Filling container and storage method therefor

Abstract

Provided are: a filling container with which a disproportionation reaction of HFO such as trifluoroethylene is suppressed and transportation and storage can be safely carried out; and a storage method therefor. A filling container according to the present invention comprises a composition containing a first component and a second component and a container filled with the composition, wherein: the first component is at least one selected from the group consisting of trifluoroethylene, 1,2-difluoroethylene, and 1,1-difluoroethylene; the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene, difluoromethane, fluoromethane, 1,1-difluoroethane, fluoroethane, 1,1,1,3,3-pentafluorobutane, dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen; the amount of the first component is at most 62.6 mass% with respect to the total amount of the first component and the second component; and the container is made of a material having a tensile strength of at least 400 N / mm2 and a yield ratio of at least 60%.

Description

Filled container and its storage method

[0001] The present invention relates to a filled container containing a specific hydrofluoroolefin and a method for storing the same.

[0002] Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which have been used as refrigerants for freezers and air conditioners, working fluids for heat cycles such as power generation systems and heat pipes, solvents, and cleaning agents (hereinafter, these applications may be collectively referred to as simply refrigerants), have high ozone depletion potentials (ODPs). Therefore, hydrofluorocarbons (HFCs) have been developed as alternatives to these compounds.

[0003] However, HFCs are also subject to regulation as substances that cause global warming, and there is a demand for a switch to refrigerants with lower global warming potential (GWP), such as hydrofluoroolefins (HFOs). Among HFOs, trifluoroethylene (HFO-1123) has very low GWP and ODP and is promising as a next-generation medium; however, it undergoes a disproportionation reaction under conditions of high temperature, high pressure, and the presence of an ignition source. If the disproportionation reaction propagates due to a layer short or the like in a refrigerant compressor, a sudden increase in temperature and pressure may occur, leading to an accident caused by the rupture of the refrigerant compressor.

[0004] In order to suppress such a disproportionation reaction, for example, Patent Document 1 describes that mixing an inert substance to prepare a composition having a trifluoroethylene content of 70 mol % or less is effective, and that the working fluid can be used stably in the presence of an ignition source.

[0005] International Publication No. 2015 / 115551

[0006] However, HFOs that are easily disproportionated, such as trifluoroethylene, 1,2-difluoroethylene (HFO-1132), and 1,1-difluoroethylene (HFO-1132a), may undergo disproportionation reactions due to strong impacts from outside the container when stored or transported in a filled container, even in the absence of an ignition source. In practice, the impact energy that a filled container receives from outside the container during storage or transport is expected to be greater than the minimum ignition energy caused by an ignition source when the refrigerant is in use. For this reason, there is concern that HFOs that are easily disproportionated, such as trifluoroethylene, may undergo disproportionation reactions when filled containers are stored or transported.

[0007] Therefore, from the viewpoint of safe handling, it is necessary to suppress the disproportionation reaction of HFOs such as trifluoroethylene in a filled container where no ignition source exists.

[0008] The present invention has been made under these circumstances, and aims to provide a filled container and a storage method thereof that can suppress the disproportionation reaction of HFOs such as trifluoroethylene and enable safe transportation and storage.

[0009] The present invention is based on the discovery that a container filled with a composition in which a specific component is blended with an HFO such as trifluoroethylene is effective in suppressing disproportionation reactions.

[0010] The present invention provides the following means: [1] A filled container having a composition containing a first component and a second component, and a container filled with the composition, wherein the first component is at least one selected from the group consisting of trifluoroethylene, 1,2-difluoroethylene, and 1,1-difluoroethylene, and the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene, difluoromethane, fluoromethane, 1,1-difluoroethane, fluoroethane, 1,1,1,3,3-pentafluorobutane, dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen, and the amount of the first component is 62.6 mass% or less based on the total amount of the first component and the second component, and the container has a tensile strength of 400 N / mm ２[2] A filled container made of a material having a yield ratio of 60% or more and a yield strength of 200% or more. [2] A filled container according to [1], wherein the sum of the first component and the second component is 90.0% by mass or more of the total amount of the composition. [3] A filled container according to [1] or [2], wherein the first component is 40.0% by mass or more of the total amount of the composition. [4] A filled container according to any of [1] to [3], wherein the first component is trifluoroethylene. [5] A filled container according to any of [1] to [4], wherein the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene and difluoromethane. [6] A filled container according to any of [1] to [4], wherein the yield strength of the container is 255 N / mm ２ [7] A filled container according to any one of [1] to [5], wherein the internal volume of the container is 5 L or more. [8] A filled container according to any one of [1] to [7], wherein the wall thickness of the container is 2.5 mm or more. [9] A filled container according to any one of [1] to [8], wherein the internal pressure of the filled container is 6.0 MPa or less.

[10] A filled container according to any one of [1] to [9], wherein the internal temperature of the filled container is 60°C or less.

[11] A method for storing a filled container having a composition containing a first component and a second component, and a container filled with the composition, wherein the first component is at least one selected from the group consisting of trifluoroethylene, 1,2-difluoroethylene, and 1,1-difluoroethylene, and the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene, difluoromethane, fluoromethane, 1,1-difluoroethane, fluoroethane, 1,1,1,3,3-pentafluorobutane, dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen, and the amount of the first component is 62.6 mass% or less relative to the total amount of the first component and the second component, and the container has a tensile strength of 400 N / mm ２ A method for storing a filled container made of a material having the above properties and a yield ratio of 60% or more.

[0011] According to the present invention, a filled container in which the disproportionation reaction of HFOs such as trifluoroethylene is suppressed and a method for storing the same are provided. Therefore, the filled container of the present invention is effective for the safe transportation and storage of HFOs.

[0012] The definitions and meanings of terms and notations used in this specification are shown below. A preferred numerical range can be any combination of preferred lower and upper limits. Halogenated hydrocarbons may be expressed by common names based on their type and refrigerant number. Furthermore, for HFOs that have geometric isomers, the notation of a compound without a description of the E- and Z-isomers means a generic name that includes the E-, Z-, and a mixture of the E- and Z-isomers.

[0013] The filled container of the present invention is a filled container having a composition containing a first component and a second component, and a container filled with the composition, wherein the first component is at least one selected from the group consisting of trifluoroethylene, 1,2-difluoroethylene, and 1,1-difluoroethylene, and the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene, difluoromethane, fluoromethane, 1,1-difluoroethane, fluoroethane, 1,1,1,3,3-pentafluorobutane, dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen, and the amount of the first component is 62.6 mass% or less based on the total amount of the first component and the second component, and the container has a tensile strength of 400 N / mm ２ and is made of a material having a yield ratio of 60% or more.

[0014] In such a filled container, the disproportionation reaction of the HFO of the first component is suppressed during transportation, storage, etc., and thus the risk of explosion, etc. due to the disproportionation reaction is suppressed. Specifically, the present invention provides a filled container for HFO whose safety has been fully confirmed in an impact test (a test based on the acetylene container porous material performance test based on the High Pressure Gas Safety Act) in the examples described below. In other words, the filled container of the present invention can suppress the disproportionation reaction of HFO caused by impact energy during transportation, storage, etc., when there is no ignition source in the internal space of the container filled with the HFO, not when there is an ignition source such as a heat cycle system.

[0015] In the present invention, from the viewpoint of safety during transportation and storage, a disproportionation reaction is deemed to have occurred when the internal pressure of the filled container during or immediately after the impact test in the examples increases to 1.5 times or more the internal pressure of the filled container before the test. Furthermore, the occurrence of a black foreign matter inside the container after the impact test and the occurrence of an increase in the hydrogen fluoride concentration (detected as a fluoride ion concentration in the examples) in the gas inside the container after the impact test may also be used as criteria for determining that a disproportionation reaction has occurred.

[0016] [Composition] The composition filled in the filled container of the present invention contains a first component and a second component.

[0017] The first component is at least one selected from the group consisting of trifluoroethylene (HFO-1123), 1,2-difluoroethylene (HFO-1132a), and 1,1-difluoroethylene (HFO-1132). The first component is any of these HFOs, and may contain one type alone or two or more types. In a preferred embodiment of the present invention, the first component is trifluoroethylene.

[0018] The second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene (HFO-1234yf), difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen. The second component may be a single component or may contain two or more components. In a preferred embodiment of the present invention, the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene and difluoromethane, and more preferably 2,3,3,3-tetrafluoropropene.

[0019] The composition contains a first component and a second component, and the content of the first component is 62.6 mass% or less, preferably 62.5 mass% or less, and more preferably 62.1 mass% or less, based on the total amount of the first component and the second component. Furthermore, from the viewpoint of the transport efficiency of the HFO of the first component, the content of the first component is preferably 50.0 mass% or more, more preferably 53.0 mass% or more, and even more preferably 55.0 mass% or more.

[0020] From the viewpoint of the transport efficiency of the HFO of the first component, the content of the first component in the total amount of the composition is preferably 40.0 mass% or more, more preferably 45.0 mass% or more, even more preferably 50.0 mass% or more, and still more preferably 55.0 mass% or more. Furthermore, from the viewpoint of sufficiently suppressing the disproportionation reaction of the first component, the upper limit of the content of the first component in the total amount of the composition is preferably 62.6 mass% or less, more preferably 62.5 mass% or less, and even more preferably 62.1 mass% or less.

[0021] The content of the second component is 37.4% by mass or more, preferably 37.5% by mass or more, and more preferably 37.9% by mass or more, based on the total amount of the first component and the second component. From the viewpoint of the transport efficiency of the HFO of the first component, the content of the second component is preferably 50.0% by mass or less, more preferably 47.0% by mass or less, and even more preferably 45.0% by mass or less.

[0022] The content of the second component in the total amount of the composition is preferably 37.4% by mass or more, more preferably 37.5% by mass or more, and even more preferably 37.9% by mass or more, from the viewpoint of sufficiently suppressing the disproportionation reaction of the first component. Furthermore, the upper limit of the content of the second component in the total amount of the composition is preferably 60.0% by mass or less, more preferably 55.0% by mass or less, even more preferably 50.0% by mass or less, and still more preferably 45% by mass or less, from the viewpoint of transport efficiency of the HFO of the first component.

[0023] The composition may contain components other than the first component and the second component. The other components may be added or may be contained as impurities. When other components are contained, the total amount of the first component and the second component is preferably 90.0 mass% or more, more preferably 95.0 mass% or more, and even more preferably 99.0 mass% or more, based on the viewpoints of sufficient suppression of the disproportionation reaction of the first component, transport efficiency, and the like. That is, the content of the other components in the total amount of the composition is preferably 10.0 mass% or less, more preferably 5.0 mass% or less, even more preferably 1.0 mass% or less, and may even be 0 mass%. In a preferred embodiment of the present invention, the total amount of the first component and the second component is 100 mass% based on the total amount of the composition. The content of each component in the composition can be measured by gas chromatography, unless otherwise specified.

[0024] Examples of other components that may be added include HFOs other than the first component and the second component, HFCs, hydrochlorofluoroolefins (HCFOs), chlorofluoroolefins (CFOs), other halogen compounds, hydrocarbon compounds, etc. The other components may be used alone or in combination of two or more. Examples of HFOs include 2-fluoropropene (HFO-1261yf), 1,1,2-trifluoropropene (HFO-1243yc), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 3,3,3-trifluoropropene (HFO-1243zf), and 1,1,1,4,4,4-hexafluorobutene (HFO-1336mzz). Examples of HFCs include 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), and 1,1,2,2,3,3,4-heptafluorocyclopentane (HFC-c447ef). Examples of HCFOs include 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 2-chloro-1,1,3,3-tetrafluoropropene (HCFO-1224xc), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1-chloro-1,2-difluoroethylene (HCFO-1122), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). Examples of CFOs include 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb), and 1,2-dichloro-1,2-difluoroethylene (CFO-1112).Other halogen compounds include, for example, iodomethane (CH. ３ I), diiodomethane (CH ２ I ２ ), dibromomethane (CH ２ Br ２ ), bromomethane (CH ３ Br), dichloromethane (CH ２ Cl ２ ), chloroiodomethane (CH ２ ClI), dibromochloromethane (CHBr ２ Cl), tetraiodomethane (CI ４ ), tetrabromomethane (CBr ４ ), bromotrichloromethane (CBrCl ３ ), dibromodichloromethane (CBr ２ Cl ２ ), tribromofluoromethane (CBr ３ F), fluoroiodomethane (CH ２ FI), difluoroiodomethane (CHF ２ I), difluorodiiodomethane (CF ２ I ２ ), dibromodifluoromethane (CBr ２ F ２ ), trifluoroiodomethane (CF ３ I), 1,1,1-trifluoro-2-iodoethane (CF ３ CH ２ Examples of the hydrocarbon compounds include cyclopropane, isobutane, pentane, isopentane, etc.

[0025] Examples of other components that may be contained as impurities include unavoidable components such as by-products and solvents used in the production of the first and second components. In consideration of simplifying the purification steps of the first and second components and the removal limit, the content of other components that may be contained as impurities may be 50 ppm by mass or more, or may be 100 ppm by mass or more, relative to the total amount of the composition. In consideration of ensuring safety during transportation and storage of the filled container, the content of other components that may be contained as impurities is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less, relative to the total amount of the composition.

[0026] Other components that may be contained as impurities include hydrogen fluoride, methane, chloromethane, dichlorodifluoromethane (CFC-12), 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), chlorodifluoromethane (HCFC-22), chlorofluoromethane (HCFC-31), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), 1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a), 1-chloro-1,2,2-trifluoroethane (HCFC-133), 2-chloro-1,1,1-trifluoroethane (HCFC-133a), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 2-chloro-1,1-difluoroethane (HCFC-142), 1-chloro-1,1-difluoroethane (HCFC-142b), trifluoromethane (HFC-23), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane fluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), Fluoroethylene (HFO-1141), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 3,3,3-trifluoropropene (HFO-1243zf), 3,3-difluoropropene (HFO-1252zf), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), 1-chloro-2-fluoroethylene (HCFO-1131), 1,2-dichloro-1,Examples include 2-difluoroethylene (CFO-1112), chlorotrifluoroethylene (CFO-1113), tetrafluoroethylene (FO-1114), hexafluoropropene (FO-1216), and perfluorocyclobutane (FC-318).

[0027] Further, components that may be contained as impurities include water and oxygen. When water is contained in the composition, the content of water is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, even more preferably 100 ppm by mass or less, and even more preferably 50 ppm by mass or less, based on the total amount of the composition, from the viewpoint of suppressing the disproportionation reaction of the first component. Furthermore, from the viewpoint of reducing the operation and cost burden required for removing water from the composition, the lower limit of the content of water based on the total amount of the composition may be 0.1 ppm by mass or more, or may be 1 ppm by mass or more. The content of water in the composition can be measured using a Karl Fischer moisture meter.

[0028] When oxygen is contained in the composition, the content of oxygen is, from the viewpoint of suppressing the disproportionation reaction of the first component, preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, even more preferably 100 ppm by mass or less, and still more preferably 50 ppm by mass or less, relative to the total amount of the composition. Furthermore, from the viewpoint of reducing the operation and cost burden required for removing oxygen from the composition, the lower limit of the content of water relative to the total amount of the composition may be 0.1 ppm by mass or more, or may be 1 ppm by mass or more.

[0029] [Container] The container in the filled container of the present invention has a tensile strength of 400 N / mm ２ and is made of a material having a yield ratio of 60% or more.

[0030] The structure and material of the container are not limited as long as the container can be filled and sealed with the composition under internal pressure. Examples of containers include pressure-resistant containers such as storage tanks and cylinders. Note that the container in the present invention does not perform its intended function as a refrigerant or heat transfer medium when the composition is filled inside the container. Specifically, the container in the present invention does not include refrigeration and freezing equipment (built-in showcases, separate showcases, commercial freezers and refrigerators, vending machines, ice makers, etc.), air conditioning equipment (room air conditioners, store-use packaged air conditioners, building-use packaged air conditioners, facility-use packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.), power generation systems (waste heat recovery power generation, etc.), heat transport devices (heat pipes, etc.), and secondary cooling machines. The container in the present invention does not have an ignition source in the internal space of the container in which the composition is filled.

[0031] The container may have a cylindrical body and lids at both ends of the body, forming the container in a sealed state. The body and lid may be separate members, or may be integrally formed. Examples of materials for the container include carbon steel, manganese steel, chromium-molybdenum steel, other low-alloy steels, stainless steel, aluminum alloys, copper, iron, aluminum, nickel, titanium, metallic silicon, silicon steel, tin, magnesium, and zinc. The material may be one of these alone or two or more. In a preferred embodiment of the present invention, the container is made of high-pressure gas container steel as specified in JIS G 3116:2020.

[0032] The tensile strength and yield strength of the container in the present invention are measured values ​​of the constituent material of the body of the container in accordance with JIS Z 2241:2011 (based on ISO 6892-1) cited in JIS G 3116:2020. The test specimen for the tensile test is a No. 5 test specimen of JIS Z 2241:2011. The measurement is performed in air at room temperature (25°C), and the maximum stress during uniform elongation during the tensile test is defined as the tensile strength, and the 0.2% proof stress is defined as the yield strength. The yield ratio is calculated from the ratio of the yield strength to the tensile strength.

[0033] The tensile strength of the container is set to 400 N / mm in consideration of safety when handling the filled container. ２ or more, preferably 440 N / mm ２ More preferably, 490 N / mm ２ More preferably, 540 N / mm ２ From a practical standpoint, the tensile strength of the container is preferably 1100 N / mm ２ or less, more preferably 1000 N / mm ２ More preferably, 900 N / mm ２ The following is the result.

[0034] In consideration of safety during handling of the filled container, the yield ratio of the container is 60% or more, preferably 63% or more, more preferably 66% or more, and even more preferably 67% or more. From a practical standpoint, the yield ratio of the container is preferably 90% or less, more preferably 85% or less.

[0035] The yield strength of the container is preferably 255 N / mm 3 in consideration of safety when handling the filled container. ２ More preferably, 295 N / mm ２ More preferably, 325 N / mm ２ More preferably, 365 N / mm ２ That's all.

[0036] From the viewpoint of transport efficiency of the filled container, the internal volume of the container is preferably 5 L or more, more preferably 7.5 L or more, and even more preferably 10 L or more. From the viewpoint of practical use, the internal volume of the container is preferably 1300 L or less, more preferably 500 L or less, even more preferably 100 L or less, still more preferably 50 L or less, and even more preferably 20 L or less.

[0037] In consideration of the pressure resistance of the filled container, the thicker the container, the more preferable, and preferably 2.5 mm or more, more preferably 2.7 mm or more. Furthermore, in consideration of the transportation efficiency of the filled container and the manufacturing efficiency of the container, the container wall thickness is preferably 23.0 mm or less, more preferably 10.0 mm or less, even more preferably 8.0 mm or less, still more preferably 5.0 mm or less, and even more preferably 3.5 mm or less. The container wall thickness in the present invention is a value measured at the body of the container.

[0038] The internal pressure of the filled container is preferably 6.0 MPa or less, more preferably 3.6 MPa or less, and even more preferably 3.0 MPa or less, from the viewpoint of suppressing the disproportionation reaction of the first component. Furthermore, from the viewpoint of the transport efficiency of the filled container, the internal pressure is preferably 1.0 MPa or more, and more preferably 1.5 MPa or more. The internal pressure of the container in the present invention is a gauge pressure.

[0039] From the viewpoint of suppressing the disproportionation reaction of the first component, the internal temperature of the filled container is preferably 60° C. or lower, more preferably 50° C. or lower, and even more preferably 40° C. or lower. From the viewpoint of ease of handling the filled container, the internal temperature of the filled container is preferably 5° C. or higher, more preferably 10° C. or higher, and even more preferably 15° C. or higher.

[0040] [Storage method] The method for storing a filled container of the present invention is a method for storing a filled container having a composition containing a first component and a second component, and a container filled with the composition, wherein the first component is at least one selected from the group consisting of trifluoroethylene, 1,2-difluoroethylene, and 1,1-difluoroethylene, the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene, difluoromethane, fluoromethane, 1,1-difluoroethane, fluoroethane, 1,1,1,3,3-pentafluorobutane, dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen, the amount of the first component is 62.6 mass% or less based on the total amount of the first component and the second component, and the container has a tensile strength of 400 N / mm ２ and is made of a material having a yield ratio of 60% or more.

[0041] That is, the method for storing a filled container of the present invention is characterized by storing the first and second components in the above-described embodiment of the filled container of the present invention. According to this storage method, the HFO of the first component can be safely stored in a state in which the disproportionation reaction is suppressed.

[0042] The filled container in the storage method is the same as the filled container of the present invention described above, and therefore description thereof will be omitted. Note that storage as used in the present invention is not limited to storage at the location where the filled container is manufactured by filling the container with a composition, but also includes storage at the location where the filled container is used, as well as temporary storage locations (e.g., warehouses) and storage in transportation means (e.g., fixed to a transportation vehicle or transportation ship) before and after transportation to the location of use.

[0043] The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples. Examples 1 to 3 are examples, and Example 4 is a comparative example.

[0044] [Example 1] A high-pressure gas cylinder with an internal volume of 12.5 L and a wall thickness of 2.8 mm (material: SG365 steel, tensile strength 540 N / mm ２ , yield strength 365N / mm ２ A filling container was prepared (filling amount 2.49 kg, container internal pressure 2.0 MPa, internal temperature 30°C) filled with a mixture (composition) of trifluoroethylene (HFO-1123) and 2,3,3,3-tetrafluoropropene (HFO-1234yf) in a mass ratio of 56.1 / 43.9 (yield ratio 68%).

[0045] The filled container was evaluated by the following impact test. An explosive impact was applied to the filled container in accordance with the Acetylene Porous Material Performance Test based on the High-Pressure Gas Safety Act. The maximum internal pressure of the filled container was measured, and the interior of the container after the test was observed with a fiberscope camera. Furthermore, the composition of the contents of the container after the test was analyzed by gas chromatography. Furthermore, the gas inside the container before and after the test was passed through a 7.9% by mass sodium bicarbonate solution, and the fluoride ion concentration was measured by gas chromatography to confirm whether or not there was an increase in the fluoride ion concentration in the gas inside the container after the test.

[0046] The maximum pressure reached by the filled container of Example 1 during the test was 2.0 MPa, and no abnormalities were found inside the container after the test, and no significant changes were found in the composition of the composition. The filled container of Example 1 did not experience any change in internal pressure due to the impact during the test, nor any significant changes in the composition, and no increase in the fluoride ion concentration of the gas inside the container after the test was confirmed, so no disproportionation reaction of trifluoroethylene occurred, and safety against impact was confirmed.

[0047] Example 2 A high-pressure gas container (material: same as in Example 1) with an internal volume of 12.5 L and a wall thickness of 3.4 mm was filled with a mixture (composition) of trifluoroethylene (HFO-1123) and 2,3,3,3-tetrafluoropropene (HFO-1234yf) in a mass ratio of 62.1 / 37.9 (filling amount 2.46 kg, internal container pressure 2.0 MPa, internal temperature 33°C), and an impact test was carried out in the same manner as in Example 1.

[0048] The maximum pressure reached by the filled container of Example 2 during the test was 2.2 MPa, and no abnormalities were found inside the container after the test, and no significant changes were found in the composition of the composition. Although the internal pressure of the filled container of Example 2 increased by 1.1 times (0.2 MPa) due to the impact during the test, there was no significant change in the composition of the composition, and no increase in the fluoride ion concentration of the gas inside the container after the test was confirmed, so that no disproportionation reaction of trifluoroethylene occurred, and safety against impact was confirmed.

[0049] Example 3 A high-pressure gas container (material: same as in Example 1) with an internal volume of 12.5 L and a wall thickness of 3.4 mm was filled with a mixture (composition) of trifluoroethylene (HFO-1123) and difluoromethane (HFC-32) in a mass ratio of 62.6 / 37.4 (filling amount 2.36 kg, internal container pressure 2.6 MPa, internal temperature 35°C), and an impact test was carried out in the same manner as in Example 1.

[0050] The maximum pressure reached by the filled container of Example 3 during the test was 2.6 MPa, and no abnormalities were found inside the container after the test, and no significant changes were found in the composition of the composition. The filled container of Example 2 did not experience any change in internal pressure due to the impact during the test, nor any significant changes in the composition, and no increase in the fluoride ion concentration of the gas inside the container after the test was confirmed, so no disproportionation reaction of trifluoroethylene occurred, and safety against impact was confirmed.

[0051] Example 4 A high-pressure gas container (material: same as in Example 1) with an internal volume of 12.5 L and a wall thickness of 3.4 mm was filled with a mixture (composition) of trifluoroethylene (HFO-1123) and difluoromethane (HFC-32) in a mass ratio of 62.7 / 37.3 (filling amount 2.20 kg, internal container pressure 1.8 MPa, internal temperature 20°C), and an impact test was carried out in the same manner as in Example 1.

[0052] The pressure in the filled container of Example 3 during the test exceeded 25 MPa, the upper limit of the measurable range of the pressure gauge, and the presence of black foreign matter was confirmed inside the container after the test. The fluoride ion concentration of the gas inside the container after the test had increased by 3.5 mg / L. The filled container of Example 3 experienced a significant increase in internal pressure due to the impact during the test, and judging from the presence of foreign matter inside the container and the increase in fluoride ion concentration after the test, it is presumed that a disproportionation reaction of trifluoroethylene had occurred.

[0053] In addition, compounds that are known to be mixed with trifluoroethylene (HFO-1123) to form mixtures that are less likely to undergo disproportionation reactions upon ignition than mixtures with difluoromethane (HFC-32) include fluoromethane (HFC-41), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen (see Journal of Loss Prevention in the Process Industries, 2018, Vol. 54, pp. 179-182). Therefore, it can be said that these compounds, other than 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (HFC-32), can also be used as second components that are effective in suppressing the disproportionation reactions of the HFOs in the first component.

Claims

1. A filled container having a composition containing a first component and a second component, and a container filled with the composition, wherein the first component is at least one selected from the group consisting of trifluoroethylene, 1,2-difluoroethylene, and 1,1-difluoroethylene, and the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene, difluoromethane, fluoromethane, 1,1-difluoroethane, fluoroethane, 1,1,1,3,3-pentafluorobutane, dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen, the amount of the first component is 62.6 mass% or less based on the total amount of the first component and the second component, and the container has a tensile strength of 400 N / mm ２ and a yield ratio of 60% or more.

2. A filled container as described in claim 1, wherein the total amount of the first component and the second component is 90.0 mass% or more of the total amount of the composition.

3. A filled container as described in claim 1 or 2, wherein the first component is present in an amount of 40.0 mass% or more of the total amount of the composition.

4. A filled container according to claim 1 or 2, wherein the first component is trifluoroethylene.

5. The filled container according to claim 1 or 2, wherein the second component is at least one member selected from the group consisting of 2,3,3,3-tetrafluoropropene and difluoromethane.

6. The yield strength of the container is 255 N / mm ２ The filled container according to claim 1 or 2.

7. A filled container according to claim 1 or 2, wherein the internal volume of the container is 5 L or more.

8. A filled container as claimed in claim 1 or 2, wherein the wall thickness of the container is 2.5 mm or more.

9. A filled container according to claim 1 or 2, wherein the internal pressure of the filled container is 6.0 MPa or less.

10. A filled container as described in claim 1 or 2, wherein the internal temperature of the filled container is 60°C or less.

11. A method for storing a filled container having a composition containing a first component and a second component, and a container filled with the composition, wherein the first component is at least one selected from the group consisting of trifluoroethylene, 1,2-difluoroethylene, and 1,1-difluoroethylene, and the second component is at least one selected from the group consisting of 2,3,3,3-tetrafluoropropene, difluoromethane, fluoromethane, 1,1-difluoroethane, fluoroethane, 1,1,1,3,3-pentafluorobutane, dimethyl ether, carbon dioxide, propane, butane, argon, helium, and nitrogen, the amount of the first component is 62.6 mass% or less based on the total amount of the first component and the second component, and the container has a tensile strength of 400 N / mm ２ A method for storing a filled container made of a material having the above properties and a yield ratio of 60% or more.