JP3324922B2 - Method for producing silicon trichloride - Google Patents
Method for producing silicon trichlorideInfo
- Publication number
- JP3324922B2 JP3324922B2 JP33475395A JP33475395A JP3324922B2 JP 3324922 B2 JP3324922 B2 JP 3324922B2 JP 33475395 A JP33475395 A JP 33475395A JP 33475395 A JP33475395 A JP 33475395A JP 3324922 B2 JP3324922 B2 JP 3324922B2
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- Japan
- Prior art keywords
- weight
- aluminum
- tcs
- iron
- 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.)
- Expired - Lifetime
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、三塩化ケイ素の製
造方法に関する。さらに詳しくは高い選択率で三塩化ケ
イ素を製造する方法に関する。[0001] The present invention relates to a method for producing silicon trichloride. More specifically, the present invention relates to a method for producing silicon trichloride with high selectivity.
【０００２】[0002]
【従来の技術】三塩化ケイ素（以下、ＴＣＳと略す）
は、多結晶シリコン製造原料として有用な化合物であ
る。一般に、ＴＣＳは金属ケイ素と塩化水素を反応させ
ることにより製造できるが、この際、かなりの量の四塩
化珪素（以下、ＳＴＣと略す）が副生することが知られ
ている。例えば特公昭６１−４７６８号公報には、鉄化
合物（主に、ＦｅＣｌ2）を触媒とし、その存在下でＴ
ＣＳを得ることが記載されている。この方法において
は、反応温度を変えることでＴＣＳとＳＴＣの生成割合
（以下ＴＣＳの生成割合をＴＣＳ選択率と記す）が決定
されている。2. Description of the Related Art Silicon trichloride (hereinafter abbreviated as TCS)
Is a compound useful as a raw material for producing polycrystalline silicon. In general, TCS can be produced by reacting metallic silicon with hydrogen chloride. At this time, it is known that a considerable amount of silicon tetrachloride (hereinafter abbreviated as STC) is produced as a by-product. For example, Japanese Patent Publication No. 61-4768 discloses that an iron compound (mainly, FeCl 2 ) is used as a catalyst and T
It is described that CS is obtained. In this method, the production ratio of TCS and STC (hereinafter, the production ratio of TCS is referred to as TCS selectivity) is determined by changing the reaction temperature.
【０００３】[0003]
【発明が解決しようとする課題】ところが、本発明者が
追試したところ、上記方法は、反応温度と鉄化合物触媒
によってＴＣＳ選択率を制御しているが、この反応はか
なりの発熱反応であるため反応温度の制御が難しく、反
応温度の上昇と共にＴＣＳ選択率が激減してＴＣＳの選
択率が十分に満足できないものであった。こうしたこと
から、ＳＴＣの副生を生じることなく高い選択率でＴＣ
Ｓを製造する方法を開発することが大きな課題であっ
た。However, the present inventor has conducted additional tests. According to the above method, the TCS selectivity is controlled by the reaction temperature and the iron compound catalyst. However, this reaction is a considerably exothermic reaction. It was difficult to control the reaction temperature, and the TCS selectivity was drastically reduced with the rise of the reaction temperature, so that the TCS selectivity was not sufficiently satisfied. From these facts, it is possible to obtain TC with high selectivity without producing STC by-product.
Developing a method for producing S has been a major challenge.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意研究を続けた結果、反応系内に、ア
ルミニウム原子を０.０５〜５重量％に維持しつつ、連
続的に金属ケイ素と塩化水素を反応さすと共に、鉄原子
を０.１〜５重量％になるように系外に取り出すこと
で、上記の課題が解決されることを見い出し、本発明を
完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, while maintaining aluminum atoms in the reaction system at 0.05 to 5% by weight, continuous It was found that the above problems could be solved by reacting metallic silicon with hydrogen chloride and extracting iron atoms out of the system so as to be 0.1 to 5% by weight. Reached.
【０００５】即ち、本発明は、金属ケイ素と塩化水素と
を、鉄およびアルミニウム含有触媒の存在下、アルミニ
ウム原子を０.０５〜５重量％および鉄原子を０.１〜５
重量％に維持しつつ連続的に反応せしめる三塩化ケイ素
（ＴＣＳ）の製造方法である。That is, according to the present invention, metal silicon and hydrogen chloride are added in the presence of a catalyst containing iron and aluminum in an amount of 0.05 to 5% by weight of aluminum atoms and 0.1 to 5% by weight of iron atoms.
This is a method for producing silicon trichloride (TCS), which is continuously reacted while maintaining its weight percentage.
【０００６】以下、本発明について更に詳しく説明す
る。まず、本発明で使用する金属ケイ素としては、公知
のものが何ら制限なく使用されるが、鉄原子が０.１〜
５重量％、アルミニウム原子が０.０５〜５重量％含ま
れるものが好ましい。Hereinafter, the present invention will be described in more detail. First, as the metal silicon used in the present invention, known silicon can be used without any limitation, but the iron atom is 0.1 to 0.1.
Those containing 5% by weight and 0.05 to 5% by weight of aluminum atoms are preferred.
【０００７】本発明において、アルミニウム原子は、塩
化水素と反応し塩化アルミニウムに転化した後、昇華し
て系外に取り出されるために、連続的に又は断続的に系
中に供給される必要がある。アルミニウム原子の供給に
は、アルミニウム金属、アルミニウム化合物が何ら制限
なく使用されるが、アルミニウム原子を、使用する金属
ケイ素に含有させて供給するのが好ましい。In the present invention, the aluminum atoms need to be continuously or intermittently supplied into the system in order to react with hydrogen chloride and convert it to aluminum chloride, and then sublimate and take out the system. . Aluminum metal and aluminum compounds are used without any limitation for the supply of aluminum atoms, but it is preferable to supply the aluminum atoms by including them in the metal silicon used.
【０００８】本発明において、鉄原子は、アルミニウム
原子と異なり、系内に蓄積する。従って、鉄原子を５重
量％以下に維持するためには、蓄積した鉄原子を系外に
取り出す操作が必要である。鉄原子の系外への取り出し
方法は、反応ガスと共に取り出す他に、反応系内の金属
ケイ素と共に取り出す方法など、何ら制限ない方法が用
いられ、例えば反応器が流動床であれば、サイクロンの
分級効率を低く設定する方法等を用いることができる。In the present invention, iron atoms, unlike aluminum atoms, accumulate in the system. Therefore, in order to maintain the iron atoms at 5% by weight or less, it is necessary to take out the accumulated iron atoms out of the system. The method of taking out iron atoms out of the system is not limited to the method of taking out together with the reaction gas, and a method of taking out together with metallic silicon in the reaction system is used. For example, a method of setting the efficiency low can be used.
【０００９】本発明において使用される塩化水素として
は、水素などの還元性ガス、窒素、アルゴンなどの不活
性ガス等が混入していても何ら制限なく使用される。そ
の供給速度は、反応器の空塔速度で３〜５０ｃｍ／秒で
あるのが好ましい。反応温度は、未反応の塩化水素の量
を抑制し、目的物のＴＣＳを高選択率で得るために、一
般に２５０〜４００℃の範囲であることが好ましい。本
発明の反応圧力は、好ましくは１気圧以上、より好まし
くは１〜１５気圧である。The hydrogen chloride used in the present invention can be used without any limitation, even if a reducing gas such as hydrogen or an inert gas such as nitrogen or argon is mixed therein. The feed rate is preferably 3 to 50 cm / sec as the superficial velocity of the reactor. The reaction temperature is generally preferably in the range of 250 to 400 ° C. in order to suppress the amount of unreacted hydrogen chloride and obtain the target TCS at a high selectivity. The reaction pressure of the present invention is preferably 1 atm or more, more preferably 1 to 15 atm.
【００１０】また、本発明で使用される反応器として
は、固定層式、流動層式など公知のものが何ら制限なく
使用されるが、反応生成熱の除熱効率を高めるため、流
動層式反応器を用いるのが好ましい。以上の方法でＴＣ
Ｓを高選択率で得ることができる。As the reactor used in the present invention, a known reactor such as a fixed-bed reactor or a fluidized-bed reactor is used without any limitation. However, in order to increase the efficiency of removing heat of reaction formation, a fluidized-bed reactor is used. It is preferable to use a vessel. TC by the above method
S can be obtained with a high selectivity.
【００１１】[0011]
【発明の効果】本発明の方法では、金属ケイ素と塩化水
素を反応せしめる系内に、アルミニウム原子を０.０１
〜５重量％になるように供給することで、反応温度の上
昇によるＴＣＳ選択率の低下を抑制すると共に、高選択
率でＴＣＳを生成させる触媒作用を有効に発現させる。
一方、鉄原子はＳＴＣの副生を促進する触媒作用を示す
ため、反応系内に０.１〜５重量％に維持するように抜
き出すことで、反応温度の影響を受けずにＴＣＳを高選
択率で製造することができるようになる。According to the method of the present invention, 0.01 is added to an aluminum atom in a system for reacting metallic silicon with hydrogen chloride.
By supplying so as to be ５5% by weight, a decrease in TCS selectivity due to an increase in reaction temperature is suppressed, and a catalytic action for generating TCS with high selectivity is effectively exhibited.
On the other hand, since iron atoms have a catalytic action to promote by-products of STC, by extracting them in the reaction system so as to maintain 0.1 to 5% by weight, TCS can be selected without being affected by the reaction temperature. It can be manufactured at a rate.
【００１２】[0012]
【実施例】以下、実施例をあげて本発明を具体的に説明
するが、本発明は、これらの実施例に何ら限定されるも
のではない。EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.
【００１３】実施例１ 内径５０ｍｍのステンレス製流動層式反応器でＴＣＳを
製造した。反応器に金属ケイ素（鉄０.１５重量％、ア
ルミニウム０.２５重量％含有する）を５００ｇ仕込
み、次いで塩化水素３.９１ｇ（０.１０７モル）／ｍｉ
ｎと水素０.２１４ｇ（０.１０７モル）／ｍｉｎを混合
し、反応器に供給した。反応温度３５０℃、大気圧下、
金属ケイ素を６０ｇ（２.１４モル）／ｈｒの速度で供
給した。５時間後にＴＣＳ選択率をガスクロマトグラフ
ィーで分析したところ、９３モル％であった。反応器内
の鉄およびアルミニウムの濃度は、それぞれ０.２１重
量％および０.１８重量％であった。Example 1 TCS was produced in a stainless steel fluidized bed reactor having an inner diameter of 50 mm. The reactor is charged with 500 g of metallic silicon (containing 0.15% by weight of iron and 0.25% by weight of aluminum), and then 3.91 g (0.107 mol) / mi of hydrogen chloride.
n and 0.214 g (0.107 mol) / min of hydrogen were mixed and supplied to the reactor. Reaction temperature 350 ° C, under atmospheric pressure,
Metallic silicon was fed at a rate of 60 g (2.14 mol) / hr. After 5 hours, the TCS selectivity was analyzed by gas chromatography to be 93 mol%. The concentrations of iron and aluminum in the reactor were 0.21% and 0.18% by weight, respectively.
【００１４】実施例２〜４ 実施例１において、反応温度をそれぞれ表１に示したよ
うに代えた以外は、実施例１と同様にしてＴＣＳを製造
した。結果を表１に示す。Examples 2 to 4 TCS was prepared in the same manner as in Example 1, except that the reaction temperature was changed as shown in Table 1. Table 1 shows the results.
【００１５】[0015]
【表１】 [Table 1]
【００１６】実施例５〜１０ 実施例１において、金属ケイ素のアルミニウムおよび鉄
の含有量を表２に示したように代えた以外は、実施例１
と同様にしてＴＣＳを製造した結果を表２に示す。Examples 5 to 10 Example 1 was repeated except that the contents of aluminum and iron in metallic silicon were changed as shown in Table 2.
Table 2 shows the results of producing a TCS in the same manner as described above.
【００１７】[0017]
【表２】 [Table 2]
【００１８】実施例１１ 実施例１において、金属ケイ素のアルミニウムおよび鉄
の含有量をそれぞれ、痕跡と０.５重量％に代え、供給
する金属ケイ素に金属アルミニウムを０.５重量％含ま
せて供給した以外は実施例１と同様にＴＣＳの製造をし
たところ、ＴＣＳ選択率は９４モル％であった。反応器
内のアルミニウムおよび鉄の濃度は、それぞれ０.１５
重量％および０.８９重量％であった。Example 11 In Example 1, the contents of aluminum and iron in metallic silicon were replaced with traces and 0.5% by weight, respectively, and the metallic silicon supplied was supplied with 0.5% by weight of metallic aluminum. A TCS was produced in the same manner as in Example 1 except that the TCS selectivity was 94 mol%. The concentration of aluminum and iron in the reactor was 0.15 each.
% And 0.89% by weight.
【００１９】実施例１２ 内径２９８ｍｍのステンレス製流動層式反応器でＴＣＳ
を製造した。反応器に金属ケイ素（鉄０.５１重量％、
アルミニウム０.３２重量％含有する）を１８０００ｇ
仕込み、次いで塩化水素２７９.８ｇ（７.６０モル）／
ｍｉｎ、水素１５.２０ｇ（７.６０モル）／ｍｉｎを混
合し、反応器に供給した。反応温度を３５０℃、大気圧
下、金属ケイ素を４２６２ｇ（１５２.０モル）／ｈｒ
の速度で供給した。反応開始から５０ｈｒ毎に反応器内
の金属ケイ素を９,０００ｇ抜き出した後、新たに金属
ケイ素を９,０００ｇ供給する操作を繰り返した。結果
を表３に示す。Example 12 TCS was conducted in a fluidized-bed stainless steel reactor having an inner diameter of 298 mm.
Was manufactured. Metal silicon (0.51% by weight of iron,
18000g containing 0.32% by weight of aluminum)
Charge, then 279.8 g (7.60 mol) of hydrogen chloride /
min and 15.20 g (7.60 mol) / min of hydrogen were mixed and supplied to the reactor. At a reaction temperature of 350 ° C. and under atmospheric pressure, 4262 g (152.0 mol) / hr of silicon metal was added.
At a rate of After extracting 9,000 g of metal silicon from the reactor every 50 hours from the start of the reaction, the operation of supplying 9,000 g of new metal silicon was repeated. Table 3 shows the results.
【００２０】[0020]
【表３】 [Table 3]
【００２１】比較例１〜４ 実施例１において、金属ケイ素のアルミニウムおよび鉄
の含有量を、それぞれ０.０４重量％と０.１５重量％に
代え、反応温度を表１に示したように代えた以外は実施
例１と同様にしてＴＣＳを製造した結果を表１に示す。Comparative Examples 1 to 4 In Example 1, the contents of aluminum and iron in metallic silicon were changed to 0.04% by weight and 0.15% by weight, respectively, and the reaction temperature was changed as shown in Table 1. Table 1 shows the results of producing a TCS in the same manner as in Example 1 except for the above.
【００２２】比較例５ 実施例１において、金属ケイ素のアルミニウムおよび鉄
の含有量を、それぞれ痕跡と０.５重量％に代え、塩化
第一鉄を１００ｇ添加した以外は実施例１と同様にＴＣ
Ｓを製造したところ、ＴＣＳ選択率は６０モル％であっ
た。アルミニウムおよび鉄の濃度は、それぞれ痕跡と１
１.２重量％であった。Comparative Example 5 The procedure of Example 1 was repeated, except that the contents of aluminum and iron in the metallic silicon were changed to trace and 0.5% by weight, respectively, and 100 g of ferrous chloride was added.
When S was manufactured, the TCS selectivity was 60 mol%. The concentrations of aluminum and iron were trace and 1 respectively.
It was 1.2% by weight.
【００２３】比較例６ 実施例１２において、金属ケイ素の抜き出し後、金属ケ
イ素を新たに供給する操作を行わず、実施例１２と同様
にＴＣＳを製造した。３００ｈｒ後のＴＣＳ選択率は６
５モル％であった。アルミニウムおよび鉄の濃度は、そ
れぞれ０.６５重量％と３１.５重量％であった。Comparative Example 6 In Example 12, a TCS was produced in the same manner as in Example 12, except that after the metal silicon was extracted, the operation of newly supplying metal silicon was not performed. TCS selectivity after 6 hours is 6
It was 5 mol%. The aluminum and iron concentrations were 0.65% and 31.5% by weight, respectively.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 33/00 - 33/107 C01B 7/00 C01B 9/00 ＪＩＣＳＴファイル（ＪＯＩＳ) ＷＰＩ（ＤＩＡＬＯＧ) ＣＡ（ＳＴＮ)────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C01B 33/00-33/107 C01B 7/00 C01B 9/00 JICST file (JOIS) WPI (DIALOG) CA ( STN)
Claims (1)
ルミニウム含有触媒の存在下、反応系内に鉄原子を０.
１〜５重量％およびアルミニウム原子を０.０５〜５重
量％に維持しつつ、連続的に反応せしめることを特徴と
する三塩化ケイ素の製造方法。1. A reaction system comprising a metal silicon and hydrogen chloride in the presence of a catalyst containing iron and aluminum, wherein an iron atom is added to the reaction system in an amount of 0.1 to 1.0.
A method for producing silicon trichloride, wherein the reaction is continuously performed while maintaining 1 to 5% by weight and aluminum atoms at 0.05 to 5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33475395A JP3324922B2 (en) | 1995-12-22 | 1995-12-22 | Method for producing silicon trichloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33475395A JP3324922B2 (en) | 1995-12-22 | 1995-12-22 | Method for producing silicon trichloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09169514A JPH09169514A (en) | 1997-06-30 |
| JP3324922B2 true JP3324922B2 (en) | 2002-09-17 |
Family
ID=18280852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33475395A Expired - Lifetime JP3324922B2 (en) | 1995-12-22 | 1995-12-22 | Method for producing silicon trichloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3324922B2 (en) |
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| JP7165672B2 (en) | 2017-11-20 | 2022-11-04 | 株式会社トクヤマ | Fluidized bed reactor and method for producing trichlorosilane |
-
1995
- 1995-12-22 JP JP33475395A patent/JP3324922B2/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011102265A1 (en) | 2010-02-18 | 2011-08-25 | 株式会社トクヤマ | Production method for trichlorosilane |
| KR20130008529A (en) | 2010-02-18 | 2013-01-22 | 가부시끼가이샤 도꾸야마 | Production method for trichlorosilane |
| US9321653B2 (en) | 2010-02-18 | 2016-04-26 | Tokuyama Corporation | Process for producing trichlorosilane |
| WO2015047043A1 (en) | 2013-09-30 | 2015-04-02 | 주식회사 엘지화학 | Method for producing trichlorosilane |
| KR20150037681A (en) | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Process for producing trichlorosilane |
| US9643851B2 (en) | 2013-09-30 | 2017-05-09 | Lg Chem, Ltd. | Method for producing trichlorosilane |
| KR20160069380A (en) | 2014-12-08 | 2016-06-16 | 주식회사 엘지화학 | Dispersion of silicon metal powder and process for producing chlorosilane using same |
| KR20160069371A (en) | 2014-12-08 | 2016-06-16 | 주식회사 엘지화학 | Dispersion of silicon metal powder and process for producing chlorosilane using same |
| KR20160102807A (en) | 2015-02-23 | 2016-08-31 | 주식회사 엘지화학 | Dispersion of silicon metal powder and process for producing chlorosilane using same |
| KR20170001465A (en) | 2015-06-26 | 2017-01-04 | 주식회사 엘지화학 | Apparatus and process for producing trichlorosilane |
| KR20170031878A (en) | 2015-09-14 | 2017-03-22 | 주식회사 엘지화학 | Apparatus and process for producing trichlorosilane |
| KR20170032553A (en) | 2015-09-15 | 2017-03-23 | 주식회사 엘지화학 | Process for producing trichlorosilane |
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| Publication number | Publication date |
|---|---|
| JPH09169514A (en) | 1997-06-30 |
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