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WO2008059887A1 - Procédé de séparation/collecte d'hydrogène et dispositif de séparation/collecte d'hydrogène - Google Patents

Procédé de séparation/collecte d'hydrogène et dispositif de séparation/collecte d'hydrogène Download PDF

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Publication number
WO2008059887A1
WO2008059887A1 PCT/JP2007/072113 JP2007072113W WO2008059887A1 WO 2008059887 A1 WO2008059887 A1 WO 2008059887A1 JP 2007072113 W JP2007072113 W JP 2007072113W WO 2008059887 A1 WO2008059887 A1 WO 2008059887A1
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Prior art keywords
hydrogen
gas
absorption
hydrogen chloride
chlorosilanes
Prior art date
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Ceased
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PCT/JP2007/072113
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English (en)
Japanese (ja)
Inventor
Mitsutoshi Narukawa
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority claimed from JP2007276564A external-priority patent/JP5344113B2/ja
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Publication of WO2008059887A1 publication Critical patent/WO2008059887A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0216—Other waste gases from CVD treatment or semi-conductor manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity

Definitions

  • the present invention is, for example, a hydrogen that is connected to a conversion facility that generates trichlorosilane and can recover purified hydrogen by separating hydrogen chloride and chlorosilanes contained in the product gas of the conversion reaction.
  • the present invention relates to a separation and recovery method and its equipment.
  • High-purity polycrystalline silicon includes, for example, trichlorosilane (SiHCl: TCS) and hydrogen
  • the gas discharged from the above formation reaction of polycrystalline silicon includes unreacted trichlorosilane and hydrogen as well as by-produced hydrogen chloride and chlorosilanes such as tetrachlorosilane, dichlorosilane, and hexachlorodisilane. It is. These chlorosilanes are separated by distillation according to the boiling point, and reused as necessary.
  • trichlorosilane can be obtained by a hydrogenation conversion reaction represented by the following formula (3) using tetrachlorosilane recovered by distillation separation from the exhaust gas of the production reaction as a raw material
  • Chlorosilanes such as trichlorosilane and tetrachlorosilane contained in the gas produced in the conversion reaction are recovered by cooling and aggregation, and the trichlorosilane is reused as a raw material for producing the polycrystalline silicon.
  • the product gas contains a large amount of unreacted hydrogen
  • the chlorosilanes are condensed and separated
  • the hydrogen in the mixed gas is recovered and converted as a raw material for the conversion reaction. If it is returned to the furnace and reused, the use efficiency of hydrogen can be increased and the cost can be greatly reduced.
  • the product gas contains hydrogen chloride, and when used as a raw material for the conversion reaction in a state containing hydrogen chloride, there is a problem that the conversion reaction is hindered. In order to recover and reuse hydrogen from wastewater, it is necessary to efficiently remove hydrogen chloride contained in the product gas.
  • a treatment method shown in FIG. 3 As a conventional method for removing hydrogen chloride, for example, a treatment method shown in FIG. 3 is known. In this method, first, the reaction product gas of the converter 1 is led to the cooler 2 to be cooled, and chlorosilans are condensed and collected, and removed from the product gas to form a mixed gas of hydrogen chloride and hydrogen. Next, hydrogen chloride is removed by passing the mixed gas of hydrogen chloride and hydrogen through a neutralization tower 3 in which an aqueous solution of caustic soda circulates. Hydrogen chloride and uncondensed chlorosilanes contained in the mixed gas react with caustic soda in the neutralization tower 3 to generate sodium chloride and sodium silicate and deposit them at the bottom of the tower. .
  • the mixed gas in which hydrogen remains passes through the neutralization tower 3 and is introduced into the drying tower 4.
  • the drying tower 4 is filled with zeolite, and is dried while the hydrogen-containing gas passes through the tower.
  • the dried hydrogen is returned to the evaporator 5, mixed with the supplied hydrogen and the supplied STC, introduced into the conversion furnace 1, and recycled (see Patent Document 1).
  • Patent Document 1 Japanese Patent Laid-Open No. 48-40625 (Page 4, upper right column, Fig. 1)
  • the present invention solves the above-described problems in conventional hydrogen recovery technology, and efficiently removes hydrogen chloride and chlorosilanes from a gas containing chlorosilanes and hydrogen chloride together with hydrogen, for example, a product gas of a converter.
  • a hydrogen purification and recovery method and equipment that separates and removes and recovers purified hydrogen gas that can be reused for the conversion reaction, and separates hydrogen chloride and chlorosilanes in a form that can be effectively used to prevent waste loss.
  • the present invention relates to a hydrogen separation and recovery method that has solved the above problems by having the configurations shown in the following [1] to [6].
  • a method for separating and recovering hydrogen wherein the absorption liquid absorbs chlorosilanes and hydrogen chloride and separates them from the hydrogen, and recovers the hydrogen-based gas that has passed through the absorption liquid.
  • the mixed gas is introduced into an absorption tower through which the absorption liquid flows, and the absorption liquid absorbs chlorosilanes and hydrogen chloride, and then flows out of the absorption tower.
  • the absorbed liquid is introduced into the distillation tower, and hydrogen chloride contained in the absorbent is distilled and separated.
  • the absorbent flowing out from the distillation tower is recovered, cooled, returned to the absorption tower and reused.
  • the gas that has passed through the absorbent is passed through activated carbon, and chlorosilanes and hydrogen chloride remaining in the gas are adsorbed onto the activated carbon.
  • the process of distilling the absorption liquid that absorbed chlorosilane and hydrogen chloride to gasify and separate hydrogen chloride (hydrogen chloride separation process), separate hydrogen chloride
  • the recovered chlorosilanes are recovered, cooled and returned to the absorption step (absorption liquid circulation step), the hydrogen-based gas that has passed through the absorption liquid is passed through the activated carbon, and the chlorosilanes and hydrogen chloride remaining in the gas are removed from the activated carbon.
  • a method for separating and recovering hydrogen characterized by comprising a step of separating by adsorbing to water (hydrogen purification step).
  • [6] A method of separating and recovering hydrogen from a mixed gas generated in a conversion reaction in which tetrachlorosilane and hydrogen are reacted to form trichlorosilane, wherein the mixed gas generated in the conversion reaction is cooled to trichlorosilane.
  • the hydrogen separation and recovery method according to any one of [1] to [5] above, wherein hydrogen is separated and recovered by being introduced into the absorption liquid circulation step and the hydrogen purification step.
  • the present invention also relates to a hydrogen separation and recovery facility that has solved the above-mentioned problems by having the configuration shown in the following [7] to [; 12].
  • Absorber absorption tower
  • the equipment of [7] above has a hydrogen purification device into which a hydrogen-based gas that has passed through the absorption device is introduced.
  • the hydrogen purification device is filled with activated carbon, and the gas is activated.
  • a hydrogen separation and recovery facility in which chlorosilanes and hydrogen chloride in the gas are adsorbed on the activated carbon and removed from the gas while passing through the charcoal.
  • An absorption device for bringing a mixed gas containing chlorosilanes, hydrogen chloride and hydrogen into contact with an absorption liquid mainly composed of liquid chlorosilanes, and absorbing the chlorosilane and hydrogen chloride in the mixed gas into the absorption liquid, chlorosilane And the absorption liquid that absorbed hydrogen chloride is distilled.
  • a distillation device that gasifies and separates hydrogen chloride; a circulator that collects chlorosilanes from which hydrogen chloride has been separated and cools them back to the absorption step; and a hydrogen-based gas that has passed through the absorbent passes through activated charcoal.
  • a hydrogen separation and recovery facility comprising a hydrogen purifier for separating chlorosilanes and hydrogen chloride remaining in a gas by adsorbing them on the activated carbon.
  • a mixed gas containing chlorosilanes, hydrogen and hydrogen chloride is brought into contact with an absorption liquid mainly composed of liquid chlorosilanes, and the chlorosilanes And hydrogen chloride are removed from the gas by absorbing them into the absorption liquid, so that hydrogen can be easily separated and recovered from the mixed gas.
  • the absorbing liquid used in the present invention is mainly composed of liquid chlorosilanes.
  • the liquid chlorosilane is liquid at room temperature or lower, for example, 20 ° C or lower. It is made up of By bringing the mixed gas into gas-liquid contact with an absorption liquid composed of liquid chlorosilanes, hydrogen chloride and chlorosilanes in the gas are absorbed by the absorption liquid and can be separated from hydrogen remaining in the gas.
  • Trichlorosilane, dichlorosilane, tetrachlorosilane, etc. can be used as liquid chlorosilanes at 20 ° C or lower.
  • hydrogen chloride in the method of [3] and the equipment of [9], hydrogen chloride can be distilled and separated by distilling the absorbing solution that has absorbed chlorosilanes and hydrogen chloride. it can.
  • chlorosilanes since chlorosilanes remain in a liquid state, they can be recovered and reused as an absorbing solution without the need to cool chlorosilanes to extremely low temperatures. Therefore, it is possible to increase the usage efficiency without loss of black silanes.
  • the chlorosilanes remaining in the gas are introduced into the hydrogen purifier by introducing the hydrogen-based gas that has passed through the absorption liquid (absorption tower) into the activated carbon. Since hydrogen chloride is adsorbed onto activated carbon and removed from the gas, purified hydrogen gas substantially free of chlorosilanes and hydrogen chloride can be obtained. Therefore, this hydrogen gas can be reused for the conversion reaction of trichlorosilane, and the conversion rate of the reaction can be increased. Moreover, the process of drying hydrogen is unnecessary.
  • the method of [5] and the equipment of [10] include an absorption process, a hydrogen chloride separation process by distillation, and a process of circulating and reusing chlorosilanes recovered from the distillation separation process as a reaction liquid. Since it has a hydrogen purification step and the mixed gas is processed through the above series of steps, hydrogen can be efficiently separated and recovered from the mixed gas.
  • the method of [6] and the equipment of [11] and [12] are obtained by applying the hydrogen separation and recovery technique of the present invention to the production conversion reaction of chlorosilane, and the gas generated in this conversion reaction. From which hydrogen can be efficiently separated and recovered. Specifically, the gas generated in the above conversion reaction is cooled, the chlorosilanes in the gas are condensed and separated, and the chlorosilanes condensed and collected are led to the recovery process to separate the trichlorosilane. The mixed gas containing the recovered chlorosilanes after condensation and separation is led to the absorption step, the hydrogen chloride separation step, the absorption liquid circulation step, and the hydrogen purification step to separate and recover hydrogen, and this is converted. It can be reused effectively by returning to the reaction.
  • FIG. 1 is a conceptual diagram showing an example of a hydrogen separation and recovery method or facility according to the present invention.
  • FIG. 2 is a conceptual diagram showing another example of a hydrogen separation and recovery method or facility according to the present invention.
  • FIG. 3 is a conceptual diagram showing a conventional hydrogen separation and recovery facility.
  • FIG. 1 An example of a hydrogen separation and recovery system (method or equipment) according to the present invention is shown in FIG.
  • the embodiment shown in FIG. 1 is an example in which the hydrogen separation and recovery system of the present invention is applied to a conversion facility that generates trichlorosilane by reaction of tetrachlorosilane with hydrogen.
  • the hydrogen separation and recovery equipment shown in the figure includes an absorption device 8 in which an absorption liquid mainly composed of liquid chlorosilanes and the mixed gas are in contact with each other, and hydrogen purification in which a hydrogen-based gas that has passed through the absorption device is introduced.
  • Apparatus 12 distillation apparatus 9 into which the absorption liquid extracted from the absorption apparatus 8 is introduced, circulation line 10 for returning chlorosilanes extracted from the distillation apparatus 9 to the absorption apparatus 8, and cooling provided in the circulation line 10 14 is provided.
  • this hydrogen separation and recovery equipment is connected to a conversion device that reacts tetrachlorosilane with hydrogen to produce trichlorosilane, and a cooler 7 is provided between the pipes leading from the conversion device to the absorption device. Yes.
  • a tetrachlorosilane evaporator 5 and a conversion furnace 1 are provided in a conversion facility for generating trichlorosilane.
  • Raw material hydrogen and silicon tetrachloride (STC) are introduced into the evaporator 5, mixed and introduced into the converter 1.
  • Converter 1 is set to a furnace temperature of approximately 800 ° C to approximately 1300 ° C, and hydrogen and silicon tetrachloride react to produce chlorosilanes.
  • Chlorosilanes are tetrachlorosilane, trichlorosilane, trace amounts of dichlorosilane, hexachlorodisilane, etc., which are gasified under the above reaction temperature, and a mixed gas containing these chlorosilanes, hydrogen chloride and hydrogen is converted into a converter 1 Extracted from.
  • the mixed gas (temperature: about 600 ° C to about 1100 ° C) flowing out of the converter 1 is led to the first cooler 7 and cooled to about -50 ° C to about 50 ° C. Chlorosilanes contained in the mixed gas are cooled to condensate and separated from the mixed gas.
  • the separated chlorosilanes are guided to a distillation facility (not shown), and while passing through a plurality of distillation towers, at a distillation temperature corresponding to the boiling point of the chlorosilanes, trichlorosilane, tetrachlorosilane, other High boilers are separated in stages.
  • the recovered trichlorosilane is It can be used as a raw material for producing polycrystalline silicon.
  • the mixed gas that has passed through the first cooler 7 is introduced into the absorption device 8 of the hydrogen separation and recovery facility.
  • This mixed gas contains unseparated chlorosilanes, hydrogen chloride, and hydrogen.
  • Absorption liquid mainly composed of liquid chlorosilanes is supplied to the absorption device 8, and the mixed gas comes into gas-liquid contact with the absorption liquid, and the chlorosilanes and hydrogen chloride in the gas are absorbed into the absorption liquid.
  • the absorbing liquid is mainly composed of liquid chlorosilanes, and specifically comprises liquid chlorosilanes at room temperature or lower, for example, 20 ° C or lower.
  • liquid chlorosilanes trichlorosilane, dichlorosilane, tetrachlorosilane and the like can be used.
  • an absorption tower or a publishing tank can be used.
  • the absorption tower for example, a pole ring packed tower is used.
  • a mixed gas is supplied from the bottom of the tower, the absorbing liquid is allowed to flow down from the top of the tower in a shower shape, and the mixed gas is brought into contact with the absorbing liquid as it rises in the tower.
  • the absorption liquid is stored in the tank, and a mixed gas is introduced from the bottom of the tank to publish the absorption liquid.
  • the absorption liquid extracted from the absorption device 8 is introduced into a distillation device (distillation tower) 9.
  • the distillation apparatus 9 is operated according to the boiling point of hydrogen chloride, and the hydrogen chloride contained in the absorption liquid is distilled and removed as a top component.
  • undistilled chlorosilanes are extracted as a bottom component, and can recover chlorosilanes separated from hydrogen chloride, for example, chlorosilanes having a hydrogen chloride concentration of lOOppm or less.
  • the separated hydrogen chloride can be used for various applications.
  • the separated hydrogen chloride can be sent to the process of producing trichlorosilane by reacting hydrogen chloride with metallic silicon and reused as a raw material.
  • Undistilled chlorosilanes are withdrawn from the distillation apparatus 9 and introduced into the second cooler 14 through the circulation line 10 and are at room temperature or lower, for example, 20 ° C or lower, preferably ⁇ 50 ° C to 20 ° C.
  • the chlorosilanes contained in the gaseous state are condensed and liquefied, returned to the absorption device 8 through the circulation line 10, and used again as the absorption liquid.
  • the absorbing solution is repeatedly circulated and used. If the liquid volume is increased to a certain level due to repeated absorption of chlorosilanes through circulation, a part of the liquid is extracted, and the outlet gas temperature of the cooler 14 is adjusted to the absorption tower. When the liquid volume decreases, chlorosilanes are added to adjust the circulating volume of the absorbing liquid within a certain range. Is done.
  • the absorption liquid (chlorosilanes) extracted to adjust the circulating liquid volume of the absorption liquid is sent to a distillation facility for recovering trichlorosilane and reused effectively.
  • black silanes are not extracted out of the system until a certain amount is reached, so that chlorosilanes can be used efficiently without causing substantial loss of chlorosilanes.
  • a heat exchanger 11 is provided in a pipe line extending from the absorption device 8 to the distillation device 9, and the circulation route 10 is formed so as to pass through the heat exchanger 11. It is better to make effective use of the heat.
  • the temperature of the chlorosilanes extracted from the distillation apparatus 9 is approximately 70 ° C to 120 ° C.
  • the temperature of the absorption liquid extracted from the absorption apparatus 8 is below room temperature. The temperature of the absorption liquid introduced into the distillation apparatus 9 can be increased by passing through, and the amount of heat necessary for distillation can be saved.
  • Hydrogen in the mixed gas introduced into the absorption device 8 passes through the absorption liquid in a gaseous state without being absorbed by the absorption liquid (liquid chlorosilanes). Therefore, the gas flowing out from the absorber 8 is a hydrogen-based gas, which is introduced into the hydrogen purifier 12.
  • the hydrogen purifier 12 is filled with activated carbon. While the hydrogen-based gas passes through the activated carbon packed bed, unseparated chlorosilanes and hydrogen chloride contained in the gas are adsorbed by the activated carbon and are contained in the gas. And purified hydrogen gas is obtained.
  • the purified hydrogen gas is introduced into the evaporator 5 of the conversion facility through the circulation line 13, and is reused as part of the raw material for the conversion reaction. Since this purified hydrogen gas does not contain chlorosilanes and hydrogen chloride, the above conversion reaction is not hindered and the conversion rate of the raw material can be increased.
  • the activated charcoal packed bed adsorbing chlorosilanes and hydrogen chloride can be desorbed by passing hydrogen gas under heating. This The desorption gas can be cooled and the chlorosilanes can be condensed and recovered.
  • TCS 2.7kmol / hr
  • STC 15.4kmol / hr
  • HCl 2.7kmol / hr
  • H 33.5kmol / hr
  • the above mixed gas is introduced into the cooler 7 and cooled to -50 ° C to 20 ° C to condense and collect chlorosilanes and collect the mixed gas containing uncondensed chlorosilanes. It was introduced into absorption tower 8 of the hydrogen separation and recovery facility shown in Fig. 4.
  • the absorption tower 8 was a pole ring packed tower having a tower diameter of 800 mm ⁇ and a packed bed height of 13500 mmh.
  • Table 1 shows the pressure of the mixed gas introduced into the absorption tower.
  • the temperature of the absorption tower and the amount of the circulating liquid flowing through the tower were controlled within the ranges shown in Table 1. The results are shown in Table 1.
  • the concentrations of chlorosilanes and hydrogen chloride contained in the absorption tower outlet gas were measured based on the gas chromatographic method or infrared absorption photometry (FTIR).
  • the amount of circulating liquid in the absorption tower is the amount of liquid supplied to the absorption tower of the absorption liquid.
  • the absorption rate of hydrogen chloride is given by (HC1 concentration in absorption tower outlet gas / HC1 concentration in absorption tower inlet gas).
  • the activated carbon packed bed 12 used had a tower diameter of 1600 mm ⁇ and a packing height of 9000 mmh. The results are shown in Table 1.
  • the concentrations of chlorosilanes and hydrogen chloride in the absorption tower outlet gas are both low. Most of the chlorosilanes and hydrogen chloride contained in the mixed gas are absorbed by the absorbent. I understand. In particular, the absorption rate of hydrogen chloride is 96% or more except for No. 2 and No. 3, indicating a high absorption rate. Furthermore, hydrogen chloride and chlorosilanes were not detected from the outlet gas of the hydrogen purifier, and they were completely removed, and purified hydrogen gas not containing hydrogen chloride and chlorosilanes was recovered.
  • the above embodiment is an example because the amount of circulating fluid, the absorption rate of hydrogen chloride, and the like vary depending on the size of the apparatus, the performance of the absorption tower packing, the composition of the mixed gas, and the like. Accordingly, the technical scope of the present invention is not limited to the above-described embodiments, and various changes can be made to the scope and V without departing from the spirit of the present invention.
  • the absorbent used in the present invention is mainly composed of liquid chlorosilanes.
  • the liquid chlorosila is liquid at room temperature or lower, for example, 20 ° C or lower. It is made up of By bringing the mixed gas into gas-liquid contact with an absorption liquid composed of liquid chlorosilanes, hydrogen chloride and chlorosilanes in the gas are absorbed by the absorption liquid and can be separated from hydrogen remaining in the gas. Trichlorosilane, dichlorosilane, tetrachlorosilane, etc. can be used as liquid chlorosilanes at 20 ° C or lower.
  • hydrogen chloride in the method of [3] and the equipment of [9], hydrogen chloride can be separated by distillation by distilling an absorption liquid that has absorbed chlorosilanes and hydrogen chloride. it can.
  • chlorosilanes since chlorosilanes remain in a liquid state, they can be recovered and reused as an absorbing solution without the need to cool chlorosilanes to extremely low temperatures. Therefore, black mouth It is possible to increase the use efficiency without loss of silanes.
  • the chlorosilanes remaining in the gas are introduced into the hydrogen purifier by introducing the hydrogen-based gas that has passed through the absorption liquid (absorption tower) into the activated carbon. Since hydrogen chloride is adsorbed onto activated carbon and removed from the gas, purified hydrogen gas substantially free of chlorosilanes and hydrogen chloride can be obtained. Therefore, this hydrogen gas can be reused for the conversion reaction of trichlorosilane, and the conversion rate of the reaction can be increased. Moreover, the process of drying hydrogen is unnecessary.
  • the method of [5] and the equipment of [10] include an absorption step, a hydrogen chloride separation step by distillation, and a step of circulating and reusing chlorosilanes recovered from the distillation separation step as a reaction solution, Since it has a hydrogen purification step and the mixed gas is processed through the above series of steps, hydrogen can be efficiently separated and recovered from the mixed gas.
  • the method of [6] and the equipment of [11] and [12] above apply the hydrogen separation and recovery technology of the present invention to the production and conversion reaction of chlorosilane, and the gas produced in this conversion reaction. From which hydrogen can be efficiently separated and recovered. Specifically, the gas generated in the above conversion reaction is cooled, the chlorosilanes in the gas are condensed and separated, and the chlorosilanes condensed and collected are led to the recovery process to separate the trichlorosilane. The mixed gas containing the recovered chlorosilanes after condensation and separation is led to the absorption step, the hydrogen chloride separation step, the absorption liquid circulation step, and the hydrogen purification step to separate and recover hydrogen, and this is converted. It can be reused effectively by returning to the reaction.

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Abstract

L'invention concerne un procédé et un dispositif destiné à la séparation/collecte d'hydrogène, qui peut être relié à un dispositif de conversion afin de produire du trichlorosilane et permet de séparer et de recueillir efficacement de l'hydrogène contenu dans un gaz créé par une réaction de conversion, et permet de réutiliser l'hydrogène. Sont décrits de façon spécifique : un procédé de séparation/collecte d'hydrogène comprenant les étapes consistant à : mettre en contact un gaz mixte contenant un chlorosilane, du chlorure d'hydrogène et de l'hydrogène avec une solution d'absorption comprenant principalement un chlorosilane liquide de façon à provoquer l'absorption du chlorosilane et du chlorure d'hydrogène présents dans le gaz mixte dans la solution d'absorption [étape d'absorption] ; distiller la solution d'absorption qui a absorbé le chlorosilane et le chlorure d'hydrogène pour gazéifier le chlorure d'hydrogène et séparer le chlorure d'hydrogène gazéifié [étape de séparation de chlorure d'hydrogène] ; recueillir le chlorosilane séparé du chlorure d'hydrogène, refroidir le chlorosilane recueilli et renvoyer le chlorosilane refroidi à l'étape d'absorption [étape de recyclage de la solution d'absorption] ; et faire passer un gaz qui a traversé la solution d'absorption et est principalement composé d'hydrogène à travers du charbon actif pour provoquer l'adsorption du chlorosilane et du chlorure d'hydrogène restant dans le gaz sur le charbon actif, permettant ainsi de séparer l'hydrogène du chlorosilane et du chlorure d'hydrogène [étape de purification d'hydrogène] ; et un dispositif pour la mise en œuvre du procédé.
PCT/JP2007/072113 2006-11-14 2007-11-14 Procédé de séparation/collecte d'hydrogène et dispositif de séparation/collecte d'hydrogène Ceased WO2008059887A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006308475 2006-11-14
JP2006-308475 2006-11-14
JP2007-276564 2007-10-24
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CN102574680A (zh) * 2009-10-14 2012-07-11 信越化学工业株式会社 氢气回收系统以及氢气的分离回收方法
CN110314515A (zh) * 2019-04-29 2019-10-11 新疆大全新能源股份有限公司 一种三氯氢硅生产中硅粉残渣的处理系统和处理方法
CN113321183A (zh) * 2021-05-08 2021-08-31 内蒙古新特硅材料有限公司 多晶硅生产用氢气、除杂方法及系统、多晶硅生产方法及系统
WO2022230124A1 (fr) * 2021-04-28 2022-11-03 株式会社日立製作所 Procédé et dispositif de gestion de l'alimentation et de la demande en hydrogène

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JP2006131491A (ja) * 2004-10-05 2006-05-25 Tokuyama Corp シリコンの製造方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102574680A (zh) * 2009-10-14 2012-07-11 信越化学工业株式会社 氢气回收系统以及氢气的分离回收方法
CN110314515A (zh) * 2019-04-29 2019-10-11 新疆大全新能源股份有限公司 一种三氯氢硅生产中硅粉残渣的处理系统和处理方法
WO2022230124A1 (fr) * 2021-04-28 2022-11-03 株式会社日立製作所 Procédé et dispositif de gestion de l'alimentation et de la demande en hydrogène
CN113321183A (zh) * 2021-05-08 2021-08-31 内蒙古新特硅材料有限公司 多晶硅生产用氢气、除杂方法及系统、多晶硅生产方法及系统

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