WO2020225911A1 - Agent d'adsorption pour gaz isolant, et appareil électrique isolé par gaz - Google Patents

Agent d'adsorption pour gaz isolant, et appareil électrique isolé par gaz Download PDF

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Publication number
WO2020225911A1
WO2020225911A1 PCT/JP2019/018592 JP2019018592W WO2020225911A1 WO 2020225911 A1 WO2020225911 A1 WO 2020225911A1 JP 2019018592 W JP2019018592 W JP 2019018592W WO 2020225911 A1 WO2020225911 A1 WO 2020225911A1
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WIPO (PCT)
Prior art keywords
insulating gas
zeolite
adsorbent
type zeolite
gas
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PCT/JP2019/018592
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English (en)
Japanese (ja)
Inventor
洋成 出口
有希 植村
晃明 松葉
祥子 佐本
Original Assignee
日新電機株式会社
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Publication date
Application filed by 日新電機株式会社 filed Critical 日新電機株式会社
Priority to PCT/JP2019/018592 priority Critical patent/WO2020225911A1/fr
Priority to JP2021518376A priority patent/JP7311803B2/ja
Priority to KR1020217039121A priority patent/KR20220002611A/ko
Priority to CN202080033124.3A priority patent/CN113811386A/zh
Priority to PCT/JP2020/018259 priority patent/WO2020226117A1/fr
Publication of WO2020225911A1 publication Critical patent/WO2020225911A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02B—BOARDS, SUBSTATIONS OR SWITCHING ARRANGEMENTS FOR THE SUPPLY OR DISTRIBUTION OF ELECTRIC POWER
    • H02B13/00—Arrangement of switchgear in which switches are enclosed in, or structurally associated with, a casing, e.g. cubicle
    • H02B13/02—Arrangement of switchgear in which switches are enclosed in, or structurally associated with, a casing, e.g. cubicle with metal casing
    • H02B13/035—Gas-insulated switchgear
    • H02B13/055—Features relating to the gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to an adsorbent for insulating gas and a gas insulated power device.
  • sulfur hexafluoride (SF 6 ) is widely used as an insulating gas having insulation performance and arc extinguishing performance in gas-insulated power equipment such as a gas-insulated switching device.
  • SF 6 sulfur hexafluoride
  • CO 2 carbon dioxide
  • organofluorine compounds, etc. can be used as an insulating gas to replace sulfur hexafluoride from the viewpoint of suppressing global warming.
  • zeolite may be arranged in the gas-insulated power device in order to adsorb the moisture contained in the insulating gas and the decomposition gas generated from the insulating gas at the time of extinguishing the arc (Patent Document). 1). Zeolites have pores unique to the crystal structure. Zeolites are used in various fields as adsorbents, catalysts, etc. (Non-Patent Document 2).
  • An object of the present invention is to provide an adsorbent for an insulating gas and a gas-insulated power device capable of suppressing a change in the gas concentration ratio of carbon dioxide in the insulating gas and an organic fluorine compound.
  • One aspect of the adsorbent for insulating gas that solves the above problems is an adsorbent for insulating gas that is used in an atmosphere of insulating gas containing carbon dioxide and an organic fluorine compound and contains zeolite. It contains A-type zeolite and at least one of X-type zeolite and ZSM-5 type zeolite.
  • the zeolite preferably contains a ZSM-5 type zeolite.
  • Another aspect of the adsorbent for insulating gas that solves the above problems is an adsorbent for insulating gas that is used in an atmosphere of insulating gas containing carbon dioxide and an organic fluorine compound and contains zeolite. , ZSM-5 type zeolite is included.
  • the ZSM-5 type zeolite is at least one of copper-substituted ZSM-5-type zeolite, iron-substituted ZSM-5-type zeolite, nickel-substituted ZSM-5-type zeolite, and manganese-substituted ZSM-5-type zeolite. It is preferable to include one kind.
  • the average pore diameter on a mass basis obtained from the pore diameter of the zeolite and the content of the zeolite is preferably in the range of more than 0.5 nm and less than 0.9 nm.
  • the content of the organic fluorine compound in the insulating gas is preferably in the range of 2.5% by volume or more and 20% by volume or less.
  • the organofluorine compound is heptafluorobutanenitrile (C 4 F 7 N), perfluoro (n-propyl vinyl ether) (C 5 F 10 O), perfluorobutyronitrile (C 3). It is preferably at least one selected from F 7 CN), perfluoroisobutyronitrile ((CF 3 ) 2 CFCN), and perfluoro-2-methoxypropanenitrile (CF 3 CF (OCF 3 ) CN).
  • One aspect of the gas-insulated power device that solves the above-mentioned problems includes the above-mentioned adsorbent for insulating gas.
  • the adsorbent for insulating gas of the first embodiment is used in an atmosphere of insulating gas containing carbon dioxide and an organic fluorine compound.
  • the adsorbent for insulating gas contains zeolite. Zeolites include A-type zeolite and at least one of X-type zeolite and ZSM-5 type zeolite.
  • Zeolites are classified according to their crystal structure, cations in the crystal structure, etc.
  • the A-type zeolite is a synthetic zeolite having an A-type crystal structure
  • the X-type zeolite is a synthetic zeolite having an X-type crystal structure
  • the ZSM-5 type zeolite has a ZSM-5 type crystal structure. It is a synthetic zeolite.
  • Zeolites have pores of a size defined by the crystal structure (skeleton structure).
  • the "zeolite pore diameter" referred to in the present specification is not an actually measured value, but a theoretical value defined by a crystal structure or the like.
  • Examples of the A-type zeolite include calcium-substituted A-type zeolite, sodium-substituted A-type zeolite, and potassium-substituted A-type zeolite.
  • the pore size of type A zeolite is defined by the type of crystal structure and the cations in the crystal structure.
  • the pore diameter of the calcium-substituted A-type zeolite is 0.5 nm
  • the pore diameter of the sodium-substituted A-type zeolite is 0.4 nm
  • the pore diameter of the potassium-substituted A-type zeolite is 0.3 nm.
  • Examples of the X-type zeolite include sodium-substituted X-type zeolite, calcium-substituted X-type zeolite, and lithium-substituted X-type zeolite.
  • the theoretical value of the pore size of the X-type zeolite is 0.9 nm.
  • ZSM-5 type zeolite examples include hydrogen type ZSM-5 type zeolite, copper-substituted ZSM-5 type zeolite, iron-substituted ZSM-5 type zeolite, nickel-substituted ZSM-5 type zeolite, and manganese-substituted ZSM-5 type zeolite. Zeolites can be mentioned.
  • the pore size of the ZSM-5 type zeolite is 0.58 nm.
  • the zeolite in the adsorbent for insulating gas preferably contains ZSM-5 type zeolite, and the ZSM-5 type zeolite is copper-substituted ZSM-5 type zeolite, iron-substituted ZSM-5 type zeolite, and nickel-substituted ZSM-5 type zeolite. , And at least one of the manganese-substituted ZSM-5 zeolites is more preferred.
  • the mass-based average pore diameter determined from the pore diameter of zeolite in the adsorbent for insulating gas and the blending amount of zeolite is preferably in the range of more than 0.5 nm and less than 0.9 nm, more preferably. , 0.52 nm or more and 0.8 nm or less.
  • the average pore size of zeolite in the adsorbent for insulating gas can be determined as follows.
  • the content of A-type zeolite is preferably in the range of 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more. , 95% by mass or less.
  • the content of X-type zeolite is preferably in the range of 1% by mass or more and 99% by mass or less, and more preferably 5% by mass or more. , 95% by mass or less.
  • the content of ZSM-5 type zeolite is preferably in the range of 1% by mass or more and 99% by mass or less, more preferably 5% by mass. It is in the range of% or more and 95% by mass or less.
  • the zeolite in the adsorbent for insulating gas may further contain a zeolite having a crystal structure different from that of the above-mentioned zeolite having a crystal structure.
  • the total amount of zeolite in the adsorbent for insulating gas is 100% by mass
  • the total content of A-type zeolite, X-type zeolite, and ZSM-5-type zeolite is preferably 90% by mass or more.
  • the preferable range of the total content referred to here is also applicable to the case where the zeolite in the adsorbent for insulating gas contains A-type zeolite and further contains only one of X-type zeolite and ZSM-5-type zeolite. ..
  • the adsorbent for insulating gas may contain, for example, activated carbon, alumina, silica, or the like, if necessary.
  • the organic fluorine compound contained in the insulating gas it is preferable to use an organic fluorine compound having a boiling point higher than 0 ° C.
  • the organic fluorine compound include fluoronitrile and fluoroether.
  • Organofluorine compounds include heptafluorobutanenitrile (C 4 F 7 N), perfluoro (n-propyl vinyl ether) (C 5 F 10 O), perfluorobutyronitrile (C 3 F 7 CN), and perfluoroisobutyro. It preferably contains at least one selected from lonitrile ((CF 3 ) 2 CFCN) and perfluoro-2-methoxypropanenitrile (CF 3 CF (OCF 3 ) CN).
  • the content of the organic fluorine compound (organofluorine compound gas) in the insulating gas is preferably in the range of 2.5% by volume or more and 20% by volume or less.
  • the content of carbon dioxide (carbon dioxide gas) in the insulating gas is preferably in the range of 80% by volume or more and 97.5% by volume or less.
  • the gas-insulated power device includes the above-mentioned adsorbent for insulating gas.
  • a gas-insulated power device includes a housing and a conductor arranged in the housing, and is used by filling the housing with an insulating gas. Further specific examples of the gas-insulated power device include, for example, a transformer for a gas-insulated voltage transformer (gas-insulated VT), a gas-insulated switching device (GIS), and the like.
  • the insulating gas adsorbent To use the insulating gas adsorbent, first place the insulating gas adsorbent inside the housing of the gas-insulated power equipment. Next, after the inside of the housing of the gas-insulated power device is evacuated to a predetermined degree of vacuum, the housing is filled with an insulating gas until the pressure inside the housing reaches a predetermined pressure. As a result, the zeolite in the adsorbent for insulating gas and the insulating gas are in contact with each other in the housing. At this time, for example, the water content in the insulating gas can be adsorbed by zeolite.
  • the zeolite in the adsorbent for insulating gas of the present embodiment includes an A-type zeolite and at least one of an X-type zeolite and a ZSM-5 type zeolite.
  • both carbon dioxide and organic fluorine compounds can be adsorbed on the zeolite, so that the gas concentration ratio of carbon dioxide and the organic fluorine compound in the insulating gas changes. Can be suppressed.
  • water is further adsorbed on the zeolite that has adsorbed carbon dioxide and the organofluorine compound
  • both carbon dioxide and the organofluorine compound are released by the substitution of carbon dioxide and water and the substitution of the organic fluorine compound and water.
  • the gas concentration ratio of carbon dioxide and the organofluorine compound in the insulating gas is unlikely to change even when water is further adsorbed on the zeolite adsorbing carbon dioxide and the organofluorine compound.
  • various decomposition gases may be generated from the insulating gas when the arc is extinguished by the insulating gas.
  • the adsorbent for insulating gas of the present embodiment is a combination of zeolites having different pore diameters, it is possible to exert the adsorbing ability for more kinds of decomposed gases.
  • the adsorbent for insulating gas of the first embodiment is used in an atmosphere of insulating gas containing carbon dioxide and an organic fluorine compound.
  • the adsorbent for insulating gas contains zeolite. Zeolites include A-type zeolite and at least one of X-type zeolite and ZSM-5 type zeolite. According to this configuration, it is possible to suppress a change in the gas concentration ratio of carbon dioxide and the organic fluorine compound in the insulating gas. Therefore, for example, the performance of the insulating gas preset by a predetermined gas concentration ratio can be easily maintained.
  • zeolites having different pore diameters are combined, it is possible to exert the adsorbing ability for more kinds of decomposed gases.
  • the ZSM-5 type zeolite is copper-substituted ZSM-5 type zeolite, iron-substituted ZSM-5 type zeolite, and nickel-substituted ZSM-5 type. It preferably contains at least one type of zeolite and a manganese-substituted ZSM-5 type zeolite. In this case, the hydrophobicity of the ZSM-5 type zeolite can be increased.
  • the organofluorine compound produces a large amount of decomposition gas having a relatively high hydrophobicity
  • the adsorption ability is exhibited for more kinds of decomposition gas. It becomes possible.
  • the average pore diameter based on the mass obtained from the pore diameter of zeolite and the content of zeolite is preferably in the range of more than 0.5 nm and less than 0.9 nm. In this case, the change in the gas concentration ratio of carbon dioxide and the organic fluorine compound in the insulating gas can be further suppressed.
  • the content of the organic fluorine compound in the insulating gas is preferably in the range of 2.5% by volume or more and 20% by volume or less. In this case, the insulation performance of the insulating gas can be further improved, and the condensation of the organic fluorine compound can be suppressed.
  • the zeolite in the adsorbent for insulating gas of the second embodiment contains ZSM-5 type zeolite.
  • the pore size of the ZSM-5 type zeolite is 0.58 nm.
  • the ZSM-5 type zeolite having such a pore diameter has a low ability to selectively adsorb one of the gases of carbon dioxide and the organofluorine compound.
  • the ZSM-5 type zeolite preferably contains at least one of a copper-substituted ZSM-5 type zeolite, an iron-substituted ZSM-5 type zeolite, a nickel-substituted ZSM-5 type zeolite, and a manganese-substituted ZSM-5 type zeolite.
  • the zeolite in the adsorbent for insulating gas may further contain at least one of A-type zeolite and X-type zeolite.
  • the zeolite in the adsorbent for insulating gas may further contain a zeolite having a crystal structure different from that of the above-mentioned zeolite having a crystal structure.
  • the content of ZSM-5 type zeolite in the adsorbent for insulating gas is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably, when the total amount of zeolite is 100% by mass. Is 70% by mass or more.
  • the total content of ZSM-5 type zeolite, A type zeolite, and X type zeolite is preferably 90% by mass or more.
  • the preferable range of the total content referred to here is also applicable to the case where the zeolite in the adsorbent for insulating gas contains ZSM-5 type zeolite and further contains only one of A type zeolite and X type zeolite. ..
  • the adsorbent for insulating gas may contain, for example, activated carbon, alumina, silica, or the like, if necessary.
  • the zeolite in the adsorbent for insulating gas of the second embodiment contains ZSM-5 type zeolite, it is possible to suppress a change in the gas concentration ratio of carbon dioxide and the organic fluorine compound in the insulating gas. Therefore, for example, the performance of the insulating gas preset by a predetermined gas concentration ratio can be easily maintained. Further, also in the second embodiment, the same effect as that described in the columns (2) to (4) of the first embodiment can be obtained.
  • Test Examples 1 to 4 the zeolite-containing adsorbent for insulating gas shown in the upper part of Table 1 was used.
  • the calcium-substituted type A zeolite (pore diameter: 0.5 nm) in Table 1 Zeolite (trade name), “A-5” manufactured by Tosoh Corporation was used.
  • Zeolite (trade name), “A-5” manufactured by Tosoh Corporation was used.
  • the sodium-substituted X-type zeolite (pore diameter: 0.9 nm) in Table 1 Zeolite (trade name), “F-9” manufactured by Tosoh Corporation was used.
  • the copper-substituted ZSM-5 type zeolite (pore diameter: 0.58 nm) in Table 1 HSZ (trade name) manufactured by Tosoh Corporation and "copper-substituted HSZ-800" were used.
  • Test Examples 5 and 6 In Test Examples 5 and 6, the zeolite-containing adsorbent for insulating gas shown in the upper part of Table 2 was used, and the gas concentration at the start of the test and one week after the start of the test was measured in the same manner as in Test Examples 1 to 4. The results are shown in the lower part of Table 2.
  • Test Examples 7-9 In Test Examples 7 to 9, as shown in the upper part of Table 3, the adsorbent for insulating gas used was changed, and the gas concentration at the start of the test and one week later was measured in the same manner as in Test Examples 1 to 4. .. The results are shown in the lower part of Table 3.
  • Test Examples 10 to 13 In Test Examples 10 to 13, the adsorption ability of the zeolite-containing insulating gas adsorbent shown in the upper part of Table 4 to adsorb the decomposition gas generated when the arc was extinguished using the insulating gas was evaluated.
  • an insulating gas (CO 2: 95 mass%, C 4 F 7 N: 5 wt%) to subject the blocking test (extinguishing tests) gave the insulating gas containing a decomposed gas.
  • This insulating gas and the adsorbent for insulating gas containing zeolite shown in the upper part of Table 4 were sealed in the above-mentioned pressure-resistant container, and an adsorption test was conducted in which the adsorbent was left for one week.
  • the concentration of the decomposed gas after one week was measured using a gas chromatograph / thermal conductivity detector (GC / TCD), and the adsorption capacity of the adsorbent for insulating gas to a specific decomposed gas was evaluated according to the following criteria.
  • the concentration of the decomposed gas after the adsorption test was 10% or less of the concentration of the decomposed gas before the adsorption test, it was determined that the adsorbent for insulating gas had an adsorption capacity ( ⁇ ).
  • the concentration of the decomposed gas after the adsorption test exceeded 10% and 50% or less of the concentration of the decomposed gas before the adsorption test, it was determined that the adsorbent for insulating gas had a slight adsorption capacity ( ⁇ ).
  • the insulating gas adsorbents of Test Examples 10 to 12 have more types of decomposition gas exhibiting the adsorption ability than the insulating gas adsorbent of Test Example 13. Further, it can be seen that the insulating gas adsorbents of Test Examples 11 and 12 have more types of decomposed gas exhibiting the adsorption ability than the insulating gas adsorbent of Test Example 10.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

L'agent d'adsorption pour gaz isolant de l'invention est mis en œuvre sous une atmosphère de gaz isolant contenant un dioxyde de carbone et un composé fluor organique. Cet agent d'adsorption pour gaz isolant comprend une zéolite. La zéolite inclut une zéolite de type A, et au moins une zéolite parmi une zéolite de type X et une zéolite de type ＺＳＭ－５.
PCT/JP2019/018592 2019-05-09 2019-05-09 Agent d'adsorption pour gaz isolant, et appareil électrique isolé par gaz WO2020225911A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/JP2019/018592 WO2020225911A1 (fr) 2019-05-09 2019-05-09 Agent d'adsorption pour gaz isolant, et appareil électrique isolé par gaz
JP2021518376A JP7311803B2 (ja) 2019-05-09 2020-04-30 絶縁ガス用吸着剤、及びガス絶縁電力機器
KR1020217039121A KR20220002611A (ko) 2019-05-09 2020-04-30 절연 가스 흡착제, 가스 절연 전력 기기 및 절연 가스용 흡착제의 제조 방법
CN202080033124.3A CN113811386A (zh) 2019-05-09 2020-04-30 绝缘气体用吸附剂、气体绝缘电力设备、以及绝缘气体用吸附剂的制造方法
PCT/JP2020/018259 WO2020226117A1 (fr) 2019-05-09 2020-04-30 Agent d'adsorption pour gaz isolant ainsi que procédé de fabrication de celui-ci, et appareil électrique isolé par gaz

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PCT/JP2019/018592 WO2020225911A1 (fr) 2019-05-09 2019-05-09 Agent d'adsorption pour gaz isolant, et appareil électrique isolé par gaz

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PCT/JP2020/018259 WO2020226117A1 (fr) 2019-05-09 2020-04-30 Agent d'adsorption pour gaz isolant ainsi que procédé de fabrication de celui-ci, et appareil électrique isolé par gaz

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JP2005021891A (ja) * 2004-08-26 2005-01-27 Taiyo Nippon Sanso Corp ガス精製方法及び装置
JP2010259967A (ja) * 2009-04-30 2010-11-18 Panasonic Corp 気体吸着デバイス
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JP2018506947A (ja) * 2015-02-13 2018-03-08 ゼネラル エレクトリック テクノロジー ゲゼルシャフト ミット ベシュレンクテル ハフツングＧｅｎｅｒａｌ Ｅｌｅｃｔｒｉｃ Ｔｅｃｈｎｏｌｏｇｙ ＧｍｂＨ ヘプタフルオロイソブチロニトリルとテトラフルオロメタンとを包含するガス絶縁された中または高電圧電気機器

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CN113811386A (zh) 2021-12-17

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