WO2015146766A1 - Procédé de purification et dispositif de purification pour gaz cible - Google Patents

Procédé de purification et dispositif de purification pour gaz cible Download PDF

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WO2015146766A1
WO2015146766A1 PCT/JP2015/058189 JP2015058189W WO2015146766A1 WO 2015146766 A1 WO2015146766 A1 WO 2015146766A1 JP 2015058189 W JP2015058189 W JP 2015058189W WO 2015146766 A1 WO2015146766 A1 WO 2015146766A1
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adsorption
gas
adsorption tank
tank
tanks
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PCT/JP2015/058189
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English (en)
Japanese (ja)
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岩本　純一
充 岸井
康一 志摩
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住友精化株式会社
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Priority to KR1020167029851A priority Critical patent/KR102317284B1/ko
Priority to JP2016510282A priority patent/JP6502921B2/ja
Publication of WO2015146766A1 publication Critical patent/WO2015146766A1/fr
Priority to PH12016501880A priority patent/PH12016501880A1/en

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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
    • 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
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • 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
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • 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
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/18—Noble gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • 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
    • 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
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40058—Number of sequence steps, including sub-steps, per cycle
    • B01D2259/40075—More than ten
    • 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
    • B01D2259/404—Further details for adsorption processes and devices using four beds
    • 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
    • B01D2259/41—Further details for adsorption processes and devices using plural beds of the same adsorbent in series
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y02P20/156—Methane [CH4]

Definitions

  • the present invention relates to a method and an apparatus for purifying and obtaining a target component gas by removing an impurity component from a mixed gas containing a target component such as hydrogen by using a pressure fluctuation adsorption method.
  • hydrogen has attracted attention as an energy source to replace hydrocarbons, such as raw materials for fuel cells, and as an energy storage medium for energy with large output fluctuations such as wind power generation and solar power generation.
  • a method for producing hydrogen for example, a method of separating from a hydrogen-containing gas such as coke oven gas (hereinafter referred to as “COG” where appropriate), or a method obtained by reforming a hydrocarbon-based raw material such as natural gas or methanol is known. Yes.
  • the coke oven gas contains light hydrocarbons such as carbon monoxide, carbon dioxide and methane as impurities in addition to hydrogen as a main component, and also heavy hydrocarbons, BTX (benzene, toluene, xylene), sulfur compounds Contains a small amount.
  • BTX benzene, toluene, xylene
  • sulfur compounds Contains a small amount.
  • PSA method a pressure fluctuation adsorption method
  • Purification of hydrogen gas by the PSA method is performed, for example, by introducing a mixed gas containing hydrogen into an adsorption tank filled with an adsorbent under high pressure to adsorb impurities to the adsorbent, and hydrogen-enriched gas enriched with hydrogen Is performed by repeating a cycle including a step of discharging the gas, and a step of depressurizing the inside of the adsorption tank to desorb impurities from the adsorbent and exhaust gas from the adsorption tank.
  • pre-adsorption an adsorption tank (hereinafter referred to as “pre-adsorption tank”) filled with an adsorbent for adsorbing impurities is placed before the PSA method, and impurities are adsorbed and removed from the COG.
  • Patent Document 1 COG is flowed in one direction in the pre-adsorption tank to remove these impurities, and the impurities are replaced with a new adsorption tank before breaking through the pre-adsorption tank (Patent Document 1), or the PSA method.
  • Patent Document 2 There is a method (Patent Document 2) in which the pre-adsorption tank is regenerated by desorbing impurities from the pre-adsorption tank (pre-filter) in conjunction with the main adsorption tank.
  • an object of the present invention is to provide a method and apparatus suitable for preventing an impurity component from reducing the PSA adsorbent refining ability from being affected by the impurity component.
  • a purification method of a target gas provided by the first aspect of the present invention is a method for purifying a target gas from a mixed gas containing a target component and a plurality of impurity components, and selectively adsorbs the impurity components.
  • the mixed gas is introduced into the adsorption unit in a state where the adsorption unit is at a relatively high pressure by a pressure fluctuation adsorption method using a plurality of adsorption units filled with the adsorbent to be An adsorption step of adsorbing the impurity component of the adsorbent to the adsorbent and discharging the target component-enriched gas enriched with the target component from the adsorption unit; and depressurizing the adsorption unit and discharging the gas from the adsorption unit
  • the adsorption units are connected in series.
  • the open / close valve provided between the first and second adsorption tanks communicates with the state in which the first and second adsorption tanks communicate with each other. It is characterized by switching to a state that does not.
  • the present inventor conducted the following factor analysis in order to solve the above problems.
  • the regeneration of the pre-adsorption tank can be performed by synchronizing the purification cycle by the PSA method and the adsorption / desorption of the pre-adsorption tank. is necessary.
  • the source gas is COG
  • the hydrogen contained in the pre-adsorption tank can also be recovered before the regeneration step.
  • the impurities removed by the pre-adsorption may be recovered at the same time.
  • an automatic valve (open / close valve) is provided between the pre-adsorption tank (first adsorption tank) and the main adsorption tank (second adsorption tank) for performing PSA.
  • the depressurization step includes introducing the gas mainly composed of the target component in the first adsorption tank into the second adsorption tank while communicating the first and second adsorption tanks; Discharging the gas mainly composed of impurity components in the first adsorption tank to the outside without allowing the first and second adsorption tanks to communicate with each other.
  • the gas in the second adsorption tank is introduced into another second adsorption tank, and the impurity component is introduced into the second adsorption tank.
  • the step of discharging the main gas to the outside is performed after the step of introducing the gas mainly containing the target component into the second adsorption tank.
  • a plurality of the first adsorption tanks are provided in parallel to the corresponding second adsorption tanks in series, and the gas mainly composed of the target component is adsorbed to the second adsorption tank.
  • the gas flow is made possible so that the gas can enter and exit in any one of the plurality of the first adsorption tanks provided. Switch the state.
  • the first adsorption tank is filled with a first adsorbent that selectively adsorbs at least one of the plurality of impurity components
  • the second adsorption tank contains the plurality of impurity components.
  • the second adsorbent that selectively adsorbs at least one of the other is filled.
  • the target component is hydrogen.
  • a purification apparatus for a target gas is an apparatus for purifying a target gas from a mixed gas containing a target component and a plurality of impurity components, one end of which is connected via a communication path.
  • a plurality of first gas passage ports and second gas passage ports provided at the other end portions, and filled with an adsorbent that selectively adsorbs impurity components, and connected in series to each other.
  • the main trunk road to which the means is attached, and the first and second adsorption tanks are connected to the second gas passage side of the second adsorption tank, and an on-off valve is attached.
  • the first and second adsorption tanks provided for each set of the first and second adsorption tanks are connected to the scan pass port side and closing valve is attached, and a fifth pipe having, characterized in that it comprises a.
  • a plurality of the first adsorption tanks are provided so as to be parallel to the corresponding second adsorption tanks in series, and any one of the plurality of the first adsorption tanks provided.
  • One of them is provided with switching means for switching the gas flow state so that gas can enter and exit.
  • the first adsorption tank is filled with a first adsorbent that selectively adsorbs at least one of the plurality of impurity components
  • the second adsorption tank contains the plurality of impurity components.
  • the second adsorbent that selectively adsorbs at least one of the other is filled.
  • the schematic structure of the gas purification apparatus which can be used in order to implement the purification method of the target gas which concerns on this invention is represented.
  • the gas flow state in steps 1 to 5 of the target gas purification method according to the present invention is shown.
  • the gas flow state in steps 6 to 10 of the method for purifying a target gas according to the present invention is shown.
  • the gas flow state in steps 11 to 15 of the target gas purification method according to the present invention is shown.
  • the gas flow state in steps 16 to 20 of the target gas purification method according to the present invention is shown. It is a figure which shows the principal part of the modification of the gas purification apparatus which can be used in performing the purification method of the target gas which concerns on this invention.
  • FIG. 1 shows a schematic configuration of an example of a gas purification apparatus X1 that can be used to execute a target gas purification method according to an embodiment of the present invention.
  • the gas purification apparatus X1 includes, for example, first adsorption tanks 10A, 10B, 10C, and 10D that function as pre-adsorption tanks, second adsorption tanks 20A, 20B, 20C, and 20D that function as main adsorption tanks, and a communication path 16. And pipes 31 to 35, and configured to concentrate and purify the target gas from a mixed gas containing the target gas using a pressure fluctuation adsorption method (PSA method).
  • the mixed gas may be, for example, coke oven gas (COG) when the target gas is hydrogen.
  • COG coke oven gas
  • COG contains carbon dioxide, carbon monoxide, methane, and the like as impurities, as well as heavy hydrocarbons, BTX (benzene, toluene, xylene), sulfur compounds, etc., according to the PSA method. Contains impurities that adversely affect hydrogen purification.
  • the composition of the mixed gas is not particularly limited. For example, hydrogen is 54.0 mol%, methane is 30.0 mol%, carbon monoxide is 7.0 mol%, carbon dioxide is 3.0 mol%, and other light A hydrocarbon is 4.0 mol%, and heavy hydrocarbon, BTX, a sulfur compound, etc. are 2.0 mol%. In the following description, the mixed gas is assumed to be COG, but the present invention is not limited to this.
  • the first adsorption tanks 10A to 10D and the second adsorption tanks 20A to 20D correspond to form a pair, and in this embodiment, four sets (four pairs) of first and second adsorption tanks are used. Is provided.
  • the first and second adsorption tanks (for example, the first and second adsorption tanks 10A and 20A) forming each group are connected in series through the communication path 16 in the gas flow direction. It constitutes a suction unit.
  • Each of the first adsorption tanks 10A to 10D has gas passage ports 11 and 12 at both ends.
  • Each of the second adsorption tanks 20A to 20D has gas passage ports 21 and 22 at both ends.
  • Each communication path 16 connects the first and second adsorption tanks that make up each pair, and one end of the communication path 16 is connected to the gas passage port 12 and the other end is connected to the gas passage port 21.
  • the communication passage 16 is provided with an automatic valve 16a (16b, 16c, 16d) for switching between an open state and a closed state.
  • Each of the first adsorption tanks 10A to 10D is filled with an adsorbent (first adsorbent) for selectively adsorbing heavy hydrocarbons, BTX, and sulfur compounds contained in the mixed gas (COG). Yes.
  • first adsorbent include activated carbon.
  • second adsorbent has an adsorbent (second adsorbent) for selectively adsorbing methane, carbon monoxide, carbon dioxide, and other light hydrocarbons contained in the mixed gas. Filled.
  • the second adsorbent include carbon molecular sieve (CMS) and zeolite molecular sieve (ZMS). These may be used alone or in combination. Further, when the mixed gas contains moisture, the second adsorbent may additionally contain alumina.
  • the pipe 31 is used to supply a mixed gas (raw material gas) to the first adsorption tanks 10A to 10D.
  • the main passage 31 ′ having the raw material gas introduction end E1 and the first adsorption tanks 10A to 10D are provided.
  • Branch passages 31A to 31D connected to the gas passage ports 11 respectively.
  • the branch paths 31A to 31D are respectively provided with automatic valves 31a, 31b, 31c and 31d for switching between an open state and a closed state.
  • a compressor (not shown) for pumping the mixed gas to the first adsorption tanks 10A to 10D may be provided in the main trunk path 31 'of the pipe 31.
  • the pipe 32 is a flow path for taking out the product gas (target component-enriched gas) from the second adsorption tanks 20A to 20D, the main trunk path 32 'having the product gas take-out end E2, and the second adsorption tank.
  • the branch passages 32A, 32B, 32C, and 32D are connected to the gas passage ports 22 of 20A to 20D.
  • the branch paths 32A to 32D are respectively provided with automatic valves 32a, 32b, 32c, and 32d for switching between an open state and a closed state.
  • the product gas extraction end E2 of the pipe 32 is connected to, for example, a buffer tank (not shown) for temporarily storing the product gas.
  • the pipe 33 is for supplying a part of the product gas flowing through the pipe 32 (main trunk path 32 ′) to the second adsorption tanks 20 A to 20 D, and is connected to the main trunk path 32 ′ of the pipe 32.
  • the main trunk path 33 ′ and branch paths 33A, 33B, 33C, and 33D connected to the gas passage ports 22 of the second adsorption tanks 20A to 20D are provided.
  • the main trunk path 33 ′ is provided with an automatic valve 331 for switching between an open state and a closed state, and a flow rate adjustment valve 332.
  • the branch paths 33A to 33D are provided with automatic valves 33a, 33b, 33c, and 33d for switching between the open state and the closed state, respectively.
  • the pipe 34 is for connecting any two of the second adsorption tanks 20A to 20D to each other.
  • the pipe 34 is connected to the main trunk line 34 'and one leg of the main trunk path 34', and is connected to the second adsorption tank 20 '.
  • Each of the second adsorption tanks 20A to 20D is connected to the branch paths 34A, 34B, 34C and 34D connected to the gas passage ports 22 of the tanks 20A to 20D and the other leg of the main trunk path 34 '. It has branch paths 34A ′, 34B ′, 34C ′, 34D ′ connected to the gas passage port 22.
  • a flow rate adjustment valve 341 is provided in the main trunk line 34 '.
  • the branch paths 34A to 34D and 34A 'to 34D' are respectively provided with automatic valves 34a, 34b, 34c, 34d and 34a ', 34b', 34c ', 34d' for switching between the open state and the closed state. Is provided.
  • the pipe 35 is a flow path of gas (mainly desorption gas) discharged from each of the first adsorption tanks 10A to 10D, and includes a main trunk path 35 'having a gas discharge end E3, and the first adsorption tanks 10A to 10A.
  • the branch passages 35A, 35B, 35C, and 35D are connected to the 10D gas passage 11 side.
  • the branch paths 35A to 35D are provided with automatic valves 35a, 35b, 35c, and 35d for switching between an open state and a closed state.
  • the target gas purification method according to the present invention can be executed using the gas purification apparatus X1 having the above-described configuration. Specifically, automatic valves 16a to 16d, 31a to 31d, 32a to 32d, 33a to 33d, 34a to 34d, 34a 'to 34d', 35a to 35d, 331, and flow rate control during operation of the gas purification apparatus X1 By appropriately switching the valves 332 and 341, a desired gas flow state is realized in the apparatus, and one cycle consisting of the following steps 1 to 20 is repeated.
  • an adsorption process in each of the first adsorption tanks 10A to 10D, an adsorption process, a pressure equalization (first pressure equalization pressure reduction) process, a standby process, a countercurrent pressure reduction process, a countercurrent cleaning process, A pressure (first pressure equalization pressure increase) step, a standby step, a pressure equalization (second pressure equalization pressure increase) step, and a product gas pressure increase step are performed.
  • an adsorption process a pressure equalization (first pressure equalization / reduction) process, a cocurrent flow pressure reduction process, a pressure equalization (second pressure equalization / decompression) process, a standby process, A counter-current depressurization step, a counter-current washing step, a pressure equalization (first pressure equalization pressure increase) step, a standby step, a pressure equalization (second pressure equalization pressure increase) step, and a product gas pressure increase step are performed.
  • each of the first adsorption tanks 10A to 10D is filled with activated carbon as a first adsorbent, and the lower part (close to the gas passage 21) and the upper part of each of the second adsorption tanks 20A to 20D.
  • CMS and ZMS as the second adsorbent are stacked and filled in equal amounts.
  • 2 to 5 schematically show the gas flow state in the gas purification apparatus X1 in steps 1 to 20.
  • Step 1 the gas flow state as shown in FIG. 2a is achieved, and the adsorption process is performed in the first adsorption tank 10A and the second adsorption tank 20A, and the first adsorption tank 10B and the second adsorption tank 20B.
  • the pressure equalization (second pressure equalization pressure increase) process is performed in the first adsorption tank 10C and the second adsorption tank 20C, and the countercurrent pressure reduction process is performed in the first adsorption tank 10D and the second adsorption tank 20D.
  • a pressure equalization (first pressure equalization pressure reduction) step is performed.
  • the automatic valves 16a to 16d are opened so as to synchronize the first adsorption tanks 10A to 10D and the second adsorption tanks 20A to 20D. Therefore, the first adsorbing tank 10A (10B, 10C, 10D) and the second adsorbing tank 20A (20B, 20C) form a pair in the first adsorbing tank 10A to 10D and the second adsorbing tank 20A to 20D. , 20D).
  • the process time of step 1 is, for example, 20 seconds.
  • step 1 the raw material gas (mixed gas) is introduced into the first adsorption tank 10 ⁇ / b> A via the pipe 31 and the gas passage port 11.
  • the first and second adsorption tanks 10A and 20A in the adsorption process are maintained at a predetermined high pressure, and impurities (for example, heavy hydrocarbons, BTX, sulfur compounds, etc.) in the mixed gas are first adsorbed. It is adsorbed by the first adsorbent in the tank 10A.
  • the pre-adsorbed gas (pre-adsorbed permeated gas) discharged through the gas passage port 12 of the first adsorption tank 10A is supplied to the second adsorption tank through the communication passage 16 and the gas passage port 21. 20A.
  • impurities for example, carbon monoxide, carbon dioxide, methane, etc.
  • a product gas hydrogen Enriched gas
  • the product gas is collected from the product gas take-out end E2 through the pipe 32 to, for example, an external buffer tank (not shown).
  • an external buffer tank not shown.
  • the gas in the tank in the second adsorption tank 20D discharged from the second adsorption tank 20D is introduced into the second adsorption tank 20B and the first adsorption tank 10B through the pipe 34. Since the second adsorption tank 20D and the first adsorption tank 10D have previously performed the adsorption process (see step 20 shown in FIG. 5e), the inside of the second adsorption tank 20D and the first adsorption tank 10D. However, the pressure is higher than that in the second adsorption tank 20B and the first adsorption tank 10B.
  • the inside of the second adsorption tank 20D and the first adsorption tank 10D is decompressed.
  • the pressure inside the second adsorption tank 20B and the first adsorption tank 10B is increased.
  • the gas in the tank from the first adsorption tank 10 ⁇ / b> D is introduced into the second adsorption tank 20 ⁇ / b> D through the communication path 16.
  • impurity components are preferentially adsorbed by the adsorbent in the first adsorption tank 10D.
  • the gas in the tank has a high concentration of hydrogen gas as the target gas. Such a gas having a high hydrogen concentration moves from the first adsorption tank 10D to the second adsorption tank 20D.
  • the pressure is depressurized in the countercurrent direction, so that impurities are desorbed from the first adsorbent and the second adsorbent.
  • the generated desorption gas is discharged together with the gas remaining in the second adsorption tank 20C and the first adsorption tank 10C (hereinafter, the desorption gas and the residual gas are collectively referred to as “in-vessel gas”).
  • the gas in the tank passes through the pipe 35 and is discharged from the gas discharge end E3 to the outside.
  • An off gas tank (not shown) may be installed in the main trunk path 35 ′ of the pipe 35, and the exhaust gas from the first adsorption tank may be temporarily stored in the off gas tank.
  • step 2 the gas flow state as shown in FIG. 2b is achieved, and the adsorption process continues in the first adsorption tank 10A and the second adsorption tank 20A, and the second adsorption tank 20B and the first adsorption tank.
  • the product gas pressurization step is performed, in the second adsorption tank 20C and the first adsorption tank 10C, the countercurrent cleaning process is performed, in the second adsorption tank 20D, the cocurrent depressurization process is performed, and in the first adsorption tank 10D.
  • a standby process is performed at.
  • step 2 the automatic valves 16a to 16c are opened so as to synchronize the first adsorption tanks 10A to 10C and the second adsorption tanks 20A to 20C.
  • the automatic valve 16d is in a closed state, and the first adsorption tank 10D and the second adsorption tank 20D are not in communication (not synchronized).
  • the process time of step 2 is, for example, 70 seconds.
  • Step 2 the mixed gas is introduced into the first adsorption tank 10A via the pipe 31 in succession from Step 1, and the second adsorption tank is obtained.
  • Product gas is discharged from 20A.
  • the product gas is recovered in the same manner as in Step 1, but part of it is introduced into the second adsorption tank 20B and the first adsorption tank 10B via the pipe 33, and the product gas in these adsorption tanks 20B and 10B. Is boosted.
  • step 2 the gas in the adsorption tank 20D led out from the second adsorption tank 20D is introduced into the second adsorption tank 20C through the pipe 34, and the second adsorption tank 20C and the first adsorption tank 20D.
  • the gas (mainly desorption gas) in the adsorption tank 10C is discharged from the gas passage port 11 side.
  • the tank gas is discharged from the gas discharge end E3 to the outside through the pipe 35.
  • a cocurrent depressurization step is performed in the second adsorption tank 20D.
  • the first adsorption tank 10D is not synchronized with the second adsorption tank 20D, and no gas enters and exits. It is a process. If the cocurrent depressurization step is performed also in the first adsorption tank 10D, the impurities adsorbed in the first adsorption tank 10D may flow into the second adsorption tank 20D via the communication path 16. For this reason, the first adsorption tank 10D is set as a standby process without being synchronized with the cocurrent depressurization process of the second adsorption tank 20D.
  • Step 3 the gas flow state as shown in FIG. 2c is achieved, and the adsorption process continues in the first adsorption tank 10A and the second adsorption tank 20A, and the second adsorption tank 20B and the first adsorption tank.
  • the product gas pressure-increasing step continues in 10B, the pressure equalization (first pressure equalization pressure-increasing) step in the second adsorption tank 20C and the first adsorption tank 10C, and the pressure equalization (first in the second adsorption tank 20D). 2 pressure equalization pressure reduction process is performed.
  • the first adsorption tank 10D is set as a standby process in the same manner as step 2.
  • the automatic valves 16a to 16c are open, and the automatic valve 16d is closed.
  • the process time of step 3 is, for example, 20 seconds.
  • Step 3 the mixed gas is introduced into the first adsorption tank 10A via the pipe 31 following Step 2, and the second adsorption tank is obtained.
  • Product gas is discharged from 20A.
  • a part of the product gas is introduced into the second adsorption tank 20B and the first adsorption tank 10B through the pipe 33, and the pressure increase by the product gas in these adsorption tanks 20B and 10B is continued.
  • the gas led out from the second adsorption tank 20D is introduced into the second adsorption tank 20C through the pipe 34 and also into the first adsorption tank 10C through the communication path 16. be introduced.
  • step 4 the gas flow state as shown in FIG. 2d is achieved, and the adsorption process continues in the first adsorption tank 10A and the second adsorption tank 20A, and the second adsorption tank 20B and the first adsorption tank.
  • the product gas pressure increasing process is continued, and the standby process is performed at the second adsorption tank 20C and the first adsorption tank 10C.
  • a standby process is performed in the second adsorption tank 20D, and a countercurrent depressurization process is performed in the first adsorption tank 10D.
  • the automatic valves 16a to 16c are open, and the automatic valve 16d is closed.
  • the process time of step 4 is, for example, 10 seconds.
  • step 2 and step 3 while the second adsorption tank 20D performs a cocurrent depressurization process and a pressure equalization (second pressure equalization depressurization) process, the first adsorption tank 10D is a standby process. Compared to the second adsorption tank 20D, the first adsorption tank 10D has a relatively high pressure. For this reason, when the counter-current decompression step is started by synchronizing the second adsorption tank 20D and the first adsorption tank 10D, a gas flow from the first adsorption tank 10D to the second adsorption tank 20D is generated, There is a possibility that impurities in the adsorption tank 10D may flow into the second adsorption tank 20D through the communication path 16. In order to prevent such a situation, the counter-current depressurization step is performed only on the first adsorption tank 10D until the pressure in the first adsorption tank 10D becomes approximately the same as that of the second adsorption tank 20D.
  • step 4 the mixed gas is introduced into the first adsorption tank 10A via the pipe 31 in succession from step 3, and the second adsorption tank.
  • Product gas is discharged from 20A.
  • a part of the product gas is introduced into the second adsorption tank 20B and the first adsorption tank 10B through the pipe 33, and the pressure increase by the product gas in these adsorption tanks 20B and 10B is continued.
  • the second adsorption tank 20C and the first adsorption tank 10C are subjected to the first pressure equalization (first pressure equalization pressure increase) in the previous step 3, but in the subsequent step 6 (FIG. 3a). Wait to receive the second equalization (second equalization boost).
  • the first adsorption tank 10D impurities are desorbed from the adsorbent by reducing the pressure in the countercurrent direction, and the gas in the tank (mainly desorbed gas) is discharged from the first adsorption tank 10D.
  • the second adsorption tank 20D the internal pressure of the first adsorption tank 10D is set to the second adsorption tank 20D in order to perform countercurrent pressure reduction together with the first adsorption tank 10D in the subsequent step 5 (FIG. 2e). Wait until the pressure is reduced to the same level as the internal pressure.
  • step 5 the gas flow state as shown in FIG. 2e is achieved, and the adsorption process continues in the first adsorption tank 10A and the second adsorption tank 20A, and the second adsorption tank 20B and the first adsorption tank.
  • the product gas pressure-increasing step is continuously performed at 10B, and the standby step is continuously performed in the second adsorption tank 20C and the first adsorption tank 10C.
  • a counter-current decompression step is performed in the second adsorption tank 20D and the first adsorption tank 10D.
  • the automatic valves 16a to 16d are open.
  • the process time of step 5 is, for example, 80 seconds.
  • step 5 the mixed gas is introduced into the first adsorption tank 10A via the pipe 31 in succession from step 4, and the second adsorption tank.
  • Product gas is discharged from 20A.
  • a part of the product gas is introduced into the second adsorption tank 20B and the first adsorption tank 10B through the pipe 33, and the pressure increase by the product gas in these adsorption tanks 20B and 10B is continued.
  • Step 6 Step 6 (Drawing 3a)
  • an impurity is desorbed from adsorption agent by decompressing in a countercurrent direction, and gas in a tank (mainly desorption gas) is discharged.
  • the discharged gas is introduced into the first adsorption tank 10D via the communication path 16.
  • impurities are desorbed from the adsorbent by continuously reducing the pressure in the counterflow direction, and the gas in the tank (mainly desorbed gas) is discharged from the first adsorption tank 10D.
  • the pressure (adsorption pressure) inside the first and second adsorption tanks 10A and 20A in the adsorption process is, for example, 0.6 to 4.0 MPaG.
  • the minimum pressure (desorption pressure) inside the first and second adsorption tanks (10C, 10D, 20C, 20D) in the countercurrent decompression process is, for example, 30 to 50 kPaG, preferably Is atmospheric pressure.
  • Steps 1 to 5 correspond to 1 ⁇ 4 of one cycle constituted by steps 1 to 20, and the process time of steps 1 to 5 is, for example, a total of 200 seconds.
  • the internal temperatures of the first and second adsorption tanks 10A to 10D and 20A to 20D when performing one cycle consisting of steps 1 to 20 are not particularly limited, but considering the temperature change according to the season, There is no problem if it is about 0 to 40 ° C.
  • the gas flow state as shown in FIGS. 3a to 3e is achieved.
  • the pressure equalization (the first pressure is the same as the first adsorption tank 10D in steps 1 to 5).
  • 1 pressure equalization pressure reduction process, standby process, counter-current pressure reduction process are performed, and in the second adsorption tank 20A, pressure equalization (first pressure equalization) is performed in the same manner as the second adsorption tank 20D in steps 1 to 5.
  • a decompression step, a cocurrent decompression step, a pressure equalization (second pressure equalization decompression) step, a standby step, and a countercurrent decompression step are performed.
  • the adsorption process is performed in the same manner as the first adsorption tank 10A and the second adsorption tank 20A in Steps 1 to 5.
  • a pressure equalization (second pressure equalization and pressure increase) step product in the same manner as the first adsorption tank 10B and the second adsorption tank 20B in steps 1 to 5.
  • a gas pressurization process is performed.
  • a countercurrent depressurization step In the first adsorption tank 10D and the second adsorption tank 20D, in the same manner as the first adsorption tank 10C and the second adsorption tank 20C in steps 1 to 5, a countercurrent depressurization step, a countercurrent washing step, a pressure equalization ( A first pressure equalizing / pressurizing step and a standby step are performed.
  • steps 11 to 15 the gas flow states as shown in FIGS. 4a to 4e are achieved.
  • the first adsorption tank 10A and the second adsorption tank 20A the first adsorption tank 10C in steps 1 to 5 and In the same manner as the second adsorption tank 20C, a counter-current pressure reducing step, a counter-current washing step, a pressure equalization (first pressure equalization pressure increase) step, and a standby step are performed.
  • the pressure equalization (first pressure equalization pressure reduction) process, the standby process, and the countercurrent pressure reduction process are performed in the same manner as the first adsorption tank 10D in Steps 1 to 5, and the second adsorption is performed.
  • a pressure equalization (first pressure equalization pressure reduction) step similarly to the second adsorption tank 20D in Steps 1 to 5, a pressure equalization (first pressure equalization pressure reduction) step, a cocurrent pressure reduction step, a pressure equalization (second pressure equalization pressure reduction) step, and a standby step. Then, a counter-current decompression step is performed.
  • the adsorption process is performed in the same manner as the first adsorption tank 10A and the second adsorption tank 20A in Steps 1 to 5.
  • a pressure equalization (second pressure equalization and pressure increase) step product A gas pressurization process is performed.
  • steps 16 to 20 the gas flow state as shown in FIGS. 5a to 5e is achieved.
  • the first adsorption tank 10A and the second adsorption tank 20A the first adsorption tank 10B in steps 1 to 5 and Similar to the second adsorption tank 20B, a pressure equalization (second pressure equalization pressure increase) step and a product gas pressure increase step are performed.
  • a pressure equalization (second pressure equalization pressure increase) step and a product gas pressure increase step are performed in the first adsorption tank 10B and the second adsorption tank 20B.
  • a countercurrent depressurization step, a countercurrent washing step, a pressure equalization A first pressure equalizing / pressurizing step and a standby step are performed.
  • the pressure equalization (first pressure equalization pressure reduction) process, the standby process, and the countercurrent pressure reduction process are performed in the same manner as the first adsorption tank 10D in Steps 1 to 5, and the second adsorption is performed.
  • the tank 20C similar to the second adsorption tank 20D in Steps 1 to 5, a pressure equalization (first pressure equalization / reduction) step, a cocurrent pressure reduction step, a pressure equalization (second pressure equalization / reduction) step, and a standby step. Then, a counter-current decompression step is performed.
  • the adsorption step is performed in the same manner as the first adsorption tank 10A and the second adsorption tank 20A in Steps 1 to 5.
  • the steps 1 to 20 described above are repeatedly performed in each of the first adsorption tanks 10A to 10D and the second adsorption tanks 20A to 20D, so that the first and second adsorption tanks 10A, 20A to 10D are performed. , 20D, the mixed gas is continuously introduced, and the product gas having a high hydrogen gas concentration is continuously acquired.
  • gas separation by the PSA method is performed using a plurality of sets of first and second adsorption tanks 10A to 10D and 20A to 20D arranged in series.
  • the first and second adsorption tanks 10A and 20A (10B, 20B, 10C, 20C, 10D, and 20D) of each set communicate with each other via the communication path 16, and the automatic valve 16a (16b) is connected to the communication path 16. 16c, 16d).
  • the first adsorption tank 10A (10B, 10C, 10D) and the second adsorption tank are closed by appropriately closing the automatic valve 16a (16b, 16c, 16d) during the decompression process in the gas separation by the PSA method.
  • the first and second adsorption tanks 10A and 20A (10B, 20B, 10C, 20C, 10D, and 20D) to be subjected to the decompression operation the first as shown in steps 1, 6, 11, and 16 is performed.
  • the automatic valves 16a to 16d are opened to allow the corresponding first and second adsorption tanks to communicate with each other only in a process in which impurities in the adsorption tanks 10A to 10D do not possibly flow into the second adsorption tanks 20A to 20D.
  • the impurities in the first adsorption tanks 10A to 10D are transferred to the second adsorption tanks 20A to 20D.
  • the automatic valves 16a to 16d are closed so that the corresponding first and second adsorption tanks do not communicate with each other.
  • the second adsorption tanks 20A to 20D are improved by the impurities selectively adsorbed by the adsorbent in the first adsorption tanks 10A to 10D while increasing the recovery rate of the hydrogen gas (target gas) in the product gas to be collected. It is possible to prevent the adsorption capacity of the adsorbent from decreasing.
  • the automatic valves 16a to 16d are not provided in the communication passage 16, and the first and second adsorption tanks are also communicated in steps 2, 3, 7, 8, 12, 13, 17, and 18.
  • the impurities adsorbed in the first adsorption tank flow into the second adsorption tank, and the adsorption capacity of the second adsorption tank is increased.
  • the possibility of deterioration increases.
  • the first adsorption tank needs to be enlarged.
  • the first adsorption tank 10D in step 3, the first adsorption tank 10A in step 8, the first adsorption tank 10B in step 13, and the first adsorption tank 10C in step 18 are standby processes.
  • the automatic valves 35d, 35a, 35b, and 35c may be opened to perform a countercurrent pressure reducing process.
  • steps 4, 9, 14, and 19 are omitted. Also good.
  • a configuration different from that of the above-described embodiment may be adopted for the configuration of the piping that forms the gas flow path in the apparatus for performing the target gas purification method according to the present invention.
  • the number of adsorption units is not limited to the 4-unit type shown in the above embodiment, but is 3 units or less, or 5 units or more But the same effect can be expected.
  • the first adsorption tank 10D in steps 2 and 3, the first adsorption tank 10A in steps 7 and 8, the first adsorption tank 10B in steps 12 and 13, and the first adsorption tank 10C in steps 17 and 18 are standby processes.
  • pre-adsorption tank the first adsorption tank
  • the process to synchronize according to conditions, such as a cocurrent flow pressure reduction process or a pressure equalization (second pressure equalization pressure reduction) process can be freely selected in synchronization with the second adsorption tank.
  • FIG. 6 shows a case where two first adsorption tanks (10A, 10A) are provided in parallel.
  • two first adsorption tanks (10A, 10A) are provided in parallel branch paths 161.
  • Three-way valves 17 and 18 for allowing a gas flow to either one of the adsorption tanks 10A and 10A are provided at the branch portion.
  • each pre-adsorption tank increases, but the volume of the first adsorption tank can be reduced, so that the gas discharged at the time of depressurization (decompression process)
  • the amount of entrained hydrogen gas (target gas) is reduced, and a decrease in the target gas recovery rate due to the pre-adsorption tank attached at the previous stage can be suppressed.
  • the target gas is not limited to hydrogen in the above embodiment.
  • a difficultly adsorbed component for example, argon
  • an easily adsorbed component that is selectively adsorbed by the adsorbent is used as the impurity component If it is possible to purify in such a manner, the present invention can be applied using such a hardly adsorbed component as a target gas.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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  • Industrial Gases (AREA)

Abstract

La présente invention vise à empêcher les effets de composants d'impuretés qui réduisent la capacité de purification d'un adsorbant tout en récupérant gaz cible de haute pureté avec un bon rendement, lors de la purification d'un gaz cible à partir d'un gaz mixte contenant un composant cible au moyen d'une adsorption modulée en pression. Ce procédé met en œuvre de manière répétée, pour chaque unité d'adsorption, un cycle qui inclut une étape d'adsorption dans laquelle le gaz mixte est introduit dans les unités d'adsorption, dans un état dans lequel les unités d'adsorption sont à relativement haute pression, par adsorption modulée en pression réalisée au moyen d'une pluralité d'unités d'adsorption remplies par l'adsorbant qui adsorbe sélectivement des composants d'impuretés, l'adsorbant étant amené à adsorber les composants d'impuretés dans le gaz mixte, et un gaz qui est enrichi en composant cible sortant des unités d'adsorption, et une étape de réduction de pression dans lequel la pression est réduite dans les unités d'adsorption et le gaz sort des unités d'adsorption. Chaque unité d'adsorption comprend des premières et des secondes cuves d'adsorption (10A-10D, 20A-20D) connectées en série. Dans l'étape de réduction de pression, le passage d'un état dans lequel les premières et des secondes cuves d'adsorption sont reliées à un état elles ne sont pas reliées est effectué par une soupape de tout ou rien (16) placée entre les premières et des secondes cuves d'adsorption.
PCT/JP2015/058189 2014-03-28 2015-03-19 Procédé de purification et dispositif de purification pour gaz cible WO2015146766A1 (fr)

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JP2017206422A (ja) * 2016-05-20 2017-11-24 株式会社神戸製鋼所 水素ガス製造方法及び水素ガス製造装置
JP2018161605A (ja) * 2017-03-24 2018-10-18 大陽日酸株式会社 ガス精製方法及び装置
CN111921332A (zh) * 2019-05-13 2020-11-13 纯萃材料股份有限公司 吸附装置及吸附方法

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JPS605419U (ja) * 1983-06-20 1985-01-16 新日本製鐵株式会社 圧力スイング吸脱着装置
JPH06126120A (ja) * 1992-10-13 1994-05-10 Nippon Steel Corp 分解ガス中のｃｏ濃度増大方法
WO2002051523A1 (fr) * 2000-12-26 2002-07-04 Sumitomo Seika Chemicals Co., Ltd. Procede et dispositif de separation d'un gaz objet
JP2006061831A (ja) * 2004-08-26 2006-03-09 Taiyo Nippon Sanso Corp 圧力変動吸着式ガス分離方法及び装置

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JPS55147119A (en) * 1979-02-28 1980-11-15 Air Prod & Chem Improved air fractionating method
JPS605419U (ja) * 1983-06-20 1985-01-16 新日本製鐵株式会社 圧力スイング吸脱着装置
JPH06126120A (ja) * 1992-10-13 1994-05-10 Nippon Steel Corp 分解ガス中のｃｏ濃度増大方法
WO2002051523A1 (fr) * 2000-12-26 2002-07-04 Sumitomo Seika Chemicals Co., Ltd. Procede et dispositif de separation d'un gaz objet
JP2006061831A (ja) * 2004-08-26 2006-03-09 Taiyo Nippon Sanso Corp 圧力変動吸着式ガス分離方法及び装置

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JP2018161605A (ja) * 2017-03-24 2018-10-18 大陽日酸株式会社 ガス精製方法及び装置
CN111921332A (zh) * 2019-05-13 2020-11-13 纯萃材料股份有限公司 吸附装置及吸附方法

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PH12016501880B1 (en) 2017-01-09
PH12016501880A1 (en) 2017-01-09
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