阅读说明：本技术 一种甲基三氯硅烷的利用系统 (Methyl trichlorosilane's system of utilizing ) 是由 李文 黄江波 方袁烽 王珂 于 2021-03-26 设计创作，主要内容包括：本发明涉及一种甲基三氯硅烷的利用系统,甲基三氯硅烷和无水甲醇在反应塔内反应生成含甲醇的氯化氢气体和甲基三甲氧基硅烷；含甲醇的氯化氢气体通过冷却单元除去大部分甲醇后通过脱醇单元制得氯化氢干燥气体；单质硅和氯化氢干燥气体在三氯氢硅制备组件中反应生成三氯氢硅,从而提供半导体材料的晶圆；甲基三甲氧基硅烷与水、酸和碱在反应釜中反应生成球形聚甲基硅氧烷的悬浮液,球形聚甲基硅氧烷的悬浮液分离得到滤饼,滤饼在氧化氛围下加热得到球形二氧化硅,从而提供半导体材料的封装填料。通过本发明的甲基三氯硅烷的利用系统,直接法合成有机硅单体时的过剩产品甲基三氯硅烷被用来生产高附加值的产品三氯氢硅和球形二氧化硅,意义重大。(The invention relates to a utilization system of methyltrichlorosilane, wherein methyltrichlorosilane and anhydrous methanol react in a reaction tower to generate hydrogen chloride gas containing methanol and methyltrimethoxysilane; removing most of methanol from the hydrogen chloride gas containing methanol by a cooling unit, and preparing hydrogen chloride dry gas by a dealcoholization unit; the elemental silicon and the hydrogen chloride dry gas react in the trichlorosilane preparation assembly to generate trichlorosilane, so that the semiconductor material wafer is provided; the methyl trimethoxy silane reacts with water, acid and alkali in a reaction kettle to generate suspension of spherical polymethyl siloxane, the suspension of the spherical polymethyl siloxane is separated to obtain filter cake, and the filter cake is heated in an oxidizing atmosphere to obtain spherical silicon dioxide, so that the packaging filler of the semiconductor material is provided. By the utilization system of the methyl trichlorosilane, the excess product methyl trichlorosilane in the process of directly synthesizing the organic silicon monomer is used for producing trichlorosilane and spherical silicon dioxide with high added value, and the significance is great.)

1. A utilization system of methyltrichlorosilane, characterized in that, this utilization system includes:

the method comprises the following steps that (1) in a reaction tower (1), methyl trichlorosilane and anhydrous methanol react in the reaction tower (1) to generate hydrogen chloride gas containing methanol and methyl trimethoxy silane;

the hydrogen chloride preparation assembly (2) is connected with the reaction tower (1), the hydrogen chloride preparation assembly (2) comprises a cooling unit and a dealcoholization unit, and hydrogen chloride gas containing methanol is subjected to removal of most of methanol by the cooling unit and then is subjected to dealcoholization to prepare hydrogen chloride dry gas;

the trichlorosilane preparation assembly (3) is connected with the hydrogen chloride preparation assembly (2), and the elemental silicon and the hydrogen chloride dry gas react in the trichlorosilane preparation assembly (3) to generate trichlorosilane, so that the semiconductor material wafer is provided;

the spherical silicon dioxide preparation assembly (4) is connected with the reaction tower (1), the spherical silicon dioxide preparation assembly (4) comprises a reaction kettle (41), a solid-liquid separation unit (42) and a spherical silicon dioxide preparation unit (43), the reaction kettle (41) is directly connected with the reaction tower (1), methyltrimethoxysilane reacts with water, acid and alkali in the reaction kettle (41) to generate a suspension of spherical polymethylsiloxane, the solid-liquid separation unit (42) is connected with the reaction kettle (41) to separate the suspension of spherical polymethylsiloxane to obtain a filter cake and filtrate, and the spherical silicon dioxide preparation unit (43) is connected with the solid-liquid separation unit (42) to obtain spherical silicon dioxide by heating the filter cake in an oxidation atmosphere, so that the packaging filler of the semiconductor material is provided.

2. The utilization system according to claim 1, wherein the spherical silica preparation module (4) further comprises a cation resin exchange column (44) and a rectification column (44) connected with the solid-liquid separation unit (42), wherein the filtrate obtained from the solid-liquid separation unit passes through the cation resin exchange column and then is rectified by the rectification column to obtain water and anhydrous methanol.

3. The utilization system according to claim 1, wherein the reaction vessel (41) has a water inlet (412), and water is introduced into the reaction vessel (41) through the water inlet (412); the rectifying tower (44) is provided with a water outlet (451), and water is discharged out of the rectifying tower (44) through the water outlet (451); the water outlet (451) is communicated with the water inlet (412) so that the water discharged from the rectifying tower (44) is used for synthesizing the spherical polymethylsiloxane of the reaction kettle (41).

4. The utilization system according to claim 1, wherein the reaction column (1) has an alcohol inlet (12), and anhydrous methanol is fed into the reaction column (1) through the alcohol inlet (12); the rectifying tower (44) is provided with an alcohol outlet (452), and the anhydrous methanol is discharged out of the rectifying tower (44) through the alcohol outlet (452); the alcohol outlet (452) is communicated with the alcohol inlet (12) so that the anhydrous methanol discharged from the rectifying tower (44) is used for the synthesis of the methyltrimethoxysilane in the reaction tower (1).

5. The utilization system according to claim 1, characterized in that the trichlorosilane preparation component (3) comprises an ebullated bed reactor.

6. The utilization system according to claim 1, characterized in that the bottom of the reaction tower (1) is provided with a heating device, and methanol-containing hydrogen chloride gas is discharged from the reaction tower by heating, so that pure methyltrimethoxysilane is obtained.

Technical Field

The invention relates to organic silicon, in particular to a utilization system of methyltrichlorosilane.

Background

The reaction of chloromethane and silicon powder to prepare dimethyldichlorosilane is an important basic synthesis process in the organosilicon industry, and the main reaction equation is as follows: 2CH₃Cl+Si→(CH₃)₂SiCl₂. Besides the main reaction, the process also has the side reaction to generate methyl trichlorosilane: 2Si +4CH₃Cl→(CH₃)₃SiCl+CH₃SiCl₃；Si+3CH₃Cl→C₂H₆+CH₃SiCl₃. The methyltrichlorosilane has little use in the fields of silicon resin and fumed silica, has no other industrial value, and is an excess byproduct in the process of synthesizing the organic silicon monomer by a direct method.

Disclosure of Invention

In order to solve the problem of waste of methyltrichlorosilane in the prior art, the invention aims to provide a system for utilizing methyltrichlorosilane.

The system for utilizing methyltrichlorosilane according to the present invention comprises: the methyl trichlorosilane and the anhydrous methanol react in the reaction tower to generate hydrogen chloride gas containing methanol and methyl trimethoxy silane; the hydrogen chloride preparation assembly is connected with the reaction tower and comprises a cooling unit and a dealcoholization unit, and hydrogen chloride gas containing methanol is subjected to most of methanol removal by the cooling unit and then is subjected to dealcoholization by the dealcoholization unit to prepare hydrogen chloride dry gas; the trichlorosilane preparation assembly is connected with the hydrogen chloride preparation assembly, and the elemental silicon and the hydrogen chloride drying gas react in the trichlorosilane preparation assembly to generate trichlorosilane, so that the wafer of the semiconductor material is provided; the spherical silicon dioxide preparation assembly is connected with the reaction tower and comprises a reaction kettle, a solid-liquid separation unit and a spherical silicon dioxide preparation unit, the reaction kettle is directly connected with the reaction tower, methyltrimethoxysilane reacts with water, acid and alkali in the reaction kettle to generate a suspension of spherical polymethylsiloxane, the solid-liquid separation unit is connected with the reaction kettle to separate the suspension of the spherical polymethylsiloxane to obtain a filter cake and filtrate, and the spherical silicon dioxide preparation unit is connected with the solid-liquid separation unit to obtain the spherical silicon dioxide by heating the filter cake in an oxidation atmosphere, so that the semiconductor material packaging filler is provided.

Preferably, the spherical silica preparation assembly further comprises a cation resin exchange column and a rectifying tower which are connected with the solid-liquid separation unit, wherein the filtrate obtained by the solid-liquid separation unit passes through the cation resin exchange column and then is rectified by the rectifying tower to obtain water and anhydrous methanol.

Preferably, the reaction kettle is provided with a water inlet, and water is input into the reaction kettle through the water inlet; the rectifying tower is provided with a water outlet, and water is discharged out of the rectifying tower through the water outlet; the water outlet is communicated with the water inlet so that the water discharged from the rectifying tower is used for synthesizing the spherical polymethylsiloxane of the reaction kettle.

Preferably, the reaction tower is provided with an alcohol inlet, and the anhydrous methanol is input into the reaction tower through the alcohol inlet; the rectifying tower is provided with an alcohol outlet, and the anhydrous methanol is discharged out of the rectifying tower through the alcohol outlet; the alcohol outlet is communicated with the alcohol inlet so that the anhydrous methanol discharged from the rectifying tower is used for synthesizing the methyltrimethoxysilane in the reaction tower.

Preferably, the trichlorosilane preparation component comprises an ebullated bed reactor.

Preferably, the bottom of the reaction tower is provided with a heating device, and methanol-containing hydrogen chloride gas is discharged from the reaction tower through heating, so that pure methyltrimethoxysilane is obtained.

By the utilization system of the methyl trichlorosilane, the excess product methyl trichlorosilane in the process of directly synthesizing the organic silicon monomer is used for producing trichlorosilane and spherical silicon dioxide with high added value, and the significance is great. Wherein, the trichlorosilane is a basic industrial raw material with wide application, can be used for producing polysilicon and silane coupling agent, and is a basic raw material of semiconductor industry; and spherical silica, particularly high-purity spherical silica, is an indispensable raw material for semiconductor packaging materials and 5G communication high-frequency high-speed circuit boards.

Drawings

Fig. 1 is a schematic structural view of a methyltrichlorosilane utilization system according to a preferred embodiment of the present invention.

Detailed Description

The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

As shown in FIG. 1, a system for utilizing methyltrichlorosilane according to a preferred embodiment of the present invention includes a reaction tower 1 having a chlorosilane inlet 11 and an alcohol inlet 12, wherein methyltrichlorosilane (CH)₃SiCl₃) Introducing into a reaction tower 1 through a chlorosilane inlet 11, and adding anhydrous methanol (HOCH)₃) Is fed into the reaction tower 1 through the alcohol inlet 12, and the two react to generate hydrogen chloride gas (3HCl + HOCH) containing methanol₃) And methyltrimethoxysilane (CH)₃Si(OCH₃)₃) The reaction equation is CH₃SiCl₃+4HOCH₃→3HCl+HOCH₃+CH₃Si(OCH₃)₃. The reaction tower 1 further has a gas outlet 13 and a methoxysilane outlet 14, wherein the hydrogen chloride gas (3HCl + HOCH) containing methanol₃) Methyltrimethoxysilane (CH) is discharged from the reaction column 1 via a gas outlet 13₃Si(OCH₃)₃) Is discharged from the reaction column 1 through a methoxysilane outlet 14. Further, the bottom of the reaction tower 1 is provided with a heating device, and the methanol-containing hydrogen chloride gas (3HCl + HOCH) is heated to be₃) Is discharged from the gas outlet 13 to obtain pure methyltrimethoxysilane (CH)₃Si(OCH₃)₃)。

As shown in fig. 1, the system for utilizing methyltrichlorosilane according to a preferred embodiment of the present invention further includes a hydrogen chloride production module 2 connected to a gas outlet 13 of the reaction tower 1. Specifically, the hydrogen chloride production module 2 includes a cooling unit and a dealcoholization unit, and the hydrogen chloride gas (3HCl + HOCH) containing methanol₃) Removing most of methanol (HOCH) by a cooling unit₃) And then hydrogen chloride dry gas (HCl) is produced through a dealcoholization unit.

As shown in fig. 1, the system for utilizing methyltrichlorosilane according to a preferred embodiment of the present invention further includes a trichlorosilane preparation module 3 connected to the hydrogen chloride preparation module 2. Specifically, the trichlorosilane preparation component 3 comprises a boiling bed reactor, the boiling bed reactor is provided with a silicon inlet 31 and a hydrogen chloride inlet 32, elemental silicon enters the boiling bed reactor through the silicon inlet 31, the hydrogen chloride inlet 32 is communicated with the hydrogen chloride preparation component 2, so that hydrogen chloride dry gas (HCl) enters the boiling bed reactor through the hydrogen chloride inlet 32, and the hydrogen chloride dry gas and the HCl react to generate trichlorosilane. In a preferred embodiment, industrial silicon powder with the average particle size of about 200 microns and the purity of more than 98% is heated to 400 ℃ in a powder drying furnace to obtain metallurgical silicon, the metallurgical silicon is mixed with a nickel catalyst and/or a palladium catalyst in a fluidized bed reactor, hydrogen chloride drying gas (HCl) is preheated to about 200 ℃ and then is introduced into the fluidized bed reactor, so that hydrogen chloride and elemental silicon react to obtain crude trichlorosilane, and the crude trichlorosilane is rectified to obtain pure trichlorosilane. With trichlorosilane as a raw material, polycrystalline silicon can be prepared by a siemens method, and the polycrystalline silicon can be prepared by a guhel-larski method, and the monocrystalline silicon is sliced and polished to provide a wafer, and the wafer is a material of a semiconductor front-end technology integrated circuit. It should be noted that the raw material trichlorosilane for preparing polysilicon by the siemens process known in the prior art is prepared by electrolyzing desalted water in an electrolytic cell to prepare hydrogen. After being cooled and separated from liquid, the hydrogen prepared by electrolysis enters a deaerator, and under the action of a catalyst, a trace amount of oxygen in the hydrogen reacts with the hydrogen to generate water to be removed. The deoxygenated hydrogen was dried by a series of adsorption dryers. The purified and dried hydrogen is sent into a hydrogen storage tank and then sent to hydrogen chloride synthesis, trichlorosilane hydrogen reduction and silicon tetrachloride hydrogenation processes to prepare the polysilicon. In contrast, the application originally proposes that the hydrogen chloride preparation assembly 2 and the trichlorosilane preparation assembly 3 which are connected with the reaction tower 1 are used for providing trichlorosilane which is used as a raw material for preparing polycrystalline silicon by a Siemens method.

As shown in fig. 1, the system for utilizing methyltrichlorosilane according to a preferred embodiment of the present invention includes a spherical silica preparation unit 4 connected to a methoxysilane outlet 14 of a reaction tower 1.

The spherical silica preparation assembly 4 includes a reaction vessel 41 having a methoxysilane inlet 411, a water inlet 412 and an acid inlet 413, wherein the methoxysilane inlet 411 is in communication with the methoxysilane outlet 14 such that methyltrimethoxysilane (CH)₃Si(OCH₃)₃) Pure water (H) is fed into the reaction vessel 41 through the methoxysilane inlet 411₂O) is fed into the reaction vessel 41 through the water inlet 412, and acetic acid is fed into the reaction vessel 41 through the acid inlet 413, and stirred until methyltrimethoxysilane is dissolved, wherein the reaction equation is CH₃Si(OCH₃)₃+H₂O→CH₃Si(OH)₃. In addition, the reaction kettle 41 is also provided with an alkali inlet 414, and ammonia water is input into the reaction kettle 41 through the alkali inlet 414 to generate a suspension of the spherical polymethylsiloxane, wherein the reaction equation is CH₃Si(OH)₃→CH₃SiO_nOH_m. In a preferred embodiment, 80 parts by weight of methyltrimethoxysilane (CH)₃Si(OCH₃)₃) 1000 parts by weight of pure water (H)₂O) and 1 part by weight of 5 percent acetic acid aqueous solution are stirred in a reaction kettle 41 until the methyltrimethoxysilane is dissolved, then 25 parts by weight of 5 percent diluted ammonia water is added, the stirring is stopped after the uniform stirring, and the spherical polymethylsiloxane is generated after the standing for 1 hour.

The spherical silica preparation component 4 further comprises a solid-liquid separation unit 42 connected with the reaction kettle 41, and the suspension of the spherical polymethylsiloxane is separated by the solid-liquid separation unit 42 to obtain a filter cake and filtrate.

The spherical silica production module 4 further includes a spherical silica production unit 43 connected to the solid-liquid separation unit 42. In the spherical silica preparation unit 43, the filter cake obtained by the solid-liquid separation unit 42 is dried to obtain spherical polymethylsiloxane, and the spherical polymethylsiloxane is heated to 500 to 1000 ℃ in an oxidizing atmosphere to obtain spherical silica, wherein the spherical silica is a filler of the semiconductor back-end process packaging resin, is added for the purpose of reducing the thermal expansion coefficient of the resin, and is an indispensable basic material for the semiconductor industry. In a preferred embodiment, the filter cake obtained from the solid-liquid separation unit 42 is dried to obtain spherical polymethylsiloxane with an average particle size of 1.5 microns, and the spherical polymethylsiloxane is slowly heated to 450 ℃ for 6 hours in an air atmosphere, then heated to 1000 ℃ and calcined for 12 hours to obtain spherical silica with an average particle size of 1.2 microns.

The spherical silica production module 4 further comprises a cation resin exchange column 44 and a rectification column 45 connected to the solid-liquid separation unit 42, wherein the filtrate obtained from the solid-liquid separation unit 42 is passed through the cation resin exchange column 44 to remove ammonium ions (NH)₄ ⁺→H⁺) And removing acetate ion (A) by anion resin exchange column_cO^-→OH^-) Then, the mixture is rectified by a rectifying tower 45 to obtain pure water and anhydrous methanol. Specifically, rectifying column 45 has a water outlet 451 and an alcohol outlet 452, wherein pure water exits rectifying column 45 through water outlet 451 and anhydrous methanol exits rectifying column 45 through alcohol outlet 452. Specifically, the water outlet 451 is communicated with the water inlet 412 of the reaction tank 41 to allow pure water to be used for the synthesis of the spherical polymethylsiloxane, and the alcohol outlet 452 is communicated with the alcohol inlet 12 of the reaction column 1 to allow methanol to be used for the synthesis of methyltrimethoxysilane.

By the utilization system of the methyl trichlorosilane, the excess product methyl trichlorosilane in the process of directly synthesizing the organic silicon monomer is used for producing trichlorosilane and spherical silicon dioxide with high added value, and the significance is great. Specifically, the invention skillfully prepares hydrogen chloride and methyltrimethoxysilane by utilizing the excess product of methyltrichlorosilane, wherein the hydrogen chloride is the raw material of the wafer, and the methyltrimethoxysilane is the raw material of the spherical silicon oxide. The wafer is the material of the semiconductor front end of line integrated circuit. The spherical silicon oxide is a filler of semiconductor back-end process packaging resin and is an indispensable basic material for the semiconductor industry.

The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.