CN110655086A - Method for improving silicon tetrachloride conversion rate in trichlorosilane production process - Google Patents
Method for improving silicon tetrachloride conversion rate in trichlorosilane production process Download PDFInfo
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- CN110655086A CN110655086A CN201911100030.9A CN201911100030A CN110655086A CN 110655086 A CN110655086 A CN 110655086A CN 201911100030 A CN201911100030 A CN 201911100030A CN 110655086 A CN110655086 A CN 110655086A
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- trichlorosilane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
- C01B33/10757—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane
- C01B33/10763—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane from silicon
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Abstract
The invention discloses a method for improving the conversion rate of silicon tetrachloride in a trichlorosilane production process, which takes silicon powder as a raw material, adds a catalyst, and carries out boiling hydrochlorination reaction with hydrogen chloride to prepare trichlorosilane and silicon tetrachloride, wherein the mass ratio of the catalyst to the silicon powder is 0.5-2: 1000; the catalysts are S20 type, S21 type and S22 type copper catalysts. According to the invention, the catalyst is added, and the conversion rates of trichlorosilane and silicon tetrachloride are controlled under the condition that the original reaction conditions are not changed. The catalyst is low in price and can be repeatedly used for a long time, and the reaction activity of the silicon powder can be improved, so that the silicon powder can fully react in the reactor, and the bag filtration dedusting load is reduced; the catalyst does not participate in the reaction with the materials, and the product quality is not influenced. The invention can adjust and control the conversion rate of trichlorosilane and silicon tetrachloride at about 50 percent.
Description
Technical Field
The invention relates to a trichlorosilane production process, in particular to a method for improving silicon tetrachloride conversion rate in a trichlorosilane production process.
Background
The traditional trichlorosilane production method is that hydrogen chloride reacts with silicon powder, and the main reaction is Si +3HCl → SiHCl3+H2The side reaction is Si +4HCl → SiCl4+2H2. In the generated chlorosilane mixed gas, about 85 percent of the chlorosilane mixed gas is trichlorosilane, and 15 percent of the chlorosilane mixed gas is silicon tetrachloride. The trichlorosilane is mainly used as a production raw material of the polysilicon and silane coupling agent. With the continuous improvement of the cold hydrogenation technology, the market demand of polysilicon on trichlorosilane is less and less, and the market demand of silicon tetrachloride is increased. The existing production mode can not meet the requirement of the market on the silicon tetrachloride, and meanwhile, the market load of the trichlorosilane is excessive, so that the overall production operation is influenced.
The silicon tetrachloride can be used as a synthetic raw material of micro silicon dioxide, synthetic quartz, silicon nitride and other various organic silicon compounds, such as silicate, organic silicon monomer, organic silicon oil, high-temperature insulating paint, organic silicon resin, silicon rubber and heat-resistant lining materials. The high-purity silicon tetrachloride is used for manufacturing polysilicon, high-purity silicon dioxide, optical fiber prefabricated rods and quartz fibers, the military industry is used for manufacturing smoke screen agents, and the metallurgical industry can be used for manufacturing corrosion-resistant silicon iron casting.
The field of optical fiber preform production, scientific research and production raw materials thereof is late in China, the optical fiber preform is about 90% imported, and the main production technology and process of the optical fiber are still controlled by foreign companies at present. In order to break through the technical bottleneck of the optical fiber preform, break through the situation of seriously depending on import for a long time, realize the nationalization of the optical fiber-grade silicon tetrachloride production technology, improve the competitiveness of domestic enterprises, make up for the deficiency of the market, and the construction of silicon tetrachloride production enterprises is very important.
Therefore, how to solve the problems of conversion rate of trichlorosilane and silicon tetrachloride and serious shortage of silicon tetrachloride and overload of trichlorosilane caused by market change is an urgent problem to be solved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for improving the conversion rate of silicon tetrachloride in a trichlorosilane production process, and solving the problems of excessive trichlorosilane productivity and insufficient silicon tetrachloride productivity in the prior art.
The invention solves the technical problem, and adopts the technical scheme that:
a method for improving the conversion rate of silicon tetrachloride in a trichlorosilane production process comprises the steps of taking silicon powder as a raw material, adding a catalyst, and carrying out boiling hydrochlorination reaction with hydrogen chloride to prepare trichlorosilane and silicon tetrachloride, wherein the mass ratio of the catalyst to the silicon powder is 0.5-2: 1000; the catalysts are S20 type, S21 type and S22 type copper catalysts.
The S20 type copper catalyst is a copper catalyst, the S21 type copper catalyst is a copper alloy catalyst, and the S22 type copper catalyst is a copper oxide catalyst.
Compared with the prior art, the invention adopting the technical scheme has the beneficial effects that:
by adding the catalyst, the conversion rates of trichlorosilane and silicon tetrachloride can be controlled under the condition that the original reaction conditions are not changed. The catalyst has the main function of reducing the reaction temperature of the reaction of the hydrogen chloride and the silicon powder to generate the silicon tetrachloride, is low in price, does not participate in the reaction, does not reduce the mass due to the reaction of the silicon powder and the hydrogen chloride to generate the chlorosilane, and can be repeatedly used; the catalyst is added, so that the reaction activity of the silicon powder can be improved, and the silicon powder can fully react in the reactor, thereby reducing the bag filtration dedusting load; the most reasonable proportion of the catalyst and the silicon powder is selected, and the silicon tetrachloride conversion rate can reach 50 percent by reacting under the conditions of the same pressure and temperature.
Preferably, the further technical scheme of the invention is as follows:
the Si content of the silicon powder is more than or equal to 98.5 percent, and the particle size is 20-120 meshes.
The catalyst is an S21 type copper catalyst, namely a copper alloy catalyst; the mass ratio of the copper alloy catalyst to the silicon powder is 1: 1000.
The boiling hydrochlorination reaction temperature is 340 ℃ and the pressure is 0.08 MPa.
The boiling hydrochlorination reaction is carried out in a boiling fluidized bed, and the boiling fluidized bed is a boiling bed with the diameter of 0.8-1.2 m.
And dedusting and condensing chlorosilane gas generated by the final reaction, performing pressure swing adsorption on tail gas to recover hydrogen chloride gas, and conveying the hydrogen gas to a downstream process for recycling.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
a method for improving the conversion rate of silicon tetrachloride in a trichlorosilane production process comprises the following specific process steps:
(1) preparing raw materials: and mixing the S20 type copper catalyst and the silicon powder according to the mass ratio, uniformly mixing, and adding into a silicon powder dryer.
(2) And (3) trichlorosilane production: the boiling fluidized bed is a boiling bed with the diameter of 0.8m, the boiling chlorination reaction temperature is 340 ℃, and the pressure is 0.08 Mpa; the mixture of the catalyst and the silicon powder is added into a synthesis furnace, and the mixture reacts after the hydrogen chloride is introduced to generate synthesis gas.
(3) The mass ratio of the catalyst to the silicon powder is different, and the conversion rate of the silicon tetrachloride is different.
The mass ratio of the S20 catalyst to the silicon powder is 0.5:1000Kg
The mass ratio of the S20 catalyst to the silicon powder is 1:1000Kg
The mass ratio of the S20 catalyst to the silicon powder is 1.5:1000Kg
The mass ratio of S20 to silicon powder catalyst is 2:1000Kg
Example 2:
a method for improving the conversion rate of silicon tetrachloride in a trichlorosilane production process comprises the following specific process steps:
(1) and mixing the S21 type copper catalyst and the silicon powder according to the mass ratio, uniformly mixing, and adding into a silicon powder dryer.
(2) And (3) trichlorosilane production: the boiling fluidized bed is a boiling bed with the diameter of 0.8m, the boiling chlorination reaction temperature is 340 ℃, and the pressure is 0.08 Mpa; the mixture of the catalyst and the silicon powder is added into a synthesis furnace, and the mixture reacts after the hydrogen chloride is introduced to generate synthesis gas.
(3) The mass ratio of the catalyst to the silicon powder is different, and the conversion rate of the silicon tetrachloride is different.
The mass ratio of the S21 catalyst to the silicon powder is 0.5:1000Kg
The mass ratio of the S21 catalyst to the silicon powder is 1:1000Kg
The mass ratio of the S21 catalyst to the silicon powder is 1.5:1000Kg
The mass ratio of the S21 catalyst to the silicon powder is 2:1000Kg
Example 3:
a method for improving the conversion rate of silicon tetrachloride in a trichlorosilane production process comprises the following specific process steps:
(1) and mixing the S22 type copper catalyst and the silicon powder according to the mass ratio, uniformly mixing, and adding into a silicon powder dryer.
(2) And (3) trichlorosilane production: the boiling fluidized bed is a boiling bed with the diameter of 0.8m, the boiling chlorination reaction temperature is 340 ℃, and the pressure is 0.08 Mpa; the mixture of the catalyst and the silicon powder is added into a synthesis furnace, and the mixture reacts after the hydrogen chloride is introduced to generate synthesis gas.
(3) The mass ratio of the catalyst to the silicon powder is different, and the conversion rate of the silicon tetrachloride is different.
The mass ratio of the S22 catalyst to the silicon powder is 0.5:1000Kg
The mass ratio of the S22 catalyst to the silicon powder is 1:1000Kg
The mass ratio of the S22 catalyst to the silicon powder is 1.5:1000Kg
The mass ratio of the S22 catalyst to the silicon powder is 2:1000Kg
From the above examples, it is understood that when the selected catalyst is an S21 type copper-based catalyst and the mass ratio of the S21 type copper-based catalyst to silicon powder is 1:1000, the conversion rates of trichlorosilane and silicon tetrachloride can be controlled to about 50%.
The above embodiments are merely to illustrate the technical solutions of the present invention, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention, and any modifications or partial substitutions are intended to be included within the scope of the appended claims.
Claims (6)
1. A method for improving the conversion rate of silicon tetrachloride in the production process of trichlorosilane is characterized by comprising the following steps: silicon powder is used as a raw material, a catalyst is added, and the silicon powder and hydrogen chloride are subjected to boiling hydrochlorination reaction to prepare trichlorosilane and silicon tetrachloride, wherein the mass ratio of the catalyst to the silicon powder is 0.5-2: 1000; the catalysts are S20 type, S21 type and S22 type copper catalysts.
2. The method for improving the conversion rate of silicon tetrachloride in the production process of trichlorosilane according to claim 1, which is characterized by comprising the following steps: the silicon content Si of the silicon powder is more than or equal to 98.5 percent, and the particle size is 20-120 meshes.
3. The method for improving the conversion rate of silicon tetrachloride in the production process of trichlorosilane according to claim 1, which is characterized by comprising the following steps: the catalyst is an S21 type copper catalyst, namely a copper alloy catalyst; the mass ratio of the copper alloy catalyst to the silicon powder is 1: 1000.
4. The method for improving the conversion rate of silicon tetrachloride in the production process of trichlorosilane according to claim 1, wherein the boiling hydrochlorination reaction temperature is 340 ℃ and the pressure is 0.08 MPa.
5. The method for improving the conversion rate of silicon tetrachloride in the production process of trichlorosilane according to claim 4, which is characterized by comprising the following steps: the boiling hydrochlorination reaction is carried out in a boiling fluidized bed, and the boiling fluidized bed is a boiling bed with the diameter of 0.8-1.2 m.
6. The method for improving the conversion rate of silicon tetrachloride in the production process of trichlorosilane according to claim 1, which is characterized by comprising the following steps: and dedusting and condensing chlorosilane gas generated by the final reaction, performing pressure swing adsorption on tail gas to recover hydrogen chloride gas, and conveying the hydrogen gas to a downstream process for recycling.
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Citations (8)
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|---|---|---|---|---|
| CH371098A (en) * | 1959-04-08 | 1963-08-15 | Bbc Brown Boveri & Cie | Process for producing trichlorosilane |
| JPS6259051B2 (en) * | 1979-11-17 | 1987-12-09 | Osaka Titanium | |
| CN101790492A (en) * | 2007-08-29 | 2010-07-28 | 动力工程公司 | Preparation silicon and catalystic material in the method for producing trichlorosilane |
| CN102795628A (en) * | 2012-08-03 | 2012-11-28 | 东华工程科技股份有限公司 | Improved method for preparing trichlorosilane by using low-pressure synthetic technology |
| US20120301385A1 (en) * | 2010-02-18 | 2012-11-29 | Ayao Akiyoshi | Process for producing trichlorosilane |
| CN106378133A (en) * | 2016-10-24 | 2017-02-08 | 中国科学院过程工程研究所 | Catalyst for producing trichlorosilane with silicon-hydrogen chlorination process, preparation method of catalyst and method for catalytically producing trichlorosilane |
| CN107416841A (en) * | 2017-06-22 | 2017-12-01 | 唐山三孚硅业股份有限公司 | A kind of method and device for producing silicon tetrachloride |
| TW201914957A (en) * | 2017-10-05 | 2019-04-16 | 德商瓦克化學公司 | Method for producing chlorosilanes |
-
2019
- 2019-11-12 CN CN201911100030.9A patent/CN110655086A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH371098A (en) * | 1959-04-08 | 1963-08-15 | Bbc Brown Boveri & Cie | Process for producing trichlorosilane |
| JPS6259051B2 (en) * | 1979-11-17 | 1987-12-09 | Osaka Titanium | |
| CN101790492A (en) * | 2007-08-29 | 2010-07-28 | 动力工程公司 | Preparation silicon and catalystic material in the method for producing trichlorosilane |
| US20120301385A1 (en) * | 2010-02-18 | 2012-11-29 | Ayao Akiyoshi | Process for producing trichlorosilane |
| CN102795628A (en) * | 2012-08-03 | 2012-11-28 | 东华工程科技股份有限公司 | Improved method for preparing trichlorosilane by using low-pressure synthetic technology |
| CN106378133A (en) * | 2016-10-24 | 2017-02-08 | 中国科学院过程工程研究所 | Catalyst for producing trichlorosilane with silicon-hydrogen chlorination process, preparation method of catalyst and method for catalytically producing trichlorosilane |
| CN107416841A (en) * | 2017-06-22 | 2017-12-01 | 唐山三孚硅业股份有限公司 | A kind of method and device for producing silicon tetrachloride |
| TW201914957A (en) * | 2017-10-05 | 2019-04-16 | 德商瓦克化學公司 | Method for producing chlorosilanes |
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| 刘寄声: "《多晶硅和石英玻璃的联合制备法》", 31 January 2008, 冶金工业出版社 * |
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Application publication date: 20200107 |