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WO2010113299A1 - Réacteur en phase vapeur - Google Patents

Réacteur en phase vapeur Download PDF

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Publication number
WO2010113299A1
WO2010113299A1 PCT/JP2009/056816 JP2009056816W WO2010113299A1 WO 2010113299 A1 WO2010113299 A1 WO 2010113299A1 JP 2009056816 W JP2009056816 W JP 2009056816W WO 2010113299 A1 WO2010113299 A1 WO 2010113299A1
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WO
WIPO (PCT)
Prior art keywords
reaction
reaction vessel
gas
outlet
plate
Prior art date
Application number
PCT/JP2009/056816
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English (en)
Japanese (ja)
Inventor
靖史 松尾
晃一 竹村
一利 寺内
Original Assignee
電気化学工業株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to PCT/JP2009/056816 priority Critical patent/WO2010113299A1/fr
Priority to JP2011506916A priority patent/JP5511795B2/ja
Publication of WO2010113299A1 publication Critical patent/WO2010113299A1/fr

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    • 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
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/005—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor carried out at high temperatures, e.g. by pyrolysis
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • 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
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00132—Controlling the temperature using electric heating or cooling elements
    • B01J2219/00135—Electric resistance heaters
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/0015—Controlling the temperature by thermal insulation means
    • B01J2219/00155—Controlling the temperature by thermal insulation means using insulating materials or refractories
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • B01J2219/00777—Baffles attached to the reactor wall horizontal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a gas phase reactor.
  • Trichlorosilane (SiHCl 3 ) is a special material gas used for manufacturing semiconductors, liquid crystal panels, solar cells, and the like. In recent years, demand has been steadily expanding, and growth is expected as a CVD material widely used in the electronics field.
  • Trichlorosilane is produced by the following reaction in which hydrogen (H 2 ) is added to tetrachlorosilane (SiCl 4 ). SiCl 4 + H 2 ⁇ SiHCl 3 + HCl (1)
  • This reaction is a thermal equilibrium gas phase reaction, and a positive reaction occurs by heating a raw material gas composed of gasified tetrachlorosilane and hydrogen to a high temperature of about 700 to 1400 ° C. to obtain trichlorosilane.
  • Patent Document 1 As a reaction apparatus for this type of gas phase reaction, for example, an apparatus as described in Patent Document 1 is known.
  • This device includes a reaction chamber composed of an outer chamber and an inner chamber surrounded by a heating element and formed by concentrically arranged tubes, and a diverter provided at the upper portion of the reaction chamber and interconnecting the outer chamber and the inner chamber. And a heat exchanger provided in the lower part of the reaction chamber for exchanging heat between the raw material gas introduced into the outer chamber and the reaction product gas derived from the inner chamber.
  • the raw material gas is preheated through a heat exchanger and supplied to the outer chamber, and the reaction proceeds while flowing from the outer chamber through the divertor through the inner chamber, and is cooled and discharged as a reaction product gas by the heat exchanger.
  • the reaction chamber is a double chamber through a diverter, and gas is reciprocated up and down in the order of the outer chamber and the inner chamber.
  • gas is reciprocated up and down in the order of the outer chamber and the inner chamber.
  • One object of the present invention is to provide a gas phase reaction apparatus that at least partially eliminates the disadvantages of the prior art. Another object of the present invention is to provide a gas phase reactor that maintains high heat transfer efficiency. It is a further object of the present invention to provide a gas phase reactor capable of preventing a reverse reaction as much as possible and achieving a high reaction yield, particularly a reactor suitable for a high temperature gas phase reaction of chlorosilane and hydrogen. is there.
  • a reaction vessel in which a plurality of kinds of source gases supplied from an inlet are reacted in a gas phase and discharged as a reaction product gas from an outlet;
  • a heating means attached to the reaction vessel for heating the inside of the reaction vessel;
  • a gas phase reaction apparatus provided with a reflecting member provided in the reaction vessel in the vicinity of the outlet and directing the flow of the reaction product gas toward the outlet.
  • the reaction vessel may have any structure and material suitable for high-temperature gas phase reaction, but has an inlet on one side of the vessel, and an outlet on the other side remote from the one side. And a structure that can take a predetermined distance between the inlet and the outlet, and is preferably made of a material that heats the wall surface by the heating means and transfers heat to the inside of the reaction vessel.
  • the heating means may be of any structure as long as the inside of the reaction vessel can be heated, but preferably has a structure in which the reaction vessel wall surface is heated to bring the inside of the reaction vessel to a high temperature heating state.
  • the reaction vessel can be formed of a material having excellent heat conductivity, and the reaction vessel wall can be directly heated.
  • the reaction vessel can be formed of a material having excellent heat transfer properties, and a heater can be provided outside the reaction vessel to heat the reaction vessel wall surface.
  • the reaction container is entirely contained in the storage container and insulated from the surroundings. However, particularly when the latter external heater is installed, the reaction container and the heater are provided with argon in the storage container. It is preferable to fill such an inert gas.
  • the reflection member may be any member as long as it can reflect the reaction product gas flow when it hits it and direct the reaction product gas flow toward the outlet, but the heating means heats the inside of the reaction vessel.
  • the reflecting member itself disposed in the reaction vessel is also heated and the heat transfer member moves the heat to the gas flow in the reaction vessel. Therefore, the reflecting member is preferably a plate material that receives and reflects the flow of the reaction product gas and directs the flow to the outlet, and is made of a material suitable for heat transfer, for example, a carbon plate is preferably used. it can.
  • the reaction vessel includes a cylindrical portion extending in the vertical direction, a bottom portion provided with an inflow port and provided at a lower portion of the cylindrical portion, and a top plate portion provided at an upper portion of the cylindrical portion.
  • the heating means is a heater that is disposed outside the reaction vessel and heats the cylindrical portion of the reaction vessel, and is reflective.
  • the member can be made of a plate-like material that is disposed substantially horizontally with a gap between the outlet and the inner surface of the top plate portion on the top plate portion side.
  • the reaction vessel has such a structure
  • the structure is simpler than when the gas flow path is reciprocated in the vertical direction.
  • the reflecting member is arranged at the position as described above, the space between the reflecting member and the top plate portion becomes a dead space having a low gas flow velocity, and as a result, the flow velocity of the gas flowing toward the outlet through the reflecting member.
  • the heat transfer efficiency from the reflecting member to the gas flow is improved as compared with the case where the reflecting member is not provided.
  • the heater heats the cylindrical portion of the reaction vessel and the top plate portion of the reaction vessel is not heated as much as the cylindrical portion, the top plate portion radiates heat to the outside of the reaction vessel. Since the reflecting member is provided on the top plate portion side, the gas flow does not directly hit the top plate portion, and the temperature drop of the gas flow is prevented.
  • the reflecting member may be composed of a plurality of plate-like materials arranged at intervals in the vertical direction.
  • the position of the plate-like material may be other if the lowermost plate-like body is positioned in the reaction vessel in the vicinity of the outlet and can direct the flow of the reaction product gas to the outlet.
  • the position of the plate-like body may be any position in the space from the lowest-order plate-like body to the inner surface of the top plate portion of the reaction vessel.
  • the reflection member When the reflection member has such a configuration, the gas is led out of the reaction chamber without directly contacting the top plate portion serving as the heat radiating portion, and thus the temperature drop of the reaction product gas can be prevented. Moreover, by installing a plurality of plate-like bodies, the lowermost plate-like body becomes higher than the gas temperature and contributes to the improvement of the gas temperature.
  • the reaction vessel and the reflection member can be made of a carbon member whose surface is coated with silicon carbide.
  • the reason why the carbon member is made is that such a member is excellent in heat resistance, thermal shock resistance, corrosion resistance, etc.
  • the carbon member is generated by hydrogen supplied into the reaction vessel or by combustion of hydrogen. Water that is subjected to thinning or embrittlement of the tissue. Therefore, it is preferable to apply a silicon carbide coating to the surface for long-term use in the trichlorosilane production process.
  • the gas phase reaction apparatus includes a metal outer cylinder container and a heat insulating layer lined on the outer cylinder container, and a storage container in which an inert gas is sealed. It is preferable that the reaction vessel and the heating means are accommodated. By adopting such a configuration, it is possible to prevent the heat generated from the heating means from escaping to the outside of the apparatus as much as possible, and to heat the reaction vessel as uniformly as possible.
  • the gas phase reactor according to the present invention is particularly preferably used in a reaction system in which a plurality of kinds of source gases contain tetrachlorosilane and hydrogen, and a reaction product gas contains trichlorosilane and hydrogen chloride.
  • the source gas may contain chemical species other than tetrachlorosilane and hydrogen, and the circulating fluid from other systems may be evaporated and supplied together.
  • the reaction product gas may contain chemical species other than trichlorosilane and hydrogen chloride, such as unreacted raw material components, high-boiling substances such as hexachlorodisilane, and low-boiling substances such as dichlorosilane.
  • a heat transfer member such as a perforated plate is further provided in the reaction vessel in order to further increase the heat transfer efficiency in the reaction vessel.
  • the heat transfer efficiency to the gas flow is increased, and the heat transfer member disturbs the gas flow and causes convection heat transfer. Therefore, the amount of heat transfer to the gas flow in the reaction vessel is increased, so that high heat transfer efficiency and thus high reaction yield can be achieved in the reaction vessel.
  • the perforated plate preferably has a porous portion with a gas flow rate of 2 m / s or more, and preferably has a porosity of 25% or less.
  • the perforated plate is preferably disposed with a clearance in the range of 6/1000 to 50/1000 of the inner wall diameter of the reaction vessel between the perforated plate and the inner wall of the reaction vessel.
  • the hole diameter of the part is preferably 25/1000 or less of the inner wall diameter of the reaction vessel, and the number of holes is preferably such that the open area ratio is 25% or less.
  • the thickness t of the porous plate is preferably 10 mm ⁇ t ⁇ 60 mm. This does not apply if there is no problem in manufacturing.
  • the gas phase reaction apparatus preferably includes a quenching tower that quenches the reaction product gas derived from the reaction vessel in addition to any one of the above-described various configurations.
  • the reaction product gas can be cooled as quickly as possible to freeze the equilibrium and prevent the reverse reaction from occurring as much as possible.
  • a reaction vessel in which a plurality of kinds of source gases supplied from an inlet are reacted in a gas phase and discharged as a reaction product gas from an outlet;
  • a heating means attached to the reaction vessel for heating the inside of the reaction vessel;
  • a reflection member provided in the reaction vessel in the vicinity of the outlet and directing the flow of the reaction product gas toward the outlet;
  • a gas phase reactor comprising a quenching device connected to the reaction vessel and quenching the reaction product gas led out from the outlet of the reaction vessel.
  • the gas phase reactor according to the present invention comprises: A plurality of types supplied from the inlet, comprising a cylindrical portion extending in the vertical direction, a bottom portion provided with an inlet and provided at the lower portion of the cylindrical portion, and a top plate portion provided at the upper portion of the cylindrical portion.
  • a reaction vessel that causes a gas phase reaction of the raw material gas and discharges it as a reaction product gas from an outlet provided at a position close to the top plate portion of the cylindrical portion;
  • a heating means disposed outside the reaction vessel for heating the cylindrical portion of the reaction vessel;
  • a reflective member made of a heat transfer material provided inside the reaction vessel with a gap formed between the inner surface of the top plate portion and the inner surface of the top plate portion on the top plate side from the outflow port; ,
  • a gas phase reactor comprising a quenching device connected to the reaction vessel and quenching the reaction product gas led out from the outlet of the reaction vessel.
  • FIG. 1 is a schematic longitudinal sectional view of a gas phase reaction apparatus according to a first embodiment of the present invention. It is the figure which expanded the principal part of the reaction apparatus of FIG. 1, and showed the reflector and the flow of gas typically. It is a schematic longitudinal cross-sectional view of the gaseous-phase reaction apparatus which concerns on the 2nd Embodiment of this invention.
  • the gas phase reaction apparatus 10 includes a cylindrical container 11, a reaction container 12 housed in the container 11, a container 11 and a reaction container 12. And a heater (heating means) 13 for heating the inside of the reaction vessel 12 and a quenching tower (quenching device) 14 connected to the reaction vessel 12.
  • the storage container 11 has a heat-insulating brick layer 16a lined on the inner surface of the bottom and periphery of the steel outer cylinder container 15, and a heat insulating material layer 16b such as an alumina heat insulating material lined on the upper inner surface of the outer cylinder container 15, respectively.
  • a heat insulating container which includes a cylindrical body portion 11a, a canopy portion 11b provided at the upper end of the body portion 11a, and a bottom plate portion 11c provided at the lower end of the body portion 11a, and is provided on the outer surface of the body portion 11a.
  • the supported support member 11d is supported on the foundation and installed with its axis centered up and down.
  • a through hole 11e is formed at the center of the bottom plate portion 11c, and a through hole 11f is formed at a predetermined position on the upper edge side of the body portion 11a.
  • the reaction vessel 12 is supported by a lower portion inside the storage container 11 and has a substantially cylinder made of carbon that is stored with a space between the inner wall of the body 11a of the storage container 11 and the canopy 11b with the axis centered vertically.
  • a plurality of substantially cylindrical members of a predetermined height are arranged in a substantially coaxial manner up and down in a cylindrical reaction vessel, and the butted ends are fastened by screwing or fastening by an external fitting ring.
  • the cylindrical body (tubular portion) 17 is tightly fastened by means, a carbon bottom plate member (bottom portion) 18 is provided at the lower end portion of the cylindrical body 17, and a carbon canopy member (ceiling portion) is provided at the upper end portion of the cylindrical body 17.
  • the plate portion) 19 is a cylindrical container that is airtightly fastened by fastening means similar to those of the cylindrical members.
  • the reaction vessel 12 has a bottom plate member 18 fitted into the through hole 11e of the bottom plate portion 11c of the storage vessel 11 and supported by the storage vessel 11.
  • the bottom plate member 18 has a flow of the raw material gas to the reaction vessel 12.
  • a through hole serving as the inlet 12a is formed, and an inflow pipe 20 connected to an evaporator (not shown) is connected to and attached to the through hole.
  • the canopy member 19 is made of a closing member, and a through hole serving as the outlet 12b of the reaction vessel 12 is formed on the side surface of the cylindrical member of the cylindrical body 17 close to the canopy member 19, and a reaction product gas extraction pipe is inserted into the through hole. 21 is attached.
  • the extraction pipe 21 is further inserted into the through hole 11 f of the storage container 11 and extends substantially horizontally to the outside of the storage container 11, and is connected to the quenching tower 14.
  • the heater 13 is a set of two whose front ends are electrically connected to each other, and is vertically spaced with a space in the circumferential direction of the reaction vessel 12 in a space between the inner wall of the trunk portion 11 a of the containing vessel 11 and the reaction vessel 12.
  • a plurality of long-bar-shaped carbon-made heating elements 13a disposed, and a plurality of sets of electrodes 13b that are connected to the respective base ends of the heating elements 13a and transfer electric power to the heating elements 13a. It becomes.
  • the base end side of the heating element 13 a is supported on the canopy 11 b of the storage container 11 via a heat insulating material or the like, and the distal end side of the heating element 13 a is suspended to the vicinity of the bottom plate part 11 c of the storage container 11.
  • the inside of the storage container 11 is filled with argon Ar as an inert gas, the inert gas is present around and above the reaction container 12, and when the heater 13 is applied, the heating element 13a is heated,
  • the reaction vessel 12 is heated to about 1300 ° C. from the outer periphery and the upper side together with the inert gas.
  • the quenching tower 14 instantaneously cools the reaction product gas mainly composed of a mixture of trichlorosilane and hydrogen chloride extracted from the extraction pipe 21 of the reaction vessel 12, and is disposed adjacent to the container 11.
  • a steel cylindrical tower main body 22, a spray device 23 provided with a nozzle attached to the tower main body 22 and spraying the cooling liquid inside the tower main body 22, and the cooling liquid accumulated in the tower main body 22 are taken out.
  • a pump (not shown) that circulates in the spray device 23, a cooling device (not shown) that cools the coolant, and a conduit (not shown) for taking out the reaction product gas after quenching from the top of the quenching tower 14 are provided. To do.
  • a reaction product gas introduction pipe 24 into which the extraction pipe 21 of the reaction vessel 12 is inserted is provided substantially horizontally on the side wall of the tower main body 22, and the tip of the extraction pipe 21 extends to the inside of the tower main body 22.
  • the coolant is sprayed from the top to the bottom with respect to the reaction product gas flowing out from the extraction pipe 21.
  • a reflection plate (reflecting member) 25 for directing the flow of the reaction product gas toward the outlet 12b is provided in the reaction vessel 12 in the vicinity of the outlet 12b of the reaction vessel. It has been.
  • a plurality of reflection plates 25 (three in the illustrated example) are arranged on the canopy member 19 side of the outlet 12b of the reaction vessel 12 and arranged in the vertical direction with a space between the reflection plate 25 and the inner surface of the canopy member 19.
  • Each of the reflecting plates 25 is made of a disk-shaped carbon member having an outer diameter smaller than the inner diameter of the portion of the reaction vessel 12 where the reflecting plate 25 is installed.
  • the thickness of the reflecting plate 25, the number of the reflecting plates 25, and the clearance between the reflecting plate 25 and the inner wall surface of the reaction vessel 12 are set so that the heat transfer efficiency in the reaction vessel 12 is as high as possible.
  • the reflecting plate 25 may be disposed substantially horizontally as in the illustrated example, or may be disposed in a state of being inclined downward in a direction away from the outflow port 12b.
  • the installation method of the reflecting plate 25 is arbitrary, and as shown in the example shown in the drawing, the reflecting plate 25 is arranged around the side inner surface of the canopy member 19 of the reaction vessel 12 or the inner peripheral surface of the cylindrical body 17 according to the vertical position of the reflecting plate 25.
  • a plurality of support members 26a are attached so as to be spaced apart from each other (or the corresponding cylindrical member is manufactured in advance as having a support portion), and the lowermost reflector 25 is placed thereon, and the lowermost Recesses are respectively formed at corresponding positions on the upper surface of the reflection plate 25 and the lower surface of the reflection plate 25 that is over the reflection plate 25, and a bar-like spacer member 26b is fitted into the recess on the lowermost reflection plate 25,
  • the second reflector 25 is attached by placing the next reflector 25 on the top and fitting the upper end of the spacer member 26b into the recess on the lower surface thereof.
  • the third reflector 25 can also be attached. it can.
  • the support member may be suspended from the canopy member 19 of the reaction vessel 12 and the reflection plate 25 may be attached thereto. Needless to say, the support member 26a and the spacer member 26b here are also carbon members.
  • the present inventors verified the installation effect of the reflection plate 25 installed in the reaction vessel 12 as described above. As a result, it has been found that the heat transfer efficiency in the reaction vessel 12 is significantly improved when the reflector 25 is provided.
  • a predetermined clearance for example, between the reflection plate 25 and the wall surface of the reaction vessel 12.
  • the number of the reflectors 25 may be one, but if the number is increased to two or three, the gas temperature can be suppressed from decreasing and the outlet gas temperature can be increased. However, due to the structure of the reaction vessel 12, the number of installation is up to several.
  • a graphite material having excellent airtightness is preferable, and in particular, the strength is high because of the fine particle structure, and the characteristics such as thermal expansion are the same in any direction. It is preferable to use isotropic high-purity graphite that is also excellent in heat resistance and corrosion resistance. Further, carbon is subjected to thinning or embrittlement of the structure as shown below due to hydrogen supplied into the reaction vessel or water generated by hydrogen combustion. C + 2H 2 ⁇ CH 4 C + H 2 O ⁇ H 2 + CO C + 2H 2 O ⁇ 2H 2 + CO 2 In order to prevent this, a silicon carbide film is preferably formed on the surface of the carbon member.
  • the method for forming the silicon carbide film is not particularly limited, but typically it can be formed by vapor deposition by a CVD method.
  • a method using a mixed gas of a silicon halide compound such as tetrachlorosilane or trichlorosilane and a hydrocarbon compound such as methane or propane, or methyl Silicon carbide is deposited on the surface of a heated carbon member while thermally decomposing a halogenated silicon compound such as trichlorosilane, triphenylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane with hydrogen.
  • the thickness of the silicon carbide coating is preferably 10 to 500 ⁇ m, more preferably 30 to 300 ⁇ m. If the thickness of the silicon carbide coating is 10 ⁇ m or more, the corrosion of the carbon member due to hydrogen, water, methane, etc. existing in the reaction vessel can be sufficiently suppressed, and if it is 500 ⁇ m or less, the silicon carbide coating is cracked. Cracking of the structure of the carbon member is not promoted.
  • a mixed gas of tetrachlorosilane and hydrogen gasified by the evaporator is introduced into the reaction vessel 12 from the inlet 12a at a predetermined introduction flow rate.
  • the reaction vessel 12 is heated from the outside by the heater 13, but when the outer side surface of the cylindrical body 17 of the reaction vessel 12 is heated, heat is transferred from the outer surface to the inner surface by conduction heat transfer, and the cylinder
  • the inner wall surface of the body 17 becomes high temperature, and the inside of the reaction vessel 12 is heated to a high temperature of about 700 to 1400 ° C. by radiant heat transfer or the like.
  • the gas flow flowing in the reaction vessel 12 is heated, the thermal equilibrium reaction of the formula (1) proceeds in the forward direction, and the introduced source gas becomes a reaction product gas mainly composed of trichlorosilane and hydrogen chloride, It is led from the outlet 12 b to the quenching tower 14 through the extraction pipe 21.
  • the heat transfer process related to the reflector 25 will be described in some detail.
  • the heating element 13a When the heater 13 is applied, the heating element 13a is heated, and radiant heat from the heating element 13a causes heat transfer.
  • the outer surface of the reaction vessel 12 is heated together with the argon Ar. Since the heating elements 13a of the heater 13 are arranged at equal intervals in the circumferential direction outside the cylindrical body 17 of the reaction vessel 12, the outer surface of the cylindrical body 17 of the reaction vessel 12 is heated to a high temperature together with the surrounding argon gas Ar.
  • the canopy member 19 of the reaction vessel 12 and the argon gas Ar in the vicinity thereof are not heated as much as the cylindrical body 17 and the surrounding argon gas Ar, and rather rather to the outside from the canopy member 19 of the reaction vessel 12. Heat dissipation is occurring.
  • the reaction vessel 12 is made of carbon, when the outer surface of the cylindrical body 17 is heated, heat is transferred to the inner surface of the reaction vessel 12 by conduction heat transfer, and then radiant heat transfer from the inner surface of the reaction vessel 12.
  • the reflector 25 is heated one after another by the above, but as described above, since heat radiation to the outside is generated from the canopy member 19 of the reaction vessel 12, only the lowest reflector 25 in the reflector 25 is present. The temperature becomes higher than the gas temperature, the heat transfer area is increased by the lowermost reflecting plate 25, and the amount of heat transfer to the gas flow is increased. Further, since the lowermost reflector 25 is disposed at a position slightly above the outlet 12b in a state of crossing the reaction vessel 12, the gas flow flowing upward from below collides with this and is branched.
  • the reflection plate 25 is provided inside the reaction vessel 12 heated by the heater 13, and the heat transfer efficiency in the reaction vessel 12 is radiant heat transfer by the reflection plate 25. Improved by convective heat transfer. Therefore, compared with the case where the reflecting plate 25 is not provided, the outlet gas temperature can be kept high, and a high reaction yield can be achieved. Further, since the extraction pipe 21 is provided at the outlet 12 b of the reaction vessel 12 and connected to the quenching tower 14, the reaction product gas is extracted from the extraction pipe 21 together with the effect of the reflector 25 near the outlet 12 b. Since the reaction product gas is instantaneously cooled in the quenching tower 14 from this state, the equilibrium reaction is frozen and the reverse reaction is effectively prevented.
  • FIG. 3 is a schematic cross-sectional view showing a gas phase reactor according to the second embodiment of the present invention.
  • a plurality of disc-shaped carbon porous plates 27 having a predetermined hole area ratio, hole diameter, and number of holes are provided in the reaction vessel 12 and are spaced apart in the height direction of the cylindrical body 17. It is arranged with a gap.
  • These perforated plates 27 are basically arranged at substantially equal intervals and substantially horizontally over substantially the entire length of the cylindrical body 17, but a predetermined clearance is maintained between the inner wall surface of the reaction vessel 12.
  • Each of the perforated plates 27 is basically manufactured or arranged so that the holes of the one perforated plate 27 and the perforated plates 27 positioned above and below the perforated plate 27 are not coaxial.
  • the installation method of the porous plate 27 is arbitrary, and can be installed by the same method as the reflection plate 25.
  • recesses are formed at a plurality of locations in the circumferential direction on the upper and lower surfaces of the perforated plate 27, and the upper and lower ends of a rod-like support member 28 are fitted between the recesses, and the perforated plate 27 is sequentially moved upward from the bottom of the reaction vessel 12.
  • Reflecting plate 25 in the illustrated example is stacked and installed.
  • a plurality of support edges may be attached to the inner wall surface of the reaction vessel 12 at intervals in the circumferential direction, and the porous plate 27 and the reflection plate 25 may be placed thereon.
  • the inventors verified the installation effect of the porous plate 27 installed in the reaction vessel 12 as described above. As a result, it was found that when the porous plate 27 is provided, the heat transfer efficiency in the reaction vessel 12 can be significantly improved. Moreover, it turned out that what has the following characteristics as the porous plate 27 to be used is preferable.
  • the thickness t of the porous plate is preferably 10 mm ⁇ t ⁇ 60 mm, and is not limited to this as long as there is no problem in manufacturing.
  • the aperture ratio of the perforated plate is the ratio of the total cross-sectional area of the perforations to the total area in plan view including the perforations of the perforated plate. The distance from the wall.
  • the mixed gas of tetrachlorosilane and hydrogen is heated to a high temperature while passing through the reaction vessel 12 in the same manner as in the first embodiment, so that trichlorosilane and chloride are mixed. It becomes a reaction product gas containing hydrogen as a main component, and is led from the outlet 12b to the quenching tower 14 through the extraction pipe 21.
  • the reflecting plate 25 but also the porous plate 27 is disposed in the reaction vessel 12, so that the heat transfer efficiency in the reaction vessel 12 is further improved.
  • the raw material gas and the reaction product gas flow in a mixed manner, and convective heat transfer occurs around the hole of the perforated plate 27, which also heats the gas. Since the porous plate 27 heated in this way is disposed in the reaction vessel 12, the heat transfer area in the reaction vessel 12 increases and convection heat transfer occurs. As a result, the amount of heat transfer to the gas flow increases, and the porous Since the flow rate of the gas flow increases when the gas flow passes through the hole of the plate 27, the heat transfer efficiency in the vicinity of the hole of the perforated plate 27 increases.
  • the porous plate 27 is provided in addition to the reflection plate 25 inside the reaction vessel 12 heated by the heater 13, so that the heat transfer efficiency in the reaction vessel 12 is further improved. It is done. Therefore, compared with the case where the reflecting plate 25 and the porous plate 27 are not provided, the outlet gas temperature can be kept high, and a high reaction yield can be achieved.
  • the reflecting plate 25 and the porous plate 27 are installed in the reaction vessel 12, but a structure in which the reflecting plate 25 is combined with a baffle plate or other molded filler may be used.
  • the reaction vessel 12 has a cylindrical shape with the same diameter in the vertical direction, but the vicinity of the outflow port 12b or the vicinity of the inflow port 12a may be a reduced diameter portion.
  • this Example is for confirming the installation effect about the typical example of a reflecting plate, Comprising:
  • the structure of a reflecting plate is not limited by this Example.
  • Example 1 The installation effect of the reflector was verified in the following reactor.
  • Container Outer cylinder container: SUS304, 19 mm thick Thermal insulation layer: Alumina thermal insulation, 29 mm thickness Thermal insulation brick layer: Alumina brick, 500 mm thickness Inert gas layer: Argon, 163 mm thickness
  • Reaction vessel Top plate: Carbon, 100mm thickness Inner diameter: 750mm
  • the reflection plate three disc-shaped carbon plate materials having a thickness of 20 mm and a diameter of 65 cm ⁇ were prepared.
  • the three reflectors were horizontally arranged with a support member at a distance from each other so that the lowermost reflector is located slightly above the outlet in the reaction vessel.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Silicon Compounds (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention porte sur un réacteur qui permet d'atteindre un rendement de réaction élevé en empêchant une contre-réaction ou similaire dans la mesure du possible, tout en maintenant une efficacité élevée de conduction thermique. La réaction est particulièrement appropriée pour une réaction en phase vapeur à haute température de chlorosilane et d'hydrogène. Le réacteur comprend une chambre de réaction dans laquelle plusieurs sortes de matières premières gazeuses, introduites à partir d'une ouverture d'entrée, sont mises à réagir dans une phase vapeur, et le produit de réaction gazeux ainsi obtenu est déchargé d'une ouverture de sortie ; un moyen de chauffage qui est attaché à la chambre de réaction dans le but de chauffer l'intérieur de la chambre de réaction ; et un élément de réflexion qui est disposé à l'intérieur de la chambre de réaction, près de l'ouverture de sortie, de façon à diriger le courant de produit de réaction gazeux vers l'ouverture de sortie.
PCT/JP2009/056816 2009-04-01 2009-04-01 Réacteur en phase vapeur WO2010113299A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2009/056816 WO2010113299A1 (fr) 2009-04-01 2009-04-01 Réacteur en phase vapeur
JP2011506916A JP5511795B2 (ja) 2009-04-01 2009-04-01 気相反応装置

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2009/056816 WO2010113299A1 (fr) 2009-04-01 2009-04-01 Réacteur en phase vapeur

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WO2010113299A1 true WO2010113299A1 (fr) 2010-10-07

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JP (1) JP5511795B2 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2738141A1 (fr) * 2011-07-25 2014-06-04 Tokuyama Corporation Récipient de silicium polycristallin

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49116439U (fr) * 1973-02-02 1974-10-04
JP2008137885A (ja) * 2006-11-07 2008-06-19 Mitsubishi Materials Corp トリクロロシランの製造方法およびトリクロロシラン製造装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001038195A (ja) * 1999-06-28 2001-02-13 Basf Ag 熱交換板を備えた反応器
JP2008150277A (ja) * 2006-11-21 2008-07-03 Mitsubishi Materials Corp 耐熱耐食性部材及びトリクロロシラン製造装置
JP5012449B2 (ja) * 2006-11-28 2012-08-29 三菱マテリアル株式会社 トリクロロシラン製造装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49116439U (fr) * 1973-02-02 1974-10-04
JP2008137885A (ja) * 2006-11-07 2008-06-19 Mitsubishi Materials Corp トリクロロシランの製造方法およびトリクロロシラン製造装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2738141A1 (fr) * 2011-07-25 2014-06-04 Tokuyama Corporation Récipient de silicium polycristallin
EP2738141A4 (fr) * 2011-07-25 2015-04-01 Tokuyama Corp Récipient de silicium polycristallin

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JP5511795B2 (ja) 2014-06-04

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