Azeotrope-like composition, filling container, transfer-filling method, and method of use

Abstract

An azeotrope-like composition containing 3,3,3-trifluoro-1-propyne and at least one fluoroolefin selected from the group consisting of trifluoroethylene, 1,1-difluoroethylene, and trans-1,2-difluoroethylene.

Description

Azeotrope-like composition, filled container, transfer filling method, and use method

[0001] The present disclosure relates to an azeotrope-like composition, a filled container, a transfer filling method, and a use method.

[0002] In recent years, as working media for thermal cycles that have low impact on the ozone layer and low impact on global warming, fluoroolefins having a carbon-carbon double bond that are easily decomposed by OH radicals in the atmosphere have been studied (for example, refer to Patent Document 1).

[0003] International Publication No. 2012 / 157765

[0004] An aspect of the present disclosure is to provide a novel azeotrope-like composition containing a fluoroolefin, a filled container using the same, a transfer filling method, and a use method.

[0005] This disclosure includes the following embodiments: <1> An azeotropic composition comprising at least one fluoroolefin selected from the group consisting of trifluoroethylene, 1,1-difluoroethylene, and trans-1,2-difluoroethylene, and 3,3,3-trifluoro-1-propyne. <2> The azeotropic composition according to <1>, wherein trifluoroethylene is present in an amount of 99.00 mol% or more and less than 100 mol% relative to the total content of trifluoroethylene and 3,3,3-trifluoro-1-propyne. <3> The azeotropic composition according to <2>, further comprising 1,1,1-trifluoroethane, wherein the content of 1,1,1-trifluoroethane is less than the content of 3,3,3-trifluoro-1-propyne. <4> The azeotropic composition according to <1>, wherein 1,1-difluoroethylene is present in an amount of 99.00 mol% or more and less than 100 mol% relative to the total content of 1,1-difluoroethylene and 3,3,3-trifluoro-1-propyne. <5> The azeotropic composition according to <4>, further comprising at least one selected from the group consisting of 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and carbon dioxide, wherein the total content of 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and carbon dioxide is less than the content of 3,3,3-trifluoro-1-propyne. <6> The azeotropic composition according to <1>, comprising 99.00 mol% or more and less than 100 mol% of trans-1,2-difluoroethylene with respect to the total content of trans-1,2-difluoroethylene and 3,3,3-trifluoro-1-propyne. <7> The azeotropic composition according to <6>, further comprising at least one selected from the group consisting of 1,1,1-trifluoroethane and difluoromethane, wherein the total content of 1,1,1-trifluoroethane and difluoromethane is less than the content of 3,3,3-trifluoro-1-propyne. <8> The azeotropic composition according to any one of <1> to <7>, wherein the total content of the fluoroolefin and 3,3,3-trifluoro-1-propyne is 99.00 mol% or more of the total amount of the azeotropic composition. <9> A transfer method for transferring the azeotropic composition according to any one of <1> to <8> from one container to another.<10> The transfer and filling method according to <9>, wherein the composition in the container before transfer and filling is in a state of coexistence of gas and liquid phases, and the size of the container before transfer and filling is larger than the size of the container after transfer and filling. <11> A filling container having an azeotropic composition according to any one of <1> to <8> and a storage container filled with the azeotropic composition. <12> A method of using an azeotropic composition, wherein a portion of the azeotropic composition filled in the filling container according to <11> is used.

[0006] This disclosure provides a novel azeotropic composition containing a fluoroolefin, a filling container using the same, a transfer filling method, and a method of use.

[0007] In this disclosure, numerical ranges indicated using "~" mean a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Also, in numerical ranges described in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples. In this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In this disclosure, the amount of each component means the total amount of multiple substances if there are multiple substances corresponding to each component, unless otherwise specified.

[0008] <Azeotropic Composition> The azeotropic composition of the present disclosure is trifluoroethylene (HFO-1123, CHF=CF ２ ), 1,1-difluoroethylene (HFO-1132a, CF ２ =CH ２ At least one fluoroolefin selected from the group consisting of (HFO-1132(E), CHF=CHF) and 3,3,3-trifluoro-1-propyne (CH≡CCF) ３ ) and, including.

[0009] In this disclosure, HFO-1123, HFO-1132a, and HFO-1132(E) are also referred to as "specific fluoroolefins."

[0010] In this disclosure, an azeotropic composition refers to a composition in which the concentration difference of a specific fluoroolefin between the gas phase and the liquid phase is within 5 mol% at a gas-liquid equilibrium state at 25°C. The gas-liquid equilibrium data was created using a process simulator (CHEMCAD). More specifically, the supply flow rate, supply composition, supply pressure, and supply temperature were set, the initial state was the liquid phase, and the equilibrium temperature and equilibrium composition were converged using flash (simple distillation) calculations. Thus, because the gas phase and liquid phase compositions are close, azeotropic compositions have advantages such as being less prone to compositional fluctuations even when stored and transported in storage containers, and less prone to compositional fluctuations when transferring from one container to another. Furthermore, azeotropic compositions are less prone to compositional fluctuations even when using a portion of the azeotropic composition in a storage container. Therefore, for example, when an azeotropic composition is used as a raw material for the manufacture of a chemical substance, it is possible to supply a composition with a constant composition to the synthesis apparatus, thereby maintaining the quality of the resulting synthesized product. Furthermore, in azeotropic compositions, analyzing the composition of the components in either the gas phase or the liquid phase allows for the determination of the composition of the components in the other phase, thus simplifying the analysis process.

[0011] The azeotropic composition of this disclosure preferably has a concentration difference of 3 mol% or less between the gas phase and the liquid phase of the specific fluoroolefin at a gas-liquid equilibrium state at 25°C, and more preferably 1 mol% or less.

[0012] The preferred composition of the azeotropic composition is described below. The content of each component of the azeotropic composition shown below is the content in the total amount including both the gas phase and the liquid phase when both gas and liquid phases are present. When the azeotropic composition of this disclosure contains HFO-1123 and 3,3,3-trifluoro-1-propyne, the content of HFO-1123 is preferably 99.00 mol% or more, more preferably 99.50 mol% or more, and even more preferably 99.90 mol% or more, relative to the total content of HFO-1123 and 3,3,3-trifluoro-1-propyne. Furthermore, the content of HFO-1123 is preferably less than 100 mol%, more preferably 99.99 mol% or less, and even more preferably 99.95 mol% or less, relative to the total content of HFO-1123 and 3,3,3-trifluoro-1-propyne. When the azeotropic composition of the present disclosure contains HFO-1123 and 3,3,3-trifluoro-1-propyne, the content of HFO-1123 is preferably 99.00 mol% or more and less than 100 mol%, more preferably 99.50 to 99.99 mol%, and even more preferably 99.90 to 99.95 mol%, relative to the total content of HFO-1123 and 3,3,3-trifluoro-1-propyne.

[0013] Furthermore, since the boiling point of HFO-1123 is -51°C and the boiling point of 3,3,3-trifluoro-1-propyne is -47 to -48°C, even if a compound with a boiling point in the range between these two, i.e., -51 to -47°C, is added in a smaller amount than 3,3,3-trifluoro-1-propyne, it is highly likely to form an azeotrope-like composition. Such a compound is defined as additional compound A-1. The content of additional compound A-1 is preferably less than the content of 3,3,3-trifluoro-1-propyne, and the boiling point of additional compound A-1 is preferably between the boiling point of HFO-1123 and the boiling point of 3,3,3-trifluoro-1-propyne. An example of additional compound A-1 is HFC-143a (1,1,1-trifluoroethane, boiling point: -48°C).

[0014] If the azeotropic composition further contains 1,1,1-trifluoroethane in addition to HFO-1123 and 3,3,3-trifluoro-1-propyne, it is preferable that the content of 1,1,1-trifluoroethane is less than the content of 3,3,3-trifluoro-1-propyne.

[0015] When the azeotropic composition of the present disclosure contains HFO-1132a and 3,3,3-trifluoro-1-propyne, the content of HFO-1132a is preferably 99.00 mol% or more, more preferably 99.50 mol% or more, and even more preferably 99.90 mol% or more, relative to the total content of HFO-1132a and 3,3,3-trifluoro-1-propyne. Furthermore, the content of HFO-1132a is preferably less than 100 mol%, more preferably 99.99 mol% or less, and even more preferably 99.95 mol% or less, relative to the total content of HFO-1132a and 3,3,3-trifluoro-1-propyne. When the azeotropic composition of the present disclosure contains HFO-1132a and 3,3,3-trifluoro-1-propyne, the content of HFO-1132a is preferably 99.00 mol% or more and less than 100 mol%, more preferably 99.50 to 99.99 mol%, and even more preferably 99.90 to 99.95 mol%, relative to the total content of HFO-1132a and 3,3,3-trifluoro-1-propyne.

[0016] Furthermore, since the boiling point of HFO-1132a is -83°C and the boiling point of 3,3,3-trifluoro-1-propyne is -47 to -48°C, even if a compound with a boiling point in the range between these two, i.e., -83 to -47°C, is added in a smaller amount than 3,3,3-trifluoro-1-propyne, it is highly likely to form an azeotrope-like composition. Such a compound is defined as additional compound A-2. The content of additional compound A-2 is preferably less than the content of 3,3,3-trifluoro-1-propyne, and the boiling point of additional compound A-2 is preferably between the boiling point of HFO-1132a and the boiling point of 3,3,3-trifluoro-1-propyne. Examples of additional compound A-2 include, for example, HFC-143a (1,1,1-trifluoroethane, boiling point: -48°C), HFC-32 (difluoromethane, boiling point: -52°C), HFC-23 (trifluoromethane, boiling point: -82°C), and CO２ (Carbon dioxide, boiling point: -78°C) is one example.

[0017] If the azeotropic composition further contains, in addition to HFO-1132a and 3,3,3-trifluoro-1-propyne, at least one selected from the group consisting of 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and carbon dioxide, it is preferable that the total content of 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and carbon dioxide is less than the content of 3,3,3-trifluoro-1-propyne.

[0018] If the azeotropic composition further contains, in addition to HFO-1132a and 3,3,3-trifluoro-1-propyne, at least one selected from the group consisting of 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and carbon dioxide, it is preferable that the content of each of 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and carbon dioxide is less than the content of 3,3,3-trifluoro-1-propyne.

[0019] If the azeotropic composition further contains 1,1,1-trifluoroethane and trifluoromethane in addition to HFO-1132a and 3,3,3-trifluoro-1-propyne, it is preferable that the total content of 1,1,1-trifluoroethane and trifluoromethane is less than the content of 3,3,3-trifluoro-1-propyne.

[0020] If the azeotropic composition further contains 1,1,1-trifluoroethane and carbon dioxide in addition to HFO-1132a and 3,3,3-trifluoro-1-propyne, it is preferable that the total content of 1,1,1-trifluoroethane and carbon dioxide is less than the content of 3,3,3-trifluoro-1-propyne.

[0021] If the azeotropic composition further contains at least one selected from the group consisting of trifluoromethane and carbon dioxide, in addition to HFO-1132a and 3,3,3-trifluoro-1-propyne, it is preferable that the total content of trifluoromethane and carbon dioxide is less than the content of 3,3,3-trifluoro-1-propyne.

[0022] If the azeotropic composition further contains, in addition to HFO-1132a and 3,3,3-trifluoro-1-propyne, at least one selected from the group consisting of 1,1,1-trifluoroethane, trifluoromethane, and carbon dioxide, it is preferable that the total content of 1,1,1-trifluoroethane, trifluoromethane, and carbon dioxide is less than the content of 3,3,3-trifluoro-1-propyne.

[0023] When the azeotropic composition of the present disclosure contains HFO-1132(E) and 3,3,3-trifluoro-1-propyne, the content of HFO-1132(E) relative to the total content of HFO-1132(E) and 3,3,3-trifluoro-1-propyne is preferably 99.00 mol% or more, more preferably 99.50 mol% or more, and even more preferably 99.90 mol% or more. Furthermore, the content of HFO-1132(E) relative to the total content of HFO-1132(E) and 3,3,3-trifluoro-1-propyne is preferably less than 100 mol%, more preferably 99.99 mol% or less, and even more preferably 99.95 mol% or less. When the azeotropic composition of the present disclosure contains HFO-1132(E) and 3,3,3-trifluoro-1-propyne, the content of HFO-1132(E) is preferably 99.00 mol% or more and less than 100 mol%, more preferably 99.50 to 99.99 mol%, and even more preferably 99.90 to 99.95 mol%, relative to the total content of HFO-1132(E) and 3,3,3-trifluoro-1-propyne.

[0024] Furthermore, since the boiling point of HFO-1132(E) is -53.1°C and the boiling point of 3,3,3-trifluoro-1-propyne is -47 to -48°C, even if a compound with a boiling point in the range between these two, i.e., -53.1 to -47°C, is added in a smaller amount than 3,3,3-trifluoro-1-propyne, it is highly likely to form an azeotrope-like composition. Such a compound is defined as additional compound A-3. The content of additional compound A-3 is preferably less than the content of 3,3,3-trifluoro-1-propyne, and the boiling point of additional compound A-3 is preferably between the boiling point of HFO-1132(E) and the boiling point of 3,3,3-trifluoro-1-propyne. Examples of additional compound A-3 include, for example, HFC-143a (1,1,1-trifluoroethane, boiling point: -48°C) and HFC-32 (difluoromethane, boiling point: -52°C).

[0025] If the azeotropic composition further includes, in addition to HFO-1132(E) and 3,3,3-trifluoro-1-propyne, at least one selected from the group consisting of 1,1,1-trifluoroethane and difluoromethane, it is preferable that the total content of 1,1,1-trifluoroethane and difluoromethane is less than the content of 3,3,3-trifluoro-1-propyne.

[0026] If the azeotropic composition further includes, in addition to HFO-1132(E) and 3,3,3-trifluoro-1-propyne, at least one selected from the group consisting of 1,1,1-trifluoroethane and difluoromethane, it is preferable that the respective contents of 1,1,1-trifluoroethane and difluoromethane are less than the content of 3,3,3-trifluoro-1-propyne.

[0027] Hereafter, additional compounds A-1 to A-3 will be collectively referred to as "additional compound A."

[0028] The azeotropic composition of this disclosure may contain at least one specific fluoroolefin, and may contain two or more. The total content of the specific fluoroolefin and 3,3,3-trifluoro-1-propyne is preferably 99.00 mol% or more, more preferably 99.50 mol% or more, and even more preferably 99.90 mol% or more, relative to the total amount of the azeotropic composition. Furthermore, the total content of the specific fluoroolefin and 3,3,3-trifluoro-1-propyne relative to the total amount of the azeotropic composition is preferably less than 100 mol%, more preferably 99.99 mol% or less, and even more preferably 99.95 mol% or less. The total content of the specific fluoroolefin and 3,3,3-trifluoro-1-propyne relative to the total amount of the azeotropic composition is preferably 99.00 mol% or more and less than 100 mol%, more preferably 99.50 to 99.99 mol%, and even more preferably 99.90 to 99.95 mol%. The total content of the specific fluoroolefin, 3,3,3-trifluoro-1-propyne, and additional compound A is preferably 99.00 mol% or more and less than 100 mol%, more preferably 99.50 to 99.99 mol%, and even more preferably 99.90 to 99.95 mol%, relative to the total amount of the azeotropic composition.

[0029] The azeotropic composition of this disclosure may further contain additional compound B in addition to a specific fluoroolefin, 3,3,3-trifluoro-1-propyne, and additional compound A. Additional compound B is not particularly limited and can be broadly selected within a range that does not hinder the formation of an azeotropic composition. Additional compound B may be one type or two or more types. Examples of additional compound B include fluorocarbons. Among these, fluoroethanes are preferred as additional compounds, and 1,1,1,2-tetrafluoroethane (HFC-134a) is more preferred.

[0030] If the azeotropic composition of this disclosure contains additional compound B, the content of additional compound B in the azeotropic composition is preferably greater than 0 mol% and 10 mol% or less, more preferably greater than 0 mol% and 5 mol% or less, and even more preferably greater than 0 mol% and 1 mol% or less.

[0031] The azeotropic composition of the present disclosure may contain water. If the azeotropic composition of the present disclosure contains water, the water content in the azeotropic composition is preferably 1 mol% or less, more preferably 1000 mol ppm or less, even more preferably 500 mol ppm or less, particularly preferably 100 mol ppm or less, extremely preferably 50 mol ppm or less, and significantly preferably 10 mol ppm or less.

[0032] <Filling container> The filling container of the present disclosure comprises the azeotropic composition of the present disclosure and a storage container filled with the azeotropic composition.

[0033] The azeotropic composition filled into the storage container is the same as the azeotropic composition described above. The composition of the azeotropic composition is less likely to change even when stored and transported in the filled container.

[0034] A general-purpose storage container can be used. For example, the material of the part of the storage container that comes into contact with the azeotropic composition of this disclosure is preferably resin or metal. Examples of such containers include containers in which the entire container is made of resin or metal material, and containers having a multilayer structure in which the innermost layer is made of resin or metal material. Examples of storage containers in which the material of the part that comes into contact with the azeotropic composition of this disclosure is metal include metal containers and metal-plated containers.

[0035] The shape and size of storage containers can be designed to suit the purpose. Examples include fixed storage containers such as storage tanks, transportable containers, and transport containers. Examples of transportable containers include 1L glass bottles, 20L pails, 200L drums, ton containers, aerosol cans, and high-pressure gas containers (containers that cannot be refilled, welded containers, seamless containers, etc.). Examples of transport containers include tank trucks, ISO containers, and self-loaders.

[0036] The method of sealing the storage container is not particularly limited; for example, it may be sealed with a screw-on lid or a valve. Elastic materials such as cushioning material or sealing material may be used to enhance airtightness.

[0037] <Transfer and Filling Method> The transfer and filling method of the present disclosure is a method of transferring and filling the azeotrope-like composition of the present disclosure from one container to another. The azeotrope-like composition used in the transfer and filling method is the same as the azeotrope-like composition described above. The azeotrope-like composition hardly changes in composition even when transferred and filled from one container to another. Examples of the transfer and filling method include a method using a tube or the like. The material of the tube may be any material that does not affect the azeotrope-like composition, and examples thereof include fluororesins such as PFA (a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene), stainless steel, and the like.

[0038] Examples of the container include the aforementioned storage containers and the like. In the transfer and filling method of the present disclosure, the composition in the container before transfer and filling may be in a coexisting state of a gas phase and a liquid phase, and the size of the container before transfer and filling may be larger than the size of the container after transfer and filling. That is, the composition may be subdivided from a large container into small containers. If the azeotropic property is low, the composition tends to vary for each subdivided container, but since the azeotrope-like composition is used in the transfer and filling method of the present disclosure, the composition variation for each subdivided container can be suppressed.

[0039] <Usage Method> The usage method of the azeotrope-like composition of the present disclosure is not particularly limited. Since the composition of the azeotrope-like composition hardly changes, a usage mode in which a part of the azeotrope-like composition filled in the aforementioned filling container is used may be adopted, or the entire azeotrope-like composition filled in the filling container may be used all at once. When a part of the azeotrope-like composition filled in the filling container is used, it may be used repeatedly in multiple stages or may be used continuously.

[0040] Hereinafter, the present disclosure will be described more specifically with reference to Examples, but the present disclosure is not limited to the following Examples as long as it does not exceed the gist thereof. Examples 1 to 9 are working examples.

[0041] Tables 1 to 3 show vapor-liquid equilibrium data at 25°C for mixtures of a specific fluoroolefin and 3,3,3-trifluoro-1-propyne. The "difference" in each table is the difference in mol% of the specific fluoroolefin between the gas phase and the liquid phase.

[0042]

[0043]

[0044]

[0045] The initial pressure specifications are as shown below. All molar flow rates were set to 100 mol / h. Example 1: 1.6422 MPaG Example 2: 1.64 MPaG Example 3: 1.6373 MPaG Example 4: 1.4036 MPaG Example 5: 1.4025 MPaG Example 6: 1.401 MPaG Example 7: 3.9438 MPaG Example 8: 3.927 MPaG Example 9: 3.9063 MPaG

[0046] As shown in Tables 1 to 3, in the vapor-liquid equilibrium state at 25°C, the concentration difference of the specific fluoroolefin between the vapor phase and the liquid phase is 5 mol% or less, which reveals that the composition is an azeotrope-like composition. Although Examples 1 to 9 are two-component compositions, the fact that they are azeotrope-like compositions shows that a composition containing three or more components based on these examples can also be an azeotrope-like composition.

[0047] The entire disclosure of Japanese Patent Application No. 2025-067561 is incorporated into the present disclosure by reference. All literatures, patent applications, and technical standards in the present disclosure are incorporated by reference into the present disclosure to the same extent as if each individual literature, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. An azeotropic composition comprising at least one fluoroolefin selected from the group consisting of trifluoroethylene, 1,1-difluoroethylene, and trans-1,2-difluoroethylene, and 3,3,3-trifluoro-1-propyne.

2. The azeotropic composition according to claim 1, wherein trifluoroethylene is present in an amount of 99.00 mol% or more and less than 100 mol% relative to the total content of trifluoroethylene and 3,3,3-trifluoro-1-propyne.

3. The azeotrope-like composition according to claim 2, further comprising 1,1,1-trifluoroethane, wherein the content of 1,1,1-trifluoroethane is less than the content of 3,3,3-trifluoro-1-propyne.

4. The azeotropic composition according to claim 1, wherein 1,1-difluoroethylene is contained in an amount of 99.00 mol% or more and less than 100 mol% relative to the total content of 1,1-difluoroethylene and 3,3,3-trifluoro-1-propyne.

5. The azeotrope-like composition according to claim 4, further comprising at least one selected from the group consisting of 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and carbon dioxide, wherein the total content of 1,1,1-trifluoroethane, difluoromethane, trifluoromethane, and carbon dioxide is less than the content of 3,3,3-trifluoro-1-propyne.

6. The azeotropic composition according to claim 1, wherein the trans-1,2-difluoroethylene is present in an amount of 99.00 mol% or more and less than 100 mol% relative to the total content of trans-1,2-difluoroethylene and 3,3,3-trifluoro-1-propyne.

7. The azeotrope-like composition according to claim 6, further comprising at least one selected from the group consisting of 1,1,1-trifluoroethane and difluoromethane, wherein the total content of 1,1,1-trifluoroethane and difluoromethane is less than the content of 3,3,3-trifluoro-1-propyne.

8. The azeotropic composition according to claim 1, wherein the total content of the fluoroolefin and 3,3,3-trifluoro-1-propyne is 99.00 mol% or more of the total amount of the azeotropic composition.

9. A transfer method for transferring an azeotrope-like composition according to any one of claims 1 to 8 from one container to another.

10. The transfer and filling method according to claim 9, wherein the composition in the container before transfer and filling is in a state of coexistence of gas and liquid phases, and the size of the container before transfer and filling is larger than the size of the container after transfer and filling.

11. A filling container comprising an azeotropic composition according to any one of claims 1 to 8, and a storage container filled with the azeotropic composition.

12. A method for using an azeotropic composition, comprising using a portion of the azeotropic composition filled in the filling container described in claim 11.

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