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WO2025134869A1 - Procédé d'élimination de fluor gazeux - Google Patents

Procédé d'élimination de fluor gazeux Download PDF

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Publication number
WO2025134869A1
WO2025134869A1 PCT/JP2024/043675 JP2024043675W WO2025134869A1 WO 2025134869 A1 WO2025134869 A1 WO 2025134869A1 JP 2024043675 W JP2024043675 W JP 2024043675W WO 2025134869 A1 WO2025134869 A1 WO 2025134869A1
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WO
WIPO (PCT)
Prior art keywords
gas
fluorine
metal
fluorine gas
containing compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/043675
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English (en)
Japanese (ja)
Inventor
一真 松井
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Resonac Corp
Original Assignee
Resonac Corp
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Publication date
Application filed by Resonac Corp filed Critical Resonac Corp
Priority to CN202480027078.4A priority Critical patent/CN121001957A/zh
Publication of WO2025134869A1 publication Critical patent/WO2025134869A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/083—Compounds containing nitrogen and non-metals and optionally metals containing one or more halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/10—Halides or oxyhalides of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/24—Inter-halogen compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B9/00—General methods of preparing halides
    • C01B9/08—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/04—Halides

Definitions

  • This disclosure relates to a method for removing fluorine gas.
  • fluorine-containing compound gases such as bromine pentafluoride ( BrF5 ), iodine heptafluoride (IF7 ), nitrogen trifluoride ( NF3 ), tungsten hexafluoride ( WF6 ), phosphorus trifluoride ( PF3 ), and carbonyl fluoride ( COF2 ) used as semiconductor etching gases and chamber cleaning gases.
  • BrF5 bromine pentafluoride
  • IF7 iodine heptafluoride
  • NF3 nitrogen trifluoride
  • WF6 tungsten hexafluoride
  • PF3 phosphorus trifluoride
  • COF2 carbonyl fluoride
  • Known methods for removing impurities from a fluorine-containing gas that contains both fluorine-containing compound gas and impurities in order to obtain a high-purity fluorine-containing compound gas include a cryogenic purification method in which the fluorine-containing gas is cooled to partially liquefy it (Patent Document 1), and a method in which the fluorine-containing compound gas is brought into contact with a metal fluoride to adsorb and remove metal impurities (Patent Document 2).
  • Patent Document 1 cannot be applied when the difference in boiling point or melting point between the fluorine-containing compound gas contained in the fluorine-containing gas and the impurities to be removed is small, and has the problem of requiring large-scale equipment.
  • Patent Document 2 is effective for removing metal impurities, it does not disclose a method for removing fluorine gas.
  • the objective of the present disclosure is to provide a method for removing fluorine gas from a fluorine-containing gas that contains fluorine gas and a fluorine-containing compound gas.
  • fluorine gas contained in a fluorine-containing gas can be removed by contacting the fluorine-containing gas with at least one metal salt selected from the group consisting of metal chlorides, metal bromides, and metal iodides.
  • the fluorine gas contained in the fluorine-containing gas can be adsorbed to a metal salt. That is, the fluorine gas reacts with the metal salt to form a double salt.
  • the reaction between fluorine gas and potassium halide is shown in formula (1).
  • the fluorine-containing compound gas hardly adsorbs or reacts with the metal salt, so that separation of the fluorine gas in the fluorine-containing gas containing the fluorine-containing compound gas and the fluorine gas can be achieved.
  • X is at least one selected from the group consisting of chlorine (Cl), bromine (Br), and iodine (I), and n and m are arbitrary coefficients.
  • a method for removing fluorine gas from a fluorine-containing gas containing fluorine gas and a fluorine-containing compound gas comprising the steps of: A method for removing fluorine gas, comprising the step of contacting the fluorine-containing gas with at least one metal salt selected from the group consisting of metal chlorides, metal bromides and metal iodides to remove the fluorine gas.
  • [2] The method for removing fluorine gas according to [1], wherein the fluorine-containing compound gas contains at least one selected from the group consisting of bromine pentafluoride, iodine heptafluoride, nitrogen trifluoride, tungsten hexafluoride, phosphorus trifluoride, and carbonyl fluoride.
  • the metal species of the metal salt is at least one selected from the group consisting of alkali metals and alkaline earth metals.
  • [4] The method for removing fluorine gas according to [3], wherein the metal species of the metal salt is at least one selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, cesium, and barium.
  • [5] The method for removing fluorine gas according to any one of [1] to [4], wherein in the removing step, the temperature at which the fluorine-containing gas is brought into contact with the metal salt is 0° C. or higher and 120° C. or lower.
  • fluorine gas can be removed from a fluorine-containing compound gas that contains fluorine gas as an impurity.
  • FIG. 1 is a schematic diagram showing an example of a gas treatment device for removing fluorine gas according to an embodiment of the present disclosure.
  • the method for removing fluorine gas in this embodiment is a method for removing the fluorine gas from a fluorine-containing gas that contains fluorine gas and a fluorine-containing compound gas, and includes a step of contacting the fluorine-containing gas with at least one metal salt selected from the group consisting of metal chlorides, metal bromides, and metal iodides to remove the fluorine gas.
  • the gas supplied from the supply port 4 to the inside of the purification tower 6 may be a gas consisting of only fluorine gas and fluorine-containing compound gas, or may contain other gases. That is, as shown in FIG. 1, a pipe extending from the fluorine-containing gas supply mechanism 2 and a pipe extending from the additive gas supply mechanism 3 may be joined, and the joined pipe may be connected to the supply port 4 of the purification tower 6.
  • Gases other than fluorine gas and fluorine-containing compound gas are not particularly limited, but may include, for example, inert gas. By diluting the fluorine-containing gas with an inert gas, localized heat generation can be easily suppressed, making it easier to perform the fluorine gas separation operation safely.
  • the fluorine-containing gas delivered from the fluorine-containing gas supply mechanism 2 and the inert gas delivered from the additive gas supply mechanism 3 are mixed in the piping where they join together to form a mixed gas, which is then supplied to the inside of the purification column 6 from the supply port 4.
  • the material used for the purification column 6, so long as it has corrosion resistance to the fluorine-containing compound gas and fluorine gas used there are no particular limitations on the material used for the purification column 6, so long as it has corrosion resistance to the fluorine-containing compound gas and fluorine gas used.
  • metals such as nickel, nickel-based alloys, aluminum, stainless steel, and platinum, ceramics such as alumina, and fluororesins can be used for the parts that come into contact with the fluorine-containing compound gas and fluorine gas.
  • nickel-based alloys include Inconel, Hastelloy, Monel, etc.
  • the members made of the above-mentioned metals may react with a fluorine-containing compound gas, it is preferable to perform a treatment such as passing a fluorine-containing compound gas or fluorine gas through the member before use to form a passivation film on the surface. This is because it becomes easier to suppress the generation of impurities.
  • fluororesins include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polyvinylidene fluoride (PVDF), Teflon (registered trademark), Viton, and Kalrez.
  • the content of fluorine gas contained in the fluorine-containing gas at the supply port 4 of the purification column 6, i.e., before the fluorine gas removal process may be 10 ppm by volume or more and less than 3% by volume, 100 ppm by volume or more and 2% by volume or less, or 200 ppm by volume or more and 1% by volume or less. If the amount of fluorine gas is within the above range, it is easy to achieve separation of fluorine gas without using excessively large equipment.
  • the adsorbent for fluorine gas packed in the purification column 6 is at least one metal salt selected from the group consisting of metal chlorides, metal bromides, and metal iodides.
  • the metal salt may be a solid.
  • the metal species of the metal salt may be at least one selected from the group consisting of alkali metals and alkaline earth metals, and may be at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), cesium (Cs), and barium (Ba) because they are easily available.
  • the purification column 6 may be further filled with an auxiliary agent that does not react at all or hardly reacts with the fluorine-containing compound gas and the fluorine gas.
  • an auxiliary agent that does not react at all or hardly reacts with the fluorine-containing compound gas and the fluorine gas.
  • the temperature at which the fluorine-containing gas is brought into contact with the metal salt may be 0°C or higher and 120°C or lower, 10°C or higher and 100°C or lower, or 20°C or higher and 80°C or lower.
  • the metal salt is a solid. If the operating temperature is within the above temperature range, the removal rate of the fluorine gas contained in the fluorine-containing gas is likely to be high. Furthermore, by diluting the fluorine-containing gas with an inert gas, localized heat generation due to adsorption of the fluorine gas is suppressed, and separation of the fluorine gas may be safely performed.
  • the type of inert gas is not particularly limited, but examples include nitrogen gas, argon, and helium. Of these inert gases, nitrogen gas is preferred from the viewpoints of ease of availability and low cost.
  • Adsorption treatment of a fluorine-containing gas was carried out using a gas treatment device having a configuration similar to that of the gas treatment device 1 shown in Fig. 1.
  • the gas treatment device was equipped with a stainless steel purification tower having an inner diameter of 1 inch and a length of 200 mm.
  • This purification tower was filled with 200 g of potassium bromide (manufactured by Kanto Chemical Co., Ltd.) pressed into pellets having a diameter of 3 mm and a height of 5 mm as an adsorbent.
  • a fluorine-containing compound gas at a flow rate of 10 mL/min and an additive gas at a flow rate of 20 mL/min were mixed and supplied to the purification column 6.
  • the fluorine gas contained in the gas supplied to the purification column was adsorbed by an adsorbent at 50° C.
  • the fluorine-containing compound gas was bromine pentafluoride.
  • the additive gas was a gas composed of fluorine gas and nitrogen gas, and the concentration of fluorine gas in the additive gas was 0.1% by volume.
  • Table 1 the composition of the additive gas is represented as "0.1%-F 2 /N 2 ".
  • ICP-MS inductively coupled plasma mass spectrometer
  • Example 2 to 25 Fluorine gas was removed in the same manner as in Example 1, except that the type and flow rate of the fluorine-containing compound gas, the type, composition and flow rate of the added gas, the adsorbent, and the purification column temperature were changed as shown in Table 1, and the fluorine gas concentration contained in the obtained purified gas was measured. The results are shown in Table 1. In addition, for Example 25, the gases other than fluorine gas contained in the obtained refined gas were also analyzed.
  • Examples 1 and 5 to 8 show that fluorine gas can be removed even when the temperature of the purification tower is between 0°C and 120°C. In particular, the most fluorine gas was removed from the fluorine-containing gas when the temperature of the purification tower was 50°C.
  • Example 16 show that fluorine gas can be removed even when the fluorine gas concentration in the fluorine-containing gas is 10,000 ppm by volume.
  • Examples 17 and 18 show that fluorine gas can be removed even when KF and ⁇ -Al 2 O 3 are added to the adsorbent as auxiliary agents.
  • Example 25 From the results of Example 25, it was found that when the fluorine-containing compound gas was ClF3 , fluorine gas could be removed, but a mixture of multiple halogen compounds was also obtained. This is considered to be because multiple halogen compounds were generated by the reaction of the fluorine-containing compound gas ClF3 with the adsorbent KBr.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Est prévu un procédé d'élimination de fluor gazeux d'un gaz contenant du fluor qui comprend du fluor gazeux et un composé gazeux contenant du fluor. Ce procédé d'élimination de fluor gazeux d'un gaz contenant du fluor qui comprend du fluor gazeux et un composé gazeux contenant du fluor comprend une étape d'élimination pour créer un contact entre le gaz contenant du fluor et au moins un sel métallique sélectionné dans le groupe composé de chlorures métalliques, de bromures métalliques et d'iodures métalliques.
PCT/JP2024/043675 2023-12-18 2024-12-10 Procédé d'élimination de fluor gazeux Pending WO2025134869A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202480027078.4A CN121001957A (zh) 2023-12-18 2024-12-10 氟气的除去方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-213236 2023-12-18
JP2023213236 2023-12-18

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WO2025134869A1 true WO2025134869A1 (fr) 2025-06-26

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4317805A (en) * 1979-01-25 1982-03-02 Hooker Chemicals & Plastics Corp. Removal of hydrogen fluoride from gaseous mixtures of hydrogen fluoride and hydrogen chloride
JP2005052724A (ja) * 2003-08-04 2005-03-03 Hideki Yamamoto フッ素系ガスの無害化処理方法および無害化処理装置
JP2005206461A (ja) * 2004-01-23 2005-08-04 Air Products & Chemicals Inc Ｎｆ３の精製方法
WO2007135823A1 (fr) * 2006-05-19 2007-11-29 Asahi Glass Company, Limited Procédé d'élimination d'un halogène gazeux et matière d'élimination pour un halogène gazeux
JP2010095394A (ja) * 2008-10-14 2010-04-30 Showa Denko Kk 二フッ化カルボニルの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4317805A (en) * 1979-01-25 1982-03-02 Hooker Chemicals & Plastics Corp. Removal of hydrogen fluoride from gaseous mixtures of hydrogen fluoride and hydrogen chloride
JP2005052724A (ja) * 2003-08-04 2005-03-03 Hideki Yamamoto フッ素系ガスの無害化処理方法および無害化処理装置
JP2005206461A (ja) * 2004-01-23 2005-08-04 Air Products & Chemicals Inc Ｎｆ３の精製方法
WO2007135823A1 (fr) * 2006-05-19 2007-11-29 Asahi Glass Company, Limited Procédé d'élimination d'un halogène gazeux et matière d'élimination pour un halogène gazeux
JP2010095394A (ja) * 2008-10-14 2010-04-30 Showa Denko Kk 二フッ化カルボニルの製造方法

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CN121001957A (zh) 2025-11-21

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