JP2022122449A - Method for supplying haloolefin-containing composition - Google Patents

Abstract

To provide a supply method capable of suppressing composition fluctuation upon supplying a composition containing haloolefin and carbon dioxide from a first accommodation facility to a second accommodation facility.SOLUTION: A method for supplying a haloolefin-containing composition containing haloolefin and carbon dioxide from a first accommodation facility to a second accommodation facility, comprises maintaining the haloolefin-containing composition in the first accommodation facility in a single-phase state from the start of supply to the end of supply.SELECTED DRAWING: None

Description

The present invention relates to a method of delivering a haloolefin-containing composition.

Hydrofluoroolefin (HFO) and hydrochlorofluoroolefin (HCFO) are used as working fluids for thermal cycles, foaming agents, diluent solvents, cleaning agents, propellants, extinguishing agents, gaseous dielectrics, etching gases, etc. ) and other haloolefins with low global warming potential are expected.

Mixing carbon dioxide with haloolefin facilitates control such as pressure adjustment and density adjustment, and is expected to have effects such as reduced combustibility, improved diffusibility, improved solubility, and improved environmental friendliness. However, many of these mixtures are non-azeotropic compositions, and the greater the difference in boiling points between haloolefins and carbon dioxide, the more likely composition fluctuations will occur during transfer from a storage container to another container.

Patent Document 1 relates to a non-azeotropic composition containing trifluoroethylene and tetrafluoropropene. A method is proposed to predict and set the initial composition in the supply container so that the target composition is obtained in the supply destination container.

WO2017/126447

The method described in Patent Literature 1 is not a method of suppressing the compositional variation itself due to transfer filling.
The present invention provides a method of supplying a composition containing haloolefins and carbon dioxide that can suppress composition fluctuations when supplying a composition containing haloolefins and carbon dioxide from a first accommodation facility to a second accommodation facility.

The present invention has the following aspects.
[1] A method of supplying a haloolefin-containing composition containing a haloolefin and carbon dioxide from a first accommodation facility to a second accommodation facility, wherein a A method of supplying a haloolefin-containing composition in which the haloolefin-containing composition in the facility is maintained in a single phase.
[2] The supply method of [1], wherein the one-phase state is a superheated steam state, a supercritical state, or a supercooled state.
[3] The supply of [1] or [2], which has a step of heating, pressurizing, or cooling the haloolefin-containing composition in the first accommodation facility between the start of supply and the end of supply. Method.
[4] Any one of [1] to [3], wherein one state selected from a superheated steam state, a supercritical state, and a supercooled state is changed from the start of the supply to the end of the supply. supply method.
[5] Calculated from the volume of the first accommodation facility and the mass w of the haloolefin-containing composition in the first accommodation facility in the pressure-specific enthalpy diagram of the haloolefin-containing composition When the temperature at the intersection of the isodensity line and the saturation line of the density d is t, the mass w is monitored from the start of supply to the end of supply, and the first accommodation is performed according to the change over time of the density d. The supply method according to any one of [1] to [4], wherein the temperature inside the first accommodation facility is controlled so that the temperature inside the facility is always equal to or higher than the t.
[6] In the pressure-specific enthalpy diagram of the haloolefin-containing composition, when the temperature at the point of contact between the saturation line and the isotherm is T, during the period from the start of supply to the end of supply, The supply method according to any one of [1] to [4], wherein the temperature is maintained at T or higher.
[7] The second housing equipment is a refrigeration and air conditioning equipment, heat transport equipment, electric power equipment, molten metal equipment, cleaning equipment, semiconductor equipment, sterilization equipment, fire extinguishing equipment, aerosol container, or cylinder container, [ 1] to any one of the supply methods of [6].

According to the supply method of the present invention, it is possible to suppress composition fluctuation when supplying a composition containing haloolefin and carbon dioxide from the first accommodation facility to the second accommodation facility.

1 is a graph showing a carbon dioxide pressure-specific enthalpy diagram as an example of a typical pressure-specific enthalpy diagram. 1 is a graph showing an example of a pressure-specific enthalpy diagram of a haloolefin-containing composition.

The following term definitions apply throughout the specification and claims.
Haloolefin is a general term for compounds in which some or all of the hydrogen atoms of unsaturated hydrocarbon compounds are replaced with one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms.
An abbreviation or another name of the compound may be written in parentheses after the name of the compound. Abbreviations or aliases may be used instead of compound names.
Unsaturated hydrocarbon compounds have Z-isomer (cis-isomer) and E-isomer (trans-isomer), which are geometric isomers, depending on the position of the substituent bonded to the carbon having a double bond. When a compound name or an abbreviation of a compound is used without particular mention for a compound in which Z-isomer and E-isomer exist, it means that it is Z-isomer, E-isomer, or a mixture of Z-isomer and E-isomer at any ratio. do. When (Z) or (E) is attached to the end of a compound name or compound abbreviation, it indicates that the compound is Z-isomer or E-isomer.
A numerical range represented by "-" means a numerical range having lower and upper limit values before and after "-".
The one-phase state means the state outside the saturation line in the pressure-specific enthalpy diagram (hereinafter also referred to as ph diagram) illustrated in FIG. Inside the saturation line is a two-phase state where liquid and gas exist. The one-phase state is preferably a fluid, particularly a supercooled, supercritical, or superheated vapor state.

The supply method of this embodiment is a method of supplying the haloolefin-containing composition from the first accommodation facility to the second accommodation facility.
<Haloolefin-containing composition>
A haloolefin-containing composition is a mixture comprising a haloolefin and carbon dioxide. Haloolefins may be of one type or two or more types.
The number of unsaturated bonds in the haloolefin is preferably 1-2. The haloolefin preferably has 2 to 5 carbon atoms.

Examples of haloolefins include hydrofluoroolefins (HFO), hydrochlorofluoroolefins (HCFO), chlorofluoroolefins (CFO), and hydrochloroolefins (HCO).

Specific examples of hydrofluoroolefins (HFO) include 1,1-difluoroethylene (HFO-1132a), 1,2-difluoroethylene (HFO-1132), 1,1,2-trifluoroethylene (HFO-1123) , 1-fluoropropene (HFO-1261ze), 2-fluoropropene (HFO-1261yf), 3-fluoropropene (HFO-1261zf), 1,2-difluoropropane (HFO-1252ye), 1,3,3,3 - tetrafluoropropene (HFO-1234ze), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2,3, 3,3-pentafluoro-1-propene (HFO-1225ye), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,3,3,3-pentafluoropropene (HFO -1225zc), 1,1,2-trifluoropropene (HFO-1243yc), 3,3,3-trifluoropropene (HFO-1243zf), 3,3-difluoropropene (HFO-1252zf), 1,1, 1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336mcyf), 1,3,3, 4,4,4-hexafluoro-1-butene (HFO-1336ze), tetrafluorobutene (HFO-1354), 1,1,1,2,4,4,5,5,5-nonafluoropentene (HFO -1429myz), 1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-1438mzz), 1,3,4,4,4-pentafluoro-3-trifluoro methyl-1-butene (HFO-1438ezy), (C ₂ F ₅ )(CF ₃ )C=CH ₂ , (CF ₃ ) ₂ CFCH=CF ₂ , (CF ₃ ) ₂ CFCF=CHF.

Specific examples of hydrochlorofluoroolefins (HCFO) include 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 1,2-dichloro-3,3,3-trifluoropropene ( HCFO-1233xd), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3 ,3-trifluoropropene (HCFO-1233zd), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), dichloro-3,3-difluoropropene (HCFO-1232xf), 1,2,3 -trichloro-3,3-difluoropropene (HCFO-1222xd), 2,3,3-trichloro-3-fluoropropene (HCFO-1231xf), 2,3-2,3-dichloro-3,3-difluoropropene ( HCFO-1232xf), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 2-chloro-1,1,3,3-tetrafluoropropene (HCFO-1224xc), 2-chloro -1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1-chloro-2,3,3,4,4,5,5-heptafluoropentene (HCFO-1437dycc), 1,1-dichloro -2-fluoroethylene (HCFO-1121a), 1,2-dichloro-1-fluoroethylene (HCFO-1121), 1-chloro-1-fluoroethylene (HCFO-1131a), 1-chloro-2-fluoroethylene ( HCFO-1131), 1-chloro-2,2-difluoroethylene (HCFO-1122), and 1,1,2-trifluoro-2-chloroethylene (HCFO-1113).

Specific examples of hydrochloroolefins (HCO) include chloroethylene and 1,2-dichloroethylene.

Specific examples of chlorofluoroolefins (CFO) include 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1,3-dichloro-1,2,3,3-tetra Fluoropropene (CFO-1214yb), 1,2-dichloro-1,2,difluoroethylene (CFO-1112), 1,1,2-trichloro-2-fluoroethylene, 2-chloro-1,1,3,3 , 3-pentafluoro-1-propene (CFO-1215xc).

The haloolefin-containing composition may contain one or more compounds other than the haloolefin and carbon dioxide.
Other compounds include hydrofluorocarbons (HFC), hydrochlorocarbons (HCC), hydrochlorofluorocarbons (HCFC), chlorofluorocarbons (CFC), chlorocarbons, fluorocarbons (FC), hydrocarbons (HC), hydrofluoroethers ( HFE), halogenated methane containing a bromine atom or an iodine atom, fluoronitriles, fluorosilanes, ketones, alkynes, alcohols, organic acids, and water.
Furthermore, additives such as stabilizers, fluorescent agents, perfumes, etc. may be included as necessary.

Specific examples of hydrofluorocarbons (HFCs) include 1,1,2,3-tetrafluorobutane (HFC-374pee), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1 , 1,2,2-pentafluoropropane (HFC-245cb), 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,2,3-pentafluoropropane (HFC -245eb), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1, 3-tetrafluoropropane (HFC-254fb), 1,1,1-trifluoropropane (HFC-263fb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1 , 1,3,3,3-hexafluoropropane (HFC-236fa), 2-fluoropropane (HFC-281ea), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 1 , 1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane ( HFC-152a), difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1 ,1-trifluoroethane (HFC-143a), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), fluoroethane (HFC-161), 1,1,1,2,2,3 , 4,5,5,5-decafluoropentane (HFC-43-10mee), trifluoromethane (HFC-23), and fluoromethane (HFC-41).

Specific examples of hydrochlorocarbons (HCC) include chloroform, 1,1,1,2,3-pentachloropropane (HCC-240db), and 2-chloropropane.

Specific examples of hydrochlorofluorocarbons (HCFC) include chlorodifluoromethane (HCFC-22), chlorofluoromethane (HCFC-31), trichlorodifluoroethane (HCFC-122), 1,1,2-trichloro-1,2- Difluoroethane (HCFC-122a), 1,1,1-trichloro-2,2-difluoroethane (HCFC-122b), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro -1,1,1,2-tetrafluoroethane (HCFC-124), 1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a), 2-chloro-1,1,1-tri Fluoroethane (HCFC-133a), 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1-difluoro-2-chloroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC -142a), 1-chloro-1,1-difluoroethane (HCFC-142b), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca), 1,3-dichloro- 1,1,2,2,3-pentafluoropropane (HCFC-225cb), 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab), 2,3-dichloro-1,1, 1-trifluoropropane (HCFC-243db) and 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

Specific examples of chlorofluorocarbons (CFC) include trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trichlorotrifluoroethane (CFC-113), 1, 2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), chloropentafluoroethane (CFC -115), dichlorohexafluoropropane (CFC-216), 2,2,3,3-tetrachlorohexafluorobutane (CFC-316), and dichlorooctafluorobutane (CFC-318).

Specific examples of chlorocarbons include dichloromethane (methylene chloride) and trichloroethane.

Specific examples of fluorocarbons (FC) include 1,1,1,2,2,2-hexafluoroethane (FC-116), octafluoropropane (FC-218) 1,1,1,2,2,3 , 3-heptafluoropropane (FC-227ca).

Specific examples of hydrocarbons (HC) include methane, ethane, ethene, propane, propylene, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, isohexane, and heptane.

Specific examples of hydrofluoroethers (HFE) include CHF ₂ —O—CHF ₂ , CHF ₂ —O—CH ₂ F, CH ₂ FO—CH ₂ F, CH ₂ FO—CH ₃ , cyclo- CF2- _CH2 -CF2-O, cyclo-CF2 _- CF2 _{- CH2 -} O, _{CHF2 -} O _- CF2 _{- CHF2} , _CF3 -CF2-O _- CH2F, _CHF2- O-CHF _{- CF3} , CHF2-O-CF2 _{- CHF2} , CH2F _- O-CF2 _{- CHF2} , _{CF3 -} O-CF2- _CH3 , CHF2-CHF _- O- _CHF2 , _CF3 -O-CHF-CH2F, _CF3 -CHF-O-CH2F, _CF3 -O- _{CH2 - CHF2} , CHF2 _- O- _{CH2 - CF3} , _{CHF2 -} CF2 -O _- CH2F, CHF2 _- O-CF2- _CH3 , _CHF2 -CF2-O- _CH3 , CHF2-CF2 _- O- _CH3 , _{CH2F -} O _- CHF _{- CH2} F, CHF2-CHF-O-CH2F, _CF3 -O-CHF- _CH3 , _CF3 -CHF _- O- _CH3 , CHF2 _- O- _{CH2 - CHF2} , _CF3 -O-CH _{2 -} CH2F _{, CF3 - CH2 -} O _- CH2F, _CF2H -CF2-CF2 _- O- _CH3 , _{CF3CF2CF2 -} O- _CH3 , _C4H9- O—CH ₃ can be mentioned.

Specific examples of halogenated methane containing a bromine atom or an iodine atom include (mono)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), methane tetraiodide (Cl ₄ ), carbon tetrabromide (CBr ₄ ), bromotrichloromethane (CBrCl ₃ ), dibromodichloromethane _{( CBr2Cl2} ), tribromofluoromethane ( _CBr3F ), fluoroiodomethane ( _CHFI2 ), difluoroiodomethane ( _CHF2I ), difluorodiiodomethane _{( CF2I2} ), dibromo Difluoromethane (CBr ₂ F ₂ ), trifluoroiodomethane (CF ₃ I).

Specific examples of fluoronitriles include 2,3,3,3-tetrafluoro-2-(trifluoromethyl)-propanenitrile.
Specific examples of fluorosilanes include perfluorooxiranes or hydrofluorooxiranes having 3 to 15 carbon atoms.
Specific examples of ketones include ketones, methyl ethyl ketone, methyl isobutyl ketone, and fluoroketone.
Specific examples of fluoroketones include perfluoroethyl isopropyl ketone and 1,1,1,3,4,4,4-heptafluoro-(trifluoromethyl)-2-butanone.
Specific examples of alkynes include alkynes and fluoroalkynes.
Further, specific examples of fluoroalkynes include 1-chloro-3,3,3-trifluoro-1-propyne (CF ₃ —C≡CCl).
Specific examples of alcohols include methanol, ethanol, propanol and isopropanol.
Specific examples of organic acids include methyl formate, ethyl formate and formic acid.

Specific examples of fluorescent agents include naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof. One type of fluorescent agent may be used, or two or more types may be used in combination.

The haloolefin-containing composition may contain inert gases. Specific examples of inert gases include nitrogen, oxygen, air, argon and helium.
The haloolefin-containing composition may contain water. The water content may be 200 mass ppm or less, preferably 150 mass ppm or less, more preferably 100 mass ppm or less, and even more preferably 20 mass ppm or less, based on the total mass of the haloolefin-containing composition.

With respect to the total mass of the haloolefin-containing composition, the total content of haloolefin and carbon dioxide is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass. is more preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 99% by mass or more. 100 mass % may be sufficient.
The content of carbon dioxide is, for example, 1 to 99.9% by mass, preferably 10 to 99.9% by mass, and more preferably 50 to 99.9% by mass, based on the total content of haloolefin and carbon dioxide. More preferably, 70 to 99.7% by mass is even more preferable.

Applications of the haloolefin-containing composition are not particularly limited. Examples include working fluids, foaming agents, diluent solvents, cleaning agents, propellants, extinguishing agents, sterilizing agents, gas dielectrics, etching gases, and the like.
Working fluids include refrigerants for refrigerators, refrigerants for air conditioners, working fluids for power generation systems (waste heat recovery power generation, etc.), working fluids for latent heat transfer devices (heat pipes, etc.), secondary cooling media, etc. A working medium can be exemplified.

<Accommodation facilities>
The first accommodation facility is not particularly limited. Examples include storage facilities.
The second accommodation facility is not particularly limited. Examples include storage facilities and facilities using haloolefin-containing compositions.
Specific examples of the second housing equipment include refrigeration and air conditioning equipment, heat transport equipment, electric power equipment, molten metal equipment, cleaning equipment, semiconductor equipment, sterilization equipment, fire extinguishing equipment, aerosol containers, cylinder containers, and the like.
The electric power equipment is one selected from the group consisting of, for example, a switch, a circuit breaker, a disconnecting switch, a transformer, a resistor, a reactor, a capacitor, and an insulated cable, in addition to the equipment containing the haloolefin-containing composition. have more than

<Supply method>
In this embodiment, the haloolefin-containing composition stored in the first storage facility is supplied to the second storage facility.
From the start of supply to the end of supply (hereinafter also referred to as "during supply"), the haloolefin-containing composition in the first accommodation facility is maintained in a single-phase state.
Preferably, the haloolefin-containing composition in the first containment facility is brought to a one-phase state before the feed is started.
The one-phase state during feeding is preferably a superheated vapor state, a supercritical state, or a supercooled state. Also, during supply, any one state selected from a superheated steam state, a supercritical state, and a supercooled state may be changed to another state selected from a superheated steam state, a supercritical state, and a supercooled state. . However, it is imperative that no two-phase conditions occur during feeding.

During feeding, the haloolefin-containing composition in the first containment facility can be maintained in one phase by adjusting one or both of the temperature and pressure. That is, a heating step, a pressurizing step, or a cooling step is provided as required. Heating and pressurization or cooling and pressurization may be performed simultaneously.
When heating is performed, the heating may be performed at a temperature at which the haloolefin-containing composition can be maintained in a single phase. For example, it is preferable to heat the haloolefin-containing composition in the first accommodation facility to a temperature of 30° C. or higher.
When cooling is performed, it is preferable to cool so that the temperature of the haloolefin-containing composition in the first accommodation facility does not drop below the freezing point.
The first accommodation facility used in this embodiment includes heating means for applying heat to the composition in the accommodation facility, pressurization means for applying pressure to the composition in the accommodation facility, and heat removal from the composition in the accommodation facility. It is preferable to have one or more selected from cooling means. In addition, it is preferable that the inside of the first accommodation facility is in a state where a uniform temperature/pressure state is maintained without temporary or local temperature unevenness.

If the volume of the first accommodation facility is constant, this embodiment can be implemented in the following manner.
First, a first containment facility filled with a haloolefin-containing composition to a desired density is provided.
A ph diagram of the haloolefin-containing composition is calculated, and the first storage facility is placed in either a supercritical state, a superheated vapor state, or a supercooled state depending on the density in the first storage facility. Adjust the temperature and/or pressure within the equipment.
Next, the first accommodation facility and the second accommodation facility are airtightly connected, and the haloolefin-containing composition is started to be supplied from the first accommodation facility to the second accommodation facility. Feed continuously and stop when the desired feed amount is reached.
As the density in the first containment facility gradually decreases during feeding, the temperature and/or pressure within the first containment facility is controlled to maintain a one-phase state.

By maintaining the inside of the first accommodation facility during supply in a single-phase state, it is possible to suppress composition fluctuations of the haloolefin-containing composition supplied to the second accommodation facility.
If the inside of the first accommodation facility is in a uniform one-phase state, the composition of the haloolefin-containing composition supplied to the second accommodation facility will be constant, and the composition in the first accommodation facility before the start of supply, The composition in the second accommodation facility after the end of supply is the same.

[Preferred embodiment (1)]
FIG. 2 is an example of a ph diagram for a haloolefin-containing composition. The ph diagram can be obtained by, for example, NIST (National Institute of Standards and Technology) refrigerant thermophysical property database software (product name: REFPROP ver.10.0).
The density d can be calculated from the volume of the first accommodation facility and the mass w of the haloolefin-containing composition in the first accommodation facility. In the ph diagram, when the temperature at the intersection of the isodensity line and the saturation line of density d (intersection temperature) is t, if the temperature in the first accommodation facility is t or more, the temperature in the first accommodation facility becomes a one-phase state.
If the volume of the first accommodation facility is constant, during feeding the density d in the first accommodation facility will gradually decrease and the intersection temperature t will change accordingly.
Specifically, the density d is calculated by monitoring the mass w of the haloolefin-containing composition in the first accommodation facility from the start of supply to the end of supply. By controlling the temperature in the first accommodation facility so that the temperature in the first accommodation facility is always equal to or higher than t according to the change in the density d over time, the inside of the first accommodation facility is brought into a one-phase state. can be held.

[Preferred embodiment (2)]
In the ph diagram, if the temperature at the junction of the saturation line and the isothermal line (contact temperature) is T, if the temperature in the first accommodation facility is T or higher, the density and pressure in the first accommodation facility Regardless, one-phase conditions are maintained in the first containment facility.
For example, the temperature in the first accommodation facility is adjusted to T ₁ °C (T ₁ ≥ T°C) before starting the supply, and kept at T ₁ °C during the supply. In terms of stably maintaining the one-phase state in the first accommodation facility, T ₁ ≧T+1° C. is preferable, T ₁ ≧T+3° C. is more preferable, T ₁ ≧T+5° C. is even more preferable, and T ₁ ≧T+7° C. is preferable. Especially preferred.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

<Examples 1-1 to 1-3>
A stainless steel pressure vessel with an internal volume of 20 L is used as the first storage facility, and a stainless steel pressure vessel with an internal volume of 1 L is used as the second storage facility.
The composition (source composition) of the haloolefin-containing composition in the first accommodation facility is 0.5% by mass of HCFO-1224yd(Z) and 99.5% by mass of CO ₂ .
The ph diagram of the halo-olefin-containing composition of this example was obtained using the REFPROP ver. 10.0. In the resulting ph diagram, the critical temperature is 31.6° C., the temperature at the junction of the saturation line and the isothermal line (junction temperature) is 31.7° C., and the density is 444.4 kg/m ³ .
First, the inside of the first accommodation facility is evacuated, and HCFO-1224yd (Z) and CO ₂ are filled so as to have the above supply source composition. The filling amount is adjusted so that the density in the container (the density before starting the supply) becomes the density at the contact point (444.4 kg/m ³ in this example).
After filling, the interior of the first containment facility is heated to the holding temperature by holding the first containment facility in a constant temperature bath at the holding temperature shown in the table for 1 hour. The pressure (before the start of supply) obtained from the density and holding temperature in the first accommodation facility is shown in the table (the same applies hereinafter).
On the other hand, one end of a stainless steel hose wrapped with heat insulating material is connected to the second accommodation facility. The inside of the second accommodation facility and the inside of the hose are evacuated, and the second accommodation facility is placed in a constant temperature bath at 20°C.
Next, while the first housing equipment is held in the constant temperature bath, the other end of the stainless steel hose is connected to the terminal valve of the first housing equipment, the terminal valve is opened, and the first housing equipment is connected to the first housing equipment. 2, the supply of the haloolefin-containing composition is started. The supply is terminated when the pressure in the second accommodation facility reaches 0.5 MPa.

(Evaluation of composition variation)
After the supply is completed, the inside of the second accommodation facility is heated as necessary to bring it into a one-phase state, and then the composition in the second accommodation facility is sampled. The content of CO ₂ in the sampled composition (haloolefin-containing composition) is measured by gas chromatography, and the content of haloolefin is calculated.
It is preferable that the absolute value of the difference between the haloolefin content (unit: mass %) in the supply source composition and the haloolefin content (unit: mass %) in the composition in the second accommodation facility is small. For example, the absolute value of the difference is preferably 5% by mass or less, more preferably 2% by mass or less.

<Example 1-4 to Example 5-21>
The composition of the halo-olefin-containing composition (source composition) and holding temperature are varied as shown in Tables 1-5.
The table shows the critical temperature and contact temperature in the ph diagram of the haloolefin-containing composition of each example. The densities shown in the table before the start of feeding are the densities at the juncture of the ph diagram.
Other than that, in the same manner as in Example 1-1, the haloolefin-containing composition is supplied from the first accommodation facility to the second accommodation facility, and composition fluctuation is evaluated.

Considering the measurement error of the composition of the supply source and the density before the start of supply, the estimation error of the contact temperature was estimated to be about 3%, and the composition fluctuation was evaluated according to the following criteria.
A: It can be estimated that the inside of the first accommodation facility is in a single-phase state from the start of the heating supply to the end of the supply, even if there is some temperature drop or fluctuation in the holding temperature due to filling. The absolute value of said difference is estimated to be 2% by mass or less.
B: The inside of the first accommodation facility is likely to change to a one-phase state or a two-phase state due to a temperature drop due to filling or fluctuations in the holding temperature. The absolute value of said difference is estimated to be more than 2% by weight and 5% by weight or less.
C: It can be estimated that the inside of the first accommodation facility is in a two-phase state from the start of the heating supply to the end of the supply, regardless of whether there is a temperature drop due to filling or a change in the holding temperature. The absolute value of said difference is estimated to be greater than 5% by weight.

Claims (7)

A method for supplying a haloolefin-containing composition comprising a haloolefin and carbon dioxide from a first containment facility to a second containment facility, comprising:
A method for supplying a haloolefin-containing composition, wherein the haloolefin-containing composition in the first accommodation facility is maintained in one phase from the start of supply to the end of supply. 2. The feeding method according to claim 1, wherein the one-phase state is a superheated steam state, a supercritical state or a supercooled state. 3. The supply method according to claim 1, further comprising a step of heating, pressurizing, or cooling the haloolefin-containing composition in the first accommodation facility between the start of supply and the end of supply. 4. The state according to any one of claims 1 to 3, wherein one state selected from a superheated steam state, a supercritical state and a supercooled state changes to another state from the start of the supply to the end of the supply. supply method. In the pressure-specific enthalpy diagram of the haloolefin-containing composition, the density d calculated from the volume of the first accommodation facility and the mass w of the haloolefin-containing composition in the first accommodation facility When the temperature at the intersection of the isodensity line and the saturation line is t, the mass w is monitored from the start of supply to the end of supply, and the density d in the first accommodation facility changes with time. The supply method according to any one of claims 1 to 4, wherein the temperature in the first accommodation facility is controlled so that the temperature is always equal to or higher than said t. In the pressure-specific enthalpy diagram of the haloolefin-containing composition, when the temperature at the intersection of the saturation line and the isothermal line is T,
The supply method according to any one of claims 1 to 4, wherein the temperature in the first accommodation facility is maintained at T or higher from the start of supply to the end of supply. Claims 1 to 1, wherein the second housing equipment is refrigeration and air conditioning equipment, heat transport equipment, power equipment, molten metal equipment, cleaning equipment, semiconductor equipment, sterilization equipment, fire extinguishing equipment, aerosol containers, or cylinder containers. 7. The supply method according to any one of 6.

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