WO2018055971A1 - 水素またはヘリウムの精製方法、および水素またはヘリウムの精製装置 - Google Patents
水素またはヘリウムの精製方法、および水素またはヘリウムの精製装置 Download PDFInfo
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- WO2018055971A1 WO2018055971A1 PCT/JP2017/030156 JP2017030156W WO2018055971A1 WO 2018055971 A1 WO2018055971 A1 WO 2018055971A1 JP 2017030156 W JP2017030156 W JP 2017030156W WO 2018055971 A1 WO2018055971 A1 WO 2018055971A1
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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
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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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
- B01D53/02—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
- B01D53/053—Pressure swing adsorption with storage or buffer vessel
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
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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
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0052—Physical processing only by adsorption in solids
- C01B23/0057—Physical processing only by adsorption in solids characterised by the adsorbent
- C01B23/0063—Carbon based materials
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0052—Physical processing only by adsorption in solids
- C01B23/0057—Physical processing only by adsorption in solids characterised by the adsorbent
- C01B23/0068—Zeolites
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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
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0052—Physical processing only by adsorption in solids
- C01B23/0057—Physical processing only by adsorption in solids characterised by the adsorbent
- C01B23/0073—Other molecular sieve materials
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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
Definitions
- the present invention relates to a method and an apparatus for purifying hydrogen or helium using a pressure fluctuation adsorption method.
- the concentration of volatile aromatic compounds in the gas released as waste gas is regulated to be low.
- the concentration at the ground reaching point is set to 0.7 volppm or less in a certain area.
- an absorption method, a cooling method, an adsorption method, a combustion method, and the like see, for example, Patent Document 1.
- purifying by those processes may be collect
- waste gas processing facilities there is a demand for a space-saving method with low introduction costs and operating costs.
- the adsorption method is mainly used as a method for obtaining high-purity hydrogen and helium.
- a pressure fluctuation adsorption method using synthetic zeolite or hydrophobic silica gel is employed in order to remove volatile aromatic compounds contained in the gas.
- this method also has a problem in terms of cost since a vacuum apparatus is used for desorption and a hydrophobic material is used among silica-rich zeolite and silica gel (see, for example, Patent Document 1).
- the cost for vacuum regeneration is required.
- the amount of the purge gas used increases the cost.
- the regeneration by heating also leads to an increase in cost for the energy required for heating.
- the present invention has been conceived under such circumstances, using a pressure fluctuation adsorption method, from a raw material gas containing a volatile aromatic compound as an impurity, while reducing costs, and having high purity. It is an object of the present invention to provide a method and an apparatus suitable for obtaining hydrogen or helium.
- a volatile aromatic compound is introduced as an impurity by repeating the cycle of the pressure fluctuation adsorption method using three or more adsorption towers filled with an adsorbent for each adsorption tower.
- a method is provided for purifying hydrogen or helium from a source gas comprising and containing hydrogen or helium as a major component.
- the raw material gas is introduced into the adsorption tower by a pressure fluctuation adsorption method using three or more adsorption towers filled with an adsorbent while the adsorption tower is at a predetermined high pressure.
- An adsorption step for adsorbing the volatile aromatic compound in the raw material gas to the adsorbent and discharging a product gas having a high hydrogen or helium concentration from the adsorption tower; and a column from the adsorption tower after the adsorption step is completed A depressurization step for discharging the gas remaining in the column to lower the pressure in the column, and desorbing the volatile aromatic compound from the adsorbent in the adsorption column after the depressurization step, and discharging the column gas
- Each of the adsorption towers is divided into a first area, a second area, and a third area in order from the upstream side to the downstream side in the flow direction of the raw material gas in the adsorption tower.
- the first region is filled with a silica gel-based first adsorbent having a filling ratio in the range of 15 to 75 vol%.
- the second region is filled with a zeolite-based second adsorbent having a filling ratio in the range of 15 to 75 vol%.
- the third region is filled with an activated carbon-based third adsorbent having a filling ratio in the range of 5 to 30 vol%.
- the first adsorbent is made of hydrophilic silica gel.
- an apparatus for purifying hydrogen or helium from a source gas containing a volatile aromatic compound as an impurity and containing hydrogen or helium as a main component has a first gas passage port and a second gas passage port, each having three or more adsorption towers filled with an adsorbent between the first and second gas passage ports, and a product gas.
- a storage tank for storing, a gas-liquid separation means for separating the gas discharged from the first gas passage port of the adsorption tower into a gas phase component and a liquid phase component, and a trunk connected to a source gas supply source
- a first line having a passage and a plurality of branch passages provided for each adsorption tower and connected to the first gas passage port side of the adsorption tower and provided with on-off valves, respectively,
- the second line, the main road provided with the storage tank, and the upper A third line provided for each adsorption tower and connected to the second gas passage opening side of the adsorption tower and having a plurality of branch passages each provided with an on-off valve; and the trunk in the third line And a plurality of branch passages provided for each of the adsorption towers and connected to the second gas passage opening side of the adsorption tower and each provided with an on-off valve.
- a fifth line having a plurality of branched branches.
- Each of the adsorption towers is divided into a first area, a second area, and a third area in order from the first gas passage opening to the second gas passage opening in the adsorption tower.
- the first region is filled with a silica gel-based first adsorbent having a filling ratio in the range of 15 to 75 vol%.
- the second region is filled with a zeolite-based second adsorbent having a filling ratio in the range of 15 to 75 vol%.
- the third region is filled with an activated carbon-based third adsorbent having a filling ratio in the range of 5 to 30 vol%.
- the first adsorbent is made of hydrophilic silica gel.
- the present inventors have intensively studied a method for separating hydrogen or helium from a raw material gas containing a volatile aromatic compound as an impurity by a pressure fluctuation adsorption method.
- silica gel as an adsorbent that adsorbs a volatile aromatic compound is used.
- the latter stage is filled with zeolite and activated carbon, which are adsorbents that do not adsorb volatile aromatic compounds, and after the adsorption process is completed, a relatively clean gas in the zeolite and activated carbon layer is used, and after the desorption process is completed.
- the content of volatile aromatic compounds contained as impurities in hydrogen or helium can be purified to a low volume of 1 volppm or less with a space-saving device.
- FIG. 1 shows a schematic configuration of a purification apparatus X that can be used for carrying out the method for purifying hydrogen or helium according to the present invention.
- the purification apparatus X includes three adsorption towers 10A, 10B, and 10C, a raw material gas supply source 21, a product storage tank 22, an offgas tank 23, a cooler 24, a gas-liquid separator 25, and lines 31 to 35.
- the purification apparatus X is configured to be capable of concentrating and separating hydrogen or helium from a source gas containing hydrogen or helium (crude hydrogen or crude helium) using a pressure fluctuation adsorption method (PSA method).
- PSA method pressure fluctuation adsorption method
- the source gas there can be mentioned a gas mainly containing hydrogen produced from organic hydride and containing, for example, a volatile aromatic compound (for example, toluene, benzene, methylcyclohexane, etc.) as impurities.
- a volatile aromatic compound for example, toluene, benzene, methylcyclohexane, etc.
- Each of the adsorption towers 10A, 10B, and 10C has gas passage ports 11 and 12 at both ends, and the adsorbent is filled between the gas passage ports 11 and 12.
- a plurality (three) of regions partitioned by a perforated plate (not shown) are formed, and different adsorbents are respectively provided in these regions. Is filled.
- the first adsorbent 131, the second adsorbent 131, the second adsorbent 131, the second adsorbent 131, and the second adsorbent 131 in the flow direction of the raw material gas in the adsorption towers 10A, 10B, 10C from the upstream side (gas passage port 11) toward the downstream side (gas passage port 12).
- An adsorbent 132 and a third adsorbent 133 are sequentially stacked.
- an adsorbent having a property of preferentially adsorbing volatile aromatic compounds is used.
- adsorbents include silica gel-based adsorbents (hydrophilic silica gel, hydrophobic silica gel, etc.), among which hydrophilic silica gel, particularly silica gel B type is preferable.
- hydrophilic silica gel particularly silica gel B type is preferable.
- second and third adsorbents 132 and 133 adsorbents having relatively low adsorbability for volatile aromatic compounds are used.
- Examples of the second adsorbent 132 include zeolite-based adsorbents (A-type zeolite, CaA-type zeolite, Y-type zeolite, etc.), and among these, CaA-type zeolite is preferable.
- Examples of the third adsorbent 133 include activated carbons such as coconut shells and coals. These adsorbents are generally commercially available, are readily available, and do not require pretreatment.
- Silica gel (or silica) is inherently hydrophilic because it has a hydroxyl group on the surface, and becomes hydrophobic when subjected to a hydrophobizing treatment such as high temperature heating or reaction with an alkylsilylating agent. Conventionally, this hydrophobization treatment has been a cause of cost increase.
- the first to third adsorbents 131, 132, and 133 are adjusted to have a predetermined filling ratio (volume ratio) with respect to the entire filling capacity of the adsorbent.
- the filling ratio of the first adsorbent 131 is 15 to 75 vol%, preferably 15 to 65 vol%
- the filling ratio of the second adsorbent 132 is 15 to 75 vol%, preferably 25 to 75 vol%.
- the filling ratio of the third adsorbent 133 is 5 to 30 vol%, preferably 5 to 20 vol%.
- the total of the filling ratios of the first to third adsorbents 131, 132, and 133 is 100 vol%.
- the source gas supply source 21 is a pressure vessel for storing source gas supplied into the adsorption towers 10A, 10B, and 10C.
- the concentration of the volatile aromatic compound contained in the source gas is not particularly limited, but depending on the hydrogen or helium pressure and the concentration of the volatile aromatic compound, the volatile aromatic compound may be liquefied in the pipe. Therefore, the piping (main trunk 31 'of the line 31 described later) from the source gas supply source 21 to the adsorption towers 10A, 10B, 10C is heated and / or before the adsorption towers 10A, 10B, 10C. It is preferable to install a mist trap or the like on the main road 31 '.
- the pressure of the source gas supplied from the source gas supply source 21 is not particularly limited, but is preferably as high as possible.
- a compressor (not shown) is installed in the main trunk path 31 ′ as necessary.
- a moisture removing device (not shown) on the main trunk line 31 ′ of the line 31.
- the operating temperature by the PSA method is not particularly limited and is, for example, about 10 to 40 ° C. However, it is preferable that the temperature is such that the volatile aromatic compound does not liquefy as described above (normal temperature or higher).
- the product storage tank 22 is a pressure vessel for storing gas (product gas described later) discharged from the gas passage port 12 of the adsorption towers 10A, 10B, and 10C.
- the off-gas tank 23 is a pressure vessel for storing off-gas discharged from the gas passage ports 11 of the adsorption towers 10A, 10B, and 10C.
- the cooler 24 cools off gas.
- the gas-liquid separator 25 condenses the off-gas that has passed through the cooler 24 under a predetermined pressure to separate it into a gas phase component and a liquid phase component.
- gas-liquid separation means includes the cooler 24 and the gas-liquid separator 25.
- the line 31 has a main path 31 ′ to which the source gas supply source 21 is connected, and branch paths 31 ⁇ / b> A, 31 ⁇ / b> B, and 31 ⁇ / b> C each connected to the gas passage 11 side of the adsorption towers 10 ⁇ / b> A, 10 ⁇ / b> B, and 10 ⁇ / b> C.
- the branch paths 31A, 31B, and 31C include valves that can be automatically switched between an open state and a closed state (hereinafter, valves having such a function are referred to as “automatic valves”) 31a, 31b, and 31c. Is provided.
- the line 32 includes a main path 32 ′ provided with the cooler 24 and the gas-liquid separator 25, and branch paths 32A and 32B each connected to the gas passage 11 side of the adsorption towers 10A, 10B, and 10C. , 32C. Further, an off-gas tank 23 is provided on the main trunk path 32 ′ on the upstream side of the cooler 24. A pressure control valve 321 is provided between the off-gas tank 23 and the cooler 24 in the main trunk path 32 ′. Automatic valves 32a, 32b, and 32c are provided in the branch paths 32A, 32B, and 32C.
- the line 33 includes a main path 33 ′ in which the product storage tank 22 is provided, and branch paths 33 A, 33 B, and 33 C each connected to the gas passage 12 side of the adsorption towers 10 A, 10 B, and 10 C.
- Automatic valves 33a, 33b, and 33c are provided in the branch paths 33A, 33B, and 33C.
- a pressure regulating valve 331 is provided downstream of the product storage tank 22 in the main trunk path 33 ′.
- the line 34 is for supplying a part of product gas flowing through the line 33 (main trunk line 33 ′) to the adsorption towers 10 A, 10 B, 10 C, and is connected to the main path 33 ′ of the line 33.
- An automatic valve 341 and a flow rate adjustment valve 342 are provided on the main trunk line 34 '.
- Automatic valves 34a, 34b, 34c are provided in the branch paths 34A, 34B, 34C.
- the line 35 is for connecting any two of the adsorption towers 10A, 10B, and 10C to each other, and the main road 35 'connected to the main road 34' of the line 34, and the adsorption towers 10A, 10B,
- the branch passages 35A, 35B, and 35C are connected to the 10C gas passage 12 side.
- An automatic valve 351 and a flow rate adjustment valve 352 are provided on the main trunk path 35 ′.
- Automatic valves 35a, 35b, and 35c are provided in the branch paths 35A, 35B, and 35C.
- the purification apparatus X having the above configuration can be used to carry out the hydrogen purification method according to the embodiment of the present invention.
- the automatic valves 31a to 31c, 32a to 32c, 33a to 33c, 34a to 34c, 35a to 35c, 341, 351, and the flow rate adjusting valves 342, 352 are appropriately switched in the device.
- a desired gas flow state can be realized and one cycle consisting of the following steps 1 to 9 can be repeated.
- an adsorption step, a pressure reduction step, a pressure equalization pressure reduction, a desorption step, a washing step, a pressure equalization pressure increase, and a pressure increase step are performed in each of the adsorption towers 10A, 10B, and 10C.
- 2a to 2i schematically show the gas flow state in the purification apparatus X in steps 1 to 9.
- FIGS. 2a to 2i the following abbreviations are used.
- Eq-DP Pressure equalization pressure reduction process
- Eq-PR Pressure equalization pressure increase process
- step 1 the automatic valves 31a, 33a, 32b, 34b, 35c, 351 and the flow rate adjusting valve 352 are opened, and the gas flow state as shown in FIG. 2a is achieved.
- the raw material gas is introduced from the gas passage port 11 through the line 31, and the adsorption process is performed.
- the inside of the adsorption tower 10A in the adsorption step is maintained at a predetermined high pressure, and mainly volatile aromatic compounds in the raw material gas are adsorbed by the adsorbent in the adsorption tower 10A.
- the gas (product gas) with which hydrogen was concentrated is discharged
- the product gas is sent to the product storage tank 22 through the branch path 33A and the main trunk path 33 '.
- the product gas in the product storage tank 22 is appropriately taken out of the system via the pressure control valve 331 and used for a desired application.
- the concentration of the volatile aromatic compound in the raw material gas introduced into the adsorption tower 10A is not particularly limited, but is, for example, about 100 vol ppm to 1 vol%.
- the maximum pressure (adsorption pressure) inside the adsorption tower 10A in the adsorption step is, for example, 0.1 to 1.0 MPaG (G represents a gauge pressure, and the same applies hereinafter), and preferably is 0.1. 5 to 0.8 MPaG.
- Step 1 the gas passage ports 12 of the adsorption towers 10B and 10C communicate with each other through lines 34 and 35, respectively. Since the desorption process has been performed first for the adsorption tower 10B and the adsorption process has been previously performed for the adsorption tower 10C (see step 9 shown in FIG. 2i), at the start of step 1, the adsorption tower 10C is moved to the adsorption tower 10B. The pressure in the tower is higher than that.
- a depressurization step is performed in the adsorption tower 10C, and a gas having a low impurity concentration (residual concentrated hydrogen gas) remaining in the tower of the adsorption tower 10C is discharged from the gas passage port 12, The pressure inside the tower decreases.
- the difference in the internal pressure of the adsorption tower 10C at the start and end of Step 1 is, for example, about 300 kPa.
- a cleaning process is performed in the adsorption tower 10B, and the residual concentrated hydrogen gas discharged from the adsorption tower 10C is introduced as a cleaning gas from the gas passage port 12 via the line 35, the flow rate adjustment valve 352, and the line 34, and The gas remaining in the tower is discharged.
- the gas discharged from the adsorption tower 10B is a gas having a high concentration of the volatile aromatic compound, and the gas is sent to the offgas tank 23 through the line 32 as an offgas.
- the pressure in the adsorption tower 10C is higher than the pressure in the adsorption tower 10B.
- the operation time of step 1 is about 75 seconds, for example.
- step 2 the automatic valves 31a, 33a, 34b, 35c, 351 and the flow rate adjusting valve 352 are opened, and the gas flow state as shown in FIG. 2b is achieved.
- step 2 the adsorption step is continued in the adsorption tower 10A. Also in Step 2, the gas passages 12 and 12 of the adsorption towers 10B and 10C communicate with each other through lines 34 and 35, respectively. On the other hand, the automatic valve 32b is closed for the adsorption tower 10B. At the start of step 2, the pressure in the adsorption tower 10C is still higher than that in the adsorption tower 10B. Therefore, pressure equalization / pressure reduction is performed in the adsorption tower 10C, and pressure equalization / pressure increase is performed in the adsorption tower 10B.
- the gas in the adsorption tower 10C is introduced into the adsorption tower 10B via the lines 35 and 34, the pressure in the adsorption tower 10C is reduced, and the pressure in the adsorption tower 10B is increased. .
- the operation time of step 2 is, for example, about 15 seconds.
- step 3 the automatic valves 31a, 33a, 34b, 32c, 341 and the flow rate adjusting valve 342 are opened, and the gas flow state as shown in FIG. 2c is achieved.
- step 3 the adsorption step is continued in the adsorption tower 10A. Further, in Step 3, while the communication between the adsorption towers 10B and 10C is cut off, a part of the product gas discharged from the gas passage 12 of the adsorption tower 10A is transferred to the adsorption tower 10B via the line 34 and the flow rate adjusting valve 342. The pressure increasing step of the adsorption tower 10B is performed.
- Step 3 the adsorption tower 10C communicates with the off-gas tank 23 through the line 32 by opening the automatic valve 32c.
- the desorption process is performed in the adsorption tower 10C, the inside of the adsorption tower 10C is depressurized, and impurities (mainly volatile aromatic compounds) are desorbed from the adsorbent, and the gas in the tower (volatile aromatic compounds) Gas) is discharged out of the tower through the gas passage port 11 as off-gas.
- the minimum pressure (desorption pressure) inside the adsorption tower 10C in the desorption step is, for example, 0 to 50 kPaG, preferably 0 to 20 kPaG.
- the off gas discharged from the adsorption tower 10 ⁇ / b> C is sent to the off gas tank 23 through the line 32.
- the gas in the off-gas tank 23 is appropriately sent to the cooler 24 via the pressure control valve 321, and further passes through the gas-liquid separator 25, whereby the volatile aromatic compound is liquefied and recovered as a liquid phase. Can do.
- the operation time in step 3 is about 135 seconds, for example.
- the above steps 1 to 3 correspond to 1/3 of the cycle constituted by steps 1 to 9, and the process time of these steps 1 to 3 is about 225 seconds in total.
- Steps 4 to 6 the operation performed on the adsorption tower 10A in Steps 1 to 3 is performed on the adsorption tower 10B, and the operation performed on the adsorption tower 10B in Steps 1 to 3 is performed.
- the operation performed on the adsorption tower 10C and the operation performed on the adsorption tower 10C in steps 1 to 3 are performed on the adsorption tower 10A.
- step 4 the automatic valves 31b, 33b, 32c, 34c, 35a, 351 and the flow rate adjusting valve 352 are opened, and the gas flow state as shown in FIG. 2d is achieved.
- step 5 the automatic valves 31b, 33b, 34c, 35a, 351 and the flow rate adjusting valve 352 are opened, and the gas flow state as shown in FIG. 2e is achieved.
- Step 6 the automatic valves 31b, 33b, 34c, 32a, 341 and the flow rate adjusting valve 342 are opened, and the gas flow state as shown in FIG. 2f is achieved.
- steps 4, 5, and 6 the adsorption tower 10A sequentially performs the same operation as the adsorption tower 10C in steps 1, 2, and 3, and the adsorption tower 10B performs steps 1, 2, and 3, respectively.
- the adsorption column 10C sequentially performs the same operation as the adsorption column 10B in steps 1, 2, and 3.
- Steps 7 to 9 the operation performed on the adsorption tower 10A in Steps 1 to 3 is performed on the adsorption tower 10C, and the operation performed on the adsorption tower 10B in Steps 1 to 3 is performed.
- the operation performed on the adsorption tower 10A and the operation performed on the adsorption tower 10C in steps 1 to 3 are performed on the adsorption tower 10B.
- step 7 the automatic valves 31c, 33c, 32a, 34a, 35b, 351 and the flow rate adjusting valve 352 are opened, and the gas flow state as shown in FIG. 2g is achieved.
- step 8 the automatic valves 31c, 33c, 34a, 35b, 351 and the flow rate adjusting valve 352 are opened, and the gas flow state as shown in FIG. 2h is achieved.
- step 9 the automatic valves 31c, 33c, 34a, 32b, 341 and the flow rate adjusting valve 342 are opened, and the gas flow state as shown in FIG. 2i is achieved.
- steps 7, 8, and 9 the adsorption tower 10A sequentially performs the same operation as the adsorption tower 10B in steps 1, 2, and 3, and the adsorption tower 10B performs steps 1, 2, and 3, respectively.
- the adsorption column 10C sequentially performs the same operation as the adsorption column 10A in steps 1, 2, and 3.
- the cycle consisting of the above steps 1 to 9 is repeatedly performed in each of the adsorption towers 10A, 10B, and 10C, whereby the raw material gas is continuously introduced into any of the adsorption towers 10A, 10B, and 10C, and Concentrated hydrogen gas (product gas) is continuously obtained.
- the residual gas in the tower is transferred to another adsorption tower after the desorption process. Introduce and perform the cleaning process.
- the gas in the adsorption tower after completion of the adsorption process is a gas having a low impurity concentration (residual concentrated hydrogen gas), and the adsorption tower after the desorption process can be efficiently washed using the gas. Further, since the product gas is not used for cleaning, it is possible to suppress a decrease in the hydrogen recovery rate.
- the adsorbent filled in each of the adsorption towers 10A, 10B, and 10C is filled with a silica gel-based adsorbent as the first adsorbent 131 on the most upstream side in the flow direction of the raw material gas.
- the volatile aromatic compound can be desorbed and regenerated.
- the first adsorbent 131 is used in an amount of 15 to 75 vol% of the entire adsorbent filling capacity. As a result, the volatile aromatic compound can be efficiently adsorbed and removed, and the cost can be reduced because the vacuum equipment is unnecessary. Further, if hydrophilic silica gel is used as the first adsorbent 131, the volatile aromatic compound can be appropriately adsorbed and removed without pretreatment, which contributes to cost reduction.
- the filling ratio of the first adsorbent 131 is less than 15 vol%, the volatile aromatic compound may not be sufficiently removed.
- the filling ratio of the first adsorbent 131 exceeds 75 vol%, the ratio of the cleaning gas remaining in the second adsorbent 132 and the third adsorbent 133 is decreased, and the cleaning gas amount is decreased. Cleaning may be insufficient.
- the second adsorbent 132 (zeolite-based adsorbent) and the third adsorbent 133 (activated carbon-based adsorbent) stacked after the first adsorbent 131 (downstream side) do not adsorb volatile aromatic compounds. . That is, the adsorption process is completed before the first adsorbent 131 is saturated with the volatile aromatic compound, and the second adsorbent 132 and the third adsorbent 133 do not substantially adsorb the volatile aromatic compound. . On the other hand, the second adsorbent 132 and the third adsorbent 133 adsorb more hydrogen than the first adsorbent 131.
- the cleaning gas discharged from the adsorption tower in the depressurization process after completion of the adsorption process and used for cleaning other adsorption towers in the desorption process and in the cleaning process remains in the tower at the start of the depressurization process.
- the adsorption tower after completion of the desorption process can be effectively cleaned using the cleaning gas having an increased hydrogen content.
- the present invention is not limited to these embodiments, and various modifications can be made without departing from the spirit of the invention.
- a configuration different from the above-described embodiment may be adopted for the configuration of the line (pipe) forming the gas flow path in the apparatus for carrying out the method for purifying hydrogen or helium according to the present invention.
- the number of adsorption towers is not limited to the three-column type shown in the above embodiment, and the same effect can be expected even when there are four or more towers.
- Example 1 In this example, the purification apparatus X shown in FIG. 1 was used and the purification method using the pressure fluctuation adsorption method (PSA method) composed of the steps described with reference to FIG. The concentrated hydrogen gas was obtained from the source gas as the product gas.
- PSA method pressure fluctuation adsorption method
- adsorption towers 10A, 10B, and 10C cylindrical ones having an inner diameter of 35 mm were used, and the adsorbent filling capacity was about 1 L (liter).
- silica gel B type (Fuji Silica Silica B type manufactured by Fuji Silysia Chemical Co.) as the first adsorbent 131
- second adsorbent CaA-type zeolite 132 (Union Showa 5AHP)
- activated carbon Cataler PGAR
- the filling ratio (volume ratio) of these adsorbents was 30 vol% for the first adsorbent 131, 60 vol% for the second adsorbent 132, and 10 vol% for the third adsorbent 133.
- As the source gas crude hydrogen gas containing 8500 volppm of toluene as an impurity was used, and the source gas was supplied at a flow rate of 5.2 NL / min.
- the operating conditions by the PSA method are as follows: adsorption tower temperature is 40 ° C., adsorption pressure is 0.8 MPaG, desorption pressure is 20 kPaG, cleaning pressure difference is 300 kPa, cycle time (one cycle time composed of steps 1 to 9) Was 675 seconds.
- Example 2 In the same manner as in Example 1, except that the filling ratio of the adsorbent was 40 vol% for the first adsorbent 131, 50 vol% for the second adsorbent 132, and 10 vol% for the third adsorbent 133, was purified. Moreover, when the impurity concentration in the obtained concentrated hydrogen gas (product gas) was measured with a hydrogen flame ion detector (FID), the toluene concentration in the product gas was below the lower limit of quantification (0.1 volppm or less), and hydrogen gas The recovery rate was 70%. The results of this example are shown in Table 1.
- Example 3 In the same manner as in Example 1, except that the filling ratio of the adsorbent was 20 vol% for the first adsorbent 131, 70 vol% for the second adsorbent 132, and 10 vol% for the third adsorbent 133, was purified. Moreover, when the impurity concentration in the obtained concentrated hydrogen gas (product gas) was measured with a hydrogen flame ion detector (FID), the toluene concentration in the product gas was below the lower limit of quantification (0.1 volppm or less), and hydrogen gas The recovery rate was 80%. The results of this example are shown in Table 1.
- Example 4 In the same manner as in Example 1, except that the filling ratio of the adsorbent was 70 vol% for the first adsorbent 131, 20 vol% for the second adsorbent 132, and 10 vol% for the third adsorbent 133, was purified. Moreover, when the impurity concentration in the obtained concentrated hydrogen gas (product gas) was measured with a hydrogen flame ion detector (FID), the toluene concentration in the product gas was 0.67 volppm, and the hydrogen gas recovery rate was 92%. there were. The results of this example are shown in Table 1.
- Example 5 In the same manner as in Example 1, except that the filling ratio of the adsorbent was 30 vol% for the first adsorbent 131, 40 vol% for the second adsorbent 132, and 30 vol% for the third adsorbent 133, was purified. Moreover, when the impurity concentration in the obtained concentrated hydrogen gas (product gas) was measured with a flame ion detector (FID), the toluene concentration in the product gas was 0.43 volppm, and the hydrogen gas recovery rate was 85%. there were. The results of this example are shown in Table 1.
- X purification apparatus 10A, 10B, 10C Adsorption tower 11 Gas passage (first gas passage) 12 Gas passage (second gas passage) 131 First adsorbent 132 Second adsorbent 133 Third adsorbent 21
- Source gas supply source 22 Product storage tank 23
- Off-gas tank 24 Cooler (gas-liquid separation means) 25
- Gas-liquid separator (gas-liquid separation means) 31 lines (1st line) 32 lines (second line) 33 lines (3rd line) 34 lines (4th line) 35 lines (5th line) 31 ', 32', 33 ', 34', 35 'Main roads 31A to 31C, 32A to 32C, 33A to 33C, 34A to 34C, 35A to 35C Branch passages 31a to 31c, 32a to 32c, 33a to 33c, 34a to 34c, 35a to 35c, 341 and 351 Automatic valves 321 and 331 Pressure regulating valves 342 and 352 Flow regulating valves
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Abstract
Description
AS:吸着工程
DP:減圧工程
DS:脱着工程
RN:洗浄工程
PR:昇圧工程
Eq-DP:均圧減圧工程
Eq-PR:均圧昇圧工程
本実施例では、図1に示した精製装置Xを用いて、図2を参照して説明した各ステップからなる圧力変動吸着法(PSA法)を利用した精製方法により、以下に示す条件下で、原料ガスから製品ガスとしての濃縮水素ガスを取得した。
吸着剤の充填比率を、第1吸着剤131が40vol%、第2吸着剤132が50vol%、第3吸着剤133が10vol%とした以外は、実施例1と同様にして、原料ガスから水素の精製を行った。また、得られた濃縮水素ガス(製品ガス)における不純物濃度を水素炎イオン検出器(FID)で測定したところ、製品ガス中のトルエン濃度は定量下限以下(0.1volppm以下)であり、水素ガス回収率は70%であった。本実施例の結果を表1に示した。
吸着剤の充填比率を、第1吸着剤131が20vol%、第2吸着剤132が70vol%、第3吸着剤133が10vol%とした以外は、実施例1と同様にして、原料ガスから水素の精製を行った。また、得られた濃縮水素ガス(製品ガス)における不純物濃度を水素炎イオン検出器(FID)で測定したところ、製品ガス中のトルエン濃度は定量下限以下(0.1volppm以下)であり、水素ガス回収率は80%であった。本実施例の結果を表1に示した。
吸着剤の充填比率を、第1吸着剤131が70vol%、第2吸着剤132が20vol%、第3吸着剤133が10vol%とした以外は、実施例1と同様にして、原料ガスから水素の精製を行った。また、得られた濃縮水素ガス(製品ガス)における不純物濃度を水素炎イオン検出器(FID)で測定したところ、製品ガス中のトルエン濃度は0.67volppmであり、水素ガス回収率は92%であった。本実施例の結果を表1に示した。
吸着剤の充填比率を、第1吸着剤131が30vol%、第2吸着剤132が40vol%、第3吸着剤133が30vol%とした以外は、実施例1と同様にして、原料ガスから水素の精製を行った。また、得られた濃縮水素ガス(製品ガス)における不純物濃度を水素炎イオン検出器(FID)で測定したところ、製品ガス中のトルエン濃度は0.43volppmであり、水素ガス回収率は85%であった。本実施例の結果を表1に示した。
吸着剤の充填比率を、第1吸着剤131が80vol%、第2吸着剤132が10vol%、第3吸着剤133が10vol%とした以外は、実施例1と同様にして、原料ガスから水素の精製を行った。また、得られた濃縮水素ガス(製品ガス)における不純物濃度を水素炎イオン検出器(FID)で測定したところ、製品ガス中のトルエン濃度は2000volppmであり、水素ガス回収率は90%であった。本比較例の結果を表1に示した。
吸着剤の充填比率を、第1吸着剤131が10vol%、第2吸着剤132が80vol%、第3吸着剤133が10vol%とした以外は、実施例1と同様にして、原料ガスから水素の精製を行った。また、得られた濃縮水素ガス(製品ガス)における不純物濃度を水素炎イオン検出器(FID)で測定したところ、製品ガス中のトルエン濃度は3000volppmであり、水素ガス回収率は75%であった。本比較例の結果を表1に示した。
吸着剤の充填比率を、第1吸着剤131が30vol%、第2吸着剤132が30vol%、第3吸着剤133が40vol%とした以外は、実施例1と同様にして、原料ガスから水素の精製を行った。その結果を表1に示した。また、得られた濃縮水素ガス(製品ガス)における不純物濃度を水素炎イオン検出器(FID)で測定したところ、製品ガス中のトルエン濃度は2volppmであり、水素ガス回収率は75%であった。本比較例の結果を表1に示した。
10A,10B,10C 吸着塔
11 ガス通過口(第1ガス通過口)
12 ガス通過口(第2ガス通過口)
131 第1吸着剤
132 第2吸着剤
133 第3吸着剤
21 原料ガス供給源
22 製品貯留タンク
23 オフガスタンク
24 冷却器(気液分離手段)
25 気液分離器(気液分離手段)
31 ライン(第1ライン)
32 ライン(第2ライン)
33 ライン(第3ライン)
34 ライン(第4ライン)
35 ライン(第5ライン)
31’,32’,33’,34’,35' 主幹路
31A~31C,32A~32C,33A~33C,34A~34C,35A~35C
分枝路
31a~31c,32a~32c,33a~33c,34a~34c,35a~35c,341,351 自動弁
321,331 圧力調節弁
342,352 流量調整弁
Claims (11)
- 吸着剤が充填された3塔以上の吸着塔を用いて行う圧力変動吸着法のサイクルを各吸着塔について繰り返すことにより、不純物として揮発性芳香族化合物を含み、且つ主成分として水素またはヘリウムを含む原料ガスから水素またはヘリウムを精製するための方法であって、前記サイクルは、
上記吸着塔が所定の高圧である状態にて、上記吸着塔に上記原料ガスを導入して当該原料ガス中の上記揮発性芳香族化合物を上記吸着剤に吸着させ、当該吸着塔から水素またはヘリウムの濃度が高い製品ガスを排出する吸着工程と、
上記吸着工程を終えた上記吸着塔から塔内に残留するガスを排出して塔内の圧力を低下させる減圧工程と、
上記減圧工程を終えた上記吸着塔における上記吸着剤から上記揮発性芳香族化合物を脱着させ、塔内ガスを排出する脱着工程と、
上記減圧工程にある他の吸着塔から排出されたガスを上記脱着工程を終えた上記吸着塔に導入して塔内に残留するガスを排出する洗浄工程と、を含んでおり、
上記各吸着塔は、上記吸着塔における上記原料ガスの流れ方向において上流側から下流側に向けて順に第1領域、第2領域および第3領域に区分されており、上記第1領域には、上記吸着剤の充填容量全体に対し、充填比率が15~75vol%の範囲であるシリカゲル系の第1吸着剤が充填されており、上記第2領域には、充填比率が15~75vol%の範囲であるゼオライト系の第2吸着剤が充填されており、上記第3領域には、充填比率が5~30vol%の範囲である活性炭系の第3吸着剤が充填されている、水素またはヘリウムの精製方法。 - 上記第1吸着剤は、親水性シリカゲルを含む、請求項1に記載の精製方法。
- 上記第2吸着剤は、CaA型ゼオライトを含む、請求項1に記載の精製方法。
- 上記第3吸着剤は、椰子殻活性炭または石炭活性炭を含む、請求項1に記載の精製方法。
- 上記洗浄工程と上記吸着工程との間に上記吸着塔の圧力を所定の吸着圧力まで高めるための昇圧工程をさらに含む、請求項1に記載の精製方法。
- 上記減圧工程は、上記吸着塔から排出された残留ガスを上記洗浄工程にある他の吸着塔に洗浄ガスとして導入する第1減圧ステップと、当該第1減圧ステップに引き続いて、上記吸着塔から排出された残留ガスを上記昇圧工程にある他の吸着塔に導入する第2減圧ステップと、を含む、請求項5に記載の精製方法。
- 上記昇圧工程は、上記第1減圧ステップにある他の吸着塔から排出された残留ガスを上記吸着塔に導入する第1昇圧ステップと、当該第1昇圧ステップに引き続いて、上記吸着工程にある他の吸着塔からの製品ガスの一部を上記吸着塔に導入する第2昇圧ステップと、を含む、請求項6に記載の精製方法。
- 不純物として揮発性芳香族化合物を含み、且つ主成分として水素またはヘリウムを含む原料ガスから水素またはヘリウムを精製するための装置であって、
各々が第1ガス通過口および第2ガス通過口を有し、当該第1および第2ガス通過口の間において吸着剤が充填された3塔以上の吸着塔と、
製品ガスを貯留するための貯留タンクと、
上記吸着塔の上記第1ガス通過口から排出されるガスを気相成分と液相成分とに分離する気液分離手段と、
原料ガス供給源に接続された主幹路、および、上記吸着塔ごとに設けられて当該吸着塔の上記第1ガス通過口側に接続され且つ開閉弁が各々に設けられた複数の分枝路、を有する第1ラインと、
上記気液分離手段が設けられた主幹路、および、上記吸着塔ごとに設けられて当該吸着塔の上記第1ガス通過口側に接続され且つ開閉弁が各々に設けられた複数の分枝路、を有する第2ラインと、
上記貯留タンクが設けられた主幹路、および、上記吸着塔ごとに設けられて当該吸着塔の上記第2ガス通過口側に接続され且つ開閉弁が各々に設けられた複数の分枝路、を有する第3ラインと、
上記第3ラインにおける上記主幹路に接続された主幹路、および、上記吸着塔ごとに設けられて当該吸着塔の上記第2ガス通過口側に接続され且つ開閉弁が各々に設けられた複数の分枝路、を有する第4ラインと、
上記第4ラインにおける上記主幹路に接続された主幹路、および、上記吸着塔ごとに設けられて当該吸着塔の上記第2ガス通過口側に接続され且つ開閉弁が各々に設けられた複数の分枝路、を有する第5ラインと、を備え、
上記各吸着塔は、上記吸着塔における上記第1ガス通過口から上記第2ガス通過口に向けて順に第1領域、第2領域および第3領域に区分されており、上記第1領域には、上記吸着剤の充填容量全体に対し、充填比率が15~75vol%の範囲であるシリカゲル系の第1吸着剤が充填されており、上記第2領域には、充填比率が15~75vol%の範囲であるゼオライト系の第2吸着剤が充填されており、上記第3領域には、充填比率が5~30vol%の範囲である活性炭系の第3吸着剤が充填されている、水素またはヘリウムの精製装置。 - 上記第1吸着剤は、親水性シリカゲルよりなる、請求項8に記載の精製装置。
- 上記第2吸着剤は、CaA型ゼオライトを含む、請求項8に記載の精製装置。
- 上記第3吸着剤は、椰子殻活性炭または石炭活性炭を含む、請求項8に記載の精製装置。
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CN110921625B (zh) * | 2019-11-19 | 2023-02-28 | 安徽中科皖能科技有限公司 | 合成氨弛放气中氢气和氦气的分离回收装置 |
CN113735078A (zh) * | 2020-05-27 | 2021-12-03 | 中国石油化工股份有限公司 | 从lng工厂的bog尾气中回收氦气的方法、系统及回收的氦气 |
WO2023128071A1 (ko) * | 2021-12-31 | 2023-07-06 | 한국에너지기술연구원 | 암모니아 분해가스로부터 수소 정제용 압력변동흡착장치 및 이를 이용한 수소 정제 방법 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001070727A (ja) * | 1999-08-13 | 2001-03-21 | Praxair Technol Inc | 水素製造のための圧力変動式吸着法 |
JP2001300244A (ja) * | 2000-04-20 | 2001-10-30 | Mitsubishi Kakoki Kaisha Ltd | 水素製造用圧力変動吸着装置の吸着塔 |
WO2004076030A1 (ja) * | 2003-02-25 | 2004-09-10 | Sumitomo Seika Chemicals Co., Ltd. | オフガス供給方法、および目的ガス精製システム |
WO2013190731A1 (ja) * | 2012-06-21 | 2013-12-27 | 住友精化株式会社 | アンモニア精製システム |
JP2016002531A (ja) * | 2014-06-18 | 2016-01-12 | 株式会社神戸製鋼所 | Psa装置及びpsa装置を用いた吸着除去方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3306841A (en) * | 1964-12-28 | 1967-02-28 | Universal Oil Prod Co | Gas separation process |
JP3011094B2 (ja) | 1995-05-27 | 2000-02-21 | システム エンジ サービス株式会社 | 廃棄ガスに含まれるガス状炭化水素の処理・回収方法 |
JP2925522B2 (ja) | 1997-06-17 | 1999-07-28 | システム エンジ サービス株式会社 | ガス状炭化水素を含む廃棄ガスから炭化水素を液状で回収する方法 |
JP3974013B2 (ja) | 2001-12-28 | 2007-09-12 | システム エンジ サービス株式会社 | 揮発性炭化水素含有排ガスの処理方法及び該方法を実施するための装置 |
JP4203281B2 (ja) * | 2002-08-09 | 2008-12-24 | 日本ジョイント株式会社 | 表面処理方法 |
CN101528592A (zh) * | 2006-10-20 | 2009-09-09 | 住友精化株式会社 | 氢气的分离方法和分离装置 |
AU2007318658A1 (en) * | 2006-11-08 | 2008-05-15 | Sumitomo Seika Chemicals Co., Ltd. | Hydrogen gas separation method and separation apparatus |
CN1994525A (zh) * | 2006-12-11 | 2007-07-11 | 唐莉 | 从氯乙烯或氯碱生产放空气中分离回收氢气的方法 |
KR100896455B1 (ko) * | 2007-07-09 | 2009-05-14 | 한국에너지기술연구원 | 압력변동흡착장치 및 이를 이용한 수소 정제 방법 |
CN101347708B (zh) * | 2007-07-18 | 2010-12-01 | 中国石油化工股份有限公司 | 一种储罐逸散含硫恶臭废气的处理方法 |
CN101732945A (zh) * | 2009-12-25 | 2010-06-16 | 成都赛普瑞兴科技有限公司 | 从含氯硅烷尾气中回收氢气的方法 |
CN102078740B (zh) * | 2010-12-13 | 2013-02-27 | 甘肃银光聚银化工有限公司 | 一种利用变压吸附法从水煤气中分离并提纯氢气的方法 |
JP5738900B2 (ja) * | 2011-01-25 | 2015-06-24 | 住友精化株式会社 | アンモニア精製システムおよびアンモニアの精製方法 |
CN102199433A (zh) * | 2011-03-05 | 2011-09-28 | 何巨堂 | 一种以co2为燃烧过程控温组分的煤炭化工艺 |
CN103523752A (zh) * | 2012-07-03 | 2014-01-22 | 陕西天宏硅材料有限责任公司 | 多晶硅生产中还原转化尾气回收所得氢气的纯化工艺 |
AU2013363333A1 (en) * | 2012-12-18 | 2015-07-30 | Invista Technologies S.A.R.L. | Process for producing hydrogen cyanide and recovering hydrogen |
CN104338412B (zh) * | 2013-08-07 | 2016-09-28 | 中国石油化工股份有限公司 | 一种变压吸附塔的装填方法 |
-
2017
- 2017-08-23 WO PCT/JP2017/030156 patent/WO2018055971A1/ja active Application Filing
- 2017-08-23 CN CN201780058839.2A patent/CN109790020A/zh active Pending
- 2017-08-23 KR KR1020197009112A patent/KR102382274B1/ko active IP Right Grant
- 2017-08-23 JP JP2018540924A patent/JP6905534B2/ja active Active
- 2017-08-25 TW TW106128928A patent/TWI728176B/zh active
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2019
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001070727A (ja) * | 1999-08-13 | 2001-03-21 | Praxair Technol Inc | 水素製造のための圧力変動式吸着法 |
JP2001300244A (ja) * | 2000-04-20 | 2001-10-30 | Mitsubishi Kakoki Kaisha Ltd | 水素製造用圧力変動吸着装置の吸着塔 |
WO2004076030A1 (ja) * | 2003-02-25 | 2004-09-10 | Sumitomo Seika Chemicals Co., Ltd. | オフガス供給方法、および目的ガス精製システム |
WO2013190731A1 (ja) * | 2012-06-21 | 2013-12-27 | 住友精化株式会社 | アンモニア精製システム |
JP2016002531A (ja) * | 2014-06-18 | 2016-01-12 | 株式会社神戸製鋼所 | Psa装置及びpsa装置を用いた吸着除去方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7148748B1 (ja) | 2022-03-11 | 2022-10-05 | 大陽日酸株式会社 | ガス精製装置 |
WO2023171786A1 (ja) * | 2022-03-11 | 2023-09-14 | 大陽日酸株式会社 | ガス精製装置 |
JP2023132478A (ja) * | 2022-03-11 | 2023-09-22 | 大陽日酸株式会社 | ガス精製装置 |
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TWI728176B (zh) | 2021-05-21 |
KR102382274B1 (ko) | 2022-04-01 |
JPWO2018055971A1 (ja) | 2019-07-11 |
KR20190059278A (ko) | 2019-05-30 |
JP6905534B2 (ja) | 2021-07-21 |
CN109790020A (zh) | 2019-05-21 |
PH12019500651B1 (en) | 2019-08-05 |
TW201821147A (zh) | 2018-06-16 |
PH12019500651A1 (en) | 2019-08-05 |
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