WO2011111538A1 - フッ素ガス生成装置 - Google Patents
フッ素ガス生成装置 Download PDFInfo
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- WO2011111538A1 WO2011111538A1 PCT/JP2011/054103 JP2011054103W WO2011111538A1 WO 2011111538 A1 WO2011111538 A1 WO 2011111538A1 JP 2011054103 W JP2011054103 W JP 2011054103W WO 2011111538 A1 WO2011111538 A1 WO 2011111538A1
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- gas
- fluorine gas
- adsorbent
- cylindrical member
- hydrogen fluoride
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
-
- 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
- B01D53/0407—Constructional details of adsorbing systems
- B01D53/0423—Beds in columns
-
- 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
- B01D53/0407—Constructional details of adsorbing systems
- B01D53/0446—Means for feeding or distributing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/685—Halogens or halogen compounds by treating the gases with solids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/021—Process control or regulation of heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- 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
- B01D2256/26—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2047—Hydrofluoric acid
Definitions
- the present invention relates to a fluorine gas generator that generates fluorine gas.
- an electrolytic bath for electrolyzing hydrogen fluoride in an electrolytic bath made of a molten salt containing hydrogen fluoride is provided, and a main gas mainly composed of fluorine gas is generated on the anode side, and hydrogen gas is supplied on the cathode side.
- a fluorine gas generator that generates a by-product gas as a main component is known.
- the fluorine gas generated from the molten salt is mixed with the fluorine gas generated from the anode of the electrolytic cell. Therefore, in order to separate the hydrogen fluoride from the gas generated from the anode and purify the fluorine gas, a purifier having a treatment cylinder filled with an adsorbent such as sodium fluoride (NaF) is provided.
- an adsorbent such as sodium fluoride (NaF)
- the fluorine and hydrogen gas generated from the electrolytic cell contains hydrogen fluoride vaporized from the molten salt contained in the electrolytic cell and the mist component of the molten salt itself, and these components cause the deterioration of the adsorbent. It has become.
- the adsorbent near the inlet of the processing cylinder may expand or melt due to high concentration of hydrogen fluoride, and the adsorbent may be clogged. When such clogging occurs, the flow of gas is suppressed, causing a problem of blocking.
- Patent Document 1 provides an isolation means for forming a space between a gas inlet and an adsorbent in a purifier filled with an adsorbent such as sodium fluoride (NaF), The mist component droplets are diffused and settled in this space, making it difficult for the adsorbent and molten salt mist component droplets to come into contact with each other.
- adsorbent such as sodium fluoride (NaF)
- the adsorbent that adsorbs hydrogen fluoride is densely packed. In such a configuration, it is difficult to completely prevent clogging in the purification apparatus.
- the present invention has been made in view of the above problems, and provides a fluorine gas generator that can stably supply a high-purity fluorine gas by preventing clogging of a purification apparatus that adsorbs and removes hydrogen fluoride.
- the purpose is to provide.
- the present inventors are provided in a purification apparatus that adsorbs and removes hydrogen fluoride, and inside the cylindrical member that allows gas generated in an electrolytic cell to pass through,
- An adsorbent holder for holding the adsorbent is provided, and the adsorbent holder is further formed with a space for securing a gas flow path passing through the inside of the cylindrical member in the internal space of the cylindrical member.
- the present invention is a fluorine gas generation device that generates fluorine gas by electrolyzing hydrogen fluoride in a molten salt containing hydrogen fluoride
- the fluorine gas generation device includes hydrogen fluoride.
- Electrolysis of hydrogen fluoride in an electrolytic bath made of molten salt generates a main product gas mainly composed of fluorine gas on the anode side and a by-product gas mainly composed of hydrogen gas on the cathode side.
- An electrolytic cell and a purification device that removes fluorine hydrogen mixed in the main gas with an adsorbent are provided, and the purification device adjusts the temperature of the cylindrical member that allows the main gas to pass therethrough and the temperature of the cylindrical member.
- a temperature controller and an adsorbent holder provided in the cylindrical member, wherein the adsorbent holder has a gap for securing a flow path of the main gas in the cylindrical member.
- a fluorine gas generating device characterized in that there.
- a plurality of the adsorbent holders are provided in the cylindrical member so that the flow path of the main gas is meandering. Device.
- the adsorbent holder is a basin member
- the basin member includes a bottom plate portion provided with a notch for circulating gas, and an outer edge excluding the notch portion of the bottom plate portion.
- An outer edge side wall portion erected on the notch portion side of the bottom plate portion, and an upper end opening of the basin-shaped member body, and the outer edge side wall portion is formed into the cylindrical shape.
- the fluorine gas generator is arranged so as to be inscribed in the inner wall of the member.
- the present invention is a fluorine gas generating device, wherein the bottom plate portion is provided with a through hole.
- the fluorine gas generation is characterized in that a distance between the basin member and a basin member arranged adjacent thereto is 1/5 or more of the inner diameter of the cylindrical member and less than or equal to the inner diameter.
- the present invention is the fluorine gas generation device characterized in that the area of the bottom plate part provided with the notch part is 50% or more and 95% or less of the area of the inner diameter part of the cylindrical member. .
- a gap that is not filled with an adsorbent is formed inside a cylindrical member that is provided in a purification apparatus and allows gas generated in an electrolytic cell to pass therethrough, and a gas flow path is always secured. Therefore, even when a part of the adsorbent is clogged, it is possible to provide a fluorine gas generation device that can supply high-purity fluorine gas stably without clogging. .
- FIG. 3 is a cross-sectional view taken along the line AA in FIG. 2. It is an example of the tray-shaped member which concerns on embodiment of this invention. It is the schematic of the experimental apparatus which performed the refinement
- the fluorine gas generation device 100 generates fluorine gas by electrolysis and supplies the generated fluorine gas to the external device 4.
- the external device 4 is, for example, a semiconductor manufacturing device.
- fluorine gas is used as a cleaning gas, for example, in a semiconductor manufacturing process.
- the fluorine gas generation device 100 includes an electrolytic cell 1 that generates fluorine gas by electrolysis, a fluorine gas supply system 2 that supplies the fluorine gas generated from the electrolytic cell 1 to the external device 4, and the generation of fluorine gas. And a by-product gas processing system 3 for processing the generated by-product gas.
- the electrolytic bath 1 stores a molten salt containing hydrogen fluoride (HF).
- HF hydrogen fluoride
- KF potassium fluoride
- the inside of the electrolytic cell 1 is partitioned into an anode chamber 11 and a cathode chamber 12 by a partition wall 6 immersed in the molten salt.
- the anode 7 and the cathode 8 are immersed, respectively.
- main gas mainly composed of fluorine gas (F 2 ) is generated at the anode 7, and hydrogen gas (H 2 ) is generated at the cathode 8.
- F 2 fluorine gas
- H 2 hydrogen gas
- By-product gas as a main component is generated.
- a carbon electrode is used for the anode 7, and soft iron, monel, or nickel is used for the cathode 8.
- a first gas chamber 11a into which fluorine gas generated at the anode 7 is guided, and a second gas chamber 12a into which hydrogen gas generated at the cathode 8 is guided. are partitioned by the partition wall 6 so that the mutual gas cannot pass.
- the first air chamber 11a and the second air chamber 12a are completely separated by the partition wall 6 in order to prevent a reaction due to the contact of fluorine gas and hydrogen gas.
- the molten salt in the anode chamber 11 and the cathode chamber 12 is not separated by the partition wall 6 but communicates through the lower portion of the partition wall 6.
- each of the fluorine gas and the hydrogen gas generated from the anode 7 and the cathode 8 of the electrolytic cell 1 hydrogen fluoride is vaporized from the molten salt by the vapor pressure and mixed.
- each of the fluorine gas generated at the anode 7 and guided to the first air chamber 11a and the hydrogen gas generated at the cathode 8 and guided to the second air chamber 12a includes hydrogen fluoride gas. Yes.
- a first main passage 15 for supplying fluorine gas to the external device 4 is connected to the first air chamber 11a.
- the first main passage 15 is provided with a first pump 17 for deriving and transporting fluorine gas from the first air chamber 11a.
- a positive displacement pump such as a bellows pump or a diaphragm pump is used.
- a purification device 20 is provided upstream of the first pump 17 in the first main passage 15 to collect hydrogen fluoride mixed in the fluorine gas and purify the fluorine gas. The purification device 20 will be described in detail later.
- a second main passage 30 for discharging hydrogen gas to the outside is connected to the second air chamber 12a.
- the second main passage 30 is provided with a second pump 31 for deriving and transporting hydrogen gas from the second air chamber 12a.
- An abatement part 34 is provided downstream of the second pump 31 in the second main passage 30, and the hydrogen gas transported by the second pump 31 is rendered harmless by the abatement part 34 and released.
- the fluorine gas generation device 100 also includes a raw material supply system 5 for supplying hydrogen fluoride, which is a raw material of fluorine gas, to the molten salt in the electrolytic cell 1 for replenishment. Below, the raw material supply system 5 is demonstrated.
- the electrolytic cell 1 is connected through a raw material supply passage 41 and a hydrogen fluoride supply source 40 in which hydrogen fluoride for replenishing the electrolytic cell 1 is stored. Hydrogen fluoride stored in the hydrogen fluoride supply source 40 is supplied into the molten salt of the electrolytic cell 1 through the raw material supply passage 41.
- a carrier gas supply passage 46 that guides the carrier gas supplied from the carrier gas supply source 45 into the raw material supply passage 41 is connected to the raw material supply passage 41.
- the carrier gas is a gas for introducing hydrogen fluoride into the molten salt, and nitrogen gas which is an inert gas is used. Nitrogen gas is supplied together with hydrogen fluoride into the molten salt in the cathode chamber 12, hardly dissolves in the molten salt, and is discharged from the second air chamber 12 a through the second main passage 30.
- the purification apparatus 20 is an apparatus that removes hydrogen fluoride mixed in fluorine gas by adsorbing hydrogen fluoride mixed in fluorine gas on an adsorbent such as sodium fluoride (NaF).
- the purification apparatus 20 is connected to an inlet path 51a for introducing the fluorine gas generated at the anode 7 and an outlet path 52a for deriving the fluorine gas from the purification apparatus 20. Further, the purification apparatus 20 includes a cylindrical member 31a through which fluorine gas passes, and further, an adsorbent holder for holding an adsorbent that adsorbs hydrogen fluoride is provided inside the cylindrical member 31a. It is done.
- the cylindrical member here refers to a container for containing an adsorbent that adsorbs hydrogen fluoride inside, allowing the fluorine gas generated from the electrolytic cell 1 to pass therethrough, and adsorbing and removing hydrogen fluoride in the fluorine gas.
- the shape is not particularly limited.
- the material of the cylindrical member is preferably one having resistance to fluorine gas and hydrogen fluoride gas, and examples thereof include alloys such as stainless steel, monel, nickel, and metals.
- a number of porous beads made of sodium fluoride (NaF) are used as the adsorbent. Since the adsorption capacity of sodium fluoride varies depending on the temperature, a heater 41a is provided around the cylindrical member 31a as a temperature controller for adjusting the temperature in the cylindrical member 31a.
- the temperature controller is not particularly limited as long as the temperature in the cylindrical member can be adjusted.
- a heating / cooling device using a heater, steam heating, a heating medium or a refrigerant may be used.
- alkali metal fluorides such as NaF, KF, RbF, and CsF can be used. Among them, NaF is particularly preferable.
- the adsorbent holder is disposed inside the cylindrical member 31a so as to form a gap for securing a gas flow path. Thereby, even when a part of the adsorbent is clogged, the gas can be circulated without being blocked.
- the adsorbent holder means a unit that is provided in the cylindrical member of the refining device and that stores and holds a predetermined amount of adsorbent in the space in the cylindrical member. Further, a plurality of adsorbent holders may be provided at a certain interval.
- the adsorbent holder is provided with a through hole.
- the through-hole here is not particularly limited as long as it is a size of a hole capable of holding the adsorbent and allowing gas to pass therethrough, and is appropriately designed.
- the adsorbent holder is preferably porous or mesh.
- the specific shape of the adsorbent holder is not particularly limited as long as the gas flow path in the cylindrical member is ensured and the adsorbent can be accommodated and held, but for example, a wire mesh (mesh shape)
- the method of providing the adsorbent material holder in the cylindrical member of the purification apparatus is not particularly limited as long as it is arranged so as to form a gap for securing a gas flow path in the cylindrical member.
- Examples thereof include a method of suspending the adsorbent holder in such a form in a space in the cylindrical member, a method of fixing the adsorbent holder on the inner wall of the cylindrical member, and the like.
- the gas flow path can always be secured, the blockage can be prevented, and the gas can be purified efficiently.
- the adsorbent holder is particularly preferably a bonoid member.
- the term “bowl-shaped member” refers to a flat container that can accommodate an object, and is not particularly limited in shape, such as a substantially circular shape or a substantially square shape, as long as it can accommodate an adsorbent. It is designed appropriately depending on the shape.
- a tray member will be cited, and the purification apparatus 20 provided with the tray member will be described with reference to FIG.
- a basin member will be described as an example of the adsorbent holder, but the adsorbent holder in the present invention is not limited to a basin member.
- FIG. 3 is a cross-sectional view of the purification apparatus 20 taken along the line AA.
- FIG. 4 is a figure which shows an example of the structure of the tray-shaped member used as an adsorbent holder.
- FIGS. 2 and 3 an outline of the purification apparatus 20 provided with a tray-like member will be described.
- a part of the tray-shaped member 211 is fixed to the inner wall of the cylindrical member 31 a provided in the purification device 20.
- a notch 212 for circulating gas is formed in a part of the basin member 211. By providing this notch 212, the gas can always flow and does not completely block. It has become.
- the adsorbent 70 is filled in the basin member 211.
- the position where the basin-shaped member 211 is fixed to the inner wall of the cylindrical member 31a is not particularly limited as long as the gas flow can be secured.
- the gas and the adsorbent are sufficiently brought into contact with each other to improve the gas purification efficiency.
- the tray-shaped member 211 in the flow direction from the gas inlet to the outlet direction of the gas in the cylindrical member 31a, the tray-shaped member 211 is connected to the inner wall of the cylindrical member 31a so that the notches 212 are alternately left and right.
- the distance between the basin member 211 and the basin member disposed adjacent thereto is 1/5 or more of the inner diameter of the cylindrical member 31a and less than or equal to the inner diameter. It is preferable to do. If this distance is shorter than 1/5, the gas may not flow smoothly. If the distance is longer than the inner diameter, the gas flow cannot be sufficiently meandered, and the gas can be sufficiently absorbed with the adsorbent. It cannot be contacted.
- the number of tray members 211 (the number of stages) is preferably provided in a plurality of stages in order to completely prevent clogging of the purification apparatus and improve the adsorption capability of hydrogen fluoride (see Example 1 described later), It is preferable to set appropriately according to the situation of the apparatus such as the amount of hydrogen fluoride to be adsorbed and the size of the purification apparatus to be used.
- the size and arrangement of the basin member 211 are not particularly limited as long as they do not impede the gas flow, and the situation such as the size of the cylindrical member on which the basin member is provided. It is preferable to set as appropriate.
- the tray-shaped member 211 of the present invention includes a bottom plate portion 211 a provided with a notch portion 212 for circulating gas, and an outer edge erected on the outer edge excluding the notch portion 211 of the bottom plate portion 211 a. It has the side wall part 211b, the notch side wall part 211c standingly arranged by the notch part side of the baseplate part 211a, and the upper end opening part 211d of the tray-shaped member 211 main body.
- the side wall part 211b except the notch part 212 of the tray upper member 211 may be provided so as to be inscribed in the inner wall in the cylindrical member 31a.
- the position where the tray-like member 211 provided with the notch 212 is arranged is not particularly limited as long as it has a shape that can secure the gas flow, and is appropriately designed.
- the area of the bottom plate portion 211a provided with the notch portion 212 is set to the inner diameter portion of the cylindrical member 31a.
- the area is preferably 50% or more, more preferably 50 to 95%, still more preferably 85 to 95%. If it is less than 50%, the amount of the adsorbent 70 is sufficiently accommodated, and the gas flow is made meandering so that it is difficult to sufficiently contact the adsorbent. On the other hand, when it is larger than 95%, the pressure loss becomes large and the gas may not flow smoothly, which is not preferable.
- the method of arranging and fixing the basin member 211 in the space in the cylindrical member 31a may be arranged so that the basin members 211 are brought into contact with each other or separated from each other as long as the gas flow can be secured.
- the height of the cutout side wall portion 211c is set to the outer side wall. It may be made lower than the height of the portion 211b, and the gas flow path may be secured by a gap due to this height difference.
- a through-hole may be appropriately provided in the member constituting the basin member 211.
- the through holes may be provided in all the members constituting the basin-shaped member 211, in order to increase the surface area of the adsorbent in contact with the gas, in particular, the through holes are provided in the bottom plate part 211a and the notched side wall part 211c.
- the through hole may be provided in the bottom plate portion 211a and / or the notched side wall portion 211c.
- a method for providing the through hole in the tray-shaped member 211 is not particularly limited, and examples thereof include punching. Moreover, as what has a through-hole, it is good to use a porous or mesh-shaped member. In particular, in order to increase the surface area of the gas and the adsorbent, it is particularly preferable to form the bottom plate portion 211a in a mesh shape (see Example 1 described later).
- the gas flow path is secured in the notch portion 212, so that it can be prevented from being completely blocked.
- the material of the member constituting the basin member 211 is preferably one having resistance to fluorine gas and hydrogen fluoride gas, and examples thereof include alloys such as stainless steel, monel, nickel, and metals. . Moreover, it is preferable to use the same material as described above in the case of a porous or mesh material.
- the fluorine gas generated in the anode 7 of the electrolytic cell 1 is guided to the purification device 20 through the first main passage 15, passes through the open inlet valve 13a, and the cylindrical member 31a of the purification device 20. Is introduced into the cylindrical member 31a through the inlet passage 51a. At this time, the temperature inside the cylindrical member 31a is adjusted by the heater 41a provided around the cylindrical member 31a.
- the temperature in the cylindrical member 31a is preferably set as appropriate depending on the desired purity of fluorine (the concentration of hydrogen fluoride in the fluorine gas), but the concentration of hydrogen fluoride in the fluorine gas introduced from the electrolytic cell 1 In order to make the content less than 1000 ppm, it is preferable to set the temperature in the cylindrical member 31a within the range of 70 to 100 ° C.
- the fluorine gas passes through the inside of the cylindrical member 31a provided with the adsorbent holder, and at this time, the fluorine gas comes into contact with the adsorbent accommodated and held in the adsorbent holder provided in the cylindrical member 31a. However, hydrogen fluoride is adsorbed. At this time, the fluorine gas circulates through the gap in the cylindrical member, and the gas that has passed through the cylindrical member 31a is discharged from the outlet passage 52a to the outside of the refining device 20 and is supplied to the external device 4 such as a semiconductor manufacturing device. Led to.
- the generation of the fluorine gas generated in the anode 7 of the electrolytic cell 1 has been described.
- the hydrogen gas generated in the cathode 8 of the electrolytic cell 1 is the same using a purification apparatus having the same configuration. By performing various operations, it is possible to purify the hydrogen gas generated at the cathode.
- FIGS. 1 and 2 show the case where the direction of the gas flowing through the purification device flows from the lower part to the upper part of the cylindrical member.
- purifier You may make it flow from the lower part of a cylindrical member to upper part or from upper part to the lower part.
- a void that is not filled with an adsorbent is formed inside the cylindrical member that allows the gas generated in the electrolytic cell provided in the purification apparatus to pass therethrough. Therefore, even if a part of the adsorbent is clogged, a fluorine gas generation device capable of supplying high-purity fluorine gas stably without being blocked is provided. be able to.
- the gas flow path is always secured in the cylindrical member, so that the clogging filled in the purification apparatus is clogged. Therefore, it is possible to effectively use the adsorbent in a portion where no adsorption occurs, and the adsorbent can be used efficiently.
- two or more purification apparatuses may be installed and used while switching.
- the purification apparatus may be provided only on the cathode side that generates hydrogen gas, or may be provided on the anode side where fluorine gas is generated and on the cathode side where hydrogen gas is generated.
- the present invention can be applied to an apparatus that generates fluorine gas, and can reduce the load of maintenance work for collecting and replacing an adsorbent that adsorbs and removes hydrogen fluoride.
- a purification capability test of a purification device applicable to the embodiment of the present invention was conducted.
- a purification capability test a differential pressure measurement at a refiner gas inlet A and an outlet B in repeated use and a hydrogen fluoride concentration at the outlet gas were measured.
- a purification device using a tray-type container as a tray-shaped member that is an example of an adsorbent holder will be referred to as a tray-type purification device.
- the vertical filling and refining device referred to here represents a device that densely fills the inside of a cylindrical member provided in the refining device with the adsorbent as it is.
- Example 1 As the tray-shaped member, a substantially circular tray-type container (made of stainless steel, outer diameter 80 mm) shown in FIG. 4 is used, and the area of the bottom plate part of the tray-type container is 90% of the area of the inner diameter part of the cylindrical member. Thus, a notch was provided in a part of the tray-type container. Also, the tray-type container uses a container in which the bottom plate portion is punched out, a mesh-like metal sheet is inserted, and a through-hole (mesh shape) is provided in the bottom plate portion and the notched side wall portion of the tray-type container. did.
- the tray-type container was made of stainless steel, the cylindrical member was cylindrical (inner diameter 80 mm), and the material was stainless steel.
- the positions of the cutouts are made to be substantially perpendicular to the inner wall in the cylindrical member alternately from the left and right from the gas inlet to the outlet so that the gas flow is meandering. 8 stages were provided.
- the tray type container was disposed so that all of the outer edge side wall portions except the cutout portion were inscribed in the inner wall in the cylindrical member.
- 80 g of sodium fluoride was filled in each of the tray type containers (total amount of 640 g in 8 stages).
- the temperature in a cylindrical member was adjusted with the heater provided in the cylindrical member outer periphery with 100 degreeC.
- 9% hydrogen fluoride gas diluted with nitrogen gas was circulated at a flow rate of 0.7 cm / sec for 15 hours, and the differential pressure between the gas inlet A and the gas outlet B of the purifier was measured with a pressure gauge.
- the hydrogen fluoride concentration at the gas outlet B after flowing for 15 hours was analyzed by Fourier transform infrared spectroscopy (FT-IR).
- the temperature inside the cylindrical member was adjusted to 250 ° C. by a heater provided on the outer periphery of the cylindrical member, and nitrogen gas was circulated at a flow rate of 2.1 cm / sec and adsorbed on the adsorbent (sodium fluoride). The desorption operation of hydrogen fluoride was performed.
- the adsorption process for adsorbing the same hydrogen fluoride to the adsorbent and the desorption process of hydrogen fluoride were performed 15 times, and the differential pressure measurement and the hydrogen fluoride concentration measurement were measured at each time. As shown in Table 1, even when repeated 15 times, in the tray type refiner, no large pressure difference was generated between the gas inlet A and the gas outlet B of the refiner. Further, the hydrogen fluoride concentration at the gas outlet B in all 15 times was 1000 ppm or less.
- Example 1 Experimental conditions similar to those in Example 1 except that a vertical filling purification apparatus (packed with 640 g of sodium fluoride as an adsorbent densely) without an adsorbent holder inside the cylindrical member was used as the purification apparatus. The purification ability test was conducted at
- the hydrogen fluoride concentration at the gas outlet B was 1000 ppm or less at all 15 times, but the differential pressure became 10000 Pa or more at the 6th repetition and was completely blocked. did.
- tray type purification apparatus has the same purification ability as the vertical filling purification apparatus and is not easily blocked.
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Abstract
Description
盆状部材としては、図4に示す、略円状のトレイ型容器(ステンレス製、外径80mm)を用い、トレイ型容器の底板部の面積が筒状部材の内径部の面積の90%になるように、トレイ型容器の一部に切欠部を設けた。また、トレイ型容器は、底板部を繰り抜き加工し、メッシュ状の金属シートを挿入し、トレイ型容器の底板部と切欠側壁部に、貫通孔(メッシュ状)が設けられている容器を使用した。なお、トレイ型容器の材質はステンレス製のものを使用し、筒状部材としては、円筒型(内径80mm)、材質はステンレスのものを使用した。
精製装置として、筒状部材内部に吸着剤保持具を設けていない縦型充填精製装置(吸着剤であるフッ化ナトリウム640gをそのまま密に充填)を用いた以外は実施例1に同様な実験条件で精製能力試験を行った。
1 電解槽
2 フッ素ガス供給系
3 副生ガス供給系
4 外部装置
5 原料供給系
7 陽極
8 陰極
11a 第1気室
12a 第2気室
15 第1メイン通路
17 第1ポンプ
31 第2ポンプ
20 精製装置
211 盆状部材
211a 底板部
211b 外縁側壁部
211c 切欠側壁部
211d 上端開口部
212 切欠部
Claims (6)
- フッ化水素を含む溶融塩中のフッ化水素を電気分解することによって、フッ素ガスを生成するフッ素ガス生成装置であって、
前記フッ素ガス生成装置は、
フッ化水素を含む溶融塩からなる電解浴中でフッ化水素を電解することによって陽極側にフッ素ガスを主成分とする主生ガスを発生させると共に、陰極側に水素ガスを主成分とする副生ガスを発生させる電解槽と、
前記主生ガスに混入したフッ素水素を吸着剤によって除去する精製装置を備え、
前記精製装置は、
前記主生ガスを通過させる筒状部材と、
前記筒状部材の温度を調節する温度調節器と、
前記筒状部材内に設けられた吸着剤保持具と、を備え、
前記吸着剤保持具は、前記筒状部材内に前記主生ガスの流路を確保するための空隙を形成するように設けられていることを特徴とするフッ素ガス生成装置。 - 前記吸着剤保持具は、前記筒状部材内において、前記主生ガスの流路が蛇行状となるように、複数以上、設けられていることを特徴とする請求項1に記載のフッ素ガス生成装置。
- 前記吸着剤保持具は、盆状部材であり、該盆状部材は、ガスを流通させるための切欠部が設けられた底板部と、前記底板部の切欠部を除く外縁に立設された外縁側壁部と、前記底板部の切欠部側に立設する切欠側壁部と、前記盆状部材本体の上端開口部と、を有し、前記外縁側壁部を、前記筒状部材の内壁に内接するように配置したことを特徴とする請求項1又は請求項2に記載のフッ素ガス生成装置。
- 前記底板部には、貫通孔が設けられていることを特徴とする請求項3に記載のフッ素ガス生成装置。
- 前記吸着剤保持具は、前記筒状部材内に、離隔して複数以上設けられ、前記盆状部材とその隣に配置された盆状部材との距離が、前記筒状部材の内径の1/5以上、内径以下、であることを特徴とする請求項3又は請求項4に記載のフッ素ガス生成装置。
- 前記切欠部が設けられた底板部の面積が、前記筒状部材の内径部の面積の50%以上、95%以下であることを特徴とする請求項3乃至請求項5の何れかに記載のフッ素ガス生成装置。
Priority Applications (4)
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KR1020127024044A KR20120127646A (ko) | 2010-03-09 | 2011-02-24 | 불소 가스 생성 장치 |
US13/574,177 US20120318665A1 (en) | 2010-03-09 | 2011-02-24 | Apparatus for Generating Fluorine Gas |
EP11753198A EP2511399A1 (en) | 2010-03-09 | 2011-02-24 | Apparatus for generating fluorine gas |
CN2011800130419A CN102803568A (zh) | 2010-03-09 | 2011-02-24 | 氟气生成装置 |
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JP2010-051316 | 2010-03-09 | ||
JP2010051316 | 2010-03-09 | ||
JP2011020868A JP2011208276A (ja) | 2010-03-09 | 2011-02-02 | フッ素ガス生成装置 |
JP2011-020868 | 2011-02-02 |
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WO2011111538A1 true WO2011111538A1 (ja) | 2011-09-15 |
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PCT/JP2011/054103 WO2011111538A1 (ja) | 2010-03-09 | 2011-02-24 | フッ素ガス生成装置 |
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US (1) | US20120318665A1 (ja) |
EP (1) | EP2511399A1 (ja) |
JP (1) | JP2011208276A (ja) |
KR (1) | KR20120127646A (ja) |
CN (1) | CN102803568A (ja) |
WO (1) | WO2011111538A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014008543A1 (en) * | 2012-07-10 | 2014-01-16 | Lynas Services Pty Ltd | Method and apparatus for removing fluoride compounds |
CN113874553A (zh) * | 2019-12-27 | 2021-12-31 | 昭和电工株式会社 | 氟气的制造方法及氟气制造装置 |
CN113950542A (zh) * | 2019-12-27 | 2022-01-18 | 昭和电工株式会社 | 氟气的制造方法及氟气制造装置 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107337180B (zh) * | 2017-07-10 | 2019-08-23 | 洛阳森蓝化工材料科技有限公司 | 一种纯化氟气的填料及其制备方法和应用 |
US20240139670A1 (en) | 2021-03-02 | 2024-05-02 | Resonac Corporation | Hydrogen fluoride gas removal device and method for removing hydrogen fluoride gas |
CN113413724B (zh) * | 2021-06-01 | 2022-06-21 | 海南启航未来智能科技有限公司 | 一种除烟除味环保装置 |
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JP2009215588A (ja) | 2008-03-10 | 2009-09-24 | Toyo Tanso Kk | フッ素ガス発生装置 |
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JP3617835B2 (ja) * | 2002-09-20 | 2005-02-09 | 東洋炭素株式会社 | フッ素ガス発生装置 |
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2011
- 2011-02-02 JP JP2011020868A patent/JP2011208276A/ja active Pending
- 2011-02-24 WO PCT/JP2011/054103 patent/WO2011111538A1/ja active Application Filing
- 2011-02-24 EP EP11753198A patent/EP2511399A1/en not_active Withdrawn
- 2011-02-24 CN CN2011800130419A patent/CN102803568A/zh active Pending
- 2011-02-24 KR KR1020127024044A patent/KR20120127646A/ko not_active Application Discontinuation
- 2011-02-24 US US13/574,177 patent/US20120318665A1/en not_active Abandoned
Patent Citations (4)
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JPS5275659A (en) * | 1975-12-20 | 1977-06-24 | Takeda Chem Ind Ltd | Gaseous phase reactor |
JPH03270712A (ja) * | 1990-03-20 | 1991-12-02 | Matsushita Electric Ind Co Ltd | 除湿ユニット |
JP2005264231A (ja) * | 2004-03-18 | 2005-09-29 | L'air Liquide Sa Pour L'etude & L'exploitation Des Procede S Georges Claude | フッ素ガス生成装置 |
JP2009215588A (ja) | 2008-03-10 | 2009-09-24 | Toyo Tanso Kk | フッ素ガス発生装置 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014008543A1 (en) * | 2012-07-10 | 2014-01-16 | Lynas Services Pty Ltd | Method and apparatus for removing fluoride compounds |
CN113874553A (zh) * | 2019-12-27 | 2021-12-31 | 昭和电工株式会社 | 氟气的制造方法及氟气制造装置 |
CN113950542A (zh) * | 2019-12-27 | 2022-01-18 | 昭和电工株式会社 | 氟气的制造方法及氟气制造装置 |
CN113874553B (zh) * | 2019-12-27 | 2024-02-09 | 株式会社力森诺科 | 氟气的制造方法及氟气制造装置 |
CN113950542B (zh) * | 2019-12-27 | 2024-03-05 | 株式会社力森诺科 | 氟气的制造方法及氟气制造装置 |
Also Published As
Publication number | Publication date |
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CN102803568A (zh) | 2012-11-28 |
KR20120127646A (ko) | 2012-11-22 |
JP2011208276A (ja) | 2011-10-20 |
EP2511399A1 (en) | 2012-10-17 |
US20120318665A1 (en) | 2012-12-20 |
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