Composition containing refrigerant, heat transfer medium, and heat cycle system

Abstract

The present invention provides a refrigerant-containing composition having a lower GWP than that of R410A and having a COP equivalent to that of R410A. Specifically, the present invention provides a composition containing a refrigerant, the refrigerant containing CO2 (R744) and a compound (A), the compound (A) being at least one type selected from the group consisting of trans-1, 2-difluoroethylene [(E)-HFO-1132], cis-1, 2-difluoroethylene [(Z)-HFO-1132], vinyl fluoride (HFO-1141), and 3, 3, 3-trifluoropropyne (TFP).

Description

[0001] This case is the divisional application with the filing date of April 18, 2019 and the application number of 201980027803.7 (PCT / JP2019 / 016616) and the invention title of "Composition Containing Refrigerant, Heat Transfer Medium and Heat Cycle System". Technical Field

[0002] The present invention relates to a composition containing a refrigerant, a heat transfer medium and a heat cycle system. Background Art

[0003] Global warming is being studied worldwide as a profound problem. Among them, the development of heat cycle systems for air conditioners, refrigeration devices, etc., which have less burden on the environment, has become increasingly important.

[0004] Currently, various mixed refrigerants with a low global warming potential (GWP) that can replace R410A used as an air-conditioning refrigerant for household air conditioners, etc. have been proposed (Patent Documents 1 and 2).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2016-056374

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2017-186563 Summary of the Invention

[0009] Technical Problem to be Solved by the Invention

[0010] In Patent Documents 1 and 2, there is no description of a refrigerant having the characteristics of having a lower GWP than R410A and having a coefficient of performance (hereinafter, also simply referred to as COP) equivalent to that of R410A.

[0011] The technical problem solved by the present invention is to provide a composition containing a refrigerant, which has the characteristics of having a lower GWP than R410A and having a COP equivalent to that of R410A.

[0012] Technical Solution for Solving the Technical Problem

[0013] The present invention provides an invention in the following listed manners.

[0014] Item 1. A composition containing a refrigerant, wherein the refrigerant contains CO2 (R744) and Compound A, and the Compound A is at least one selected from trans-1,2-difluoroethylene [(E)-HFO-1132], cis-1,2-difluoroethylene [(Z)-HFO-1132], vinyl fluoride (HFO-1141), and 3,3,3-trifluoropropyne (TFP).

[0015] Item 2. The composition according to Item 1, wherein the total amount of R744 and the Compound A is set to 100% by mass, the composition contains 0.1 to 50% by mass of R744, and contains 50 to 99.9% by mass of the Compound A.

[0016] Item 3. The composition according to Item 1 or 2, wherein the refrigerant further contains Compound B, and the Compound B is at least one selected from tetrafluoromethane (FC-14), trifluoromethane (HFC-23), difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-152), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-trifluoroethane (HFC-143), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene [(E)-HFO-1234ze], 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 3,3,3-trifluoropropene (HFO-1243zf), and difluoropropene (HFO-1252).

[0017] Item 4. The composition according to any one of Items 1 to 3, which is used as a substitute refrigerant for R410A.

[0018] Item 5. The composition according to any one of Items 1 to 4, which further contains a refrigeration oil, and the composition is used as a working fluid for a refrigeration device.

[0019] Item 6. A refrigeration device, which contains the composition according to any one of Items 1 to 5 as a working fluid.

[0020] Item 7. A heat transfer medium, which contains the composition according to any one of Items 1 to 5.

[0021] Item 8. A heat cycle system, which uses the heat transfer medium according to Item 7.

[0022] Effects of the Invention

[0023] The refrigerant-containing composition of the present invention has the characteristics of having a lower GWP compared to R410A and having the same COP as R410A. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of an experimental device for judging flammability (flammable or non-flammable).

[0025] SYMBOL DESCRIPTION

[0026] 1: Ignition source

[0027] 2: Sample inlet

[0028] 3: Springs

[0029] 4: 12-liter glass flask

[0030] 5: Electrodes

[0031] 6: Stirrer

[0032] 7: Insulated chamber DETAILED DESCRIPTION

[0033] The inventors of the present invention conducted intensive research to solve the above technical problems and found that a composition containing CO2 (R744) and a specific olefinic fluorocarbon as a refrigerant has the above characteristics.

[0034] Based on the above insights, further repeated research was carried out, and as a result, the present invention was completed. The present invention includes the following embodiments.

[0035] <DEFINITION OF TERMS>

[0036] In this specification, the expressions "containing" and "comprising" are used to include the concepts of "substantially consisting of..." and "consisting only of...".

[0037] In this specification, the term "refrigerant" includes at least compounds labeled with an R-based refrigerant number (ASHRAE number) indicating the type of refrigerant specified by ISO817 (International Organization for Standardization), and also includes substances that have not yet been assigned a refrigerant number but have the same refrigerant characteristics as them.

[0038] From the aspect of the structure of the compounds, refrigerants are roughly classified into "fluorohydrocarbon compounds" and "non-fluorohydrocarbon compounds". "Fluorohydrocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). As "non-fluorohydrocarbon compounds", propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), ammonia (R717), etc. can be cited.

[0039] In this specification, the term "refrigerant-containing composition" includes at least: (1) the refrigerant itself (including mixtures of refrigerants); (2) a composition that further contains other components and can be used to obtain a working fluid for a refrigeration device by mixing with at least a refrigeration oil; (3) a working fluid for a refrigeration device containing a refrigeration oil.

[0040] In this specification, among these three modes, the composition of (2) is denoted as "refrigerant composition" to distinguish it from the refrigerant itself (including mixtures of refrigerants).

[0041] In this specification, the term "substitute", when used in the context of "substituting" a first refrigerant with a second refrigerant, as the first type, means that in a device designed to operate with the first refrigerant, it is possible to operate with the second refrigerant under optimal conditions with only minor component changes (at least one of refrigeration oil, gasket, packing, expansion valve, dryer, and other components) and equipment adjustment as needed. That is, this type refers to "substituting" the refrigerant to operate the same device. As the modes of "substitute" of this type, in ascending order of the degree of change or adjustment required for replacement with the second refrigerant, there can be "drop in substitute", "nearly drop in substitute", and "retrofit".

[0042] As the second type, the term "substitute" also includes the case of mounting and using a second refrigerant in order to use a device designed to operate with the second refrigerant for the same use as the known use of the first refrigerant. This type refers to "substituting" the refrigerant to provide the same use.

[0043] In this specification, the term "refrigeration device" refers to all devices that achieve a temperature lower than the surrounding external gas by removing the heat of an object or space and maintain that low temperature. In other words, in a broad sense, a refrigeration device is a conversion device that obtains energy from the outside to work for energy conversion in order to transfer heat from a low-temperature side to a high-temperature side. In the present invention, in a broad sense, a refrigeration device and a heat pump have the same meaning.

[0044] In addition, in the present invention, in a narrow sense, the refrigeration device and the heat pump are distinguished and used according to the difference in the temperature range utilized and the operating temperature. In this case, a device that places a low-temperature heat source in a temperature range lower than the atmospheric temperature is sometimes referred to as a refrigeration device, while a device that places a low-temperature heat source near the atmospheric temperature and drives a refrigeration cycle to utilize the generated heat release effect is referred to as a heat pump. In addition, devices such as air conditioners that have a "cooling mode" and a "heating mode", although they are the same device, there are also devices that have the functions of both a narrow-sense refrigeration device and a narrow-sense heat pump. In this specification, unless otherwise specified, both "refrigeration device" and "heat pump" are used in a broad sense.

[0045] In this specification, the so-called "vehicle-mounted air-conditioning device" is a type of refrigeration device used in vehicles such as gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen-powered vehicles. The vehicle-mounted air-conditioning device refers to a refrigeration device including the following refrigeration cycle: the refrigerant in liquid form exchanges heat using an evaporator, the evaporated refrigerant gas is sucked in by a compressor, the adiabatically compressed refrigerant gas is cooled by a condenser to be liquefied, and then it adiabatically expands through an expansion valve and is supplied again as a liquid refrigerant to the evaporator.

[0046] In this specification, the so-called "turbo refrigerator" is a type of large refrigeration device, which refers to a refrigeration device including the following refrigeration cycle: the refrigerant in liquid form exchanges heat using an evaporator, the evaporated refrigerant gas is sucked in by a centrifugal compressor, the adiabatically compressed refrigerant gas is cooled by a condenser to be liquefied, and then it adiabatically expands through an expansion valve and is supplied again as a liquid refrigerant to the evaporator. In addition, the above-mentioned "large refrigerator" refers to a large air conditioner for air conditioning within a building unit.

[0047] In this specification, the so-called "non-flammable" refrigerant means that the WCF (Worst case of formulation for flammability, the most flammable component) component, which is the most easily combustible component in the allowable concentration of the refrigerant in the US ANSI / ASHRAE34-2013 standard, is judged as "category 1".

[0048] In this specification, the so-called "slightly flammable" refrigerant means that the WCF component is judged as "category 2L" in the US ANSI / ASHRAE34-2013 standard.

[0049] In this specification, the so-called "weakly flammable" refrigerant means that the WCF component is judged as "category 2" in the US ANSI / ASHRAE34-2013 standard.

[0050] In this specification, the so-called temperature glide can be paraphrased as the absolute value of the difference between the starting temperature and the ending temperature of the phase change process of the refrigerant-containing composition of the present invention within the components of the refrigerant system.

[0051] In this specification, GWP means a value obtained based on the values in the 4th Report of the IPCC (Intergovernmental Panel on Climate Change).

[0052] 1. Refrigerant

[0053] 1-1 Refrigerant component

[0054] <Mixed refrigerant containing R744 and compound A>

[0055] The refrigerant of the present invention is a mixed refrigerant containing CO2 (R744) as an essential component and containing compound A, and the compound A is at least one selected from trans-1,2-difluoroethylene [(E)-HFO-1132], cis-1,2-difluoroethylene [(Z)-HFO-1132], vinyl fluoride (HFO-1141), and 3,3,3-trifluoropropyne (CF3C≡CH; TFP).

[0056] By having such a composition, the refrigerant of the present invention has (1) a GWP that is sufficiently lower than the GWP (2088) of R410A, and (2) a COP equivalent to that of R410A, which are the characteristics generally required for R410A alternative refrigerants. In addition, at least a part of the refrigerant of the present invention further has (3) characteristics such as a refrigerating capacity equivalent to that of R410A.

[0057] The compound A of the present invention is at least one compound selected from (E)-HFO-1132, (Z)-HFO-1132, HFO-1141, and TFP.

[0058] When using the above compound A alone, among the above compounds A, from the viewpoints of having a COP equivalent to that of R410A and a refrigerating capacity equivalent to or higher than that of R410A, (E)-HFO-1132, HFO-1141, or TFP is preferred, and (E)-HFO-1132 or HFO-1141 is more preferred.

[0059] When two or more of the above-mentioned Compound A are used in combination, from the viewpoint of having a COP equivalent to that of R410A and a refrigerating capacity equivalent to or higher than that of R410A, it is preferable to use at least one compound selected from (E)-HFO-1132 and HFO-1141.

[0060] Regarding the refrigerant of the present invention, it is preferable that the refrigerant is a mixed refrigerant containing 0.1 to 50% by mass of R744 and 50 to 99.9% by mass of the above-mentioned Compound A when the total amount of R744 and the above-mentioned Compound A is 100% by mass. In this case, the refrigerant of the present invention has a GWP of 1 or less, has a COP equivalent to that of R410A, and is more excellent in the refrigerating capacity ratio based on R410A.

[0061] Regarding the refrigerant of the present invention, it is more preferable that the refrigerant is a mixed refrigerant containing 2.5 to 10% by mass of R744 and 90 to 97.5% by mass of the above-mentioned Compound A when the total amount of R744 and the above-mentioned Compound A is 100% by mass. In this case, the refrigerant of the present invention has a GWP of 1 or less, a temperature glide of 15°C or less, has a COP equivalent to that of R410A, and is further excellent in the refrigerating capacity ratio based on R410A.

[0062] The refrigerant of the present invention is preferably a mixed refrigerant containing 99.9% by mass or less of (E)-HFO-1132, (Z)-HFO-1132, HFO-1141 or TFP as a compound, and more preferably a mixed refrigerant containing 95% by mass or less of the above substances. When the content of the compound is within this range, for example, in a compressor, the polymerization reaction of the refrigerant that may occur locally in an environment of 200°C or higher and 8 MpaG or higher (an environment with high temperature and pressure) can be suppressed, and thus the refrigerant can be stably maintained.

[0063] <Mixed Refrigerant Containing R744, Compound A and Compound B>

[0064] As Compound A in this item, the Compound A described in the item of <Mixed Refrigerant Containing R744 and Compound A> can be used.

[0065] The refrigerant of the present invention is preferably a mixed refrigerant containing, in addition to CO2 (R744) and the above-mentioned compound A, compound B, and the above-mentioned compound B is at least one selected from tetrafluoromethane (FC-14), trifluoromethane (HFC-23), difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-152), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-trifluoroethane (HFC-143), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene [(E)-HFO-1234ze], 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 3,3,3-trifluoropropene (HFO-1243zf), and difluoropropene (HFO-1252).

[0066] By having such a composition, the refrigerant of the present invention has many characteristics desired as an R410A alternative refrigerant, such as (1) a sufficiently small GWP, (2) a COP equivalent to that of R410A, and (3) a refrigerating capacity equivalent to that of R410A.

[0067] Examples of compound B of the present invention include FC-14, HFC-23, HFC-32, HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-152, HFC-143a, HFC-143, HFC-227ea, HFO-1234yf, (E)-HFO-1234ze, HFO-1225ye, HFO-1243zf, or HFO-1252. These compound Bs can be used alone or in combination of two or more.

[0068] When the above-mentioned compound B is used alone, among the above-mentioned compound Bs, from the viewpoints of GWP, COP, and refrigerating capacity, HFC-32, HFC-134, HFC-134a, HFC-152a, HFC-152, HFO-1234yf, (E)-HFO-1234ze, HFO-1225ye, HFO-1243zf, or HFO-1252 is preferred, HFC-32 or (E)-HFO-1234ze is more preferred, and HFC-32 is particularly preferred.

[0069] When two or more of the above-mentioned compounds B are used in combination, from the viewpoints of flammability, GWP, COP, and refrigerating capacity, a combination of HFC-134 and HFC-32, a combination of HFC-134a and HFC-32, or a combination of HFC-134, HFC-134a, and HFC-32 is preferred. Among these combinations, a combination of HFC-134a and HFC-32 is more preferred.

[0070] Regarding the refrigerant of the present invention, it is preferred that the refrigerant is a mixed refrigerant containing 0.1 to 10% by mass of R744 and 10 to 50% by mass of the above-mentioned compound B when the total amount of R744, the above-mentioned compound A, and the above-mentioned compound B is 100% by mass. In this case, the refrigerant of the present invention has properties such that the GWP is 750 or less and the COP is equivalent to that of R410A, and the refrigerating capacity ratio based on R410A is more excellent.

[0071] The refrigerant of the present invention is preferably a mixed refrigerant represented by any one of the following (1) to (6).

[0072] (1) A mixed refrigerant in which the total amount of R744, the above-mentioned compound A, and the above-mentioned compound B is 100% by mass, containing 0.1 to 10% by mass of R744, containing 30 to 52% by mass of HFC-134a as the above-mentioned compound B, and the balance being the above-mentioned compound A.

[0073] (2) A mixed refrigerant in which the total amount of R744, the above-mentioned compound A, and the above-mentioned compound B is 100% by mass, containing 0.1 to 10% by mass of R744, containing 30 to 52% by mass of HFC-134a as the above-mentioned compound B, containing 0.1 to 30% by mass of HFC-32, and the balance being the above-mentioned compound A.

[0074] (3) A mixed refrigerant in which the total amount of R744, the above-mentioned compound A, and the above-mentioned compound B is 100% by mass, containing 0.1 to 10% by mass of R744, containing 30 to 52% by mass of HFC-134 as the above-mentioned compound B, and the balance being the above-mentioned compound A.

[0075] (4) A mixed refrigerant in which the total amount of R744, the above-mentioned compound A, and the above-mentioned compound B is 100% by mass, containing 0.1 to 10% by mass of R744, containing 30 to 52% by mass of HFC-134 as the above-mentioned compound B, containing 0.1 to 30% by mass of HFC-32, and the balance being the above-mentioned compound A.

[0076] (5) The total amount of R744, the above-mentioned compound A and the above-mentioned compound B is set to 100% by mass, and the refrigerant mixture contains 0.1 to 10% by mass of R744, contains HFC-134a and HFC-134 as the above-mentioned compound B in such a manner that their total amount reaches 30 to 52% by mass, and the balance is the above-mentioned compound A.

[0077] (6) The total amount of R744, the above-mentioned compound A and the above-mentioned compound B is set to 100% by mass, and the refrigerant mixture contains 0.1 to 10% by mass of R744, contains HFC-134a and HFC-134 as the above-mentioned compound B in such a manner that their total amount reaches 30 to 52% by mass, and contains 0.1 to 30% by mass of HFC-32, and the balance is the above-mentioned compound A.

[0078] When the refrigerant of the present invention is the refrigerant mixture shown in any one of the above (1) to (6), it has properties such as a GWP of 750 or less, non-flammability, and a COP equivalent to that of R410A, and the refrigerating capacity ratio based on R410A is further excellent.

[0079] The refrigerant of the present invention may be a refrigerant mixture that contains, in addition to R744, the above-mentioned compound A and the above-mentioned compound B, other additional refrigerants within a range not impairing the above-mentioned characteristics and effects. In this case, the total amount of R744, the above-mentioned compound A and the above-mentioned compound B is preferably 99.5% by mass or more and less than 100% with respect to the entire refrigerant of the present invention, more preferably 99.75% by mass or more and less than 100%, and still more preferably 99.9% by mass or more and less than 100%.

[0080] The above-mentioned additional refrigerant is not particularly limited and can be widely selected from known refrigerants widely used in this field. The above-mentioned refrigerant mixture may contain the above-mentioned additional refrigerant alone or may contain two or more of the above-mentioned additional refrigerants.

[0081] 1-2 Use

[0082] The refrigerant of the present invention can be preferably used as a working fluid in a refrigeration device.

[0083] The refrigerant-containing composition of the present invention is suitable for use as a substitute refrigerant for HFC refrigerants such as R410A, R407C, R404A, and HCFC refrigerants such as R22. Among these, the refrigerant-containing composition of the present invention is particularly suitable for use as a substitute refrigerant for R410A.

[0084] 2. Refrigerant composition

[0085] The refrigerant composition of the present invention contains at least the refrigerant of the present invention and can be used for the same applications as the refrigerant of the present invention.

[0086] In addition, the refrigerant composition of the present invention can also be used to obtain a working fluid for a refrigeration device by mixing with at least a refrigeration oil.

[0087] In the refrigerant composition of the present invention, in addition to the refrigerant of the present invention, at least one other component is further contained. The refrigerant composition of the present invention can contain at least one of the following other components as needed.

[0088] As described above, when the refrigerant composition of the present invention is used as a working fluid in a refrigeration device, generally, it is used by mixing with at least a refrigeration oil.

[0089] Therefore, the refrigerant composition of the present invention preferably contains substantially no refrigeration oil. Specifically, in the refrigerant composition of the present invention, the content of the refrigeration oil is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, further preferably 0 to 0.25% by mass, and particularly preferably 0 to 0.1% by mass, based on the whole refrigerant composition.

[0090] 2-1 Water

[0091] The refrigerant composition of the present invention can contain a trace amount of water.

[0092] The water content ratio in the refrigerant composition is preferably 0 to 0.1% by mass, more preferably 0 to 0.075% by mass, further preferably 0 to 0.05% by mass, and particularly preferably 0 to 0.025% by mass, based on the whole refrigerant.

[0093] By containing a trace amount of moisture in the refrigerant composition, the intramolecular double bond of the unsaturated fluorohydrocarbon compound that can be contained in the refrigerant is stabilized, and the oxidation of the unsaturated fluorohydrocarbon compound also becomes difficult to occur. Therefore, the stability of the refrigerant composition is improved.

[0094] 2-2 Tracer

[0095] When the refrigerant composition of the present invention is diluted, contaminated, or undergoes any other change, in order to be able to trace the change, a tracer is added to the refrigerant composition of the present invention at a detectable concentration.

[0096] The refrigerant composition of the present invention can contain a single one of the above tracers or two or more.

[0097] As the above-mentioned tracer, there is no particular limitation, and it can be appropriately selected from commonly used tracers. It is preferable to select a compound that does not become an impurity inevitably mixed into the refrigerant of the present invention as the tracer.

[0098] As the above-mentioned tracer, for example, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, bromides, iodides, alcohols, aldehydes, ketones, nitrous oxide (N2O), etc. can be cited. Among these, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers are preferred.

[0099] Specifically, the following compounds (hereinafter, also referred to as tracer compounds) are more preferably used as the above-mentioned tracer.

[0100] HCC-40 (chloromethane, CH3Cl)

[0101] HFC-41 (fluoromethane, CH3F)

[0102] HFC-161 (fluoroethane, CH3CH2F)

[0103] HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)

[0104] HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)

[0105] HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)

[0106] HCFC-22 (chlorodifluoromethane, CHClF2)

[0107] HCFC-31 (chlorofluoromethane, CH2ClF)

[0108] CFC-1113 (chlorotrifluoroethylene, CF2=CClF)

[0109] HFE-125 (trifluoromethyl-difluoroether, CF3OCHF2)

[0110] HFE-134a (trifluoromethyl-fluoroether, CF3OCH2F)

[0111] HFE-143a (trifluoromethyl-methyl ether, CF3OCH3)

[0112] HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)

[0113] HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

[0114] The above tracer compound may be present in the refrigerant composition at a total concentration of 10 parts per million by weight (ppm) to 1000 ppm. The tracer compound is preferably present in the refrigerant composition at a total concentration of 30 ppm to 500 ppm, more preferably at a total concentration of 50 ppm to 300 ppm, still more preferably at a total concentration of 75 ppm to 250 ppm, and particularly preferably at a total concentration of 100 ppm to 200 ppm.

[0115] 2 - 3 Ultraviolet fluorescent dye

[0116] The refrigerant composition of the present invention may contain a single ultraviolet fluorescent dye or two or more thereof.

[0117] The above ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0118] Examples of the above ultraviolet fluorescent dye include naphthalenedicarboximide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, benzoxanthene, and fluorescein, and their derivatives. Among these, naphthalenedicarboximide and coumarin are preferred.

[0119] 2 - 4 Stabilizer

[0120] The refrigerant composition of the present invention may contain a single stabilizer or two or more thereof.

[0121] The above stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0122] Examples of the above stabilizer include nitro compounds, ethers, amines, etc.

[0123] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrobenzene styrene.

[0124] Examples of ethers include 1,4 - dioxane, etc.

[0125] Examples of amines include 2,2,3,3,3 - pentafluoropropylamine, diphenylamine, etc.

[0126] Examples of the above stabilizer, in addition to the above nitro compounds, ethers, and amines, also include butylhydroxydimethylbenzene, benzotriazole, etc.

[0127] The content ratio of the above stabilizer is not particularly limited, and is generally 0.01 to 5% by mass, preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, still more preferably 0.25 to 1.5% by mass, and particularly preferably 0.5 to 1% by mass, relative to the whole refrigerant.

[0128] In addition, the method for evaluating the stability of the refrigerant composition of the present invention is not particularly limited, and can be evaluated by a commonly used method. As an example of such a method, a method of evaluating according to ASHRAE Standard 97-2007 using the amount of free fluoride ions as an index can be cited. In addition, a method of evaluating using the total acid number as an index can also be cited. This method can be carried out, for example, in accordance with ASTM D 974-06.

[0129] 2 - 5 Polymerization inhibitor

[0130] The refrigerant composition of the present invention may contain a single polymerization inhibitor or two or more kinds thereof.

[0131] As the above polymerization inhibitor, there is no particular limitation, and it can be appropriately selected from commonly used polymerization inhibitors.

[0132] As the above polymerization inhibitor, for example, 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, benzotriazole, etc. can be cited.

[0133] The content ratio of the above polymerization inhibitor is not particularly limited, and is generally 0.01 to 5% by mass, preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, still more preferably 0.25 to 1.5% by mass, and particularly preferably 0.5 to 1% by mass, relative to the whole refrigerant.

[0134] 3. Working fluid containing refrigeration oil

[0135] The working fluid containing refrigeration oil of the present invention contains at least the refrigerant or refrigerant composition of the present invention and refrigeration oil, and is used as the working fluid in a refrigeration device. Specifically, the working fluid containing refrigeration oil of the present invention can be obtained by mixing the refrigeration oil used in the compressor of the refrigeration device with the refrigerant or refrigerant composition.

[0136] The content ratio of the above refrigeration oil is not particularly limited, and is generally 10 to 50% by mass, preferably 12.5 to 45% by mass, more preferably 15 to 40% by mass, still more preferably 17.5 to 35% by mass, and particularly preferably 20 to 30% by mass, relative to the whole working fluid containing refrigeration oil.

[0137] 3-1 Refrigeration oil

[0138] The composition of the present invention may contain a single type of refrigerant oil or two or more types thereof.

[0139] As the above-mentioned refrigerant oil, there is no particular limitation, and it can be appropriately selected from commonly used refrigerant oils. At this time, according to needs, a refrigerant oil that is more excellent in terms of functions such as improving the compatibility of the mixture with the refrigerant of the present invention (the mixed refrigerant of the present invention) and the stability of the mixed refrigerant of the present invention can be appropriately selected.

[0140] As the base oil of the above-mentioned refrigerant oil, for example, at least one selected from polyalkylene glycol (PAG), polyol ester (POE), and polyethylene ether (PVE) is preferred.

[0141] In addition to containing the above-mentioned base oil, the above-mentioned refrigerant oil may also contain additives.

[0142] The above-mentioned additives may be at least one selected from antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents, and defoamers.

[0143] As the above-mentioned refrigerant oil, from the perspective of lubrication, a refrigerant oil having a kinematic viscosity of 5 to 400 cSt at 40 °C is preferred.

[0144] The working fluid containing the refrigerant oil of the present invention may further contain at least one additive according to needs. As additives, for example, the following compatibilizers and the like can be cited.

[0145] 3-2 Compatibilizer

[0146] The working fluid containing the refrigerant oil of the present invention may contain a single type of compatibilizer or two or more types thereof.

[0147] As the above-mentioned compatibilizer, there is no particular limitation, and it can be appropriately selected from commonly used compatibilizers.

[0148] As the above-mentioned compatibilizer, for example, polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorinated hydrocarbon, ester, lactone, aryl ether, fluoroether, 1,1,1-trifluoroalkane, etc. can be cited. Among these, polyoxyalkylene glycol ether is preferred.

[0149] 4. Operation method of refrigeration device

[0150] The operating method of the refrigeration device of the present invention is a method of operating a refrigeration device using the refrigerant of the present invention.

[0151] Specifically, the operation method of the refrigeration device of the present invention includes: a step of circulating the refrigerant-containing composition of the present invention as a working fluid in the refrigeration device.

[0152] As the above refrigeration device, for example, at least one selected from air conditioning equipment, refrigerators, freezers, chillers, ice makers, refrigerated display cabinets, frozen display cabinets, refrigeration and freezing units, refrigerators for refrigerated and frozen warehouses, vehicle-mounted air conditioning equipment, turbo refrigerators, and screw refrigerators can be cited.

[0153] 5. Heat transfer medium and heat cycle system using the same

[0154] The heat transfer medium of the present invention contains the refrigerant-containing composition of the present invention.

[0155] The heat transfer medium of the present invention can be suitably used in various heat cycle systems. By having the heat transfer medium of the present invention, the heat cycle system can become a heat cycle system with high cooling capacity.

[0156] In addition, since the GWP of the refrigerant of the present invention is sufficiently small, compared with the case of using existing refrigerants, by having the heat transfer medium of the present invention, high safety can be imparted to the heat cycle system.

[0157] Moreover, since the temperature glide of the heat transfer medium of the present invention is also low, a heat cycle system with high stability can be provided.

[0158] The type of the heat cycle system is not particularly limited. As examples of the heat cycle system, indoor air conditioners, air handling units for stores, air handling units for buildings, air handling units for equipment, split air conditioners formed by connecting one or more indoor units and outdoor units through refrigerant pipes, window air conditioners, portable air conditioners, rooftop or central air conditioners that convey cold and warm air through ducts, gas engine heat pumps, air conditioning devices for trains, air conditioning devices for automobiles, built-in display cabinets, split display cabinets, industrial refrigerators, ice makers, integrated refrigeration devices, vending machines, automotive air conditioners, refrigeration devices for cooling containers or refrigerators for maritime transportation, etc., vehicle-mounted air conditioning equipment, turbo refrigerators, or heat cycle dedicated machines can be cited. As examples of the heat cycle dedicated machines, for example, hot water supply devices, floor heating devices, snow melting devices, etc. can be cited.

[0159] The heat cycle systems listed in the above examples only need to have the heat transfer medium of the present invention, and there is no particular limitation on other configurations. For example, they can be configured in the same configuration as known heat cycle systems.

[0160] Examples

[0161] Hereinafter, examples will be listed for more detailed description. However, the present invention is not limited to these examples.

[0162] Examples 1 to 18 and Comparative Examples 1 to 3

[0163] The GWP of the mixed refrigerants prepared in each of the examples and comparative examples, and the GWP of R410A (R32 = 50% / R125 = 50%) were evaluated based on the values in the 4th report of the IPCC (Intergovernmental Panel on Climate Change).

[0164] In addition, the COP, refrigerating capacity of the mixed refrigerants prepared in each of the examples and comparative examples, and the COP and refrigerating capacity of R410A were obtained by performing theoretical calculations of the refrigeration cycle of the mixed refrigerants under the following conditions using the National Institute of Science and Technology (NIST), the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0).

[0165] Evaporation temperature: 45°C

[0166] Condensation temperature: 5°C

[0167] Superheat temperature: 5 K

[0168] Subcooling temperature: 5 K

[0169] Compressor efficiency: 70%

[0170] In addition, the GWP, COP, and refrigerating capacity calculated based on these results are shown in Tables 1 to 6. Among them, the COP ratio and refrigerating capacity ratio represent the ratio (%) relative to R410A.

[0171] The coefficient of performance (COP) is calculated using the following formula.

[0172] COP = (refrigerating capacity or heating capacity) / power consumption

[0173] Regarding the flammability of the mixed refrigerant, the mixed composition of the mixed refrigerant was made into the WCF concentration and the burning rate was measured according to the ANSI / ASHRAE 34-2013 standard. When the burning rate is 10 cm / s or less, it is designated as "Class 2L (slightly flammable)".

[0174] The combustion rate test is carried out as follows. First, the purity of the mixed refrigerant used is 99.5% or more, and the cycle of freezing, pumping, and thawing is repeated until no trace of air can be seen on the vacuum gauge, thereby performing degassing. The combustion rate is measured using the closed method. The initial temperature is set to the ambient temperature. Ignition is carried out by generating an electric spark between electrodes at the center of the specimen chamber. The duration of the discharge is set to 1.0 - 9.9 ms, and the ignition energy is typically about 0.1 - 1.0 J. The spread of the flame is visualized using schlieren photography. A cylindrical container (inner diameter: 155 mm, length: 198 mm) with two acrylic windows that are transparent to light is used as the specimen chamber, and a xenon lamp is used as the light source. A high-speed digital camera records the schlieren images of the flame at a frame rate of 600 fps and saves them on a PC.

[0175] The combustion range of the mixed refrigerant is measured using a measuring device based on ASTM E681 - 09 (refer to Figure 1 ).

[0176] Specifically, in order to be able to visually observe and video-record the combustion state, a spherical glass flask with an internal volume of 12 liters is used, and the glass flask is configured to be able to release gas from the upper lid when excessive pressure is generated due to combustion. Regarding the ignition method, it occurs through the discharge from an electrode held at a height of 1 / 3 from the bottom. The test conditions are as follows.

[0177] <Test Conditions>

[0178] Test container: φ280 mm spherical (internal volume: 12 liters)

[0179] Test temperature: 60°C ± 3°C

[0180] Pressure: 101.3 kPa ± 0.7 kPa

[0181] Moisture: 0.0088 g ± 0.0005 g per 1 g of dry air

[0182] Refrigerant composition / air mixing ratio: 1 vol.% scale ± 0.2 vol.%

[0183] Refrigerant composition mixing: ± 0.1 wt.%

[0184] Ignition method: AC discharge, voltage 15 kV, current 30 mA, neon transformer

[0185] Electrode spacing: 6.4 mm (1 / 4 inch)

[0186] Ignition: 0.4 s ± 0.05 s

[0187] Judgment criteria:

[0188] · The situation where the flame spreads more than 90 degrees centered on the ignition point = Flame propagation (combustible)

[0189] · The situation where the flame spreads less than 90 degrees centered on the ignition point = Flame non - propagation (non - combustible)

[0190] [Table 1]

[0191]

[0192] [Table 2]

[0193]

[0194] [Table 3]

[0195]

[0196] [Table 4]

[0197]

[0198] [Table 5]

[0199]

[0200] [Table 6]

[0201]

Claims

1. A refrigerant-containing composition, characterized in that: The refrigerant contains Compound A and Compound B, Compound A is trans-1,2-difluoroethylene [(E)-HFO-1132], Compound B is difluoropropene (HFO-1252).

2. The composition according to claim 1, characterized in that: The refrigerant further contains CO2 (R744).

3. The composition according to claim 2, characterized in that: Taking the total amount of R744 and Compound A as 100% by mass, it contains 0.1 to 50% by mass of R744 and 50 to 99.9% by mass of Compound A.

4. The composition according to claim 1 or 2, characterized in that: The refrigerant further contains at least one compound selected from tetrafluoromethane (FC-14), trifluoromethane (HFC-23), difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-152), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-trifluoroethane (HFC-143), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene [(E)-HFO-1234ze], 1,2,3,3,3-pentafluoropropene (HFO-1225ye) and 3,3,3-trifluoropropene (HFO-1243zf).

5. The composition according to any one of claims 1 to 3, characterized in that: The composition is used as a substitute refrigerant for R410A.

6. The composition according to any one of claims 1 to 3, characterized in that: It further contains refrigeration oil, The composition is used as a working fluid for a refrigeration device.

7. A refrigeration device, characterized in that: It contains the composition according to any one of claims 1 to 6 as a working fluid.

8. A heat transfer medium, characterized in that: It contains the composition according to any one of claims 1 to 6.

9. A heat cycle system, characterized in that: It uses the heat transfer medium according to claim 8.

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