KR20170031878A - Apparatus and process for producing trichlorosilane - Google Patents

Apparatus and process for producing trichlorosilane Download PDF

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KR20170031878A
KR20170031878A KR1020150129388A KR20150129388A KR20170031878A KR 20170031878 A KR20170031878 A KR 20170031878A KR 1020150129388 A KR1020150129388 A KR 1020150129388A KR 20150129388 A KR20150129388 A KR 20150129388A KR 20170031878 A KR20170031878 A KR 20170031878A
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reaction
metal silicon
tubular reactor
reactor
liquid
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KR102012914B1 (en
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유진형
김유석
김정규
이정우
장은수
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주식회사 엘지화학
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/02—Feed or outlet devices therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Abstract

The present invention relates to an apparatus for effectively producing trichlorosilane from tetrachlorosilane. According to the present invention, the apparatus comprises a tubular reactor in which metal silicon particles are filled. The inner diameter of the tubular reactor is steadily decreased from an inlet of a reaction material to an outlet of a reaction product.

Description

[0001] APPARATUS AND PROCESS FOR PRODUCING TRICHLOROSILANE [0002]

The present invention relates to a process for producing trichlorosilane, and more particularly to a process for producing trichlorosilane from tetrachlorosilane more efficiently.

Trichlorosilane (SiHCl 3 : TCS) is a compound useful as a raw material for producing a high-purity polycrystalline silicon (also referred to as polysilicon), and is used for precipitating high-purity polysilicon by reacting with hydrogen at a high temperature of 1000 ° C. or higher. This reaction is mainly represented by the following reaction formulas (1) and (2).

4 SiHCl 3 ? Si + 3 SiCl 4 + 2H 2 (1)

SiHCl 3 + H 2 ? Si + 3HCl (2)

The trichlorosilane used in the polysilicon precipitation reaction is generally prepared by the reaction of metal silicon with hydrogen chloride. For example, Patent Document 1 discloses a method of producing trichlorosilane by a reaction of the following reaction formula (3) by reacting metal silicon and hydrogen chloride in the presence of an iron- and aluminum-containing catalyst using a fluidized bed reactor .

Si + 3HCl -> SiHCl 3 + H 2 (3)

The gas produced by the reaction of metal silicon with hydrogen chloride is cooled to below -10 ° C to condense and separate trichlorosilane, which contains other byproducts of chlorosilane in addition to trichlorosilane. Trichlorosilane is separated and recovered from the condensate containing these chlorosilanes by distillation and used as raw materials for producing polysilicon. Further, tetrachlorosilane (SiCl 4 : STC) separated by distillation is mainly converted to trichlorosilane (TCS) by the reaction of the following formula (4) and reused for the production of polysilicon.

3 SiCl 4 + 2H 2 + Si? 4 SiHCl 3 (4)

On the other hand, in Patent Document 2, metal silicon particles, hydrogen chloride, tetrachlorosilane and hydrogen having a size of about 100 to 300 탆 are supplied into a fluidized bed reactor filled with metal silicon particles, and trichloro The production of trichlorosilane (the reaction of the formula (3)) and the reaction of the production of the siloxane (reaction of the formula (3)) and the reaction of the production of the trichlorosilane by the reaction of the metal silicon, tetrachlorosilane and hydrogen (See FIG. 1). In the above method, since the size of the metal silicon particles gradually decreases as the reaction progresses, it is necessary to replenish the metal silicon particles. However, since the replenishment timing is determined based on the temperature change of the raw material, the reaction temperature is not constant and fluctuates, resulting in a problem that the quality of the product is uneven depending on the reaction time.

Japanese Patent No. 3324922 Japanese Patent Laid-Open No. 56-73617

A problem to be solved by the present invention is to provide a method for efficiently converting chlorosilanes, particularly tetrachlorosilane, into trichlorosilane in the exhaust gas of a polysilicon production process by reaction of trichlorosilane with hydrogen chloride, And to provide a manufacturing apparatus.

According to an aspect of the present invention,

A tubular reactor filled with metal silicon particles,

Wherein the tubular reactor has a shape in which the inner diameter thereof gradually decreases toward the reaction product outlet from the reaction material inlet.

According to one embodiment, the filling density of the metal silicon particles filled in the tubular reactor may gradually increase from the inlet to the outlet.

According to one embodiment, the pressure inside the tubular reactor gradually increases from the inlet to the outlet, and the pressure difference between the inlet and the outlet may be 1.5 times or more.

According to one embodiment, there is provided a liquid reaction material feeder for feeding a liquid reaction material containing liquid tetrachlorosilane to the tubular reactor;

A gas phase reaction material feed port for feeding a gas phase reaction raw material containing a reducing gas to the tubular reactor; And

And a reaction product outlet for discharging the reaction product containing trichlorosilane produced by contacting and reacting with the metal silicon particles while the reaction raw materials of the liquid and gaseous phases are transferred into the tubular reactor.

According to one embodiment, the liquid or gaseous reaction raw material may further comprise means for supplying a halide.

According to one embodiment, the reactor may have a pressure difference of at least 1 bar between the reaction material inlet and the reactor interior.

According to one embodiment, the internal pressure of the tubular reactor may be from 1 bar to 100 bar.

According to one embodiment, the average particle size of the metal silicon particles to be filled in the tubular reactor may be 3 to 100 [mu] m.

According to one embodiment, the filled metal silicon particles may be partially or completely consumed as the reaction progresses, and may further include a metal silicon particle input port for replenishing metal silicon particles.

According to one embodiment, the metal silicon particles filled in the tubular reactor may be filled in a volume ratio of 10% to 99% with respect to the internal volume of the tubular reactor.

The present invention, in order to solve the other technical problems, provides a method for producing trichlorosilane using the above apparatus.

The reaction in the tubular reactor may be a liquid phase reaction.

The reaction may be carried out at 300 to 1000 ° C.

According to one embodiment, it may further comprise the step of replenishing or refilling the metal silicon particle particles exhausted by the reaction.

According to one embodiment, the liquid phase reaction raw material may be supplied with a dispersion liquid in which metal silicon fine particles having smaller particle diameters than metal silicon particles filled in the tubular reactor are dispersed in the reactor.

According to one embodiment, the metal silicon fine particles dispersed in the dispersion may be included in an amount of 0.5 to 5 parts by weight based on 10 parts by weight of liquid tetrachlorosilane, and the average particle diameter may be less than 3 μm.

According to the present invention, in order to further facilitate the three-phase reaction of liquid tetrachlorosilane, gaseous hydrogen and hydrogen chloride, and metal silicon requiring high pressure, metal silicon is filled in the tubular reactor, It is possible to more easily form a high-pressure environment.

1 is a schematic view of a fluidized bed process according to the prior art.
2 is a schematic flow chart of a process for producing trichlorosilane using an apparatus according to the present invention.
Figures 3 and 4 are schematic cross-sectional views of an apparatus according to one embodiment of the present invention.

The method for producing trichlorosilane according to the present invention is characterized in that the reaction of metal silicon and hydrogen chloride by the above reaction formula (3) and the reaction of tetrachlorosilane with metal silicon and hydrogen by the reaction formula (4) simultaneously proceed to produce trichlorosilane But the liquid phase reaction is carried out. Therefore, it can be expressed as the following reaction formula (5).

3SiCl 4 (l) + HCl ( l) + 3H 2 (g) + Si (s) → 4SiHCl 3 (l) + HCl (l) + H 2 (l) (5)

As a method for more efficiently obtaining conditions of high pressure necessary for a three-phase reaction involving a reaction raw material containing liquid tetrachlorosilane, gaseous hydrogen and hydrogen chloride, and solid-phase metal silicon, it is preferable to use only a liquid tetrachlorosilane The reaction efficiency can be maximized by naturally inducing the pressure inside the reactor to increase.

The apparatus for producing trichlorosilane according to the present invention comprises a tubular reactor packed with metal silicon particles, wherein the tubular reactor has a shape in which its inner diameter gradually decreases from the reaction material inlet to the reaction product outlet.

Specifically,

A liquid reaction material inlet for supplying a liquid reaction material containing liquid tetrachlorosilane to the tubular reactor;

A gas phase reaction material inlet for supplying a gas phase reaction raw material containing a reducing gas to the tubular reactor; And

And a reaction product outlet for discharging the reaction product containing trichlorosilane produced by contacting and reacting with the metal silicon particles while the reaction raw materials of the liquid and gaseous phases are transferred into the tubular reactor.

In addition, the apparatus may further comprise means for supplying the liquid or gaseous reaction raw material with a halide.

The present invention also provides a method for producing trichlorosilane using the above production apparatus.

That is, a gaseous reaction raw material containing a liquid phase reaction raw material containing a liquid tetrachlorosilane and a reducing gas is introduced into a tubular reactor filled with metal silicon particles, and the liquid and gaseous reaction raw materials are transferred into the tubular reactor And then contact and react with the metal silicon particles to produce trichlorosilane.

The apparatus for producing trichlorosilane according to the present invention can form a high-pressure environment by reacting a reaction raw material containing liquid tetrachlorosilane, hydrogen and hydrogen chloride into a reactor filled with metal silicon, Since the inner diameter of the reactor gradually decreases in the flow direction of the fluid from the inlet to the outlet of the product, it is possible to have a wider reaction surface area in the initial stage where the inner diameter is wide. As the reaction progresses, The reaction raw material can stably maintain the liquid phase and the density of the charged metal silicon particles gradually tends to increase at a narrow inner diameter so that the flow of the fluid is gradually retarded, Sufficient to be fully reacted and exhausted It is possible to secure the tip of time and area.

In the above-mentioned reaction formula, hydrogen and hydrogen chloride are fed into the gaseous phase, but dissolved in tetrachlorosilane, so that they can be subjected to a liquid phase reaction, or they can be mixed in the form of a mixture before they are added to the reactor. The reaction products resulting from the reaction may be present in a liquid phase due to the internal pressure of the reactor immediately after the reaction.

According to the present invention, the reaction proceeds in a liquid phase in the reactor, which requires a high pressure in the reactor. The present invention can stabilize the reaction by filling the metal silicon in the reactor so that the internal pressure can be improved naturally as the liquid reaction raw material is added, and the higher pressure is maintained more efficiently.

In the process according to the present invention, tetrachlorosilane (STC), hydrogen chloride, hydrogen, and metal silicon powder are injected together into a high-temperature and high-pressure tubular reactor together with reactants, and metal silicon reacts with STC, (TCS). Therefore, at the outlet of the tubular reactor, it is most preferable that the metal silicon powder is not completely consumed in the reaction. In order for the metal silicon powder to be completely consumed in the reaction, the length of the tubular reactor may be sufficiently long, or the local pressure may be increased by introducing the fluid flow interrupting means. The present invention can be applied to a reactor in which only a reaction raw material containing tetrachlorosilane and gaseous hydrogen and hydrogen chloride is fed into the reactor without using a process of dispersing metal silicon additionally by using a tubular reactor containing metal silicon filled therein.

In addition, since the reaction according to the present invention is a high-temperature and high-pressure reaction, the influence of pressure is great, and therefore, the tubular reactor filled with the metal silicon not only maintains a uniform pressure as a whole but also acts as a flow- A small scale eddy current is formed by collision with the liquid phase, and not only the pressure difference of the reaction system is generated, but also the retention time and the contact time are increased to improve the efficiency of the reaction.

Hereinafter, an embodiment according to the method of the present invention will be described in more detail with reference to FIG.

As shown in Fig. 2, the gaseous tetrachlorosilane (1) passes through the cooler (10) and is converted into liquid tetrachlorosilane (2). The liquid tetrachlorosilane 2 is combined with the hydrogen chloride / hydrogen 4 and pressurized by the pump 20 so that the reaction starting material containing the liquid tetrachlorosilane / hydrogen chloride compound 7 is introduced into the tubular reactor 30, And the reaction proceeds. In the reactor 30, metal silicon for forming trichlorosilane is charged by reacting with the reaction raw material including the tetrachlorosilane / hydrogen chloride compound (7). Therefore, by supplying the liquid reaction raw material to the reactor , The reaction efficiency can be improved by raising the pressure inside the reactor (30). The reactor 30 is provided with heating means (not shown) for providing an optimum reaction temperature and can be designed to provide sufficient residence time and contact area.

3 and 4 are cross-sectional views of the reactor 30. As the reaction tube is filled with metal silicon, each of the reaction tubes 30 functions as a fluid flow disturbing means that interrupts the flow, so that the pressure of the liquid fluid flowing inside thereof naturally rises So that the inside diameter of the outlet 18 through which the product is discharged than the inlet 17 into which the tetrachlorosilane / hydrogen chloride compound 7 is introduced is made smaller As a result, the reaction efficiency can be further improved because the inflow product flows into the outflow port and gradually increases in the shape in which the inner diameter is decreased. Further, since the density of the metal silicon near the outlet 18 is increased, By reducing the space through which the particles escape, the silicon particles of the derivative contained in the resulting trichlorosilane may be absent or reduced , The purification process may be absent or may become simpler.

The shape of the reactor 30 can be used without restriction as long as it has a structure in which the inner diameter decreases from the inlet to the outflow port and gradually changes in the density of the metal particles. For example, as shown in FIG. 3, A truncated cone structure in which the inner diameter gradually decreases until the inner diameter gradually decreases from a predetermined position as shown in FIG.

Since the tubular reactor 30 according to the present invention has a shape in which the inner diameter gradually decreases, the filling density of the metal silicon filled in the reactor tends to gradually increase in accordance with the flow direction of the fluid, May be gradually increased, thereby improving the efficiency of the high-pressure reaction.

For example, it is preferable that the pressure inside the tubular reactor gradually increases from the inlet to the outlet, and the pressure difference between the inlet and the outlet is 1.5 times or more.

The inlet of the tubular reactor through which the reaction material flows may further include a differential pressure sensor (not shown) for controlling the differential pressure between the inside of the reactor and the inlet of the reaction material

The manufacturing method according to the present invention can produce trichlorosilane by injecting only tetrachlorosilane without additionally dispersing or injecting metal silicon powder by filling the inside of the tubular reactor with metal silicon, Can be omitted and can be produced in a simpler process. In the product, the generation of fine metal nanoparticles can be reduced, and the purification process can be further facilitated.

The present invention can be applied to a reactor containing a metal silicon powder, wherein the metal silicon powder is a nano-sized metal silicon powder having a diameter smaller than that of the metal silicon particles filled in the reactor.

At this time, it is preferable that the metal silicon particles added together with the liquid tetrochlorosilane are exhausted to the reaction, and in this case, a step (for example, a filtering step) for separating the metal silicon particles remaining after the reaction may be omitted .

The tubular reactor 30 may further include a metal silicon inlet (not shown) for replenishing the exhausted metal silicon from the reaction.

The effluent 8 from the reactor 30 is present in a liquid state due to the pressure inside the reactor. In order to separate the trichlorosilane and hydrogen chloride / hydrogen in the liquid reaction product, a pressurized or reduced pressure distillation apparatus may be used. However, Liquid trichlorosilane can be easily obtained by using trichlorosilane, hydrogen chloride, and hydrogen, which are present in a liquid state immediately after the reaction, in a state in which the silane is a liquid and hydrogen chloride and hydrogen are gases.

The reaction tube according to the present invention is preferably a horizontal tubular reactor. The design of the horizontal tubular reactor is preferably such that the reaction source comprising the metal silicon and the tetrachlorosilane is allowed to remain in a state where it can be fully reacted.

The reaction temperature may be suitably determined in consideration of the material and the capability of the production apparatus. However, if the reaction temperature is higher than necessary, the selectivity of trichlorosilane is lowered and chlorosilane other than trichlorosilane such as tetrachlorosilane or dichlorosilane The amount of silane by-products increases. This reaction is also an exothermic reaction. The reaction in which tetrachlorosilane reacts with hydrogen in the same reactor to form trichlorosilane is an endothermic reaction. Therefore, in consideration of the conditions of these two reactions, the reaction temperature may be variously set, and is generally set in the range of 300 to 1000 ° C. And most preferably in the range of 250 to 400 占 폚, but is not limited thereto. As the pressure of the reactor increases, the selectivity of trichlorosilane increases and the reactivity of tetrachlorosilane also increases. Typically in the range of 5 bar to 100 bar.

In the reactor according to the present invention, the pressure inside the reactor is increased by the flow of the reaction material through the metal silicon filled in the reactor. The pressure difference between the inlet of the reaction material and the inside of the reactor is 1 bar to 100 bar, 10 bar to 70 bar, and more preferably from 30 bar to 60 bar. If the differential pressure is too low, the effect of the present invention can not be obtained. If the differential pressure is higher than a certain level, the reaction may be affected or the flow of the fluid may be difficult. And the amount of metal silicon to be filled in the reactor can be adjusted to control the differential pressure.

Hereinafter, each reactant will be described in more detail.

Tetrachlorosilane

The tetrachlorosilane used in this reaction is not particularly limited, but tetrachlorosilane, which is a by-product in the production of polysilicon from trichlorosilane, is used in order to make effective use of tetrachlorosilane produced as a by- .

Metal silicon particles

The metal silicon particles to be filled in the tubular reactor are solid metal particles containing metal elements of metallurgical grade such as metal silicon, silicon iron, or polysilicon. There are no particular restrictions on the content or content of impurities such as iron compounds contained in the metal silicon. However, if the average particle diameter of the metal silicon is too small, the flow of the liquid reaction product may be excessively limited, so that it is preferably at least about 3 microns. Also, if the size is too large, the differential pressure effect intended by the present invention is insignificant, and therefore, it is preferable that the size is about 150 microns or less. Preferably, particles of the order of 5 to 63 microns are used.

In addition, it is preferable that the silicon particles to be charged into the reactor are provided in a volume ratio of 10 to 99%, preferably 50 to 90%, with respect to the internal volume of the tubular reactor.

Nanosized metal silicon powder or fine particles

The metal silicon used in the above reaction is a solid particle material containing a metal element silicon such as metal silicon, iron silicon, or polysilicon, which is a metallurgical agent. There are no particular restrictions on the content or content of impurities such as iron compounds contained in the metal silicon. However, the average particle diameter of the metal silicon is used in the form of fine particles of about 3 microns or less, preferably about 0.5 to 3 microns. In the present invention, the nano-size refers to 3 microns or less.

In the present invention, nano-sized metal silicon fine particles may be used in order to uniformly disperse the silicon metal fine particles in the liquid tetrachlorosilane to prevent aggregation and precipitation, and to increase the contact area between the silicon metal fine particles and tetrachlorosilane. The mixing ratio of the metal silicon fine particles and tetrachlorosilane is preferably 1:20 to 200, more preferably 1:50 to 150, in terms of weight ratio.

The amount of the metal silicon fine particles to be added can be appropriately selected within a range such that the distance between the metal silicon fine particles dispersed in tetrachlorosilane is 10 to 1000 nm, more preferably 50 to 500 nm.

Preferably, the step of separating the metal silicon fine particles remaining in the reaction from the reaction product can be omitted by preventing the nano-sized metal silicon fine particles from being used and remaining in the reaction.

Reducing gas

In the reaction according to the invention, the reducing gas helps to form trichlorosilane by reacting with tetrachlorosilane. A typical reducing gas is hydrogen.

As the source of hydrogen, various industrially available hydrogen may be used, and hydrogen or the like discharged during the production of polysilicon may be appropriately purified and used.

The ratio of tetrachlorosilane and hydrogen is generally 1 to 5 moles of hydrogen to 1 mole of tetrachlorosilane, but a ratio of 1 to 3 moles of hydrogen to 1 mole of tetrachlorosilane is more preferable. The feed rate can be set in an appropriate range according to the type and size of the reaction apparatus to be used.

Halide

The halide used in the reaction with the metal silicon is typically hydrogen chloride, and even if hydrogen or the like is mixed, it is used without any limitation. However, in general, chlorosilanes such as trichlorosilane, tetrachlorosilane, and dichlorosilane react with moisture because of high hydrolysis ability. Therefore, if water is contained in the hydrogen chloride, the yield of the produced trichlorosilane may be lowered. Therefore, it is preferable that the hydrogen chloride is in a dry state. Since the hydrogen chloride is dispersed in the molecular unit, it can be sufficiently distributed around the silicon nanoparticles dispersed in the liquid reaction product, thereby increasing the reaction efficiency.

The ratio of tetrachlorosilane and hydrogen chloride is generally 0.1 to 1 mole of hydrogen chloride per mole of tetrachlorosilane, but more preferably 0.2 to 0.5 mole of hydrogen chloride per mole of tetrachlorosilane. The feed rate can be set in an appropriate range according to the type and size of the reaction apparatus to be used.

Reactor

Since the reaction according to the present invention proceeds in a liquid phase, it is preferable to use a tubular reactor, particularly a microtubular reactor, as the reactor. The tubular reactor preferably has an inner diameter in the range of 1 to 50 mm to ensure uniform dispersion of reactants and sufficient residence time.

The reaction temperature may be suitably determined in consideration of the material and the capability of the production apparatus. However, if the reaction temperature is higher than necessary, the selectivity of trichlorosilane lowers and chlorine other than trichlorosilane such as tetrachlorosilane or dichlorosilane The amount of by-products in the silane increases. This reaction is also an exothermic reaction. The reaction in which tetrachlorosilane reacts with hydrogen in the same reactor to form trichlorosilane is an endothermic reaction. Therefore, in consideration of the conditions of these two reactions, the reaction temperature may be variously set, and is generally set in the range of 300 to 1000 ° C. And most preferably in the range of 250 to 400 占 폚, but is not limited thereto.

As the pressure of the reactor increases, the selectivity of trichlorosilane increases and the reactivity of tetrachlorosilane also increases. And is generally set in the range of 1 bar to 100 bar.

In the present invention, the inner diameter of the reactor gradually decreases in the flow direction of the fluid from the inlet of the reaction material to the outlet of the product, so that the reaction can proceed under higher pressure as the reaction proceeds.

According to one embodiment, as the reactor interior diameter decreases during the passage to the inlet and outlet of the reactor, the pressure may rise gradually, for example, the outlet pressure may be 1.5 to 5 times higher than the inlet pressure have.

Reaction catalyst

In the process according to the present invention, a catalyst may be used to enhance the reaction efficiency but it is not necessarily used.

As the catalyst, any known catalyst component in the reaction of metallic silicon and hydrogen chloride can be used without limitation. Specific examples of such a catalyst component include a metal or a chloride of a Group VIII element such as iron, cobalt, nickel, palladium, and platinum, and a metal or a chloride such as aluminum, copper, or titanium. These catalysts may be used alone or in combination of a plurality of catalysts. The amount of the catalyst component to be used is not particularly limited as far as the trichlorosilane is used in an amount sufficient to improve the production efficiency, and may be suitably determined in consideration of the capability of the production apparatus.

The catalyst component may be present by adding it to the reaction system, but when the metal silicon to be used contains a catalyst component such as an iron compound as an impurity, this impurity can be effectively used as a catalyst component. Needless to say, even when metal silicon containing a catalyst component as an impurity is used, there is no problem even if a catalyst component is further added into the reaction system in order to enhance reactivity between metal silicon and hydrogen chloride.

The method according to the present invention is characterized in that, in the production of trichlorosilane in the liquid phase reaction using liquid phase tetrachlorosilane using a tubular reactor, metal silicon particles are previously filled in the tubular reactor whose inner diameter is gradually decreased, The pressure inside the reactor can be gradually increased in accordance with the direction of flow of the fluid, and the effect can be achieved not only by facilitating the reaction proceeding under the high pressure condition, The reaction material retention time and the contact area can be improved and the reaction efficiency can be improved.

10. Cooler
17. Reaction feed inlet
18. Product outlet
20. Pump
30. Tubular Reactor
40. Metal silicon

Claims (16)

A tubular reactor filled with metal silicon particles,
Wherein the tubular reactor has a shape in which its inner diameter gradually decreases toward the reaction product outlet from the reaction material inlet. The method according to claim 1,
Wherein the filling density of the metal silicon particles filled in the tubular reactor gradually increases from the inlet to the outlet. The method according to claim 1,
Wherein the pressure in the tubular reactor gradually increases from the inlet to the outlet and the pressure difference between the inlet and the outlet is at least 1.5 times. The method according to claim 1,
A liquid reaction material feed port for feeding a liquid reaction material containing liquid tetrachlorosilane to the tubular reactor;
A gas phase reaction material feed port for feeding a gas phase reaction raw material containing a reducing gas to the tubular reactor; And
And a reaction product outlet for discharging a reaction product containing trichlorosilane produced by contacting and reacting with the metal silicon particles while the liquid and gaseous reaction raw materials are transferred into the tubular reactor, . 5. The method of claim 4,
Wherein the liquid or gaseous reaction raw material further comprises means for supplying a halide. The method according to claim 1,
Wherein the reactor has a differential pressure between the inlet of the reaction material and the inside of the reactor of 1 bar or more. The method according to claim 1,
Wherein the internal pressure of the tubular reactor is from 1 bar to 100 bar. The method according to claim 1,
Wherein the average particle size of the metal silicon particles to be filled in the tubular reactor is 3 to 100 占 퐉. The method according to claim 1,
Wherein the filled metal silicon particles are partially or completely consumed as the reaction progresses, and further comprising a metal silicon particle inlet for filling and charging the metal silicon particles. The method according to claim 1,
Wherein the metal silicon particles filled in the tubular reactor are filled in a volume ratio of 10% to 99% with respect to the inner volume of the tubular reactor. A process for the production of trichlorosilane using the apparatus of any one of claims 1 to 10. 12. The method of claim 11,
Wherein the reaction in the tubular reactor is a liquid phase reaction. 13. The method of claim 12,
Wherein the reaction is carried out at 300 to < RTI ID = 0.0 > 1000 C. < / RTI > 12. The method of claim 11,
Further comprising the step of replenishing or refilling the metal silicon particle particles exhausted by said reaction. 13. The method of claim 12,
And supplying a dispersion liquid in which the metallic silicon fine particles having smaller particle diameters than the metal silicon particles filled in the tubular reactor are dispersed in the liquid raw material for reaction to the reactor. 16. The method of claim 15,
The metal silicon fine particles dispersed in the dispersion may be contained in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of liquid tetrachlorosilane, and the average particle diameter is less than 3 占 퐉.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5673617A (en) 1979-11-17 1981-06-18 Osaka Titanium Seizo Kk Manufacture of trichlorosilane
KR19980024696A (en) * 1996-09-19 1998-07-06 미우라 유이찌 Method for producing silicon trichloride
JP3324922B2 (en) 1995-12-22 2002-09-17 株式会社トクヤマ Method for producing silicon trichloride
KR20150037681A (en) * 2013-09-30 2015-04-08 주식회사 엘지화학 Process for producing trichlorosilane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5673617A (en) 1979-11-17 1981-06-18 Osaka Titanium Seizo Kk Manufacture of trichlorosilane
JP3324922B2 (en) 1995-12-22 2002-09-17 株式会社トクヤマ Method for producing silicon trichloride
KR19980024696A (en) * 1996-09-19 1998-07-06 미우라 유이찌 Method for producing silicon trichloride
KR20150037681A (en) * 2013-09-30 2015-04-08 주식회사 엘지화학 Process for producing trichlorosilane

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