonia (Japanese Patent Publication No. Sho 42-12061), the melting point of ammonia is -77.
Since the solidification and deposition of ammonia occurs in the distillation near atmospheric pressure because it is at 0 ° C, a method of keeping the distillation pressure at 3 atm or more is performed.
発明が解決しようとする問題点 しかしながら、これらの方法によれば生成したシラン
中に含まれる原料成分及び反応器での反応残渣を再利用
することなく無駄に廃棄しており、それに伴う処理設備
を設ける必要がある。Problems to be Solved by the Invention However, according to these methods, the raw material components contained in the produced silane and the reaction residue in the reactor are wastefully discarded without being reused, and the treatment equipment accompanying it is discarded. It is necessary to provide.
また、アンモニアとシラン類の分離に際しては、３気
圧以上に蒸留圧力を保持することから自然発火性の有る
シラン類の漏洩に細心の注意が必要であるばかりかシラ
ン類の分解を伴う。従って安全上常圧でアンモニアを分
離、且つ、経済的にシラン類を高収率で収得出来る製造
方法が望まれるところである。Further, when the ammonia and the silanes are separated, since the distillation pressure is maintained at 3 atm or higher, it is necessary to pay close attention to the leakage of the silanes which are pyrophoric, and the silanes are decomposed. Therefore, for safety, it is desired to provide a production method capable of separating ammonia at atmospheric pressure and economically obtaining silanes in a high yield.
問題点を解決するための手段 本発明者らは、鋭意研究を行い本発明を完成するに到
ったものである。Means for Solving the Problems The inventors of the present invention have made extensive studies and completed the present invention.
すなわち、本発明は、ケイ化マグネシウムとハロゲン
化アンモニウムを液体アンモニアの存在下に反応せし
め、反応生成ガスを冷却凝縮して非凝縮分として得られ
たシラン類を更にハロゲン化水素酸で洗浄してシラン類
を取り出し、かつ反応系より反応残渣を取り出して連続
的にシラン類を製造する方法であって、反応系より抜き
出される反応残渣を熱分解してアンモニアガスを得、該
得られたアンモニアガスを該反応系に導入すると共に、
シラン類を洗浄した洗浄液より分離したハロゲン化アン
モニウムを該反応系に循環することを特徴とするシラン
類の連続的製造方法、を要旨とするものである。That is, in the present invention, magnesium suicide and ammonium halide are reacted in the presence of liquid ammonia, the reaction product gas is cooled and condensed, and silanes obtained as a non-condensed component are further washed with hydrohalic acid. A method for continuously producing silanes by taking out silanes and taking out a reaction residue from the reaction system, wherein the reaction residue taken out from the reaction system is thermally decomposed to obtain ammonia gas, and the obtained ammonia is obtained. Introducing gas into the reaction system,
It is a gist of a continuous production method of silanes, characterized in that ammonium halide separated from a cleaning liquid in which silanes are washed is circulated in the reaction system.
図面の説明 本発明の方法を図面により更に詳細に説明する。第１
図は、本発明のシラン類の連続的製造方法の一実施例を
示すフロー図である。DESCRIPTION OF THE DRAWINGS The method of the present invention will be described in more detail with reference to the drawings. First
FIG. 1 is a flow chart showing an embodiment of the continuous silane production method of the present invention.
ケイ素含有合金例えばケイ化マグネシウムと、塩化ア
ンモニウムや臭化アンモニウムのごときハロゲン化アン
モニウムが各々配管（10）、（11）を介して混合層
（８）に供給され、ここで混合して配管（12）より反応
器（１）に供給する。配管（13）より液体アンモニアも
該反応器（１）に供給し混煉することよりシラン類を発
生させる。反応は発熱反応であり、反応熱はアンモニア
の蒸発潜熱により除去される。反応器（１）から発生す
る反応生成ガスであるシラン類の大部分と反応熱によっ
て蒸発したアンモニアは配管（15）を介し第１凝縮器
（３）に送られる。反応残渣は配管（14）よりハロゲン
化マグネシウムのアンモニウム塩と少量のシラン類が液
体アンモニアの泥状物として排出され熱分解器（２）に
導入される。該熱分解器（２）で約300℃に加熱された
ハロゲン化マグネシウムのアンモニウム塩は熱分解され
てアンモニアガスを発生する。泥状物と同伴してきたシ
ラン類及び該発生アンモニアは共に配管（16）より回収
され、反応器からの反応生成ガスと合流して第１凝縮器
（３）に導入され約−50℃に冷却される。ここで凝縮し
た大部分のアンモニアは反応器（１）に循環使用され
る。Silicon-containing alloys such as magnesium silicide and ammonium halides such as ammonium chloride and ammonium bromide are supplied to the mixing layer (8) via the pipes (10) and (11), respectively, and mixed there to form the pipe (12). ) To reactor (1). Liquid ammonia is also supplied to the reactor (1) through the pipe (13) and mixed to generate silanes. The reaction is exothermic, and the heat of reaction is removed by the latent heat of vaporization of ammonia. Most of the silanes, which are reaction product gases generated from the reactor (1), and ammonia evaporated by the heat of reaction are sent to the first condenser (3) via the pipe (15). From the reaction residue, the ammonium salt of magnesium halide and a small amount of silanes are discharged as a sludge of liquid ammonia through the pipe (14) and introduced into the pyrolyzer (2). The ammonium salt of magnesium halide heated to about 300 ° C. in the pyrolyzer (2) is pyrolyzed to generate ammonia gas. The silanes and the generated ammonia that have been entrained with the muddy substance are both collected from the pipe (16), merged with the reaction product gas from the reactor and introduced into the first condenser (3), and cooled to about -50 ° C. To be done. Most of the ammonia condensed here is recycled to the reactor (1).
一方未凝縮ガスのシラン類と余剰のアンモニアは、配
管（17）を通り吸収塔（４）に導入され、配管（18）よ
り供給されるハロゲン化水素酸で洗浄され余剰のアンモ
ニアとジボラン等の不純物が除去される。該吸収塔
（４）で除去された余剰のアンモニアは、ハロゲン化ア
ンモニウム水溶液として配管（20）より排出し、晶出器
（５）に回収される。該晶出器（５）で分離されたハロ
ゲン化アンモニウムは混合層（８）へ送られ更に反応器
（１）へと循環使用される。On the other hand, uncondensed silanes and excess ammonia are introduced into the absorption tower (4) through the pipe (17) and washed with hydrohalic acid supplied from the pipe (18) to remove excess ammonia and diborane. Impurities are removed. The excess ammonia removed in the absorption tower (4) is discharged as an ammonium halide aqueous solution from the pipe (20) and is collected in the crystallizer (5). The ammonium halide separated in the crystallizer (5) is sent to the mixed layer (8) and further recycled to the reactor (1).
吸収塔（４）から不純物の除去された水分を含むシラ
ン類は、配管（19）より脱水塔（６）に導入し除湿され
た後配管（９）を介し第２凝縮器（７）に送られ高純度
のシラン類が凝縮回収される。The moisture-containing silanes from which impurities have been removed from the absorption tower (4) are introduced into the dehydration tower (6) from the pipe (19) and dehumidified, and then sent to the second condenser (7) via the pipe (9). The high-purity silanes are condensed and recovered.
発明の効果 本発明の方法によれば、反応による反応熱は反応生成
ガスに同伴して取り出されるアンモニアの蒸発潜熱で相
殺され且つ、反応に必要とするアンモニアは常圧で凝縮
回収される。EFFECTS OF THE INVENTION According to the method of the present invention, the heat of reaction due to the reaction is offset by the latent heat of vaporization of ammonia taken out along with the reaction product gas, and the ammonia required for the reaction is condensed and recovered at atmospheric pressure.
更に、反応器から取り出される反応残渣を熱分解する
ことで、シラン類を含むアンモニアとハロゲン化マグネ
シウムとに分離され、該分離されたハロゲン化マグネシ
ムは、発火性のシラン類が存在しない状態で取り出され
るため、安全で、極めて有利な方法である。Further, by thermally decomposing the reaction residue taken out from the reactor, it is separated into ammonia containing silanes and magnesium halide, and the separated halogenated magnesium is taken out in the absence of pyrophoric silanes. Therefore, it is a safe and extremely advantageous method.
また、未凝縮の反応生成ガスを、反応に用いるハロゲ
ン化アンモニウムと同じハロゲンを持つハロゲン化水素
酸で洗浄することにより、ハロゲン化アンモニウムも回
収し反応器へ循環することから、実質上ハロゲン化水素
酸だけの供給で反応が行えるので、極めて経済的なシラ
ンの製造方法でありその産業上の利用可能性は大なると
云わざるを得ない。In addition, by washing the uncondensed reaction product gas with hydrohalic acid having the same halogen as the ammonium halide used in the reaction, the ammonium halide is also recovered and circulated to the reactor, so that it is substantially hydrogen halide. Since the reaction can be carried out by supplying only the acid, it is a very economical method for producing silane, and it must be said that its industrial applicability is great.
実施例 以下実施例により本発明を更に具体的に説明する。EXAMPLES The present invention will be described in more detail with reference to the following examples.
実施例１ ケイ化マグネシウム500g/Hと塩化アンモニウム1420g/
Hを混合層（８）にて混合し、次いで反応器（１）に連
続供給する。同時に液体アンモニアを5950g/Hも反応器
に供給しながら約１時間混煉する。モノシラン160g、ジ
シラン10gを含むアンモニアガス1450kgが反応器（１）
より発生し、次の第１凝縮器（３）に送られる。反応器
（１）より排出される反応残渣は、塩化マグネシウム12
60g/Hとシラン類を含む液体アンモニア4490g/Hのスラリ
ーであり、該スラリーが熱分解器（２）に送られ、300
℃で加熱分解される。発生したシラン類を含む4490g/H
のアンモニアガスは、該熱分解器（２）を出て該反応器
（１）より発生した反応生成ガスを混合されて第１凝縮
器（３）に送られる。第１凝縮器（３）に送られて来た
反応生成ガス及び熱分解生成ガスは、約−50℃で冷却凝
縮される。凝縮した液体アンモニアは5950g/Hで上記反
応器（１）に循環する。第１凝縮器（３）を出たシラン
類と余剰のアンモニアを含む未凝縮ガスは吸収塔（４）
に送られ、35％の塩酸3000g/Hで洗浄されることによ
り、余剰のアンモニアとジボラン等の不純物が除去され
て塩化アンモニウム水溶液として晶出器（５）に回収さ
れる。回収分離した塩化アンモニウムは1520g/Hで前記
混合層（８）へ循環使用する。一方、塩酸で洗浄されて
不純物の除去された水分を含む未凝縮ガスは、脱水塔
（６）更には第２凝縮器（７）を通り脱水されたモノシ
ラン160g/H及びジシラン10g/Hが凝縮回収された。この
時の収率はケイ素基準で各々76％、５％であった。Example 1 Magnesium silicide 500 g / H and ammonium chloride 1420 g / H
H is mixed in the mixing layer (8) and then continuously fed to the reactor (1). At the same time, 5950 g / H of liquid ammonia is also fed to the reactor and mixed for about 1 hour. 1450 kg of ammonia gas containing 160 g of monosilane and 10 g of disilane is the reactor (1)
Generated, and sent to the next first condenser (3). The reaction residue discharged from the reactor (1) is magnesium chloride 12
A slurry of 60 g / H and 4490 g / H of liquid ammonia containing silanes, the slurry being sent to the pyrolyzer (2),
It is decomposed by heating at ℃. 4490g / H including generated silanes
The ammonia gas of 1 is discharged from the pyrolyzer (2), mixed with the reaction product gas generated from the reactor (1), and sent to the first condenser (3). The reaction product gas and the thermal decomposition product gas sent to the first condenser (3) are cooled and condensed at about -50 ° C. The condensed liquid ammonia is circulated to the reactor (1) at 5950 g / H. The uncondensed gas containing the silanes and the surplus ammonia discharged from the first condenser (3) is absorbed in the absorption tower (4).
And is washed with 3000 g / H of 35% hydrochloric acid to remove excess ammonia and impurities such as diborane, and is recovered in the crystallizer (5) as an ammonium chloride aqueous solution. The recovered and separated ammonium chloride is recycled at 1520 g / H to the mixed layer (8). On the other hand, the uncondensed gas containing water, which has been washed with hydrochloric acid to remove impurities, passes through the dehydration tower (6) and the second condenser (7) to condense dehydrated monosilane 160 g / H and disilane 10 g / H. Recovered. The yields at this time were 76% and 5%, respectively, based on silicon.
第１図は、本発明のシラン類の連続的製造方法の一実施
例を示すフローシート図である。 図において、 （１）……反応器 （２）……熱分解器 （３）……第１凝縮器 （４）……吸収塔 （５）……晶出器 （６）……脱水塔 （７）……第２凝縮器 （８）……混合層 （10）……ケイ化マグネシウム供給配管 （11）……ハロゲン化アンモニウム供給配管 （13）……液体アンモニア供給配管 （18）……ハロゲン化水素酸供給配管FIG. 1 is a flow sheet diagram showing an example of the continuous method for producing silanes of the present invention. In the figure, (1) ... Reactor (2) ... Pyrolyzer (3) ... First condenser (4) ... Absorption tower (5) ... Crystallizer (6) ... Dehydration tower ( 7) …… Second condenser (8) …… Mixed layer (10) …… Magnesium silicide supply pipe (11) …… Ammonium halide supply pipe (13) …… Liquid ammonia supply pipe (18) …… Halogen Hydrofluoric acid supply pipe
Claims (1)
ウムを液体アンモニアの存在下に反応せしめ、反応生成
ガスを冷却凝縮して非凝縮分として得られたシラン類を
更にハロゲン化水素酸で洗浄してシラン類を取り出し、
かつ反応系より反応残渣を取り出して連続的にシラン類
を製造する方法であって、反応系より抜き出される反応
残渣を熱分解してアンモニアガスを得、該得られたアン
モニアガスを該反応系に導入すると共に、シラン類を洗
浄した洗浄液より分離したハロゲン化アンモニウムを該
反応系に循環することを特徴とするシラン類の連続的製
造方法。1. A silane obtained by reacting magnesium silicide with ammonium halide in the presence of liquid ammonia, cooling and condensing the reaction product gas to obtain non-condensed silanes, and further washing with hydrohalic acid. Take out the kind
And a method for continuously producing silanes by taking out a reaction residue from the reaction system, wherein the reaction residue extracted from the reaction system is thermally decomposed to obtain ammonia gas, and the obtained ammonia gas is used as the reaction system. A continuous production method of silanes, which comprises introducing into the reaction system and circulating ammonium halide separated from a cleaning liquid in which the silanes are washed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7968287A JPH0829928B2 (en) | 1987-04-02 | 1987-04-02 | Continuous production method of silanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7968287A JPH0829928B2 (en) | 1987-04-02 | 1987-04-02 | Continuous production method of silanes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63248711A JPS63248711A (en) | 1988-10-17 |
| JPH0829928B2 true JPH0829928B2 (en) | 1996-03-27 |
Family
ID=13696971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7968287A Expired - Lifetime JPH0829928B2 (en) | 1987-04-02 | 1987-04-02 | Continuous production method of silanes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0829928B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110395736B (en) * | 2018-04-25 | 2023-02-03 | 台湾特品化学股份有限公司 | Catalyst-promoted silane reaction generation and a system for full recovery of process by-products |
| CN115044101B (en) * | 2022-05-19 | 2023-06-30 | 湖北华欣有机硅新材料有限公司 | Production process and production device of composite silane |
-
1987
- 1987-04-02 JP JP7968287A patent/JPH0829928B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63248711A (en) | 1988-10-17 |
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