CN113811386A - Adsorbent for insulating gas, gas-insulated electric power equipment, and method for producing adsorbent for insulating gas - Google Patents
Adsorbent for insulating gas, gas-insulated electric power equipment, and method for producing adsorbent for insulating gas Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 204
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 196
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 196
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 98
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 48
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 48
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims description 35
- 239000011148 porous material Substances 0.000 claims description 31
- 150000004812 organic fluorine compounds Chemical class 0.000 claims description 20
- UWNGUOVHDOXBPJ-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(trifluoromethoxy)propanenitrile Chemical compound FC(F)(F)OC(F)(C#N)C(F)(F)F UWNGUOVHDOXBPJ-UHFFFAOYSA-N 0.000 claims description 10
- AASDJASZOZGYMM-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile Chemical compound FC(F)(F)C(F)(C#N)C(F)(F)F AASDJASZOZGYMM-UHFFFAOYSA-N 0.000 claims description 6
- BOZRBIJGLJJPRF-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanenitrile Chemical compound FC(F)(F)C(F)(F)C(F)(F)C#N BOZRBIJGLJJPRF-UHFFFAOYSA-N 0.000 claims description 4
- -1 perfluoro Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 235
- 239000013078 crystal Substances 0.000 description 14
- 229910018503 SF6 Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 4
- 229960000909 sulfur hexafluoride Drugs 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The adsorbent for an insulating gas is used in an insulating gas atmosphere containing carbon dioxide and an organofluorine compound. The adsorbent for insulating gas contains zeolite. The zeolite comprises a type a zeolite and at least one of an X type zeolite and a ZSM-5 type zeolite.
Description
Technical Field
The present invention relates to an adsorbent for insulating gas, a gas-insulated power equipment, and a method for producing an adsorbent for insulating gas.
Background
Sulfur hexafluoride (SF) is widely used as an insulating gas having insulating performance and arc extinguishing performance in gas-insulated electric power equipment such as a gas-insulated switchgear6). However, sulfur hexafluoride has a greater global warming potential than carbon dioxide (CO)2) Therefore, carbon dioxide, organofluorine compounds, and the like have been proposed as insulating gases in place of sulfur hexafluoride in order to suppress global warming (patent document 1 and non-patent document 1).
On the other hand, in a gas-insulated power equipment, zeolite is sometimes disposed in the equipment in order to adsorb moisture contained in the insulating gas or a decomposition gas generated from the insulating gas at the time of arc extinction (patent document 1). Zeolites have inherent pores in the crystal structure. Zeolites are used in various fields as adsorbents, catalysts, and the like (non-patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-004494
Non-patent document
Non-patent document 1: "SF6Development trends and future prospects of gas replacement technology ", electric comments, No. 10 in 2017, and p.12-17
Non-patent document 2: "Zeolite Synthesis catalogues (ゼオライト Gross and カタログ)", Tosoh corporation
Disclosure of Invention
Problems to be solved by the invention
When a mixed gas of carbon dioxide and an organofluorine compound is used as an insulating gas of a gas-insulated power equipment, the gas concentration ratio of carbon dioxide to the organofluorine compound is likely to change when the mixed gas is brought into contact with an adsorbent. As the gas concentration ratio of carbon dioxide to the organofluorine compound in the insulating gas changes in this way, for example, the insulating performance may be degraded.
The purpose of the present invention is to provide an adsorbent for insulating gas, a gas-insulated power device, and a method for producing an adsorbent for insulating gas, which are capable of suppressing a change in the gas concentration ratio of carbon dioxide to an organofluorine compound in the insulating gas.
Means for solving the problems
An adsorbent for insulating gas according to one embodiment for solving the above problems is an adsorbent for insulating gas containing zeolite, which is used in an insulating gas atmosphere containing carbon dioxide and an organofluorine compound, wherein the zeolite contains a-type zeolite and at least one zeolite of X-type zeolite and ZSM-5-type zeolite.
In the insulating gas adsorbent, the zeolite preferably contains a ZSM-5 type zeolite.
In the insulating gas adsorbent, it is preferable that the zeolite comprises the X-type zeolite, the a-type zeolite adsorbs carbon dioxide in advance, and the X-type zeolite adsorbs an organic fluorine compound in advance.
Another embodiment of the adsorbent for insulating gas for solving the above problems is an adsorbent for insulating gas containing zeolite, wherein the zeolite contains ZSM-5 type zeolite, and is used in an insulating gas atmosphere containing carbon dioxide and an organofluorine compound.
In the adsorbent for insulating gas, 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.
In the insulating gas adsorbent, the mass-based average pore diameter determined from the pore diameter of the zeolite and the content of the zeolite is preferably in a range of more than 0.5nm and less than 0.9 nm.
In the insulating gas adsorbent, the content of the organic fluorine compound in the insulating gas is preferably in a range of 2.5 vol% to 20 vol%.
In the adsorbent for insulating gas, the organic fluorine compound is preferably selected from heptafluorobutyronitrile (C)4F7N), perfluoro (N-propyl vinyl ether) (C5F10O), perfluoroisobutyronitrile ((CF)3)2CFCN) and perfluoro-2-methoxypropionitrile (CF)3CF(OCF3) CN).
A gas-insulated power plant according to an aspect for solving the above problems includes the above adsorbent for insulating gas.
A method for producing an adsorbent for insulating gas according to an embodiment for solving the above problems is a method for producing an adsorbent for insulating gas containing zeolite, which is used in an insulating gas atmosphere containing carbon dioxide and an organofluorine compound, wherein the zeolite contains a-type zeolite and X-type zeolite, and the method may include the steps of: a first contact step of contacting the type A zeolite with an adsorption gas containing carbon dioxide; and a 2 nd contact step of contacting the X-type zeolite with an adsorption gas containing an organofluorine compound.
In the method for producing the adsorbent for insulating gas, it is preferable that the adsorption gas contains carbon dioxide and an organic fluorine compound, and the first contacting step and the second contacting step are simultaneously performed by contacting a mixture of the a-type zeolite and the X-type zeolite with the adsorption gas.
Drawings
FIG. 1 is a graph showing the relationship between the number of elapsed days and the gas concentration in the adsorbents for insulating gas of test examples 14 to 16.
FIG. 2 is a graph showing the relationship between the number of elapsed days and the gas partial pressure in the adsorbents for insulating gas of test examples 14 to 16.
Detailed Description
(embodiment 1)
Next, embodiment 1 of the adsorbent for insulating gas and the gas-insulated electric power equipment will be described.
The adsorbent for insulating gas of embodiment 1 is used in an insulating gas atmosphere containing carbon dioxide and an organofluorine compound. The adsorbent for insulating gas contains zeolite. The zeolite comprises a type A zeolite and at least one of a type X zeolite and a type ZSM-5 zeolite.
Zeolites are classified according to their crystal structure, the cations in the crystal structure, and the like. The zeolite A is a synthetic zeolite having a crystal structure of type A, the zeolite X is a synthetic zeolite having a crystal structure of type X, and the zeolite ZSM-5 is a synthetic zeolite having a crystal structure of type ZSM-5. Zeolites have pores of a size defined by the crystal structure (framework structure). The "pore diameter of zeolite" referred to in the present specification is not an actual measurement 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 diameter of the a-type zeolite is defined by the kind of crystal structure and the cation in the crystal structure. The pore diameter of the calcium-substituted A-type zeolite was 0.5nm, the pore diameter of the sodium-substituted A-type zeolite was 0.4nm, and the pore diameter of the potassium-substituted A-type zeolite was 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 zeolite X is 0.9 nm.
Examples of the ZSM-5 type zeolite 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. The ZSM-5 type zeolite had a pore size of 0.58 nm.
The zeolite in the adsorbent for insulating gas preferably comprises a ZSM-5 type zeolite, and the ZSM-5 type zeolite more preferably comprises 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 average pore diameter on a mass basis determined from the pore diameter of zeolite and the amount of zeolite blended in the adsorbent for an insulating gas is preferably in a range of more than 0.5nm and less than 0.9nm, and more preferably in a range of 0.52nm to 0.8 nm. For example, in the case of zeolite having a calcium-substituted A-type zeolite (pore size: 0.5nm) content of 80 mass% and a sodium-substituted X-type zeolite (pore size: 0.9nm) content of 20 mass%, the average pore size of the zeolite in the insulating gas adsorbent can be determined as follows.
Average pore diameter [ nm ] of 0.5 × 80/100+0.9 × 20/100 of 0.58
By further increasing the average pore diameter, adsorption of carbon dioxide can be further suppressed. By further reducing the average pore diameter, adsorption of the organofluorine compound can be further suppressed.
When the total amount of zeolite in the insulating gas adsorbent is 100 mass%, the content of a-type zeolite is preferably in the range of 1 mass% to 99 mass%, more preferably in the range of 5 mass% to 95 mass%. When the total amount of zeolite in the insulating gas adsorbent is 100 mass%, the content of the X-type zeolite is preferably in the range of 1 mass% to 99 mass%, more preferably in the range of 5 mass% to 95 mass%. When the total amount of zeolite in the insulating gas adsorbent is 100 mass%, the content of the ZSM-5-type zeolite is preferably in the range of 1 mass% to 99 mass%, more preferably in the range of 5 mass% to 95 mass%.
The zeolite in the adsorbent for an insulating gas may further contain a zeolite having a crystal structure different from that of the zeolite having the crystal structure described above. When the total amount of zeolite in the insulating gas adsorbent is 100 mass%, the total content of the a-type zeolite, the X-type zeolite, and the ZSM-5-type zeolite is preferably 90 mass% or more. The preferred range of the total content described here can also be applied to the case where the zeolite in the adsorbent for an insulating gas contains an a-type zeolite and further contains only one of an X-type zeolite and a ZSM-5-type zeolite. The adsorbent for insulating gas may contain, for example, activated carbon, alumina, silica, or the like as needed.
Next, the insulating gas will be described.
As the organic fluorine compound contained in the insulating gas, an organic fluorine compound having a boiling point higher than 0 ℃ is preferably used. Examples of the organic fluorine compound include fluoronitrile and fluoroether.
The organofluorine compound preferably comprises a compound selected from heptafluorobutyronitrile (C)4F7N, CAS accession number: 375-00-8), perfluoro (n-propyl vinyl ether) (C5F10O, CAS accession number: 1623-05-8), perfluoroisobutyronitrile ((CF)3)2CFCN, CAS accession number: 42532-60-5) and perfluoro-2-methoxypropionitrile (CF)3CF(OCF3) CN).
The content of the organic fluorine compound (organic fluorine compound gas) in the insulating gas is preferably in a range of 2.5 vol% or more and 20 vol% or less. By increasing the content of the organic fluorine compound in the insulating gas, the insulating performance of the insulating gas can be further improved. By reducing the content of the organofluorine compound in the insulating gas, the condensation of the organofluorine compound can be suppressed. The content of carbon dioxide (carbonic acid gas) in the insulating gas is preferably in the range of 80 vol% or more and 97.5 vol% or less.
Next, the operation of the gas-insulated power equipment and the insulating gas adsorbent will be described.
The gas-insulated power equipment is provided with the insulating gas adsorbent. The gas-insulated power equipment includes a case and a conductor disposed in the case, and is used by filling the case with an insulating gas. Further specific examples of the gas-insulated electric power equipment include a transformer for a gas-insulated meter (gas-insulated VT), a gas-insulated switchgear (GIS), and the like.
When the adsorbent for insulating gas is used, first, the adsorbent for insulating gas is disposed in a housing of a gas-insulated electric power equipment. Next, the inside of the case of the gas insulated power equipment is evacuated to a predetermined degree of vacuum, and then the insulating gas is filled into the case until the pressure inside the case reaches a predetermined pressure. As a result, the zeolite in the insulating gas adsorbent comes into contact with the insulating gas in the case. At this time, for example, moisture in the insulating gas can be adsorbed by the zeolite.
Here, the zeolite in the adsorbent for insulating gas of the present embodiment includes a-type zeolite and at least one of X-type zeolite and ZSM-5-type zeolite. By combining zeolites having different pore diameters in this manner, both of the carbon dioxide and the organofluorine compound can be adsorbed by the zeolites, and thus, a change in the gas concentration ratio of the carbon dioxide to the organofluorine compound in the insulating gas can be suppressed. When the zeolite having adsorbed carbon dioxide and the organofluorine compound further adsorbs moisture, both carbon dioxide and the organofluorine compound are released by the substitution of carbon dioxide with moisture and the substitution of the organofluorine compound with moisture. Thus, even when the zeolite having adsorbed carbon dioxide and the organofluorine compound further adsorbs moisture, the gas concentration ratio of carbon dioxide to the organofluorine compound in the insulating gas does not easily change.
In the case of the gas-insulated power equipment filled with the insulating gas as described above, when arc extinction is performed by the insulating gas, a plurality of kinds of decomposition gases may be generated from the insulating gas. In this case, since the adsorbent for insulating gas of the present embodiment is combined with zeolites having different pore diameters, it can exert adsorption capability for a wider variety of decomposed gases.
Next, the effects of embodiment 1 will be described.
(1) The adsorbent for insulating gas of embodiment 1 is used in an insulating gas atmosphere containing carbon dioxide and an organofluorine compound. The adsorbent for insulating gas contains zeolite. The zeolite comprises a type a zeolite and comprises at least one zeolite of type X zeolite and ZSM-5 type zeolite. According to this configuration, it is possible to suppress a change in the gas concentration ratio of the carbon dioxide and the organofluorine compound in the insulating gas. Therefore, for example, the performance of the insulating gas can be easily maintained at a predetermined gas concentration ratio.
In addition, since the adsorbent for insulating gas according to embodiment 1 is combined with zeolites having different pore diameters, it is possible to exert adsorption capability for a wider variety of decomposed gases.
(2) In the case where the zeolite in the adsorbent for an insulating gas contains a ZSM-5 type zeolite, the ZSM-5 type zeolite is preferably 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. In this case, the hydrophobicity of the ZSM-5 type zeolite can be increased. Since the organofluorine compound generates a large amount of decomposed gas having high hydrophobicity, the use of the substituted ZSM-5 type zeolite can exert adsorption capacity for a wider variety of decomposed gases.
(3) In the insulating gas adsorbent, the average pore diameter on a mass basis determined from the pore diameter of zeolite and the content of zeolite is preferably in the range of more than 0.5nm and less than 0.9 nm. In this case, the change in the gas concentration ratio of the carbon dioxide to the organofluorine compound in the insulating gas can be further suppressed.
(4) The content of the organic fluorine compound in the insulating gas is preferably in a range of 2.5 vol% to 20 vol%. In this case, the insulating performance of the insulating gas can be further improved, and the condensation of the organofluorine compound can be suppressed.
(embodiment 2)
Next, embodiment 2 of the adsorbent for insulating gas will be described focusing on differences from embodiment 1.
The zeolite in the insulating gas adsorbent according to embodiment 2 contains a ZSM-5 type zeolite. The ZSM-5 type zeolite had a pore size of 0.58 nm. The ZSM-5 type zeolite having such a fine pore size has a low ability to selectively adsorb any one of carbon dioxide and an organofluorine compound. The ZSM-5 type zeolite is preferably 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 an insulating gas may further include at least one of a type a zeolite and a type X zeolite.
The zeolite in the adsorbent for an insulating gas may further contain a zeolite having a crystal structure different from that of the zeolite having the crystal structure described above. The content of the ZSM-5-type zeolite in the adsorbent for insulating gas is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more, assuming that the total amount of zeolite is 100 mass%. When the total amount of zeolite in the insulating gas adsorbent is 100 mass%, the total content of the ZSM-5-type zeolite, the a-type zeolite, and the X-type zeolite is preferably 90 mass% or more. The preferred range of the total content as described herein can also be applied to the case where the zeolite in the adsorbent for an insulating gas contains a ZSM-5 type zeolite and further contains only one of an a type zeolite and an X type zeolite. The adsorbent for insulating gas may contain, for example, activated carbon, alumina, silica, or the like as needed.
Since the zeolite in the insulating gas adsorbent according to embodiment 2 contains the ZSM-5 type zeolite, it is possible to suppress a change in the gas concentration ratio of carbon dioxide to the organofluorine compound in the insulating gas. Therefore, for example, the performance of the insulating gas can be easily maintained at a predetermined gas concentration ratio. In embodiment 2, the same effects as those described in columns (2) to (4) of embodiment 1 can be obtained.
(embodiment 3)
Next, embodiment 3 of the adsorbent for insulating gas will be described focusing on differences from embodiment 1.
The zeolite in the insulating gas adsorbent according to embodiment 3 includes an a-type zeolite having carbon dioxide adsorbed thereon in advance and an X-type zeolite having an organofluorine compound adsorbed thereon in advance. According to this configuration, adsorption of the insulating gas can be suppressed when the adsorbent for the insulating gas is started to be used in an insulating gas atmosphere containing carbon dioxide and the organofluorine compound. This can suppress a change in the gas concentration ratio of carbon dioxide to the organofluorine compound in the insulating gas, and can also suppress a decrease in the gas amount of the insulating gas.
When the zeolite in the insulating gas adsorbent adsorbs moisture in the insulating gas, both carbon dioxide and the organofluorine compound are released by the substitution of carbon dioxide with moisture and the substitution of the organofluorine compound with moisture. Thus, even when the zeolite having adsorbed carbon dioxide and the organofluorine compound adsorbs moisture, the gas concentration ratio of carbon dioxide to the organofluorine compound in the insulating gas does not easily change.
The organic fluorine compound to be adsorbed in advance by the X-type zeolite of the adsorbent for insulating gas may be one type, or two or more types. The organofluorine compound previously adsorbed by the X-type zeolite of the adsorbent for an insulating gas may be the same compound as or a different compound from the organofluorine compound in the insulating gas filled in the case of the gas-insulated power equipment.
The method for producing the adsorbent for insulating gas comprises a 1 st contact step of contacting zeolite A with an adsorption gas containing carbon dioxide. In the first contact step 1, carbon dioxide can be adsorbed on the a-type zeolite in advance. The method for producing the adsorbent for insulating gas comprises a 2 nd contact step of contacting X-type zeolite with an adsorption gas containing an organofluorine compound. In the second contact step 2, the organic fluorine compound can be adsorbed on the X-type zeolite in advance.
In the method for producing the adsorbent for insulating gas, the 1 st contact step and the 2 nd contact step can be simultaneously performed by contacting a mixture of the a-type zeolite and the X-type zeolite with an adsorption gas containing carbon dioxide and an organofluorine compound. In this case, the adsorbent for insulating gas can be easily produced.
In the method for producing the adsorbent for insulating gas, the gas concentration ratio of carbon dioxide to the organofluorine compound in the adsorption gas may be the same as or different from the gas concentration ratio of carbon dioxide to the organofluorine compound in the insulating gas filled in the case of the gas-insulated power equipment. When the gas concentration ratio of the carbon dioxide to the organofluorine compound in the adsorption gas is the same as the gas concentration ratio of the carbon dioxide to the organofluorine compound in the insulating gas, the gas production facility and the gas storage facility can be shared, and therefore, the gas production and management can be easily performed.
The pressure conditions and temperature conditions in the 1 st contact step and the 2 nd contact step in the method for producing an adsorbent for an insulating gas are preferably conditions under which the adsorbing gas does not liquefy. Examples of the conditions in the 1 st and 2 nd contact steps include a pressure range of 0.05MPa (G) or more and 1MPa (G) or less; -a temperature in the range of-10 ℃ to 40 ℃; 4 hours or more. The conditions in the 1 st contact step and the conditions in the 2 nd contact step may be the same or different from each other.
Examples
Next, test examples will be described.
(test examples 1 to 4)
In test examples 1 to 4, adsorbents for insulating gas containing the zeolite shown in the upper stage of table 1 were used. Zeoram (trade name) "A-5" manufactured by Tosoh corporation was used as the calcium-substituted A-type zeolite (pore size: 0.5nm) in Table 1. Zeoram (trade name) "F-9" manufactured by Tosoh corporation was used as the sodium-substituted X-type zeolite (pore size: 0.9nm) in Table 1. As the copper-substituted ZSM-5 type zeolite (pore size: 0.58nm) in Table 1, HSZ (trade name) "copper-substituted HSZ-800" manufactured by Tosoh corporation was used.
Next, 17.8g of an adsorbent for an insulating gas and the insulating gas were sealed in a metal pressure-resistant container (under a dry atmosphere having a rated pressure of 0.7MPa (G), a capacity of 1L and a water concentration of 100ppm or less), and the container was left for 1 week. After 1 week, CO in the pressure-resistant vessel was measured using a gas chromatograph/thermal conductivity detector (GC/TCD)2And an organic fluorine compound (which is perfluoroisobutyronitrile ((CF)3)2CFCN, CAS accession number: 42532-60-5), represented by the formula in the tables and figures below: c4F7N) is represented by N). The results are shown in the lower stage of table 1. The gas concentration at the start of the test was measured by a blank test in which only the insulating gas was sealed without sealing the insulating gas adsorbent in the pressure-resistant vessel.
[ Table 1]
In the column of "increase/decrease in gas concentration" in table 1, the difference [% ] between the gas concentration at the start of the test and the gas concentration after 1 week is shown in absolute value.
It is found that the increase/decrease values of the gas concentration are smaller in the case of using the adsorbents for insulating gas of test examples 1 and 2 than in the case of using the adsorbents for insulating gas of test examples 3 and 4.
(test examples 5 and 6)
In test examples 5 and 6, the gas concentrations at the start of the test and after 1 week were measured in the same manner as in test examples 1 to 4 using the insulating gas adsorbent containing the zeolite shown in the upper stage of table 2. The results are shown in the lower stage of table 2.
[ Table 2]
As is clear from table 2, the increase/decrease value of the gas concentration was smaller in the case of using the adsorbent for insulating gas of test example 5 than in the case of using the adsorbent for insulating gas of test example 6.
(test examples 7 to 9)
In test examples 7 to 9, the insulating gas adsorbent used was changed as shown in the upper stage of table 3, and the gas concentrations at the start of the test and after 1 week were measured in the same manner as in test examples 1 to 4. The results are shown in the lower stage of table 3.
[ Table 3]
As is clear from table 3, the increase/decrease value of the gas concentration is smaller in the case of using the adsorbent for insulating gas of test example 7 than in the case of using the adsorbents for insulating gas of test examples 3 and 4 shown in table 1, for example. As is clear from table 3, the increase/decrease value of the gas concentration was smaller in the case of using the adsorbent for insulating gas of test example 8 than in the case of using the adsorbent for insulating gas of test example 9.
(test examples 10 to 13)
In test examples 10 to 13, the adsorbents for insulating gas containing the zeolite shown in the upper stage of table 4 were evaluated for their adsorption ability to adsorb decomposed gas generated during arc extinction using the insulating gas.
First, by introducing an insulating gas (CO)2: 95% by mass of the above organic solventFluorine compound (molecular formula: C)4F7N): 5 mass%) was subjected to an open circuit test (arc extinction test) to obtain an insulating gas containing a decomposition gas. The insulating gas and an adsorbent for the insulating gas containing zeolite shown in the upper stage of table 4 were sealed in the above-mentioned pressure-resistant vessel, and left for 1 week to perform an adsorption test. The concentration of the decomposed gas after 1 week was measured using a gas chromatograph/thermal conductivity detector (GC/TCD), and the adsorption capacity of the adsorbent for insulating gas for a specific decomposed gas was evaluated according to the following criteria.
When the concentration of the decomposed gas after the adsorption test is 10% or less of the concentration of the decomposed gas before the adsorption test, the adsorbent for the insulating gas is determined to have the adsorption capacity (°).
When the concentration of the decomposed gas after the adsorption test is greater than 10% and not more than 50% of the concentration of the decomposed gas before the adsorption test, the adsorbent for insulating gas is judged to have a slight adsorption capacity (Δ).
When the concentration of the decomposed gas after the adsorption test is greater than 50% of the concentration of the decomposed gas before the adsorption test, the adsorbent for insulating gas is judged to have no adsorption capacity (x).
[ Table 4]
As is clear from table 4, the adsorbents for insulating gas of test examples 10 to 12 exhibited more types of decomposition gases having adsorption ability than the adsorbent for insulating gas of test example 13. It is also understood that the adsorbents for insulating gas of test examples 11 and 12 exhibit more types of decomposition gases having adsorption ability than the adsorbent for insulating gas of test example 10.
(test example 14)
In test example 14, as shown in the upper stage of table 5, the same zeolite-containing adsorbent for insulating gas as in test example 1 was used. In test example 14, the amount of the adsorbent for insulating gas to be sealed in the pressure-resistant vessel described below was changed.
That is, in test example 14A pressure-resistant container made of metal (under a dry atmosphere having a rated pressure of 0.7MPa (G), a capacity of 1L and a water concentration of 100ppm or less) was sealed with 4.2g of an adsorbent for an insulating gas and allowed to stand for 1 week. After 1 week, CO in the pressure-resistant vessel was measured using a gas chromatograph/thermal conductivity detector (GC/TCD)2And the above organofluorine compound (formula: C)4F7N) gas concentration. Calculating CO from the pressure in the pressure vessel and the mole fraction of the gas2And the above organofluorine compound (formula: C)4F7N) partial pressure. The results are shown in the lower stage of table 5 and fig. 1 and 2. The gas concentration at the start of the test was measured by a blank test in which only the insulating gas was sealed without sealing the insulating gas adsorbent in the pressure-resistant vessel.
(test example 15)
In test example 1, the adsorbent for insulating gas was obtained by performing a contact step of contacting the zeolite of test example 14 with an adsorption gas. Adsorbing CO from gas2Is 95 vol%, and the above-mentioned organofluorine compound (molecular formula: C) in the adsorption gas4F7N) was contained in an amount of 5% by volume.
The gas concentrations at the start of the test and after 1 week and the gas partial pressures at the start of the test and after 1 week were measured for the obtained insulating gas adsorbent in the same manner as in test example 14. The results are shown in the lower stage of table 5 and fig. 1 and 2.
(test example 16)
In test example 16, an insulating gas adsorbent was obtained in the same manner as in test example 15. The gas concentrations at the start of the test and after 1 week and the partial pressures of the gas at the start of the test and after 1 week were measured in the same manner as in example 14, except that 0.57g of water was added to the pressure resistant vessel and the pressure resistant vessel was brought to a water concentration of 92,701 ppm. The results are shown in the lower stage of table 5 and fig. 1 and 2.
[ Table 5]
As is clear from table 5 and fig. 1, in test examples 14 to 16, the increase and decrease values of the gas concentration can be reduced in the same manner as in test example 1.
As shown in table 5 and fig. 2, when the adsorbents for insulating gas of test examples 15 and 16 were used, a decrease in the gas partial pressure was suppressed as compared with the case of using the adsorbent for insulating gas of test example 14. That is, when the adsorbents for insulating gas of test examples 15 and 16 were used, the amount of insulating gas can be suppressed from decreasing, as compared with the case of using the adsorbent for insulating gas of test example 14.
Claims (11)
1. An adsorbent for insulating gas, which is an adsorbent for insulating gas containing zeolite and used in an insulating gas atmosphere containing carbon dioxide and an organic fluorine compound, wherein,
the zeolite comprises a type a zeolite and comprises at least one of a type X zeolite and a ZSM-5 type zeolite.
2. The adsorbent for insulating gas according to claim 1, wherein the zeolite comprises the ZSM-5 type zeolite.
3. The adsorbent for insulating gas according to claim 1 or 2, wherein,
the zeolite comprises the zeolite X, and the zeolite X,
the A-type zeolite adsorbs carbon dioxide in advance, and the X-type zeolite adsorbs an organic fluorine compound in advance.
4. An adsorbent for insulating gas, which is an adsorbent for insulating gas containing zeolite and used in an insulating gas atmosphere containing carbon dioxide and an organic fluorine compound, wherein,
the zeolite comprises a ZSM-5 type zeolite.
5. The adsorbent for insulating gas according to claim 2 or 4, wherein the ZSM-5 type zeolite 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.
6. The adsorbent for insulating gas according to any one of claims 1 to 5, wherein a mass-based average pore diameter determined from the pore diameter of the zeolite and the content of the zeolite is in a range of more than 0.5nm and less than 0.9 nm.
7. The adsorbent for insulating gas according to any one of claims 1 to 6, wherein a content of the organofluorine compound in the insulating gas is in a range of 2.5 vol% or more and 20 vol% or less.
8. The adsorbent for insulating gas according to any one of claims 1 to 7, wherein the organofluorine compound is selected from heptafluorobutyronitrile (C)4F7N), perfluoro (N-propyl vinyl ether) (C5F10O), perfluoroisobutyronitrile ((CF)3)2CFCN) and perfluoro-2-methoxypropionitrile (CF)3CF(OCF3) CN).
9. A gas-insulated power equipment comprising the adsorbent for insulating gas according to any one of claims 1 to 8.
10. A process for producing an adsorbent for insulating gas containing zeolite, which is used in an insulating gas atmosphere containing carbon dioxide and an organic fluorine compound, wherein,
the zeolite comprises a type A zeolite and a type X zeolite,
the method comprises the following steps:
a first contact step of contacting the A-type zeolite with an adsorption gas containing carbon dioxide; and
a 2 nd contact step of contacting the X-type zeolite with an adsorption gas containing an organofluorine compound.
11. The method for producing an adsorbent for insulating gas according to claim 10,
the adsorption gas contains carbon dioxide and an organofluorine compound,
the 1 st contact step and the 2 nd contact step are simultaneously performed by contacting the mixture of the a-type zeolite and the X-type zeolite with the adsorption gas.
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| PCT/JP2019/018592 WO2020225911A1 (en) | 2019-05-09 | 2019-05-09 | Insulating gas adsorbent and gas-insulated power equipment |
| JPPCT/JP2019/018592 | 2019-05-09 | ||
| PCT/JP2020/018259 WO2020226117A1 (en) | 2019-05-09 | 2020-04-30 | Adsorbent for insulation gases, gas-insulated power apparatus and method for producing adsorbent for insulation gases |
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| CN1341475A (en) * | 2000-08-28 | 2002-03-27 | 波克股份有限公司 | Temp. -change adsorptive process |
| JP2003311148A (en) * | 2002-04-19 | 2003-11-05 | Nippon Sanso Corp | Adsorbent, and method and apparatus for purifying gas |
| CN103506069A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Molecular sieve dewaxing adsorbent and preparation method thereof |
| CN105340143A (en) * | 2013-04-22 | 2016-02-17 | Abb技术有限公司 | Process for providing a contamination-reducing component to an electrical apparatus |
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| JPH0656713A (en) * | 1991-04-27 | 1994-03-01 | Hoechst Ag | Method for purifying chlorofluorohydrocarbon |
| DE10233898A1 (en) | 2002-07-25 | 2004-02-12 | Solvay Fluor Und Derivate Gmbh | Fluorinated hydrocarbon recovery from gas mixtures e.g. perfluorinated hydrocarbon and nitrogen, by adsorption on hydrophobic zeolite with a silica dioxide : alumina ratio of 80:1. |
| JP2005021891A (en) * | 2004-08-26 | 2005-01-27 | Taiyo Nippon Sanso Corp | Method and apparatus for gas refining |
| JP5719995B2 (en) * | 2009-04-30 | 2015-05-20 | パナソニックＩｐマネジメント株式会社 | Gas adsorption device |
| GB0918069D0 (en) * | 2009-10-15 | 2009-12-02 | Ineos Fluor Holdings Ltd | Process |
| WO2015071303A1 (en) * | 2013-11-12 | 2015-05-21 | Abb Technology Ag | Water and contamination absorber for c02 insulated electrical apparatus for the generation, transmission, distribution and/or usage of electrical energy |
| FR3032828B1 (en) * | 2015-02-13 | 2017-03-17 | Alstom Technology Ltd | GAS INSULATED MEDIUM OR HIGH VOLTAGE ELECTRICAL APPARATUS COMPRISING HEPTAFLUOROISOBUTYRONITRILE AND TETRAFLUOROMETHANE |
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| CN1341475A (en) * | 2000-08-28 | 2002-03-27 | 波克股份有限公司 | Temp. -change adsorptive process |
| JP2003311148A (en) * | 2002-04-19 | 2003-11-05 | Nippon Sanso Corp | Adsorbent, and method and apparatus for purifying gas |
| CN103506069A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Molecular sieve dewaxing adsorbent and preparation method thereof |
| CN105340143A (en) * | 2013-04-22 | 2016-02-17 | Abb技术有限公司 | Process for providing a contamination-reducing component to an electrical apparatus |
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