Electrical equipment

Abstract

This electric equipment has a metal tank in which a conductor member is arranged, wherein the metal tank is filled with a dielectric, the dielectric comprising at least one selected from the group consisting of 1-chloro-2,3,3,3-tetrafluoropropene, and 1,1,1,4,4,4-hexafluoro-2-butene, and the surface of the conductor member includes at least one selected from the group consisting of metal and metal oxide.

Description

Technical Field

[0001] The present disclosure relates to electrical equipment.

Background Art

[0002] Electrical equipment such as gas-insulated switchgear houses a conductor to which a high voltage is applied in a metal tank and fills the tank with a dielectric as an insulating gas, thereby ensuring insulation performance. Conventionally, for example, SF6 has been known as a dielectric used in such electrical equipment. However, although SF6 has high insulation performance, its global warming potential (GWP) is large. Therefore, from the perspective of reducing environmental impact, the use of hydrofluoroolefin (hereinafter also referred to as HFO) and hydrochlorofluoroolefin (hereinafter also referred to as HCFO) as dielectrics to replace SF6 has been studied. Patent Document 1 states that a dielectric containing HFO is useful for electrical insulation.

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2018-525327

Summary of the Invention

Problems to be Solved by the Invention

[0004] HFO and HCFO having geometric isomers undergo isomerization reactions depending on temperature conditions and coexisting metals. Geometric isomers often have different boiling points. If isomerization of the dielectric proceeds in electrical equipment and the boiling point of the dielectric changes, the insulation performance of the electrical equipment may deteriorate. For example, if the boiling point of the dielectric increases due to isomerization of the dielectric, the condensation temperature of the dielectric becomes higher, and there is a risk that the insulation performance deteriorates due to liquefaction of the dielectric in the tank. In addition, if the boiling point of the dielectric decreases due to isomerization of the dielectric, the pressure in the tank increases, so there are concerns from a safety perspective in the design of the equipment.

[0005] The present disclosure has been made in view of the above problems, and an object thereof is to provide electrical equipment in which isomerization of a dielectric used as an insulating gas is suppressed. [Means for solving the problem]

[0006] This disclosure includes the following [1] to [6]. [1] Having a metal tank in which a conductive member is arranged inside, and a dielectric is filled into the metal tank, The dielectric material includes at least one selected from the group consisting of 1-chloro-2,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene. An electrical installation in which the surface of the conductor member includes one or more selected from the group consisting of metals and metal oxides. [2] The electrical equipment according to [1], wherein the metal is at least one selected from the group consisting of aluminum, copper, silver, tin, zinc, iron, and chromium, or an alloy containing at least one selected from the group consisting of aluminum, copper, silver, tin, zinc, iron, and chromium. [3] The electrical equipment according to [1] or [2], wherein the dielectric comprises at least one selected from the group consisting of the Z and E isomers of 1-chloro-2,3,3,3-tetrafluoropropene and the Z and E isomers of 1,1,1,4,4,4-hexafluoro-2-butene. [4] The electrical equipment according to any one of [1] to [3], wherein the dielectric comprises the Z isomer and E isomer of 1-chloro-2,3,3,3-tetrafluoropropene, and the mass ratio expressed as Z isomer / E isomer in the total mass of 1-chloro-2,3,3,3-tetrafluoropropene is 99 / 1 to 50 / 50. [5] The electrical equipment described in any of [1] to [4], wherein the electrical equipment further comprises equipment selected from the group consisting of switches, circuit breakers, disconnectors, transformers, resistors, reactors, capacitors, and insulated cables. [6] Having a metal tank in which a conductive member is arranged inside, the metal tank is filled with a dielectric, The dielectric comprises at least one selected from the group consisting of 1-chloro-2,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene, An electrical installation in which, after 1008 hours under a temperature of 160°C, the change in the peak area of ​​the Z isomer contained in the dielectric from its initial value ΔZ and the change in the peak area of ​​the Z isomer contained in the dielectric from its initial value ΔE satisfy the following equations 1 and 2. Formula 1: -1.0area%≦ΔZ≦1.0are% Formula 2: -1.0area%≦ΔE≦1.0are% [Effects of the Invention]

[0007] According to this disclosure, it is possible to provide electrical equipment in which isomerization of the dielectric used as an insulating gas is suppressed. [Brief explanation of the drawing]

[0008] [Figure 1] This is a cross-sectional view showing an example of the configuration of the electrical equipment disclosed herein. [Figure 2] This graph shows Δ(ΔZ) in Example 1 and Δ(ΔE) in Example 2. [Modes for carrying out the invention]

[0009] The electrical equipment of this disclosure will be described below with reference to the drawings. Figure 1 is a cross-sectional view showing an example of the configuration of the electrical equipment of this disclosure. In Figure 1, a gas-insulated switchgear is shown as an example of gas-electric equipment. The electrical equipment 10 shown in Figure 1 has a metal tank 11 in which a conductive member 12 is placed. The metal tank 11 is filled with a dielectric (not shown) as an insulating gas. In Figure 1, the conductor member 12 is supported by the support member 13, insulated from the metal tank 11. The metal tank 11 is an airtight container, space, etc. A high voltage is applied to the conductor member 12.

[0010] Here, the surface of the conductor member 12 includes one or more materials selected from the group consisting of metals and metal oxides. Preferably, the metal is at least one selected from the group consisting of aluminum, copper, silver, tin, zinc, iron, and chromium, or an alloy containing at least one selected from the group consisting of aluminum, copper, silver, tin, zinc, iron, and chromium. The metal oxide may be an oxide obtained by oxidizing the aforementioned metal, or an oxide of another metal. Preferably, the metal oxide is one or more selected from the group consisting of zinc oxide, iron oxide, and aluminum oxide. The conductor member may consist of multiple materials. In particular, the core portion (the interior of the conductor member) may consist of materials other than metals and metal oxides. If the core portion of the conductor member consists of other materials, at least a portion of the surface of the conductor member is covered with one or more materials selected from the group consisting of metals and metal oxides.

[0011] From the viewpoint of suppressing dielectric isomerization, it is preferable that at least a portion of the surface of the conductive member that comes into contact with the dielectric filled inside the metal tank 11 is made of one or more materials selected from the group consisting of metals and metal oxides.

[0012] To maintain dielectric purity and equipment performance, electrical equipment 10 may contain adsorbent desiccants, acid scavengers, etc., sealed inside the device. The adsorbent is preferably one that adsorbs organic substances in the dielectric and decomposition products of the dielectric generated during use. Examples of adsorbents include activated carbon, activated alumina, silica gel, zeolite, metal oxides with adsorption properties, and porous materials, with zeolite, metal oxides with adsorption properties, and porous materials being particularly preferred. The adsorbent may be used alone or in combination of two or more types.

[0013] Examples of zeolites include synthetic zeolites with a silica / alumina molar ratio of 5 or higher (high-silica synthetic zeolites) and synthetic zeolites that have a proton (H) as a cation (proton-exchange synthetic zeolites). Examples of metal oxides with adsorption properties include CuO, Co3O4, and MnO2. Examples of the porous material include a porous material coated with calcium carbonate. The desiccant preferably efficiently adsorbs moisture in the dielectric. For example, calcium, calcium sulfate, particularly drierite, calcium carbonate, calcium hydride, calcium chloride, potassium carbonate, potassium hydroxide, copper(II) sulfate, calcium oxide, magnesium, magnesium oxide, magnesium sulfate, magnesium perchlorate, sodium, sodium sulfate, aluminum, lithium aluminum hydride, aluminum oxide, activated alumina, montmorillonite, phosphorus pentoxide, silica gel, cellulose filter, etc. are preferred. The desiccant may be used alone or in combination of two or more.

[0014] In the electrical equipment 10 of the present disclosure, the dielectric filled inside the metal tank 11 contains at least one selected from the group consisting of 1-chloro-2,3,3,3-tetrafluoropropene (hereinafter also referred to as HCFO-1224yd), and 1,1,1,4,4,4-hexafluoro-2-butene (hereinafter also referred to as HFO-1336mzz).

[0015] When the electrical equipment 10 is in use, a high voltage is applied to the conductor member 12, so the inside of the metal tank 11 becomes hot. In particular, the region near the conductor member 12 is considered likely to become hot. Depending on the combination of the types of the dielectric filled, the surface material of the conductor member 12 described above acts as a catalyst for the isomerization reaction of at least one selected from the group consisting of HFO and HCFO filled as the dielectric inside the metal tank 11 in a high-temperature environment. Thus, it is considered that the isomerization reaction of HFO and HCFO can proceed.

[0016] The inventors of the present application used, as the dielectric filled inside the metal tank 11, at least one selected from the group consisting of HCFO-1224yd and HFO-1336mzz, and when the surface material of the conductor member is a predetermined material, compared with other HCFOs and HFOs, for example, 1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as HCFO-1233zd) used in the examples described later, it was found that the isomerization reaction was significantly suppressed.

[0017] (HCFO-1224yd) HCFO-1224yd (CF3CF=CHCl) is an olefin having a double bond between carbon atoms. Therefore, it has a short lifespan in the atmosphere and a small ozone depletion coefficient and global warming potential.

[0018] It is known that HCFO-1224yd has geometric isomers. The boiling point of the Z isomer of HCFO-1224yd (hereinafter also referred to as HCFO-1224yd(Z)) is 15°C, and the boiling point of the E isomer of HCFO-1224yd (hereinafter also referred to as HCFO-1224yd(E)) is 17°C. By a known production method, a composition of HCFO-1224yd(Z) and HCFO-1224yd(E) can be obtained, and the two can be separated by distillation.

[0019] As the dielectric filled inside the metal tank 11, HCFO-1224yd may be used alone as either the Z isomer or the E isomer, or a mixture containing both the Z isomer and the E isomer may be used. When using only one of the Z isomer or the E isomer, HCFO-1224yd(Z) with a lower boiling point is more preferable because it is less likely to liquefy inside electrical equipment. When using a composition containing Z and E isomers, it is preferable to use an isomer composition with a high proportion of HCFO-1224yd(Z) considering productivity. When using an isomer composition, the mass ratio (Z / E ratio) expressed as HCFO-1224yd(Z) / HCFO-1224yd(E) in the total mass of HCFO-1224yd packed as dielectric is preferably 99 / 1 to 50 / 50, more preferably 99 / 1 to 80 / 20, and even more preferably 99 / 1 to 95 / 5.

[0020] Methods for producing HCFO-1224yd include, for example, (1) a method of dehydrochlorinating 1,2-dichloro-2,3,3,3-tetrafluoropropane (hereinafter also referred to as HCFC-234bb), and (2) a method of hydrogen reduction of 1,1-dichloro-2,3,3,3-tetrafluoropropene (hereinafter also referred to as CFO-1214ya). The following details each method.

[0021] (1) Dechlorination reaction of HCFC-234bb The dehydrochlorination reaction of HCFC-234bb is carried out by contacting it with a base dissolved in a solvent (i.e., a base in solution) in the liquid phase. HCFC-234bb can be produced, for example, by reacting 2,3,3,3-tetrafluoropropene (hereinafter also referred to as HFO-1234yf) with chlorine in a solvent.

[0022] (2) Method for hydrogen reduction of CFO-1214ya CFO-1214ya is reduced to HFO-1234yf by reduction with hydrogen in the presence of a catalyst. HCFO-1224yd is obtained as an intermediate in the reduction reaction to HFO-1234yf. In addition to HCFO-1224yd, various fluorine-containing compounds are produced as by-products in the reduction reaction to HFO-1234yf. CFO-1214ya is known to be produced by defluorinating a hydrogen-free reaction using, for example, 3,3-dichloro-1,1,1,2,2-pentafluoropropane as a starting material, in an alkaline aqueous solution in the presence of a correlation transfer catalyst, or by a gas-phase reaction in the presence of a catalyst such as chromium, iron, copper, or activated carbon.

[0023] (HFO-1336mzz) HFO-1336mzz(CF3CH=CHCF3) is an olefin with a double bond between carbon atoms. Therefore, it has a short lifetime in the atmosphere and low ozone depletion potential and global warming potential.

[0024] HFO-1336mzz is known to have geometric isomers; the Z isomer of HFO-1336mzz (hereinafter also referred to as HFO-1336mzz(Z)) has a boiling point of 33°C, and the E isomer of HFO-1336mzz (hereinafter also referred to as HFO-1336mzz(E)) has a boiling point of 7.5°C. Compositions containing HFO-1336mzz(Z) and HFO-1336mzz(E) can be obtained by known manufacturing methods, and the two can be separated by distillation.

[0025] As the dielectric material to be filled inside the metal tank 11, HFO-1336mzz may be either the Z isomer or the E isomer alone, or it may contain both the Z and E isomers. When using only one of the Z or E isomers, HFO-1336mzz(E), which has a lower boiling point, is preferable because it is less likely to liquefy in electrical equipment.

[0026] As a method for producing HFO-1336mzz, for example, as disclosed in U.S. Patent Nos. 7,795,482 and 8,399,721, it can be prepared by contacting CF3-CCl=CCl-CF3 with hydrogen in the presence of a catalyst.

[0027] Furthermore, HFO-1336mzz can be prepared by contacting CF3-CHCl2 with copper in the presence of an amide solvent and 2,2'-bipyridine, as disclosed in U.S. Patent No. 8,436,216.

[0028] Furthermore, HFO-1336mzz can be produced by (1) contacting CCl3-CF3 with hydrogen in the presence of a ruthenium-containing catalyst to produce 1316mxx (2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene); or (2) contacting 1316mxx with hydrogen in the presence of a catalyst containing copper, nickel, copper-nickel, or copper-palladium to produce E- or Z-1326mxxz (1,1,1,4,4,4-hexafluoro-2-chloro (1) to provide (2) butene; (2) to provide a composition containing hexafluoro-2-butyne by contacting 1326mxz with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkylammonium salt; (3) to provide a composition containing hexafluoro-2-butyne by contacting hexafluoro-2-butyne with hydrogen and a catalyst (proceding in order from (1) to (4) above), as disclosed in International Publication No. 2015 / 120250. Other steps other than (1) to (4) may also be included.

[0029] Furthermore, HFO-1336mzz can be prepared as disclosed in International Publication No. 2015 / 142981 by (1) contacting 3,3,3-trifluoro-1-propene with carbon tetrachloride to provide 2,4,4,4-tetrachloro-1,1,1-trifluorobutane; and (2) contacting 2,4,4,4-tetrachloro-1,1,1-trifluorobutane.

[0030] The dielectric material used to fill the inside of the metal tank 11 may contain only one of HCFO-1224yd or HFO-1336mzz, or both. As the dielectric material to be filled inside the metal tank 11, HCFO-1224yd is preferred because, even if an isomerization reaction proceeds within the electrical equipment, the difference in boiling points between the Z and E forms is small, making it less likely to liquefy within the electrical equipment.

[0031] The total volume of HCFO-1224yd and HFO-1336mzz filled inside the metal tank 11 is preferably 70% by volume or less, 60% by volume or less, 50% by volume or less, 40% by volume or less, 30% by volume or less, 25% by volume or less, 20% by volume or less, 15% by volume or less, 10% by volume or less, or 5% by volume or less, relative to the total volume of dielectric material filled inside the metal tank 11, from the viewpoint of achieving the condensation temperature necessary for HCFO-1224yd and HFO-1336mzz to exist only in the gas phase. Furthermore, the total volume of HCFO-1224yd and HFO-1336mzz is preferably 1% by volume or more, 2% by volume or more, or 3% by volume or more, relative to the total volume of dielectric material filled inside the metal tank 11, from the viewpoint of insulation performance and arc extinguishing performance.

[0032] The dielectric material filling the inside of the metal tank 11 may include other dielectric materials in addition to HCFO-1224yd and HFO-1336mzz. Specific examples of other dielectric materials are shown below. Other dielectrics include difluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoro-1-propene, (E)-1,3,3,3-tetrafluoropropene, and (Z)-1,3,3,3-tetrafluoropropene. Among these, (E)-1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoro-1-propene, (E)-1,3,3,3-tetrafluoropropene, and (Z)-1,3,3,3-tetrafluoropropene are preferred. However, when using other dielectrics that have geometric isomers, the isomerization reaction proceeds more easily compared to HCFO-1224yd and HFO-1336mzz. Therefore, if the amount of other dielectrics filling the metal tank 11 is large, the impact on electrical equipment due to the isomerization of the other dielectrics becomes a problem. For this reason, the molar ratio of the above-mentioned other dielectrics in the dielectric filling the metal tank 11 is preferably 30% or less, more preferably 20% or less, even more preferably 10% or less, and particularly preferably 5% or less.

[0033] The dielectric material filled inside the metal tank 11 may contain, as a first trace component, at least one selected from the group consisting of fluorocarbons, chlorofluorocarbons, fluoroolefins, chlorofluoroolefins other than HCFO-1224yd and HFO-1336mzz, chlorofluoroalkynes, methanol, ethanol, acetone, hexane, ethylene, and carbon monoxide.

[0034] Fluorocarbons are saturated hydrocarbon compounds that contain a fluorine atom as a halogen atom in their molecule but do not contain a chlorine atom. Fluorocarbons may or may not contain a hydrogen atom in their molecule. Chlorofluorocarbons are saturated hydrocarbon compounds that contain fluorine and chlorine atoms as halogen atoms in their molecules. Chlorofluorocarbons may or may not contain hydrogen atoms in their molecules. Fluoroolefins are ethylene-based hydrocarbon compounds that contain a fluorine atom as a halogen atom in their molecule but do not contain a chlorine atom. Fluoroolefins may or may not contain a hydrogen atom in their molecule. Chlorofluoroolefins are ethylene-based hydrocarbon compounds that contain fluorine and chlorine atoms as halogen atoms in their molecules. Chlorofluoroolefins may or may not contain hydrogen atoms in their molecules. Chlorofluoroalkynes are acetylene-based hydrocarbon compounds that contain fluorine and chlorine atoms as halogen atoms in their molecules. Chlorofluoroalkynes may or may not contain hydrogen atoms in their molecules.

[0035] Examples of fluorocarbons include 1,1,1,2-tetrafluoropropane, 1,1,1,3-tetrafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2,2,3,3-heptafluoropropane, tetrafluoromethane, trifluoromethane, and fluoroethane. Examples of chlorofluorocarbons include 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 2-chloro-1,1,1,2-tetrafluoropropane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, and chlorotrifluoromethane. Other fluoroolefins besides HFO-1336mzz include 2,4,4,4-tetrafluoro-1-butene and tetrafluoroethylene. Examples of chlorofluoroolefins other than HCFO-1224yd include 1,1-dichloro-2,3,3,3-tetrafluoropropene, 2-chloro-3,3,3-trifluoropropene, (Z)-2-chloro-1,3,3,3-tetrafluoropropene, (E)-2-chloro-1,3,3,3-tetrafluoropropene, and 2-chloro-1,1,3,3,3-pentafluoro-1-propene. Examples of chlorofluoroalkynes include 1,1-dichloro-2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoro-1-propyne.

[0036] Examples of the first trace component mentioned above include compounds that are by-products and present as impurities in the dielectric during the production of HCFO-1224yd or HFO-1336mzz, or solvents used in the production of HCFO-1224yd or HFO-1336mzz.

[0037] If the dielectric material filled inside the metal tank 11 contains a first trace component, the mass content of the first trace component is preferably 15,000 ppm or less, and more preferably 10,000 ppm or less, relative to the total mass of the dielectric material filled inside the metal tank 11 (the total mass of HCFO-1224yd, HFO-1336mzz, and other dielectric materials; the same applies hereinafter), from the viewpoint of ensuring further stability. On the other hand, from the viewpoint of simplifying the process of reducing the content of the first trace component, the mass-based content of the first trace component is preferably 4 ppm or more, more preferably 50 ppm or more, and even more preferably 100 ppm or more, relative to the total dielectric material filled inside the metal tank 11.

[0038] The dielectric material filled inside the metal tank 11 may contain, as a second trace component, at least one selected from the group consisting of chlorine, hydrogen fluoride, hydrogen chloride, acetic acid, carbonyl fluoride, phosgene, trifluoroacetic acid fluoride, formyl chloride, and chloroform. When the second trace component is included, from the viewpoint of ensuring further stability, the mass-based content of the second trace component is preferably 5000 ppm or less, more preferably 3000 ppm or less, even more preferably 1000 ppm or less, even more preferably 500 ppm or less, even more preferably 250 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, and even more preferably 20 ppm or less, relative to the total dielectric material filled inside the metal tank 11. On the other hand, from the viewpoint of simplifying the process of reducing the content of the second trace component, the mass-based content of the second trace component is preferably 5 ppm or more, and more preferably 10 ppm or more, relative to the total dielectric material filled inside the metal tank 11.

[0039] In addition to the dielectric, the metal tank 11 may be filled with at least one diluent gas selected from the group consisting of helium, xenon, methane, nitrous oxide, nitrogen, carbon dioxide, air, and oxygen. When a diluent gas is filled in addition to the dielectric material inside the metal tank 11, the volume ratio of the dielectric material in the total of the dielectric material and diluent gas filled in the metal tank 11 is preferably 70 volume% or less, more preferably 60 volume% or less, even more preferably 50 volume% or less, even more preferably 40 volume% or less, even more preferably 30 volume% or less, even more preferably 25 volume% or less, even more preferably 20 volume% or less, even more preferably 15 volume% or less, even more preferably 10 volume% or less, and even more preferably 5 volume% or less, from the viewpoint of achieving the condensation temperature necessary for the dielectric material to exist only in the gas phase. On the other hand, from the viewpoint of insulation performance and arc extinguishing performance, the volume ratio of the dielectric material in the total of the dielectric material and diluent gas filled in the metal tank 11 is preferably 1 volume% or more, more preferably 2 volume% or more, and even more preferably 3 volume% or more.

[0040] When a diluent gas is filled into the metal tank 11 in addition to the dielectric, a desirable combination of the dielectric and the diluent gas is a combination of at least one of (E)-1-chloro-2,3,3,3-tetrafluoropropene and (Z)-1-chloro-2,3,3,3-tetrafluoropropene and at least one selected from the group consisting of air, nitrogen, oxygen, and carbon dioxide.

[0041] The electrical equipment 10 shown in Figure 1 may be equipped with various devices in series or parallel along the circuit (electrical circuit) including the conductor member 12. Examples of such devices include switches, circuit breakers, disconnectors, etc. for disconnecting the circuit; transformers, resistors, reactors, capacitors, etc. for changing the voltage of the circuit; and insulated cables. For insulation of the inside or outside of such equipment such as switches, circuit breakers, disconnectors, transformers, resistors, reactors, capacitors, etc., dielectrics and diluent gases filled inside the metal tank 11, as well as hydrogen, helium, SF6, or a mixture thereof, may be used.

[0042] Furthermore, solid insulators, insulating oils, gel-like insulators, etc., may be used for insulation of the inside or outside of the above-mentioned equipment. The inside or outside of the above-mentioned equipment may also be insulated by a vacuum. Examples of solid insulators include insulating resin materials. Examples of insulating resin materials include thermoplastic resins and thermosetting resins. Examples of thermoplastic resins include vinyl chloride-based, polyester-based, and nylon-based resins. Examples of thermosetting resins include epoxy-based and urethane-based resins. Examples of insulating oils include mineral oils, vegetable oils, animal oils, and fluorinated oils.

[0043] The electrical equipment of this disclosure satisfies the following equations 1 and 2 when measured by gas chromatography after 1008 hours under a temperature of 160°C, the change in the peak area of ​​the Z isomer contained in the dielectric from its initial value ΔZ and the change in the peak area of ​​the Z isomer contained in the dielectric from its initial value ΔE. Formula 1: -1.0area%≦ΔZ≦1.0are% Formula 2: -1.0area%≦ΔE≦1.0are%

[0044] From the viewpoint of further suppressing dielectric isomerization, it is more preferable that ΔZ and ΔE satisfy the following equations 1-2 and 2-2, and even more preferable that they satisfy the following equations 1-3 and 2-3.

[0045] Formula 1-2: -0.7area%≦ΔZ≦0.7area% Formula 2-2: -0.7area%≦ΔE≦0.7area%

[0046] Formula 1-3: -0.5area%≦ΔZ≦0.5are% Formula 2-3: -0.5area%≦ΔE≦0.5are%

[0047] The aforementioned ΔZ and ΔE are measured using a gas chromatograph. For example, the Agilent Technologies GC System 7890A can be used as a gas chromatograph, and DB-1 GC columns can be used.

[0048] The methods for calculating ΔZ and ΔE are described below. After placing the electrical equipment filled with the dielectric material to be measured (hereinafter referred to as the "measurement target") in a constant temperature chamber, it is heated to 40°C. A gas sample is taken from the gas phase portion (gas containing the dielectric material; the same applies hereinafter) within the measurement target and measured using a gas chromatograph. The peak areas (in "area%") of the Z isomer and E isomer contained in the dielectric material in the chromatogram are calculated, and these peak areas are set as initial values. The initial value of the Z isomer peak area is set to Z0, and the initial value of the E isomer peak area is set to E0. The object to be measured is heated in a constant temperature bath at 160°C for 1008 hours. After heating, a gas sample is taken from the gas phase within the object and measured using a gas chromatograph. The area of ​​the peak Z of the Z isomer contained in the dielectric is measured in the chromatogram obtained by measuring the gas sample after heating. 1008 and the area of ​​the peak E of the E isomer contained in the dielectric. 1008 Calculate. And the change in the peak area of ​​the Z isomer from the initial value ΔZ(Z 1008 -Z0) and the change in the peak area of ​​the E isomer from the initial value ΔE(Z 1008 Calculate -Z0). [Examples]

[0049] The present disclosure will be described in detail below with reference to examples. Examples 1 and 2 are examples, and Example 3 is a comparative example. However, the present disclosure is not limited to these examples. [Example 1] HCFO-1224yd (purity 99.4%, Z / E ratio = 99.5 / 0.5) was used as the dielectric. A Pyrex® insert tube, whose mass had been measured in advance, was inserted into a 200cc stainless steel (SUS316) pressure vessel (maximum operating temperature 300°C, maximum operating pressure 20MPa). One piece each of steel (SS400), copper, and aluminum (25mm x 30mm x 2mm each) were prepared as metal pieces and suspended together from the top of the insert tube. After sealing the pressure vessel, the inside of the vessel was evacuated. Next, 100g of liquefied dielectric material was packed into the pressure vessel, and the pressure vessel was placed in a constant temperature bath. The pressure vessel was heated to 40°C, and a gas sample was taken from the gas phase inside the pressure vessel. The gas sample was measured using a gas chromatograph, and the area of ​​the detected HCFO-1224yd(Z) and HCFO-1224yd(E) peaks in the chromatogram was calculated. This was used as the initial value (the same applies hereafter). Subsequently, the pressure vessel was maintained at 160°C in a constant temperature bath, and from 28 days (672 hours) onward, gas samples were taken from the gas phase inside the pressure vessel every 7 days (168 hours), and the progression of isomerization of HCFO-1224yd was confirmed by gas chromatography. Specifically, the change in the area of ​​the detected HCFO-1224yd(Z) and HCFO-1224yd(E) peaks from their initial values ​​(ΔZ, ΔE; units are "area%" (the same applies hereafter)) in the chromatogram was determined. A gas chromatograph, specifically the Agilent Technologies GC System 7890A, was used, and a 120m length of DB-1 GC column was installed. The results are shown in the table below. ΔZ is also shown in Figure 2.

[0050] [Example 2] The procedure was the same as in Example 1, except that HFO-1336mzz (purity 99.9%, Z / E ratio = 100 / 0) was used as the dielectric, and the progression of isomerization of HFO-1336mzz was confirmed by gas chromatography. Specifically, the change in the area of ​​the detected HFO-1336mzz(Z) and HFO-1336mzz(E) peaks from their initial values ​​(ΔZ, ΔE) in the chromatogram was determined. ΔZ is also shown in Figure 2.

[0051] [Example 3] The procedure was the same as in Example 1, except that HCFO-1233zd (purity 99.9%, Z / E ratio = 0 / 100) was used as the dielectric, and the progression of isomerization of HCFO-1233zd was confirmed by gas chromatography. Specifically, the change in the area of ​​the detected HCFO-1233zd(Z) and HCFO-1233zd(E) peaks from their initial values ​​(ΔZ, ΔE) in the chromatogram was determined. ΔE is also shown in Figure 2.

[0052] [Table 1]

[0053] In Example 1, the decrease in HCFO-1224yd(Z) due to isomerization indicated by ΔZ, and the increase in HCFO-1224yd(E) due to isomerization indicated by ΔE, were minor. In Example 2, the decrease in HFO-1336mzz(Z) due to isomerization indicated by ΔZ was hardly observed. In contrast, in Example 3, the decrease in HCFO-1233zd(E) due to isomerization indicated by ΔE, and the increase in HCFO-1233zd(Z) due to isomerization indicated by ΔZ were significant.

[0054] Example 1 demonstrates that dielectric isomerization is suppressed even when HCFO-1224yd with a purity of 99.4% is used as the dielectric. Furthermore, Example 2 demonstrates that dielectric isomerization is suppressed even when HFO-1336mzz with a purity of 99.9% is used as the dielectric. Therefore, it can be seen that dielectric isomerization is suppressed even when the concentrations of HCFO-1224yd and HFO-1336mzz contained in the dielectric are low, such as 70% by volume or less, 60% by volume or less, 50% by volume or less, 40% by volume or less, 30% by volume or less, 25% by volume or less, 20% by volume or less, 15% by volume or less, 10% by volume or less, or 5% by volume or less.

[0055] The disclosure of Japanese Patent Application No. 2020-177310, filed on 22 October 2020, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. It has a metal tank in which a conductive member is arranged inside, and the metal tank is filled with a dielectric material. The dielectric comprises at least one selected from the group consisting of 1-chloro-2,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene, An electrical installation in which, after 1008 hours under a temperature of 160°C, the change in the peak area of ​​the Z isomer contained in the dielectric from its initial value ΔZ and the change in the peak area of ​​the E isomer contained in the dielectric from its initial value ΔE, as measured by gas chromatography, satisfies the following equations 1 and 2. Formula 1: -1.0are%≦ΔZ≦1.0are% Formula 2: -1.0are%≦ΔE≦1.0are%

2. The electrical equipment according to claim 1, wherein the surface of the conductor member includes one or more selected from the group consisting of metals and metal oxides.

3. The electrical equipment according to claim 2, wherein the metal is at least one selected from the group consisting of aluminum, copper, silver, tin, zinc, iron, and chromium, or an alloy containing at least one selected from the group consisting of aluminum, copper, silver, tin, zinc, iron, and chromium.

4. The electrical equipment according to any one of claims 1 to 3, wherein the dielectric comprises a Z isomer and an E isomer of 1-chloro-2,3,3,3-tetrafluoropropene, and the mass ratio of the Z isomer to the E isomer in the total mass of 1-chloro-2,3,3,3-tetrafluoropropene is 99 / 1 to 50 / 50.

5. The electrical equipment according to any one of claims 1 to 4, wherein the electrical equipment further comprises equipment selected from the group consisting of switches, circuit breakers, disconnectors, transformers, resistors, reactors, capacitors, and insulated cables.

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