A non-flammable refrigerant with low GWP, and a system and method for providing refrigeration.

Abstract

The present invention provides a heat transfer system equipped with a refrigerant composition for use in various refrigeration applications, particularly for cooling products such as fruits, vegetables, and beverages without exposing them to temperatures below the freezing point of water. [Solution] (a) Evaporator and, (b) The refrigerant in the evaporator, wherein the refrigerant is (i) HFO-1234ze(E) in an amount of approximately 65% ​​to 90% by weight, (ii) A heat transfer system is provided comprising a refrigerant containing approximately 10% to 35% by weight of HFO-1336mzz(E).

Description

Technical Field

[0001] The present invention relates to highly efficient low global warming potential ("low GWP") refrigerants, as well as air conditioning systems and / or refrigeration systems and methods for providing safe and effective cooling, and particularly to systems and methods for cooling articles (such as fruits, vegetables, and water) without exposing them to temperatures below the freezing point of water.

Background Art

[0002] In certain refrigeration applications, it is necessary to cool articles without exposing them to temperatures below a specific temperature, such as the freezing point of water. For example, in a supermarket environment, it is common to keep certain produce at a low temperature relative to the surroundings, but at the same time, particularly since the preferred method of cooling involves indirect cooling by humid air, ambient air, it is disadvantageous to cool the produce below the freezing point of water. For these applications, having a refrigerant temperature below the freezing point of water along the evaporator is also disadvantageous because it causes frost accumulation, resulting in the need to defrost the equipment. Avoiding frost accumulation is an important aspect in these applications. Similarly, the cooling of beverages containing water, etc. should also be carried out under conditions that avoid exposing such products to temperatures below the freezing point of water because freezing of such products is not desirable at the point of sale. For convenience, the applicants refer to such applications, methods, and systems herein as "non-freezing" applications, methods, and systems.

[0003] including chlorofluorocarbons ("CFCs"), hydrochlorofluorocarbons ("HCFCs"), and hydrofluorolefins ("HFOs") Certain single-component fluorocarbons have been used in "frost-free" applications where the refrigerant temperature along the evaporator must remain above the freezing point of water so that frost does not accumulate on the coil surface, and consequently, defrosting equipment is unnecessary. In such refrigeration applications, systems, and methods, the use of single-component fluids has been considered particularly desirable because the saturation temperature of such fluids does not change during evaporation at constant pressure. The use of single-component fluids is highly desirable because it allows for the design of systems and methods using a refrigerant temperature along the evaporator that remains essentially constant during the evaporation process and is above the freezing point of water, assuming little to no pressure drop as the refrigerant flows through the evaporator. In addition, product applications also typically require a small temperature difference between the air and the refrigerant to dehumidify the air and reduce the resulting moisture content and loss of product quality. The requirement for a small temperature difference and the requirement for frost avoidance, combined with the need for the evaporator to have a specific positive superheat at the outlet, are important when selecting a particular refrigerant. A superheat degree of zero or less, i.e., where the refrigerant is not overheated, can lead to improved cooling capacity, efficiency, and a reduction in potential compressor failures. The term “superheat degree” or simply “superheating” refers to the rise in the temperature of the refrigerant at the evaporator outlet above its saturated vapor temperature (or dew point temperature).

[0004] This is illustrated in Figure 1 as an example and schematically represents a typical supermarket product cooling case. Typically, as shown in Figure 1, cooled, humidified air is supplied to the product display zone of the display case by passing both air from outside the case 102 and recirculated air 104 over the heat exchange surface of an evaporator coil 106 located inside the display case, typically in an area separate from (or at least hidden from the consumer's view of) but adjacent to the product display zone. The evaporator 106 has a single-component refrigerant inlet 108 and a single-component refrigerant outlet 110. A circulation fan 114 is also used. It is highly desirable in systems of the types illustrated above that the cooling space 112 within the refrigeration system always or substantially always have a refrigerant temperature above a certain level along the evaporator. For example, in many applications such as refrigeration of products, the minimum discharge (outlet) temperature of the air in the display case is set by design to about 2°C to 3°C to provide a safety margin to avoid having a cooling space or cooling items below the freezing point of water. In addition, to minimize the removal of moisture from the air and the resulting drying (loss of quality) of the products, the temperature difference between the air outlet and the refrigerant needs to be small, typically 2°C to 3°C. This, combined with the fact that the evaporator in these applications requires a superheat of about 3 to about 5°C, will impose constraints on the allowable evaporator gradient of the refrigerant so that the evaporation temperature does not remain above the freezing point of water and, as a result, frost does not accumulate. This is shown in Figures 2 and 3.

[0005] As an example in Figure 2, when the air discharge temperature is 3°C, a maximum evaporator gradient of 3°C (refrigerant A) is permissible. However, if the refrigerant temperature exceeds 3°C, for example, if refrigerant B has an evaporator gradient of 4°C, the refrigerant temperature will fall below the freezing point of water, and frost may accumulate.

[0006] In Figure 3, the air discharge temperature is 2°C, and the evaporator gradient is limited to approximately 2°C (refrigerant C). If the refrigerant temperature exceeds 2°C, for example, refrigerant D with an evaporator gradient of 3°C, the refrigerant temperature will reach below freezing, and frost may accumulate. In summary, to avoid frost accumulation in these applications, a gradient less than 4.5°C is preferable, a gradient less than 3°C is more preferable, and a gradient less than 2°C is most preferable.

[0007] Those skilled in the art will understand that these two desirable results are due to the fact that providing a refrigerant that is a multi-component blend of different single-component refrigerants has often been extremely difficult in the past.

[0008] Prior to the present invention, as described above, those skilled in the art have primarily used single-component refrigerants such as HFC-134a in such low-temperature sensitive applications, and have avoided refrigerant blends because blends generally undergo significant changes in boiling point temperature during evaporation. Refrigerant blends have conventionally been recognized as a major obstacle to the ability to identify blends with the correct balance of properties useful in such systems.

[0009] On the other hand, the applicants have come to understand that identifying a single-component fluid having a set of properties that provide specific advantages in the above types of applications is also difficult in many applications. For example, in many important applications, it is necessary to identify a refrigerant that simultaneously: (1) has an effective gradient, i.e., less than 4.5°C, preferably less than about 3°C, and more preferably less than about 2°C, to avoid frost formation and maintain a typical superheat, e.g., about 3°C ​​to about 5°C; (2) is non-flammable; (3) is low-toxicity or substantially non-toxic; (4) has a low global warming potential (GWP) (e.g., less than about 150, more preferably less than about 75); and (5) has heat transfer properties and other properties (such as chemical stability) that match the needs of the particular application, especially in medium-temperature heat transfer systems, and more preferably in frost-free or low-frost medium-temperature refrigeration systems. The use of a single-component refrigerant can often satisfy items (1), (2), and (3), but those skilled in the art will know that a refrigerant (single component or other) can satisfy not only items (1), (2), and (3), but most, and preferably all, of items (4) and (5). It was found that discovering such substances (if not impossible) is difficult under conventional circumstances. Here, non-flammable substances are classified as Class "1" by ASHRAE, and low-toxicity substances are classified as Class "A" by ASHRAE Standard 34-2016. Substances that are both non-flammable and low-toxicity are classified as "A1" by ASHRAE Standard 34-2016.

[0010] For example, HFC-134a has traditionally been used in certain non-freezing applications, but despite this, it does not meet the low GWP requirement (item 5 above) because it has a GWP of approximately 1300.

[0011] The applicants proceeded in a manner contrary to common sense and discovered unexpected and advantageous results. For example, the applicants found that certain blends, including carefully selected combinations of components as described in detail below, can have advantageous but unexpected non-flammable combinations while simultaneously possessing, among other things, excellent heat transfer properties, low GWP (e.g., less than about 150 GWP), low toxicity or non-toxicity, chemical stability, and lubricant compatibility. Furthermore, the applicants found that the refrigerant compositions of the present invention have particular advantages for use in medium-temperature refrigeration systems, and in particular in medium-temperature refrigeration systems where it is desirable to maintain the temperature of the cooled air above about 0°C and to avoid exposing the cooled air to temperatures below about 0°C in order to protect the articles being cooled from frost and / or to prevent frost formation on the evaporator coils, which in itself could adversely affect the overall efficiency of such systems due to the need for defrosting and / or inconsistent cooling across the coils. [Overview of the project]

[0012] The applicants have discovered a refrigeration method and system, which includes a refrigerant composition, a heat transfer composition containing a refrigerant, and a method and system for cooling materials having low-temperature constraints, such as low-temperature or non-freezing applications, using one or more of the compositions of the present invention as the refrigerant.

[0013] Accordingly, the present invention provides compositions that are preferably non-flammable, low-toxicity or substantially non-toxic, have a low global warming potential, and have excellent heat transfer performance, particularly in medium-temperature refrigeration systems and methods, and more preferably in frost-free and low-frost medium-temperature refrigeration systems.

[0014] A medium-temperature refrigeration system and method are also provided by the present invention, as described in detail below.

[0015] Furthermore, the applicants have come to understand that in many evaporators, such as direct expansion evaporators, there is a pressure loss as the refrigerant moves through the evaporator, and in many cases, this pressure drop results in a decrease in saturation temperature of approximately 1°C to 2°C.

[0016] Therefore, the refrigerant of the present invention includes a refrigerant having a GWP greater than about 75 and less than about 150, classified as A1 (non-flammable and low-toxicity) by ASHRAE, and having an evaporator gradient of less than about 3°C, more preferably less than about 2°C, and is used in a system that preferably includes an evaporator, wherein the refrigerant pressure is such that the refrigerant saturation temperature is about 1°C to about 3°C ​​from the inlet to the outlet of the evaporator. The pressure is reduced by an amount that most preferably lowers it by about 1°C to about 2°C. This means that the refrigerants of the present invention in such embodiments can achieve unexpectedly small changes in refrigerant temperature through the evaporator. For example, the change in refrigerant temperature between the evaporator inlet and outlet as a result of pressure loss is preferably less than the evaporator gradient (measured at a substantially constant evaporator inlet pressure), more preferably less than about 75% of the evaporator gradient, and even more preferably less than about 50% of the evaporator gradient. Thus, such preferred refrigerant compositions of the present invention, having a GWP greater than about 75 and less than about 150 and classified as A1 (non-flammable and low-toxicity) by ASHRAE, are such that the refrigerant temperature can change by an amount of less than about 1°C as the refrigerant moves through the evaporator (i.e., the change in refrigerant temperature between the evaporator inlet and outlet as a result of pressure loss is preferably less than about 1°C). As a result of this discovery, at least in part, the methods and systems of the present invention can be achieved by utilizing highly efficient heat exchanger designs, particularly for applications such as reversible heat pumps where the refrigerant flow changes direction in the heat exchanger depending on the operating mode (cooling or heating).

[0017] The refrigerant of the present invention also includes a refrigerant having a GWP of less than about 75, classified as A1 (non-flammable and low-toxic) by ASHRAE, and an evaporator gradient of less than about 4.5 °C, preferably used in a system including an evaporator, and the pressure of the refrigerant is reduced from the inlet to the outlet of the evaporator by an amount that reduces the saturation temperature of the refrigerant by about 0.5 °C to about 2.0 °C.

[0018] Thus, in a preferred embodiment, the refrigerant according to the present invention is used in an evaporator having a pressure drop corresponding to a saturation temperature loss approximately equivalent to the increase in refrigerant temperature due to the gradient.

Brief Description of the Drawings

[0019] [Figure 1] It represents a schematic view from a typical supermarket product cooling case. [Figure 2] It shows the evaporator gradients of Refrigerant A and Refrigerant B. [Figure 3] It shows the evaporator gradients of Refrigerant C and Refrigerant D. [Figure 4] It shows the pressure drop effect of the present invention.

Modes for Carrying Out the Invention

[0020] Description of Preferred Compositions The present invention provides a refrigerant that simultaneously accomplishes the following: (1) having a gradient of less than 4.5 to assist in reducing or avoiding frost formation and being able to maintain a typical superheat, for example, from about 3 °C to about 5 °C; (2) being non-flammable; (3) being low-toxic or substantially non-toxic; (4) having a global warming potential (GWP) of less than about 150; and (5) having heat transfer characteristics and other physical characteristics (such as chemical stability) that match the requirements of specific applications, particularly in medium-temperature heat transfer systems, and more preferably in frost-free or low-frost medium-temperature refrigeration systems.

[0021] The present invention also provides a refrigerant that simultaneously: (1) has a gradient of less than about 3°C, preferably less than about 2°C (thus substantially avoiding frost formation and maintaining a typical superheating degree, e.g., about 3°C ​​to about 5°C); (2) is non-flammable; (3) is low-toxicity or substantially non-toxic; (4) has a GWP greater than about 75 and less than about 150; and (5) has heat transfer characteristics and other physical properties (such as chemical stability) that are consistent with the needs of a particular application, especially in medium-temperature heat transfer systems, and more preferably in frost-free or low-frost medium-temperature refrigeration systems.

[0022] The present invention also provides a refrigerant that simultaneously: (1) has a gradient of less than 4.5°C; (2) is non-flammable; (3) is low-toxicity or substantially non-toxic; (4) has a GWP of less than about 75; and (5) has heat transfer properties and other physical properties (such as chemical stability) that are consistent with the needs of a particular application, especially in medium-temperature heat transfer systems, and more preferably in frost-free or low-frost medium-temperature refrigeration systems. Definition:

[0023] The term "Coefficient of Performance" (hereinafter "COP") is a widely accepted measure of refrigerant performance, particularly useful for representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration engineering, this term represents the ratio of effective refrigeration or cooling capacity to the energy applied by the compressor during vapor compression, and therefore represents the ability of a given compressor to deliver a given amount of heat for a given volumetric flow rate of a heat transfer fluid, such as a refrigerant. In other words, given a particular compressor, a refrigerant with a higher COP will deliver more cooling or heating power. One means of estimating the COP of a refrigerant under specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, for example, RCDowning, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, which is incorporated herein in its entirety by reference).

[0024] The Global Warming Potential (GWP) was developed to allow for comparison of the global warming impact of various gases. It compares the amount of heat captured by a specific mass of gas with the amount of heat captured by a similar mass of carbon dioxide over a specific time period. Carbon dioxide was selected as the standard gas by the Intergovernmental Panel on Climate Change (IPCC), and its GWP is set to 1. The larger the GWP, the more a given gas will warm the Earth over that period compared to CO2.

[0025] The term "non-flammable" is defined in ASTM Standard E-681-2009 Standard Test Method for Concentration Limits of Flammability of Chemicals (Vapors). In accordance with ASHRAE Standard 34-2016 Designation and Safety Classification of Gases This refers to compounds or compositions that are determined to be non-flammable when judged under the conditions described in Refrigerants and Appendix B1 of ASHRAE Standard 34-2016 (each standard as it existed as of the filing date of this application), the contents of which are incorporated herein by reference in their entirety ("Non-flammability Test"). Flammability is defined as the ability of a composition to ignite and / or spread flame. Flammability is determined by measuring the flame angle under this test. Non-flammable substances are classified as Class "1" according to ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants (each standard as it existed as of the filing date of this application).

[0026] As used herein, the term “evaporator gradient” means the difference between the saturation temperature of the refrigerant at the evaporator inlet and the dew point of the refrigerant at the evaporator outlet, assuming that the pressure at the evaporator outlet is the same as the pressure at the inlet. As used herein, the expression “saturation temperature” means the temperature at which a liquid refrigerant boils into vapor at a given pressure.

[0027] As used herein, the expression “non-toxic or low-toxicity” indicates that the composition is classified as Class “A” by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and is described in Appendix B1 of ASHRAE Standard 34-2016 (each standard as it exists as of the filing date of this application). Non-flammable and low-toxicity substances are classified as “A1” by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and are described in Appendix B1 of ASHRAE Standard 34-2016 (each standard as it exists as of the filing date of this application).

[0028] The term "superheating" or simply "superheating" refers to the temperature rise of the refrigerant at the evaporator outlet that exceeds the saturation vapor temperature (or dew point temperature) of the refrigerant.

[0029] As used herein, the term E-1,3,3,3-tetrafluoropropene refers to the trans isomer of HFO-1234ze and is abbreviated as HFO-1234ze(E).

[0030] As used herein, the term E-1,1,1,4,4,4-hexafluorobuta-2-ene refers to the trans isomer of HFO-1336mzz and is abbreviated as HFO-1336mzz(E).

[0031] As used herein, the term 1,1,1,2,3,3,3-heptafluoropropane will be abbreviated as HFC-227ea.

[0032] As used herein, the term “about” with respect to quantities expressed as weight percent means that the amount of the component may vary by + / - 2 weight percent. Refrigerant composition HFO-1234ze(E) and HFO-1336mzz(E):

[0033] The present invention may include HFO-1234ze(E) and HFO-1336mzz(E), may essentially consist of HFO-1234ze(E) and HFO-1336mzz(E), or may consist of HFO-1234ze(E) and HFO-1336mzz(E).

[0034] The refrigerant may consist of (a) 65% to about 90% by weight of HFO-1234ze(E) and (b) about 10% to about 35% by weight of HFO-1336mzz(E). It will be understood that the refrigerant may essentially consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts, or may consist of HFO-1234ze(E) and HFO-1336mzz(E). The refrigerant described in this paragraph may, for convenience, be referred to as "Refrigerant 1".

[0035] The refrigerant may consist of (a) approximately 76% to 90% by weight of HFO-1234ze(E) and (b) approximately 10% to 24% by weight of HFO-1336mzz(E). It will be understood that the refrigerant may essentially consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts, or may consist of HFO-1234ze(E) and HFO-1336mzz(E). The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1A".

[0036] The refrigerant can essentially consist of (a) approximately 65% ​​to 78% by weight of HFO-1234ze(E) and (b) approximately 22% to 35% by weight of HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1B".

[0037] The refrigerant can essentially consist of (a) approximately 70% to 78% by weight of HFO-1234ze(E) and (b) approximately 22% to 30% by weight of HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1C".

[0038] The refrigerant can essentially consist of (a) 69.5% to 80% by weight of HFO-1234ze(E) and (b) 20% to 30.5% by weight of HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1D".

[0039] The refrigerant can essentially consist of (a) 65 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E) and (b) 35 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1E".

[0040] The refrigerant can essentially consist of (a) 70 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E) and (b) 30 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1F".

[0041] The refrigerant can essentially consist of (a) 69.5% to 80% by weight of HFO-1234ze(E) and (b) 20% to 30.5% by weight of HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1D".

[0042] The refrigerant can essentially consist of (a) 65 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E) and (b) 35 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1E".

[0043] The refrigerant can essentially consist of (a) 70 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E) and (b) 30 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1F".

[0044] The refrigerant can essentially consist of (a) 75 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E) and (b) 25 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1G".

[0045] The refrigerant can essentially consist of (a) 78 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E) and (b) 20 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E). It will be understood that the refrigerant can consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 1H".

[0046] The refrigerant may consist of (a) approximately 76% to 80% by weight of HFO-1234ze(E) and (b) approximately 20% to 24% by weight of HFO-1336mzz(E). It will be understood that the refrigerant may essentially consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts, or may consist of HFO-1234ze(E) and HFO-1336mzz(E). The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 2".

[0047] The refrigerant may consist of (a) approximately 78% to 80% by weight of HFO-1234ze(E) and (b) approximately 20% to 22% by weight of HFO-1336mzz(E). It will be understood that the refrigerant may essentially consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts, or may consist of HFO-1234ze(E) and HFO-1336mzz(E). The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 3".

[0048] The refrigerant may contain (a) approximately 76% by weight of HFO-1234ze(E) and (b) approximately 19% by weight of HFO-1336mzz(E). It is understood that the refrigerant may essentially consist of HFO-1234ze(E) and HFO-1336mzz(E) in the above amounts, or may consist of HFO-1234ze(E) and HFO-1336mzz(E). The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 4". HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea:

[0049] The present invention may comprise HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea, or may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea.

[0050] The refrigerant may consist of (a) about 74.6% to about 78.6% by weight of HFO-1234ze(E), (b) about 17% to about 21% by weight of HFO-1336mzz(E), and (c) more than 0% to about 4.4% by weight of HFC-227ea. Preferably, the refrigerant consists of (a) 74.6% to about 78.6% by weight of HFO-1234ze(E), (b) about 17% to about 19% by weight of HFO-1336mzz(E), and (c) about 4.4% by weight of HFC-227ea. For example, the refrigerant may contain HFC-227ea in an amount of about 4.4% by weight. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the quantities mentioned above, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 5".

[0051] The refrigerant may consist of (a) approximately 78.6% by weight of HFO-1234ze(E), (b) approximately 17% by weight of HFO-1336mzz(E), and (c) approximately 4.4% by weight of HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above amounts, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 6A".

[0052] The refrigerant may consist of (a) approximately 76.6 wt% HFO-1234ze(E), (b) approximately 19 wt% HFO-1336mzz(E), and (c) approximately 4.4 wt% HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above amounts, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 6B".

[0053] The refrigerant may consist of (a) approximately 74.6 wt% HFO-1234ze(E), (b) approximately 21 wt% HFO-1336mzz(E), and (c) approximately 4.4 wt% HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above amounts, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 6C".

[0054] The refrigerant may include (a) approximately 78.6 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E), (b) 17 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E), and (c) 4.4 wt% + 2.0 wt% / -0.5 wt% HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above quantities, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 6D".

[0055] The refrigerant may include (a) approximately 76.6 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E), (b) 19 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E), and (c) 4.4 wt% + 2.0 wt% / -0.5 wt% HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above quantities, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 6E".

[0056] The refrigerant may include (a) approximately 74.6 wt% + 0.5 wt% / -2.0 wt% HFO-1234ze(E), (b) 21 wt% + 2.0 wt% / -0.5 wt% HFO-1336mzz(E), and (c) 4.4 wt% + 2.0 wt% / -0.5 wt% HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above quantities, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 6F".

[0057] The refrigerant may consist of (a) 78.6 wt% HFO-1234ze(E), (b) 17 wt% HFO-1336mzz(E), and (c) 4.4 wt% HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above amounts, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 6G".

[0058] The refrigerant may consist of (a) 76.6 wt% HFO-1234ze(E), (b) 19 wt% HFO-1336mzz(E), and (c) 4.4 wt% HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above amounts, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 6H".

[0059] The refrigerant may consist of (a) 74.6 wt% HFO-1234ze(E), (b) 21 wt% HFO-1336mzz(E), and (c) 4.4 wt% HFC-227ea. The refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above amounts, or HFO-1234ze(E) It will be understood that this can consist of HFO-1336mzz(E) and HFC-227ea. The refrigerants described in this paragraph may, for convenience, be referred to as "refrigerant 6I".

[0060] The refrigerant may consist of (a) approximately 78.6% to 80.6% by weight of HFO-1234ze(E), (b) approximately 15% to 17% by weight of HFO-1336mzz(E), and (c) approximately 4.4% by weight of HFC-227ea. It will be understood that the refrigerant may essentially consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea in the above amounts, or may consist of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant described in this paragraph may, for convenience, be referred to as "refrigerant 7".

[0061] Each of the refrigerants containing refrigerants 1-7 has a GWP of less than approximately 150. As used herein, the term "refrigerants 1-7" means each of refrigerants 1, 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, 2, 3, 4, 5, 6A, 6B, 6C, 6D, 6E, 6F, 6G, 6H, 6I, and 7, respectively.

[0062] The particular preferred refrigerants of the present invention, each of the refrigerants 1E to 1H, have a GWP of less than about 75.

[0063] Each of the refrigerants, including refrigerants 1 through 7, may be advantageously non-flammable. In other words, the refrigerant may be a Class 1 refrigerant.

[0064] Each of the refrigerants, including refrigerants 1 through 7, is non-toxic or has low toxicity. In other words, the refrigerants are Class A refrigerants.

[0065] Each of the refrigerants 1 to 7 preferably has a gradient of less than 4.5°C, more preferably less than about 3°C, and even more preferably less than about 2°C.

[0066] It will be understood that each of the refrigerants 1 to 7 in the preferred embodiment has one or more, most preferably all, of the above characteristics. Heat transfer composition:

[0067] The refrigerant of the invention may be provided in a heat transfer composition. Accordingly, the heat transfer composition of the invention includes preferred refrigerant compositions disclosed herein, and in particular the refrigerant of the invention which includes any one of refrigerants 1 to 7. Preferably, the invention relates to a heat transfer composition which includes a refrigerant, wherein each of refrigerants 1 to 7 is included in an amount of at least about 80% by weight of the heat transfer composition, or at least about 90% by weight of the heat transfer composition, or at least about 97% by weight of the heat transfer composition, or at least about 99% by weight of the heat transfer composition. The heat transfer composition may be essentially composed of a refrigerant or may consist of a refrigerant. Lubricant:

[0068] Preferably, the heat transfer composition may further contain a lubricant. The lubricant lubricates the refrigerant compressor using the refrigerant. Preferably, the lubricant is present in the heat transfer composition in an amount of about 1% to about 50% by weight, more preferably in an amount of about 10% to about 50% by weight, and most preferably in an amount of about 30% to about 50% by weight. Useful lubricants include alkylbenzenes, esters, polyol esters ("POE"), polyalkylene glycols ("PAG"), polyvinyl ethers ("PVE"), poly(α-olefins) ("PAO"), and combinations thereof. A commercially available alkylbenzene lubricant is Zerol 150®. PAG is available as GM Goodwrench Refrigeration Oil and MOPAR-56. Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters.

[0069] Commercially available POEs include neopentyl glycol diperargonic acid, available as Emery 2917® and Hatcol 2370®, and pentaerythritol derivatives such as those sold by CPI Fluid Engineering under the trade names Emkarate RL32-3MAF and Emkarate RL68H. Emkarate RL32-3MAF and Emkarate RL68H have the properties identified in the table below. [Table 1]

[0070] Examples of commercially available PVEs include polyvinyl ethers FVC-32D (registered trademark) and FVC-68D (registered trademark) by Idemitsu.

[0071] Preferred lubricants include POE and PVE, more preferably POE. Naturally, different mixtures of different types of lubricants may be used.

[0072] The heat transfer composition of the present invention may essentially consist of, or be composed of, a refrigerant containing each of the refrigerants 1 to 7, and a lubricant containing each of the preferred lubricants as described above.

[0073] A preferred heat transfer composition of the invention comprises one of the refrigerants 1 to 7 and a POE lubricant.

[0074] A preferred heat transfer composition of the invention comprises a refrigerant 6D and a POE lubricant.

[0075] A preferred heat transfer composition of the invention comprises a refrigerant 6D having a viscosity (ASTM D445) of about 31 to about 67 at 40°C and a POE lubricant.

[0076] A preferred heat transfer composition of the invention comprises a refrigerant 6D having a viscosity (ASTM D445) of about 5 to about 10 at 100°C and a POE lubricant.

[0077] A preferred heat transfer composition of the invention comprises a refrigerant 6E and a POE lubricant.

[0078] A preferred heat transfer composition of the invention comprises a refrigerant 6E and a POE lubricant having a viscosity (ASTM D445) of about 31 to about 67 at 40°C.

[0079] A preferred heat transfer composition of the invention comprises a refrigerant 6E and a POE lubricant having a viscosity (ASTM D445) of about 5 to about 10 at 100°C.

[0080] A preferred heat transfer composition of the invention comprises a refrigerant 6F and a POE lubricant.

[0081] A preferred heat transfer composition of the invention comprises a refrigerant 6F having a viscosity (ASTM D445) of about 31 to about 67 at 40°C and a POE lubricant.

[0082] A preferred heat transfer composition of the invention comprises a refrigerant 6F having a viscosity (ASTM D445) of about 5 to about 10 at 100°C and a POE lubricant.

[0083] A preferred heat transfer composition of the invention comprises a refrigerant 6G and a POE lubricant.

[0084] A preferred heat transfer composition of the invention comprises a refrigerant 6G and a POE lubricant having a viscosity (ASTM D445) of about 31 to about 67 at 40°C.

[0085] A preferred heat transfer composition of the invention comprises a refrigerant 6G and a POE lubricant having a viscosity (ASTM D445) of about 5 to about 10 at 100°C.

[0086] A preferred heat transfer composition of the invention comprises a refrigerant 6H and a POE lubricant.

[0087] A preferred heat transfer composition of the invention comprises a refrigerant 6H having a viscosity (ASTM D445) of about 31 to about 67 at 40°C and a POE lubricant.

[0088] A preferred heat transfer composition of the invention comprises a refrigerant 6H having a viscosity (ASTM D445) of about 5 to about 10 at 100°C and a POE lubricant.

[0089] A preferred heat transfer composition of the invention comprises a refrigerant 6I and a POE lubricant.

[0090] A preferred heat transfer composition of the invention comprises a refrigerant 6I and a POE lubricant having a viscosity (ASTM D445) of about 31 to about 67 at 40°C.

[0091] A preferred heat transfer composition of the invention comprises a refrigerant 6I and a POE lubricant having a viscosity (ASTM D445) of about 5 to about 10 at 100°C.

[0092] A preferred heat transfer composition of the invention comprises one of refrigerants 1 to 7 and a PVE lubricant.

[0093] A preferred heat transfer composition of the invention comprises a refrigerant 6D and a PVE lubricant.

[0094] A preferred heat transfer composition of the invention comprises a refrigerant 6E and a PVE lubricant.

[0095] A preferred heat transfer composition of the invention comprises a refrigerant 6F and a PVE lubricant.

[0096] A preferred heat transfer composition of the invention comprises a refrigerant 6G and a PVE lubricant.

[0097] A preferred heat transfer composition of the invention comprises a refrigerant 6H and a PVE lubricant.

[0098] A preferred heat transfer composition of the invention comprises a refrigerant 6I and a PVE lubricant. use

[0099] The methods and systems of the present invention may include any heat transfer system and / or any heat transfer method that absorbs heat, dissipates heat, or absorbs and dissipates heat, using a refrigerant containing each of refrigerants 1 to 7, or a heat transfer composition containing each of refrigerants 1 to 7 of the present invention. Accordingly, the present invention provides a method for heating or cooling a fluid or object using a refrigerant containing each of refrigerants 1 to 7, or using a heat transfer composition containing each of refrigerants 1 to 7 of the present invention. The invention also provides a heat transfer system comprising a refrigerant containing each of refrigerants 1 to 7, or a heat transfer composition containing each of refrigerants 1 to 7 of the present invention. It will be understood that the heat transfer system described herein may be a vapor compression system having a fluid-communicated evaporator, condenser, and compressor.

[0100] The applicants have found that substantial advantages, such as those that may arise for cooling products and / or other frozen foods, or those that may arise in connection with cooling certain electronic devices, can be achieved in connection with heat transfer systems and heat transfer methods used to absorb heat from a fluid surrounding an article, or to transfer heat to the article itself in other ways, by refrigerants containing each of refrigerants 1 to 7, or by heat transfer compositions of the present invention containing the refrigerants of the present invention, refrigerants 1 to 7. In such cases, the fluid may be air or a secondary coolant (e.g., water, glycol, water / glycol). This may include kohl mixtures, saline solutions, etc., and occurs, for example, in the case of refrigerants used in evaporators in systems and methods that require that the temperature of the article or fluid being cooled not be exposed to temperatures below a certain limit.

[0101] Therefore, generally speaking, the methods and systems of the present invention utilize apparatus and / or processes that enable the refrigerant or heat transfer composition of the present invention to absorb heat, and apparatus and / or processes that subsequently remove the absorbed heat from the refrigerant.

[0102] The present invention provides a refrigeration system, an air conditioning system, or a heat pump system comprising a refrigerant containing each of refrigerants 1 to 7, or a heat transfer composition containing each of refrigerants 1 to 7 of the present invention.

[0103] The present invention provides a refrigeration system, an air conditioning system, or a heat pump system comprising a refrigerant consisting of any one of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising the refrigerant of the present invention, each containing one of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I.

[0104] An evaporator used to absorb heat from an article or a fluid being cooled may include, for example, conduits such as cooling coils, and it will be understood that while such conduits are exposed (directly or indirectly) to the article or fluid to be cooled, the refrigerants, including each of refrigerants 1 to 7, flow through the conduits. In this way, heat flows from the fluid being cooled (e.g., air) and / or articles placed in the vicinity (e.g., fresh produce such as fruits, vegetables, and flowers) through the metal or other heat-conductive material of the conduits into the refrigerants of the present invention, including each of refrigerants 1 to 7.

[0105] The applicants have found that, in a system where the cooled discharge air is controlled to a temperature of about 2°C to about 5°C, when the cooled discharge air is at a temperature of about 2°C to about 4°C, and more preferably in a particular embodiment (e.g., cooled fresh cut fruit, vegetables, and flowers), when the cooled discharge air is at a temperature of about 2°C to about 3°C, the refrigerant compositions of the present invention, each of the refrigerants 1 to 7, have an evaporator gradient of preferably less than about 3°C, and even more preferably less than about 2°C.

[0106] The applicant's discovery of this effect, achievable according to the preferred refrigerant compositions of the present invention, each containing refrigerant 1 to 7, and the methods and systems of the present invention utilizing the heat exchanger design of the present invention, is schematically shown in Figure 4.

[0107] It will be understood that the refrigerants according to the present invention, including each of refrigerants 1 to 7, can be used in a system having an evaporator with a pressure drop corresponding to a saturation temperature loss that is approximately equivalent to the rise in refrigerant temperature due to the gradient.

[0108] Specific systems and methods of the present invention are described below. Refrigeration system

[0109] The present invention provides a refrigeration system comprising the refrigerant or heat transfer composition of the invention. The present invention also provides a method for cooling a fluid or object using the refrigeration system, the method comprising (a) evaporating the refrigerant composition of the invention, comprising each of refrigerants 1 to 7, around the fluid or object to be cooled, and (b) condensing the refrigerant.

[0110] The refrigerants and heat transfer compositions of the invention can be used in any refrigeration system. However, the applicants have found that the refrigerants, each containing refrigerants 1 to 7, and the heat transfer compositions, each containing refrigerants 1 to 7, offer particular advantages in medium-temperature refrigeration systems, especially in "frost-free" applications, such as those where the refrigerant temperature along the evaporator needs to be maintained above the freezing point of water (i.e., above 0°C). This prevents frost buildup on the evaporator surface, resulting in the elimination or reduction of the need for defrosting cycles.

[0111] The refrigerants and heat transfer compositions of the invention can be used in any refrigeration system. However, the applicants have found that the refrigerants of the invention, each containing refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or the heat transfer compositions containing the refrigerants of the invention, each containing refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, offer particular advantages in medium-temperature refrigeration systems, especially in "frost-free" applications, such as those where the refrigerant temperature along the evaporator needs to be maintained above the freezing point of water (i.e., above 0°C). This prevents frost buildup on the evaporator surface, resulting in the elimination or reduction of the need for defrosting cycles.

[0112] Accordingly, the present invention relates to a medium-temperature refrigeration system comprising a refrigerant comprising any one of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising the refrigerant of the present invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I. The present invention also provides a method for cooling a fluid or object in a medium-temperature refrigeration system, the method comprising (a) evaporating the refrigerant composition of the invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising the refrigerant of the present invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, around the fluid or object to be cooled, and (b) condensing the refrigerant. Preferably, the evaporator temperature is about -15°C to about 5°C, more preferably about -10°C to about 5°C.

[0113] As used herein, a medium-temperature refrigeration system refers to a refrigeration system utilizing one or more compressors and operating under or within the following conditions: (a) a condenser temperature of about 15°C to about 60°C, preferably about 25°C to about 45°C; (b) an evaporator temperature of about -15°C to about 5°C, preferably about -10°C to about 5°C; optionally (c) a superheat at the evaporator outlet of about 0°C to about 10°C, preferably about 1°C to about 6°C; optionally (d) a superheat in the intake line of about 5°C to about 40°C, preferably about 15°C to about 30°C. Superheat along the intake line may be generated by a heat exchanger.

[0114] Examples of medium-temperature refrigeration systems include small-scale refrigeration systems (including vending machines, ice makers, and household appliances), commercial refrigeration systems (such as supermarket refrigeration systems and walk-in coolers), residential refrigeration systems, industrial refrigeration systems, and ice rinks. It is possible.

[0115] In the case of storing perishable products such as vegetables and fruits in a medium-temperature refrigeration system, for example, the fluid to be cooled is air having a desired cooling temperature of about 2°C to about 5°C, preferably about 2°C to about 4°C, and more preferably about 2°C to about 3°C ​​(e.g., cooling fresh cut fruit, vegetables, and flowers). Furthermore, in many applications, it is preferable that the refrigerant temperature along the evaporator does not fall below about 0°C (the freezing point of water) to avoid frost formation. Preferably, at the same time, the superheat at the evaporator outlet should be maintained at a typical value of about 3°C ​​to about 5°C, preferably about 4°C.

[0116] Therefore, the invention preferably provides a medium-temperature refrigeration system comprising a refrigerant containing each of refrigerants 1 to 7, or a heat transfer composition comprising the refrigerant of the present invention, wherein the system has an evaporator temperature of about 0°C to about 5°C.

[0117] Accordingly, the invention provides a medium-temperature refrigeration system comprising, preferably, a refrigerant comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising the refrigerant of the present invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, wherein the system has an evaporator temperature of about 0°C to about 5°C.

[0118] The present invention also provides a method for cooling a fluid or object in a medium-temperature refrigeration system, the method comprising (a) evaporating a refrigerant composition of the invention, each of refrigerants 1 to 7, around the fluid or object to be cooled, and (b) condensing the refrigerants, the system having an evaporator temperature of about 0°C to about 5°C.

[0119] The refrigerant and heat transfer compositions of the invention can also be used in other refrigeration applications.

[0120] For example, the present invention relates to a low-temperature refrigeration system comprising a refrigerant comprising each of refrigerants 1 to 7, or a heat transfer composition comprising the refrigerant of the present invention comprising each of refrigerants 1 to 7. The present invention also provides a method for cooling a fluid or object in a low-temperature refrigeration system, the method comprising (a) evaporating the refrigerant composition of the invention comprising each of refrigerants 1 to 7 around the fluid or object to be cooled, and (b) condensing the refrigerant. Preferably, the evaporator temperature is about -40°C to less than about -15°C, more preferably about -40°C to about -25°C.

[0121] For example, the present invention relates to a low-temperature refrigeration system comprising a refrigerant comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising the refrigerant of the present invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I. The present invention also provides a method for cooling a fluid or object in a low-temperature refrigeration system, the method comprising (a) evaporating the refrigerant composition of the invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising the refrigerant of the present invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, around the fluid or object to be cooled, and (b) condensing the refrigerant. Preferably, the evaporator temperature is about -40°C to less than about -15°C, more preferably about -40°C to about -25°C.

[0122] As used herein, a low-temperature refrigeration system refers to a refrigeration system that utilizes one or more compressors and operates under or within the following conditions: (a) a condenser temperature of about 15°C to about 50°C, preferably about 25°C to about 45°C; (b) an evaporator temperature of about -40°C to about -15°C or less than about -15°C, preferably about -40°C to about -25°C; optionally (c) a superheat at the evaporator outlet of about 0°C to about 10°C, preferably about 1°C to about 6°C; optionally (d) a superheat in the intake line of about 15°C to about 40°C, preferably about 20°C to about 30°C.

[0123] Examples of low-temperature refrigeration systems include supermarket refrigeration systems, commercial refrigerator systems (including supermarket refrigerators), residential refrigerator systems, and industrial refrigerator systems.

[0124] Low-temperature refrigeration systems can be used to cool frozen goods.

[0125] The present invention relates to a cascade refrigeration system comprising the refrigerant or heat transfer composition of the invention.

[0126] Generally, a cascade system has two or more stages. When a cascade system has two stages, these are generally referred to as the upper and lower stages. The refrigerant of the invention, containing each of refrigerants 1 to 7, or the heat transfer composition containing the refrigerant of the invention, containing each of refrigerants 1 to 7, may be used in either the upper or lower stage of a cascade refrigeration system. However, the refrigerant of the invention, containing each of refrigerants 1 to 7, or the heat transfer composition containing the refrigerant of the invention, containing each of refrigerants 1 to 7, is preferably used in the upper stage of the cascade system. In consideration of the teachings contained herein, those skilled in the art can determine suitable refrigerants for use in the lower stage of a cascade system, which may include, for example, CO2, R1234yf, and R455A. R455A is a blend of 75.5% R1234yf, 21.5% R32, and 3% CO2. In a cascade system, this refrigerant can replace R404A.

[0127] Generally, a cascade system has two or more stages. When a cascade system has two stages, these are generally referred to as the upper and lower stages. The refrigerants of the invention, each comprising refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or the heat transfer compositions comprising the refrigerants of the invention, each comprising refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, may be used in either the upper or lower stage of a cascade refrigeration system. However, the refrigerants of the invention, each comprising refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or the heat transfer compositions comprising the refrigerants of the invention, each comprising refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, are preferably used in the upper stage of the cascade system. In consideration of the teachings contained herein, those skilled in the art can determine suitable refrigerants for use in the lower stage of a cascade system, which may include, for example, CO2, R1234yf, and R455A. R455A is a blend of 75.5% R1234yf, 21.5% R32, and 3% CO2. In cascade systems, this refrigerant can replace R404A.

[0128] Refrigerated transport creates a link within a low-temperature distribution system that enables frozen or cooled products to reach the end user in the correct temperature environment. The present invention includes the refrigerant of the invention, which includes each of refrigerants 1 to 7, or the heat containing the refrigerant of the invention, which includes each of refrigerants 1 to 7. This invention relates to a transport refrigeration system, which includes a transfer composition.

[0129] Refrigeration for transport creates links within a low-temperature distribution system that enable frozen or cooled products to reach end users in the correct temperature environment. The present invention relates to a refrigeration system for transport comprising the refrigerants of the invention, each comprising refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising the refrigerants of the invention, each comprising refrigerants 6D, 6E, 6F, 6G, 6H, and 6I.

[0130] Examples of refrigerated transport include refrigerated road vehicles (trucks and vans, etc.), railcars, and containers that can be transported by road vehicles, trains, and ships / boats. Secondary loop system

[0131] A refrigerant of the present invention, including each of refrigerants 1 to 7, or a heat transfer composition containing a refrigerant of the present invention, including each of refrigerants 1 to 7, may be used as a secondary fluid in a secondary loop system. The secondary loop system includes a primary vapor compression system loop using a primary refrigerant and has an evaporator for cooling the secondary loop fluid. The secondary fluid then provides the cooling required for the application. Because the refrigerant in such a loop may be exposed to humans near the cooling space, the secondary fluid needs to be non-flammable and low-toxicity. In other words, a refrigerant of the present invention, including each of refrigerants 1 to 7, may be used as a “secondary fluid”. Primary fluids for use in the primary loop (vapor compression cycle, external / outdoor components of the loop) may include, but are not limited to, the following refrigerants: R404A, R507, R410A, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, R1234ze(E), R1234yf, and R449A.

[0132] The refrigerants of the present invention, comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or heat transfer compositions comprising each of the refrigerants of the present invention, comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, can be used as secondary fluids in secondary loop systems. A secondary loop system comprises a primary vapor compression system loop using a primary refrigerant and having an evaporator that cools the secondary loop fluid. The secondary fluid then provides the cooling required for the application. Because the refrigerant in such a loop may be exposed to humans near the cooling space, the secondary fluid needs to be non-flammable and have low toxicity. In other words, the refrigerants of the present invention, comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, may be used as “secondary fluids”. Primary fluids for use in the primary loop (vapor compression cycle, external / outdoor components of the loop) may include, but are not limited to, the following refrigerants: R404A, R507, R410A, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, R1234ze(E), R1234yf, and R449A. Heat pump system

[0133] The present invention relates to a heat pump system comprising the refrigerant of the invention, which includes each of refrigerants 1 to 7, or a heat transfer composition comprising the refrigerant of the invention, which includes each of refrigerants 1 to 7.

[0134] The present invention also provides a method for heating a fluid or object using a heat pump, the method comprising (a) condensing a refrigerant composition of the invention, each of refrigerants 1 to 7, around the fluid or object to be heated, and (b) evaporating the refrigerants.

[0135] The present invention relates to a heat pump system comprising a refrigerant of the invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising a refrigerant of the invention comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I.

[0136] The present invention also provides a method for heating a fluid or object using a heat pump, the method comprising (a) condensing a refrigerant composition of the invention, each comprising refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, around the fluid or object to be heated, and (b) evaporating the refrigerants.

[0137] Examples of heat pumps include rotary heat pump dryers, reversible heat pumps, high-temperature heat pumps, and air-to-air heat pumps. Air conditioning system

[0138] The present invention relates to an air conditioning system comprising a refrigerant or the refrigerant of the invention, each comprising refrigerants 1 to 7, or a heat transfer composition comprising the refrigerant of the invention, each comprising refrigerants 1 to 7. The present invention also provides an air conditioning method using the air conditioning system, the method comprising (a) evaporating the refrigerant composition of the invention, each comprising refrigerants 1 to 7, around a fluid of an object to be cooled, and (b) condensing the refrigerant. The air may be conditioned directly or indirectly by the refrigerant of the invention, each comprising refrigerants 1 to 7.

[0139] The present invention relates to an air conditioning system comprising an inventive refrigerant comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising an inventive refrigerant comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I. The present invention also provides an air conditioning method using the air conditioning system, the method comprising (a) evaporating an inventive refrigerant composition comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I around a fluid of an object to be cooled, and (b) condensing the refrigerant. The air may be conditioned directly or indirectly by an inventive refrigerant comprising each of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I.

[0140] Examples of air conditioning systems include chillers, residential, industrial, commercial, and mobile air conditioning systems, as well as air conditioning systems for road vehicles such as automobiles, trucks, and buses, and for boats and trains.

[0141] A preferred refrigeration system of the present invention includes, in particular, a chiller containing the refrigerants of the present invention, each of the refrigerants 1 to 7, and more specifically, refrigerants 4 and 6A to 6I.

[0142] A preferred refrigeration system of the present invention is a residential air conditioning system containing the refrigerants of the present invention, particularly each of refrigerants 1 to 7, and more specifically refrigerants 4 and 6A to 6I.

[0143] Preferred refrigeration systems of the present invention include, in particular, industrial air conditioning systems containing the refrigerants of the present invention, each of the refrigerants 1 to 7, and more specifically, refrigerants 4 and 6A to 6I.

[0144] A preferred refrigeration system of the present invention includes, in particular, a commercial air conditioning system containing the refrigerants of the present invention, which includes each of the refrigerants 1 to 7, and more specifically, refrigerants 4 and 6A to 6I.

[0145] A preferred refrigeration system of the present invention includes, in particular, a mobile air conditioning system containing the refrigerants of the present invention, which includes each of the refrigerants 1 to 7, and more specifically, refrigerants 4 and 6A to 6I.

[0146] It will be understood that any of the above-mentioned refrigeration systems, air conditioning systems, or heat pump systems using the refrigerant of the invention, which includes each of refrigerants 1 to 7, or a heat transfer composition containing the refrigerant of the invention, which includes each of refrigerants 1 to 7, may include an intake line / liquid line heat exchanger (SL-LL HX).

[0147] It will be understood that any of the above-mentioned refrigeration systems, air conditioning systems, or heat pump systems using the refrigerant of the invention, each comprising refrigerant 6D, 6E, 6F, 6G, 6H, and 6I, or a heat transfer composition comprising the refrigerant of the invention, each comprising refrigerant 6D, 6E, 6F, 6G, 6H, and 6I, may include an intake line / liquid line heat exchanger (SL-LL HX). Organic Rankine Cycle System

[0148] A refrigerant composition of the invention, containing each of refrigerants 1 to 7, or a heat transfer composition containing each of refrigerants 1 to 7, may be used in an organic Rankine cycle (ORC). In the context of ORCs, the refrigerants used in these systems may also be classified as “working fluids.”

[0149] The refrigerant compositions of the invention, each containing refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, or the heat transfer compositions of the invention containing refrigerants 6D, 6E, 6F, 6G, 6H, and 6I, may be used in organic Rankine cycles (ORCs). In the context of ORCs, the refrigerants used in these systems may also be classified as “working fluids.”

[0150] The Rankine cycle system is known to be a simple and reliable means of converting thermal energy into mechanical shaft power.

[0151] In industrial environments, particularly when the industrial environment already contains large quantities of flammable materials in use or storage, it may be possible to use flammable working fluids such as toluene and pentane. However, in situations where the risks associated with the use of flammable and / or toxic working fluids are unacceptable, such as in power generation in densely populated areas or near buildings, it is necessary to use non-flammable and / or non-toxic refrigerants as working fluids. Furthermore, from a GWP perspective, there are concerns within the industry that these materials are environmentally friendly. There are also movements to make it acceptable.

[0152] The process for recovering waste heat in an organic Rankine cycle system involves an external (waste) heat source, such as a process stream, pumping a liquid-phase working fluid through a heat exchanger (boiler) that heats the working fluid and evaporates it into saturated or superheated steam. This steam expands through a turbine, and the waste heat energy is converted into mechanical energy. Subsequently, the gas-phase working fluid is condensed into a liquid and pumped back into the boiler to repeat the heat extraction cycle.

[0153] Therefore, the present invention relates to the use of the refrigerant of the invention, which contains each of refrigerants 1 to 7, or a heat transfer composition containing the refrigerant of the invention, which contains each of refrigerants 1 to 7, in an organic Rankine cycle.

[0154] Accordingly, the present invention provides a process for converting thermal energy into mechanical energy in a Rankine cycle, the method comprising: i) vaporizing a working fluid with a heat source and expanding the resulting vapor, or vaporizing a working fluid with a heat source and expanding the resulting vapor; and then ii) cooling the working fluid with a heat sink to condense the vapor, wherein the working fluid is a refrigerant containing each of refrigerants 1 to 7, or a refrigerant of the invention, or a heat transfer composition containing each of refrigerants 1 to 7, the refrigerant of the present invention.

[0155] Mechanical work can be transmitted to electrical devices such as generators to produce electricity.

[0156] The heat source may be provided by a thermal energy source selected from industrial waste heat, solar energy, geothermal hot water, low-pressure steam, distributed power generation equipment utilizing fuel cells, internal combustion engines, or prime movers. Preferably, the low-pressure steam is low-pressure geothermal steam or is provided by a fossil fuel power generation plant.

[0157] It will be understood that heat source temperatures can vary widely, for example, from about 90°C to over 800°C, and can depend on a multitude of factors, including geography and time of year for specific combustion gases and some fuel cells. For example, sources such as wastewater or low-pressure steam from plastic manufacturing plants and / or chemical or other industrial plants, oil refineries, etc., as well as geothermal-based systems, may have source temperatures as low as about 100°C or below, sometimes as low as about 90°C, or even as low as about 80°C. Gaseous heat sources such as exhaust gases from combustion processes or any heat source where subsequent processing to remove particulate matter and / or corrosive species leads to low temperatures may also have source temperatures as low as about 130°C or below, about 120°C or below, about 100°C or below, sometimes as low as about 90°C, or even as low as about 80°C. electronic cooling

[0158] The refrigerant composition of the invention, comprising any one of refrigerants 1 to 7, may be used in connection with electronic cooling systems and methods, such as cooling chips, electronic circuit boards, batteries (including batteries used in automobiles, trucks, buses, and other electronic transport vehicles), and computers.

[0159] The invention comprises one of the refrigerants 6D, 6E, 6F, 6G, 6H, and 6I. The medium composition may be used in connection with electronic cooling systems and methods, such as cooling chips, electronic substrates, batteries (including batteries used in automobiles, trucks, buses, and other electronic transport vehicles), and computers. Heat transfer composition

[0160] The heat transfer composition, in a low-temperature refrigeration system, includes one of the refrigerants 1 to 7 and a lubricant, as described below. [Table 2]

[0161] The heat transfer composition, in a medium-temperature refrigeration system, includes one of the refrigerants 1 to 7 and a lubricant, as described below. [Table 3]

[0162] The heat transfer composition, in a retail food refrigeration system, includes one of the refrigerants 1 to 7 and a lubricant, as described below. [Table 4]

[0163] The heat transfer composition, in a transport container refrigeration system, includes one of the refrigerants 1 to 7 and a lubricant, as described below. [Table 5] [Examples]

[0164] In the following examples, the target refrigerant compositions are identified as compositions A1 to A8 in Table 1 below. Refrigerants A1, A2, A3, A4, A4', A4'', A5, A6, A7, and A8 are defined as follows: The refrigerant compositions specified in Table 1 below are refrigerants within the scope of the present invention as described herein. Each refrigerant was subjected to thermodynamic analysis to determine its ability to match the operating characteristics of R-134a in various refrigeration systems. The analysis was performed using experimental data collected on the properties of various two-component and three-component pairs of components used in the refrigerants. In the experimental evaluation, the composition of each pair was varied over a series of relative percentages, and the mixing parameters of each pair were regressiond to the experimentally obtained data. In the examples, known vapor / liquid equilibrium behavior data available in the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database software (Refprop 9.1 NIST Standard Database 23 from April 2016) was used. The parameters selected for the analysis were the same compressor volume for all refrigerants, the same operating conditions for all refrigerants, and the same compressor adiabatic efficiency and volumetric efficiency for all refrigerants. In each example, simulations were performed using the measured vapor-liquid equilibrium data. The simulation results for each example are reported below. [Table 6] Table 1: Refrigerants evaluated for performance examples Example 1: Performance of a medium-temperature refrigeration system with and without an intake line (SL) / liquid line (LL) heat exchanger (HX)

[0165] Performance tests were conducted on refrigerants A1-A8 in a medium-temperature refrigeration system with and without an intake / liquid line heat exchanger (SL / LL HX). This analysis evaluated the efficiency (COP) of refrigerants A1-A8 in this system at different effectiveness levels of the SL-LL HX under the following conditions.

[0166] The operating conditions were as follows: • Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C • Condenser supercooling = 0.0°C (system with receptors) • Evaporation temperature = -8℃ Evaporator overheating = 5.5℃ • Compressor adiabatic efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the intake line = 10℃ • Intake line / liquid line heat exchanger heat exchange rate: 0%, 35%, 55%, 75% [Table 7] Table 2. Performance of a medium-temperature refrigeration system with SL / LL HX

[0167] Table 2 shows the performance of refrigerants in a medium-temperature refrigeration system. The results below the column with a “0%” efficiency relative to SL-LL HX represent a system without SL-LL HX. It will also be understood that refrigerants A1-A8 show improved performance compared to R134a in terms of efficiency (COP) when an SL / LL heat exchanger is used, and compositions A4, A4', and A4'' show superior performance when all relevant performance factors are considered. Example 2: Performance of a low-temperature refrigeration system with and without an intake line / liquid line heat exchanger.

[0168] Performance tests were conducted on refrigerants A1-A8 in low-temperature refrigeration systems with and without an intake / liquid line heat exchanger (SL / LL HX). This analysis evaluated the efficiency (COP) of refrigerants A1-A8 in the system at different levels of SL-LL HX effectiveness under the following conditions.

[0169] The operating conditions were as follows: • Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C • Condenser supercooling = 0.0°C (system with receptors) • Evaporation temperature = -35°C, corresponding internal temperature = -25°C Evaporator overheating = 5.5℃ • Compressor adiabatic efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the intake line = 10℃ • Intake line / liquid line heat exchanger heat exchange rate: 0%, 35%, 55%, 75% [Table 8] Table 3. Performance of a low-temperature refrigeration system with SL / LL HX

[0170] Table 3 shows the performance of refrigerants in low-temperature refrigeration systems.

[0171] The results below the column with a "0%" efficiency for SL-LL HX represent a system without SL-LL HX, and it will be understood that refrigerants A1-A8 show improved performance in terms of efficiency (COP) compared to R134a when an SL / LL heat exchanger is used, and compositions A4, A4', and A4'' show superior performance when all relevant performance factors are taken into consideration. Example 3: Performance in a medium-temperature refrigeration system with two-stage vapor injection compression

[0172] Performance tests were conducted on refrigerants A1 to A8 in a medium-temperature refrigeration system with two-stage vapor injection compression. Based on this analysis, the efficiency (COP) of refrigerants A1 to A8 in this system was evaluated under the following conditions.

[0173] The operating conditions were as follows: • Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C • Condenser supercooling = 5.0℃ • Evaporation temperature = -8°C, corresponding internal temperature = 1.7°C Evaporator overheating = 5.5℃ • Compressor adiabatic efficiency = 70% • Volumetric efficiency = 100% • Temperature rise in the intake line = 10℃ • Steam injection heat exchanger (HX) effect: 15%, 35%, 55%, 75% [Table 9] Table 4. Performance of a medium-temperature refrigeration system using two-stage compression by steam injection.

[0174] Table 4 shows the performance of refrigerants in a medium-temperature refrigeration system. Compositions A2 to A8 show improved performance compared to R134a in terms of efficiency (COP) in two-stage compression by vapor injection, and compositions A4, A4', and A4'' show superior performance when all relevant performance factors are considered. Example 4: Performance in a CO2 cascade refrigeration system

[0175] Cascade systems are generally used in applications where there is a large temperature difference between the ambient temperature and the internal temperature (e.g., about 50-80°C, such as about 60-70°C) (for example, the temperature difference between the air side of the condenser in the upper stage and the air side of the evaporator in the lower stage). For example, a cascade system may be used to freeze products in a supermarket. In the following examples, exemplary compositions of the invention were tested as refrigerants in the upper stage of a cascade refrigeration system. The refrigerant used in the lower stage of the system was carbon dioxide.

[0176] The operating conditions were as follows: • Condensation temperature = 45℃ • High-stage condensation temperature - ambient temperature = 10°C • Supercooling of the high-stage condenser = 0.0°C (system equipped with a receiver) • Evaporation temperature = -30°C, corresponding internal temperature = -18°C • Low-stage evaporator overheating = 3.3℃ • Adiabatic efficiency of high and low stage compressors = 65% • Volumetric efficiency = 100% • Temperature rise at the lower stage of the intake line = 15℃ • Temperature rise at the top of the intake line = 10°C • Intermediate heat exchanger CO2 condensation temperature = 0°C, 5°C, and 10°C ·Intermediate heat exchanger superheat = 3.3℃ • Temperature difference in the intermediate heat exchanger = 8°C [Table 10] Table 5. Performance in CO2 cascade refrigeration systems

[0177] Table 5 shows the performance of refrigerants in the upper stages of a cascade refrigeration system. Refrigerants A1-A8 are consistent with the efficiency of R134a for different condensation temperatures in the lower stages of the cycle, and compositions A4, A4', and A4'' exhibit superior performance when all relevant performance factors are considered. Example 5: Performance in a vending machine with an intake line / liquid line heat exchanger

[0178] Performance tests were conducted on refrigerants A1-A8 in vending machine refrigeration systems with and without intake / liquid line heat exchangers (SL / LL HX). This analysis evaluated the efficiency (COP) of refrigerants A1-A8 in the system at different effectiveness levels of SL-LL HX under the following conditions.

[0179] Operating conditions: • Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C Condenser supercooling = 5.5℃ • Evaporation temperature = -8℃ Evaporator overheating = 3.5℃ • Compressor adiabatic efficiency = 60% • Volumetric efficiency = 100% • Temperature rise in the intake line = 5°C • Intake line / liquid line heat exchanger heat exchange rate: 0%, 35%, 55%, 75% [Table 11] Table 6. Performance of vending machines with SL / LL HX

[0180] Table 6 shows the refrigerant performance in vending machine systems with and without SL / LL HX. The results below the column with a "0%" efficiency compared to SL-LL HX represent systems without SL-LL HX. It can also be seen that refrigerants A1-A8 show improved performance compared to R134a in terms of efficiency (COP) when an SL / LL heat exchanger is used, and compositions A4, A4', and A4'' show superior performance when all relevant performance factors are considered. Example 6: Performance of an air-source heat pump hot water heater

[0181] Performance tests were conducted on refrigerants A1 to A8 in an air-source heat pump hot water heater system. Based on this analysis, the efficiency (COP) of refrigerants A1 to A8 in this system was evaluated under the following conditions.

[0182] The operating conditions were as follows: Condensation temperature = 55℃ ·Water inlet temperature = 45℃, water outlet temperature = 50℃ • Condenser supercooling = 5.0℃ • Evaporation temperature = -5°C, corresponding ambient temperature = 10°C Evaporator overheating = 3.5℃ • Compressor adiabatic efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the intake line = 5°C • Intake line / liquid line heat exchanger heat exchange rate: 0%, 35%, 55%, 75% [Table 12] Table 7. Performance of heat pump hot water heaters

[0183] Table 7 shows the performance of refrigerants in a heat pump water heater. Refrigerants A1 - A8 show the same efficiency as R134a, and compositions A4, A4’ and A4’’ show excellent performance when all relevant performance factors are considered. Refrigerants A1 - A8 show a lower discharge temperature than R134a, indicating better reliability of the compressor. Example 7: Performance in an air-source heat pump water heater with an intake line / liquid line heat exchanger

[0184] Performance tests were conducted on refrigerants A1 - A8 in an air-source heat pump water heater system with and without an intake line / liquid line heat exchanger (SL / LL HX). This analysis was carried out to evaluate the efficiency (COP) of refrigerants A1 - A8 in this system at different effectiveness levels of the SL-LL HX under the following conditions: The efficiency (COP) of refrigerants A1 - A8 in this system was evaluated.

[0185] The operating conditions were as follows: · Condensing temperature = 55 °C · Water inlet temperature = 45 °C, water outlet temperature = 50 °C · Condenser subcooling = 5.0 °C · Evaporation temperature = -5 °C, corresponding ambient temperature = 10 °C · Evaporator superheat = 3.5 °C · Compressor adiabatic efficiency = 65% · Volumetric efficiency = 100% · Temperature rise in the intake line = 5 °C · Intake line / liquid line heat exchanger heat transfer rate: 0%, 35%, 55%, 75%

Table 13

[0186] Table 8 shows the performance of refrigerants in a heat pump hot water heater with SL / LL HX. Refrigerants A1-A8 show higher efficiency than R134a when an SL / LL heat exchanger is used, and compositions A4, A4', and A4'' show superior performance when all relevant performance factors are considered. Refrigerants A1-A8 exhibit lower discharge temperatures than R134a, indicating better compressor reliability. Example 8: Performance of mobile air conditioning systems (buses, trains, cars)

[0187] Performance tests were conducted on refrigerants A1-A8 in a mobile air conditioning system under various condenser temperature conditions. Based on this analysis, the efficiency (COP) of refrigerants A1-A8 in this system was evaluated under the following conditions.

[0188] Operating conditions: Condensation temperature = 45°C to 75°C • Condenser supercooling = 5.0℃ • Evaporation temperature = 4°C, corresponding room temperature = 35°C Evaporator overheating = 5.0℃ • Compressor adiabatic efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the intake line = 0°C [Table 14] Table 9. Performance of mobile AC systems

[0189] Table 9 shows that refrigerants A1 to A8 exhibit similar efficiencies to R134a across a range of condensation temperatures corresponding to different ambient temperatures, while compositions A4, A4', and A4'' demonstrate superior performance when all relevant performance factors are considered. Example 9: Microcascade Refrigeration System

[0190] The microcascade system combines a conventional medium-temperature DX refrigeration system, which may or may not have an intake line liquid line heat exchanger (SLHX) operating on a fluid invention, with a low-temperature cascade refrigeration where the upper stage uses the fluid invention and is connected to several small low-temperature stages, in a self-contained form using fluids such as, but not limited to, CO2, R1234yf, and R455A. As used herein, the term "medium-temperature DX refrigeration system" refers to a medium-temperature system where the evaporator is a dry evaporator.

[0191] Useful microcascade systems are disclosed in U.S. Patent Application Nos. 16 / 014,863 filed on June 21, 2018 and 16 / 015,145 filed on June 21, 2018, which claim priority to U.S. Application Nos. 62 / 522386 filed on June 21, 2017, 62 / 522846 filed on June 21, 2017, 62 / 522851 filed on June 21, 2017, and 62 / 522860 filed on June 21, 2017, and are hereby incorporated by reference in their entirety.

[0192] Operating conditions: Baseline R404A combines an MT system and an LT system ● Refrigeration capacity ○ Low temperature: 33,000 W ○ Medium temperature: 67,000 W ● Volumetric efficiency: 95% for both MT and LT ● Compressor adiabatic efficiency ○ Medium temperature = 70% and low temperature = 67% ● Condensing temperature = 105°F ● Medium-temperature evaporation temperature: 20°F ● Low-temperature evaporation temperature: -20°F ● Evaporator superheat: 10°F (both medium temperature and low temperature) ● Intake line temperature rise (due to heat transfer to the surroundings) ○ Baseline: Medium temperature: 25°F, low temperature: 50°F ○ Self-contained without cascade / SLHX: Medium temperature: 10°F, low temperature: 25°F ○ Cascade / Self-contained with SLHX: Medium temperature: 10°F, Low temperature: 15°F SLHX efficiency during use: 65% [Table 15] Table 10 - Comparison of R404A and Microcascade System

[0193] The table above shows that the microcascade system has a COP approximately 126% higher than the baseline mesothermal DX system using R404A. Example 10: Non-flammable secondary refrigerant with a pressure exceeding atmospheric pressure

[0194] Each of the refrigerants of the present invention, including each of refrigerants 1 to 7, or a heat transfer composition containing each of the refrigerants of the present invention, including each of refrigerants 1 to 7, can function as a secondary fluid. Each of the refrigerants of the invention, including each of refrigerants 1 to 7, has the properties necessary to ensure that the operating pressure of the refrigerant does not fall below atmospheric pressure at a given evaporator temperature, so that air does not enter the system and is at a level low enough to prevent significant leakage. Table 11 shows the refrigerant pressures required to evaporate temperatures in the range of -5°C to 10°C, covering a variety of operating conditions for air conditioning applications. • It can be observed from the table that all refrigerants maintain a pressure higher than atmospheric pressure. The primary refrigerant used in the vapor compression loop may be selected from the group consisting of R404A, R507, R410A, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, R1234ze(E), R1234yf, and R449A. The temperature of the air (or object) to be cooled may be between approximately 25°C and 0°C. [Table 16] Table 11: Secondary fluid Example 11: Performance in a fixed air conditioning system

[0195] Performance tests were conducted on refrigerants A1-A8 in a fixed air conditioning system under various condenser temperature conditions. Based on this analysis, the efficiency (COP) of refrigerants A1-A8 in this system was evaluated under the following conditions.

[0196] Operating conditions: Condensation temperature = 45°C to 65°C • Condenser supercooling = 5.0℃ • Evaporation temperature = 10°C, corresponding room temperature = 35°C Evaporator overheating = 5.0℃ • Compressor adiabatic efficiency = 72% • Volumetric efficiency = 100% [Table 17] Table 12. Performance in fixed AC systems

[0197] Refrigerants A1 to A8 exhibit similar efficiency to R134a across a range of condensation temperatures corresponding to different ambient temperatures, while compositions A4, A4', and A4'' demonstrate superior performance when all relevant performance factors are considered. Example 12: Performance in a commercial air conditioning system

[0198] Performance tests were conducted on refrigerants A1-A8 in a commercial air conditioning system under various condenser temperature conditions. Based on this analysis, the efficiency (COP) of refrigerants A1-A8 in this system was evaluated under the following conditions.

[0199] Operating conditions: Condensation temperature = 45°C to 65°C • Condenser supercooling = 5.0℃ • Evaporation temperature = 10℃ Evaporator overheating = 5.0℃ • Compressor adiabatic efficiency = 72% • Volumetric efficiency = 100% [Table 18] Table 13. Performance in fixed AC systems

[0200] Refrigerants A1 to A8 exhibit similar efficiency to R134a across a range of condensation temperatures corresponding to different ambient temperatures, while compositions A4, A4', and A4'' demonstrate superior performance when all relevant performance factors are considered. Example 13: Performance in refrigerated transport applications (refrigerated trucks, containers) with and without intake line (SL) / liquid line (LL) heat exchanger (HX)

[0201] Performance tests were conducted on refrigerants A1-A8 in transport refrigeration systems under medium temperature refrigeration conditions, both with and without an intake / liquid line heat exchanger (SL / LL HX). This analysis evaluated the efficiency (COP) of refrigerants A1-A8 in this system at different effectiveness levels of SL-LL HX under the following conditions.

[0202] The operating conditions were as follows: • Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C • Condenser supercooling = 0.0°C (system with receptors) • Evaporation temperature = -8℃ Evaporator overheating = 5.5℃ • Compressor adiabatic efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the intake line = 15℃ • Intake line / liquid line heat exchanger heat exchange rate: 0%, 35%, 55%, 75% [Table 19] Table 14. Performance of a medium-temperature refrigeration system with SL / LL HX

[0203] Table 14 shows the performance of refrigerants A1-A8 in transport refrigeration systems. The results below the column with a "0%" efficiency compared to SL-LL HX represent systems without SL-LL HX. It can also be seen that refrigerants A1-A8 show improved performance compared to R134a in terms of efficiency (COP) when SL / LL heat exchangers are used, and compositions A4, A4', and A4'' show superior performance when all relevant performance factors are considered. Example 14: Performance in refrigerated transport applications (refrigerated trucks, containers) with and without intake line / liquid line heat exchangers.

[0204] Performance tests were conducted on refrigerants A1-A8 in transport refrigeration systems under low-temperature refrigeration conditions, both with and without an intake / liquid line heat exchanger (SL / LL HX). This analysis evaluated the efficiency (COP) of refrigerants A1-A8 in this system at different effectiveness levels of the SL-LL HX under the following conditions.

[0205] The operating conditions were as follows: • Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C • Condenser supercooling = 0.0°C (system with receptors) • Evaporation temperature = -35°C, corresponding internal temperature = -25°C Evaporator overheating = 5.5℃ • Compressor adiabatic efficiency = 65% • Volumetric efficiency = 100% • Temperature rise in the intake line = 15℃ • Intake line / liquid line heat exchanger heat exchange rate: 0%, 35%, 55%, 75% [Table 20] Table 15. Performance of a low-temperature refrigeration system with SL / LL HX

[0206] Table 15 shows the performance of refrigerants in low-temperature refrigeration systems. The results below the column with a “0%” efficiency relative to SL-LL HX represent systems without SL-LL HX. It will also be understood that refrigerants A1-A8 show improved performance compared to R134a in terms of efficiency (COP) when an SL / LL heat exchanger is used, and compositions A4, A4', and A4'' show superior performance when all relevant performance factors are considered. Example 15: Electronic Cooling

[0207] Performance tests of refrigerants A1-A8 will be conducted to evaluate their cooling applications in various forms, including heat pipes, thermal siphons, and vapor compression cooling for electronic equipment (including cooling of chips, circuit boards, batteries (including batteries used in automobiles, trucks, buses, and other electronic transport vehicles), computers, etc.). Analysis will be performed to evaluate the performance of refrigerants A1-A8 in these applications.

[0208] Refrigerants A1-A8 exhibit similar performance to R134a, while compositions A4, A4', and A4'' exhibit superior performance when all relevant performance factors are considered. Numbered embodiments

[0209] The present invention is further illustrated by the following numbered embodiments. The subject matter of the numbered embodiments may be further combined with one or more subject matters of this specification or the claims. 1. A refrigerant comprising (a) approximately 65% ​​to 90% by weight of HFO-1234ze(E) and (b) approximately 10% to 35% by weight of HFO-1336mzz(E). 2. The refrigerant according to the numbered embodiment 1, comprising (a) about 76% to about 90% by weight of HFO-1234ze(E) and (b) about 10% to about 24% by weight of HFO-1336mzz(E). 3. The refrigerant according to numbered embodiment 1 or 2, comprising (a) about 74% to about 80% by weight of HFO-1234ze(E) and (b) about 20% to about 26% by weight of HFO-1336mzz(E). 4. The refrigerant according to numbered embodiments 1 to 3, comprising (a) approximately 76.6 wt% of HFO-1234ze(E) and (b) approximately 19 wt% of HFO-1336mzz(E). 5. A refrigerant according to any of the numbered embodiments 1 to 4, essentially consisting of HFO-1234ze(E) and HFO-1336mzz(E). 6. A refrigerant according to any of the numbered embodiments 1 to 5, comprising HFO-1234ze(E) and HFO-1336mzz(E). 7. A refrigerant comprising (a) approximately 74.6% to 78.6% by weight of HFO-1234ze(E), (b) approximately 17% to 21% by weight of HFO-1336mzz(E), and (c) more than 0% to approximately 4.4% by weight of HFC-227ea. 8. The refrigerant according to the numbered embodiment 7, comprising (a) 74.6% to 78.6% by weight of HFO-1234ze(E), (b) 17% to 21% by weight of HFO-1336mzz(E), and (c) approximately 4.4% by weight of HFC-227ea. 9. The refrigerant according to the numbered embodiment 8, comprising (a) about 78.6% by weight of HFO-1234ze(E), (b) about 17% by weight of HFO-1336mzz(E), and (c) about 4.4% by weight of HFC-227ea. 10. Numbered embodiments 1-9, containing approximately 4.4% by weight of HFC-227ea. The refrigerant listed in any of the following. 11. A refrigerant according to any of the numbered embodiments 1 to 10, essentially consisting of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. 12. A refrigerant according to any of the numbered embodiments 1 to 10, comprising HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. 13. A refrigerant according to any of the numbered embodiments 1 to 12, wherein the global warming potential is approximately 150 or less. 14. The refrigerant described in any of the numbered embodiments 1 to 13, which is non-flammable. 15. The refrigerant according to any of the numbered embodiments 1 to 14, which is non-toxic or has low toxicity. 16. The refrigerant according to any of the numbered embodiments 1 to 15, wherein the refrigerant has a gradient of less than about 3°C, preferably less than about 2°C. 17. A heat transfer composition comprising a refrigerant according to any of the numbered embodiments 1 to 16. 18. A heat transfer composition of the numbered embodiment 17, comprising a refrigerant in an amount of at least about 80% by weight of the heat transfer composition, preferably at least about 90% by weight of the heat transfer composition, more preferably at least about 97% by weight of the heat transfer composition, and more preferably at least about 99% by weight of the heat transfer composition. 19. A heat transfer composition according to the numbered embodiment 17 or 18, further comprising a lubricant. 20. The heat transfer composition according to the numbered embodiment 19, wherein the lubricant is present in the heat transfer composition in an amount of about 1% to about 50% by weight of the heat transfer composition, more preferably in an amount of about 10% to about 50% by weight of the heat transfer composition, and most preferably in an amount of about 30% to about 50% by weight of the heat transfer composition. 21. A heat transfer composition according to numbered embodiment 19 or 20, wherein the lubricant is selected from the group consisting of polyol ester (POE), polyalkylene glycol (PAG), PAG oil, polyvinyl ether (PVE), poly(α-olefin) (PAO), and combinations thereof. 22. The heat transfer composition according to the numbered embodiment 19 or 20, wherein the lubricant is POE or PVE, preferably POE. 23. A method for heating or cooling a fluid or object using a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 22. 24. A vapor compression system having a fluid-communicating evaporator, condenser, and compressor, comprising a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 23. 25. A refrigeration system comprising a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 23. 26. The refrigeration system according to the numbered embodiment 25, wherein the system is a medium-temperature refrigeration system. 27. The refrigeration system according to the numbered embodiment 26, wherein the medium-temperature refrigeration system has an evaporator temperature of about -15°C to about 5°C, preferably about -10°C to about 5°C. 28. The refrigeration system according to numbered embodiment 26 or 27, wherein the medium-temperature refrigeration system is selected from small-scale refrigeration systems (including vending machines, ice makers, and household appliances), commercial refrigeration systems (such as supermarket refrigeration systems and walk-in coolers), residential refrigeration systems, and industrial refrigeration systems. 29. The medium-temperature refrigeration system has an evaporator temperature of approximately 0°C to approximately 5°C, and is numbered A refrigeration system according to embodiment 28. 30. The refrigeration system according to numbered embodiments 26 to 29, wherein the medium-temperature refrigeration system is used to cool perishable products, including vegetables and / or fruits, or to cool beverages. 31. The refrigeration system according to numbered embodiments 26 to 30, wherein the medium temperature system has a condenser temperature of about 15°C to about 60°C, preferably about 25°C to about 45°C. 32. The refrigeration system according to numbered embodiments 26 to 31, wherein the medium-temperature system has a superheating degree of about 0°C to about 10°C at the evaporator outlet, preferably about 1°C to about 6°C at the evaporator outlet. 33. The refrigeration system according to numbered embodiments 26 to 32, wherein the medium-temperature system has a superheat of about 3°C ​​to about 5°C at the evaporator outlet, preferably about 4°C at the evaporator outlet. 34. The refrigeration system according to the numbered embodiment 25, wherein the system is a low-temperature refrigeration system. 35. The refrigeration system according to the numbered embodiment 34, wherein the low-temperature refrigeration system has an evaporator temperature of about -45°C to less than about -15°C, preferably about -40°C to about -25°C. 36. The refrigeration system according to the numbered embodiment 34 or 35, wherein the low-temperature refrigeration system is selected from ice rinks, commercial refrigeration systems (including supermarket refrigeration systems), residential refrigeration systems and industrial refrigeration systems. 37. A refrigeration system according to numbered embodiments 34 to 36, wherein the low-temperature refrigeration system is used to cool refrigerated products. 38. The refrigeration system according to numbered embodiments 34 to 37, wherein the low-temperature system has a condenser temperature of about 15°C to about 50°C, preferably about 25°C to about 45°C. 39. The refrigeration system according to numbered embodiments 34 to 38, wherein the low-temperature system has a superheating degree of about 0°C to about 10°C, preferably about 1°C to about 6°C, at the evaporator outlet. 40. The method according to the numbered embodiment 25, wherein the system is a transport refrigeration system. 41. The refrigeration system according to the numbered embodiment 40, wherein the transport refrigeration system is a container that can be transported by ship, boat, freight car, or road vehicle (e.g., truck). 42. The refrigeration system according to the numbered embodiment 25, wherein the system is a cascade refrigeration system. 43. The refrigeration system according to numbered embodiment 42, wherein the cascade refrigeration system has an upper and a lower section, and the refrigerant defined in any of numbered embodiments 1 to 16, or the heat transfer composition defined in any of numbered embodiments 17 to 22, is used in the upper section. 44. A refrigeration system according to numbered embodiment 43, wherein CO2, 1234yf, or R455A is used in the lower stage of a cascade refrigeration system. 45. A secondary loop system comprising a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 22. 46. ​​The secondary loop system according to numbered embodiment 45, wherein the secondary loop system includes a primary vapor compression system loop using a primary refrigerant, and an evaporator cools the secondary loop fluid, and the refrigerant as defined in any of numbered embodiments 1 to 16, or a heat transfer composition as defined in any of numbered embodiments 17 to 22, is used as the secondary loop fluid. 47. The primary refrigerant in question is R404A, R507, R410A, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, R1234ze (E) A secondary loop system according to a numbered embodiment 46, selected from the group consisting of R1234yf and R449A. 48. A heat pump system comprising a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 22. 49. The heat pump system according to the numbered embodiment 48, wherein the heat pump is a rotary heat pump dryer, a reversible heat pump, a high-temperature heat pump, or an air-to-air heat pump. 50. An air conditioning system comprising a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 22. 51. The air conditioning system according to the numbered embodiment 50, wherein the system is selected from chillers, residential, industrial, commercial, and mobile air conditioning systems. 52. The air conditioning system according to a numbered embodiment 51, wherein the mobile air conditioning system includes air conditioning for road vehicles such as automobiles, trucks and buses, as well as air conditioning for boats and trains. 53. The system according to any of the numbered embodiments 24 to 52, wherein the system includes an intake line and a liquid line heat exchanger. 54. An organic Rankine cycle system comprising a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 22. 55. A method for cooling a fluid or object using a refrigeration system, the method comprising: (a) evaporating a refrigerant as defined in any of the numbered embodiments 1 to 16 around a fluid of the object to be cooled; and (b) condensing the refrigerant. 56. The method according to the numbered embodiment 55, wherein the refrigeration system is a medium-temperature refrigeration system. 57. The method of the numbered embodiment 56, wherein the medium temperature refrigeration system is as defined in any of the numbered embodiments 26 to 33. 58. The method according to the numbered embodiment 55, wherein the refrigeration system is a low-temperature refrigeration system. 59. The method according to the numbered embodiment 58, wherein the medium temperature refrigeration system is as defined in any of the numbered embodiments 34 to 39. 60. The method according to the numbered embodiment 55, wherein the refrigeration system is a transport refrigeration system. 61. The method according to the numbered embodiment 60, wherein the transport refrigeration system is defined in the numbered embodiment 40. 62. The method according to the numbered embodiment 55, wherein the refrigeration system is a cascade refrigeration system. 63. The method according to the numbered embodiment 62, wherein the cascade refrigeration system is as defined in any of the numbered embodiments 42 to 44. 64. A method for cooling a fluid or object using a secondary loop system, the method comprising: (a) evaporating a primary coolant around a secondary loop fluid to transfer heat from the secondary loop fluid to the primary coolant; (b) condensing the primary coolant; and (c) circulating the secondary loop fluid through the secondary loop to absorb heat from the fluid or object to be cooled, wherein the secondary loop fluid is a coolant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 22. 65. The primary refrigerant in question is R404A, R507, R410A, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, R1234ze (E) The method according to a numbered embodiment 64, selected from the group consisting of R1234yf and R449A. 66. A method for heating a fluid or object using a heat pump, the method comprising: (a) condensing a refrigerant as defined in any of the numbered embodiments 1 to 16 around a fluid of an object to be heated; and (b) evaporating the refrigerant. 67. The method according to the numbered embodiment 66, wherein the heat pump is a rotary heat pump dryer, a reversible heat pump, a high-temperature heat pump, or an air-to-air heat pump. 68. A method of air conditioning using an air conditioning system, the method comprising: (a) evaporating a refrigerant as defined in any of the numbered embodiments 1 to 16 around a fluid of an object to be cooled; and (b) condensing the refrigerant. 69. The method according to a numbered embodiment 68, wherein the system is as defined in any of the numbered embodiments 50 to 52. 70. A process for converting thermal energy into mechanical energy in a Rankine cycle, the method comprising: i) vaporizing a working fluid with a heat source and expanding the resulting vapor, or vaporizing a working fluid with a heat source; and then ii) cooling the working fluid with a heat sink to condense the vapor, wherein the working fluid is a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 22. 71. The process according to a numbered embodiment 70, wherein the heat source is provided by a low-grade thermal energy source selected from industrial waste heat, solar energy, geothermal hot water, low-pressure steam, distributed power generation equipment utilizing fuel cells, or prime movers. 72. The process according to the numbered embodiment 70 or 71, wherein the heat source is provided by a turbine, microturbine, or internal combustion engine. 73. The process according to a numbered embodiment 72, wherein the low-pressure steam is low-pressure geothermal steam or is supplied by a fossil fuel power plant. 74. The process according to numbered embodiments 70 to 73, wherein the heat source temperature is approximately 80°C to approximately 800°C or higher. 75. A heat transfer system for cooling electronic equipment, comprising a refrigerant as defined in any of the numbered embodiments 1 to 16, or a heat transfer composition as defined in any of the numbered embodiments 17 to 23. 76. The heat transfer system according to claim 75, used for cooling one or more of the following: an electronic chip, an electronic circuit board, a battery (including batteries used in automobiles, trucks, buses, and other electronic transport vehicles), a computer, etc. 77. A heat transfer system according to any one of claims 75 and 76, comprising a heat pipe or a heat siphon.

Claims

1. (i) HFO-1234ze(E) in an amount of approximately 74.6% to 78.6% by weight, (ii) Approximately 17% to 19% by weight of HFO-1336mzz(E), (iii) Approximately 4.4% by weight of HFC-227ea, Refrigerants containing, where the term "approximately" means + / - 2% by weight.

2. The refrigerant according to claim 1, which essentially consists of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea, preferably consisting of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea.

3. The aforementioned refrigerant, (a) 78.6% by weight + 0.5% by weight / -2.0% by weight of HFO-1234ze(E), (b) 17 wt% + 2.0 wt% / -0.5 wt% HFO-1336 mzz(E), (c) HFC-227ea in a concentration of 4.4% by weight + 2.0% by weight / -0.5% by weight, Includes, The refrigerant essentially consists of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea, preferably consisting of HFO-1234ze(E), HFO-1336mzz(E), and HFC-227ea. The refrigerant according to claim 1.

4. A heat transfer composition comprising a refrigerant and lubricant according to any one of claims 1 to 3, preferably a lubricant selected from alkylbenzene, ester, polyol ester (POE), polyalkylene glycol (PAG), polyvinyl ether (PVE), poly(α-olefin) (PAO), and combinations thereof.

5. The heat transfer composition according to claim 4, wherein the lubricant comprises a polyol ester (POE).

6. The heat transfer composition according to claim 4, wherein the lubricant comprises polyvinyl ether (PVE).

7. Evaporator and, The refrigerant in the evaporator according to any one of claims 1 to 3, A heat transfer system equipped with [the necessary components].

8. The heat transfer system according to claim 7, wherein the heat transfer system is a medium-temperature refrigeration system, an air conditioning system, a heat pump system, or a system for cooling electronic equipment.

9. The heat transfer system according to claim 7, wherein the heat transfer system is a medium-temperature refrigeration system, a heat pump system, or a system for cooling electronic equipment.

10. A heat transfer system comprising a refrigerant according to any one of claims 1 to 3, or a heat transfer composition according to any one of claims 4 to 6, wherein the heat transfer system is a medium-temperature refrigeration system, an air conditioning system, a heat pump system, or a system for cooling electronic equipment.

11. The heat transfer system according to claim 10, wherein the heat transfer system is a medium-temperature refrigeration system, a heat pump system, or a system for cooling electronic equipment.

Images