Refrigerant composition for air conditioning device

Abstract

The present invention relates to a refrigerant composition for an air conditioning device, which has characteristics similar to those of R410A, has a sufficiently low global warming potential (GWP), and contains trifluoroethylene and trifluoroiodomethane.

Description

Technical Field

[0001] The present invention relates to a refrigerant composition for an air conditioning apparatus, and more particularly to a refrigerant composition for an air conditioning apparatus containing trifluoroethylene and trifluoroiodomethane. Background Art

[0002] Currently, HFC series refrigerants such as R410A and R134a are widely used as refrigerants for air conditioning apparatuses such as air conditioners (hereinafter referred to as "air conditioning apparatuses"). R410A is a binary mixed refrigerant composed of difluoromethane (CH2F2; HFC-32 or R32) and pentafluoroethane (C2HF5; HFC-125 or R125), and is an approximate azeotropic composition. It is widely used for refrigeration / heating etc. in commercial or household air conditioning systems. Since a large injection amount is required in the system and the demand is large, it can be said that it is the refrigerant with the largest consumption.

[0003] R134a (CH2FCF3) is a single refrigerant and is widely used in automotive air conditioners, household refrigerators, etc.

[0004] However, with the entry into force of the Kigali Amendment to the Montreal Protocol, in order to prevent global warming, the international community has begun to regulate HFC series refrigerants and fulfill obligations according to the emission reduction amount and detailed schedule requirements.

[0005] The global warming potential (GWP) of R410A is 2088. As concerns about global warming have increased, R32 with a GWP of 675 is used more, but due to its A2L (slightly flammable), there is a fire risk in the event of refrigerant leakage, etc., and it is limited to use in small-capacity systems with a refrigerant injection amount of 1.9 kg or less. Therefore, there is a particularly urgent need for a low global warming potential (Low GWP) refrigerant that can replace R410A for large-capacity equipment such as air conditioning systems.

[0006] The global warming potential (GWP) of R134a is 1430, and it is mainly used in automotive air conditioners. However, due to the refrigerant regulations for passenger cars (GWP = 150 or less), the use of a low global warming potential (Low GWP) refrigerant (GWP = 3) R1234yf is gradually expanding globally. However, unlike traditional internal combustion engines, pure electric vehicles do not have a heating heat source, and the trend of applying high-efficiency heat pump systems is increasing. However, due to the limitations of refrigerant physical properties, especially the heating performance requirements cannot be met in cold weather. Therefore, to solve this problem, a high-power electric heater is installed, especially at an outdoor temperature of -10°C or lower, which will result in a reduction in the winter driving range. Summary of the Invention

[0007] The present invention is proposed to solve the problems existing in the prior art, and its purpose is to provide a refrigerant composition that has the refrigeration / heating capacity to replace R410A, R1234yf, and R134a, has a sufficiently small global warming potential (GWP), is non-flammable, is non-toxic (A1 grade) and harmless to humans, and in addition to various characteristics usually required for refrigerants, can be directly used or slightly modified and used in air-conditioning devices of R410A, R134a, and R1234yf.

[0008] Moreover, the purpose of the present invention is to achieve high efficiency and meet performance requirements by using the refrigerant of the present invention alone, without the need to additionally increase expensive high-voltage electric heater components to solve the insufficient heating performance of R134a or the environmentally friendly refrigerant R1234yf used in the refrigeration / heating system (heat pump system) of electric vehicles, thereby contributing to increasing the cruising range of electric vehicles in winter.

[0009] To achieve the above object, the present invention provides a refrigerant composition for an air-conditioning device comprising trifluoroethylene and trifluoroiodomethane.

[0010] In the composition, it is characterized in that trifluoroethylene is 25-35 wt%, and trifluoroiodomethane is 65-75 wt%.

[0011] In the composition, it is characterized in that trifluoroethylene (R1123) is 25-35 wt%, trifluoroiodomethane (R13I1) is 65-75 wt%, and a small amount of propane (R290) or R32 is added.

[0012] In the composition, it is characterized in that trifluoroethylene is 30 wt% and trifluoroiodomethane is 70 wt%.

[0013] The refrigerant composition for an air-conditioning device according to the present invention has a heating capacity superior to that of R1234yf and R134a, a sufficiently small global warming potential (GWP), conforms to the specifications of ASHRAE, is non-flammable and non-toxic (A1 grade), has an ozone depletion potential (ODP) of 0, is simple to manufacture, and can be replaced by minimizing modifications such as optimizing the expansion device and heat exchanger of the air-conditioning devices used for R410A, R1234yf, and R134a.

[0014] Moreover, for electric vehicles, R1234yf is prone to fire when the battery overheats due to its slight flammability (A2L), but trifluoroiodomethane, which is a raw material of the mixed refrigerant of the present invention, is non-flammable and has an additional effect of extinguishing fire in case of fire. Therefore, it has a more advantageous effect when applied to a refrigerant direct expansion system for cooling the battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a graph showing the relationship between the mixing ratio of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) that make up the refrigerant composition for the air conditioner of the present invention and the saturated vapor pressure.

[0016] Figure 2 It is a graph showing the relationship between the mixing ratio of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) that make up the refrigerant composition for the air conditioner of the present invention and the boiling point.

[0017] Figure 3 It is a graph showing the volume capacity of the mixing ratio of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) that make up the refrigerant composition for the air conditioner of the present invention at 0°C.

[0018] Figure 4 It is a graph showing the volume capacity of different mixing ratios of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) that make up the refrigerant composition for the air conditioner of the present invention at -30°C.

[0019] Figure 5 It is a graph showing the heat of combustion of different mixing ratios of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) that make up the refrigerant composition for the air conditioner of the present invention.

[0020] Figure 6 It is an example diagram of an air conditioner for experimentally testing the refrigerant composition for the air conditioner of the present invention. Detailed Embodiments

[0021] Unless otherwise defined, all technical terms and scientific terms used in the specification of the present invention have the meanings commonly understood by those of ordinary skill in the technical field to which the present disclosure pertains. All terms used in the present disclosure are selected to more clearly illustrate the present disclosure, rather than to limit the scope of the rights of the present disclosure.

[0022] Expressions such as "comprising", "including", and "having" used in the description of the present invention should be understood as open-ended terms, suggesting the possibility of including other embodiments, unless otherwise stated in the phrase or sentence containing such an expression.

[0023] Unless otherwise specified, singular expressions used in the description of the present invention may include plural meanings, and the same applies to the singular expressions recited in the claims.

[0024] In the description of the present invention, expressions such as "first" and "second" are used to distinguish multiple structural elements from each other, and do not limit the order or importance of these structural elements.

[0025] In the description of the present invention, when it is mentioned that a certain structural element is "connected" or "coupled" to another structural element, it should be understood that a certain structural element can be directly connected or coupled to another structural element, or can be connected or coupled through a new other structural element as a medium.

[0026] <Term Glossary>

[0027] In this specification, when the term "substitute" is used in the context of "substituting the first refrigerant with the second refrigerant", in the first type, for a device designed to operate using the first refrigerant, only a small number of components (at least one of refrigeration oil, gasket, packing, expansion valve, dryer, and other components) need to be replaced and the device adjusted as needed, and then the second refrigerant can be used to operate under optimal conditions. That is, this type refers to "substituting" the refrigerant to operate on the same device.

[0028] As the ways of "substituting" in this type, in ascending order of the degree of change or adjustment required when replacing with the second refrigerant, they are "drop in", "nearly drop in", and "retrofit".

[0029] As the second type, for the same use as the existing use of the first refrigerant, using a device designed to operate using the second refrigerant and equipped with the second refrigerant is also included in the term "substitute". This type refers to "substituting" the refrigerant and providing it for the same use.

[0030] Hereinafter, with reference to the drawings, the refrigerant composition for an air conditioning device of the present invention will be described in detail.

[0031] Figure 1 It is a graph showing the relationship between the mixing ratio of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) constituting the refrigerant composition for an air conditioning device of the present invention and the saturated vapor pressure, Figure 2 It is a graph showing the relationship between the mixing ratio of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) constituting the refrigerant composition for an air conditioning device of the present invention and the boiling point, Figure 3 It is a graph showing the volume capacity at 0 °C of the mixing ratio of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) constituting the refrigerant composition for an air conditioning device of the present invention, Figure 4It is a graph showing the volume capacity of different mixing ratios of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) that make up the refrigerant composition for the air conditioner of the present invention at -30°C. Figure 5 It is a graph showing the heat of combustion of different mixing ratios of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) that make up the refrigerant composition for the air conditioner of the present invention. Figure 6 It is an example diagram of an air conditioner for experimentally testing the refrigerant composition for the air conditioner of the present invention.

[0032] The refrigerant composition of the present invention contains trifluoroethylene (Trifluoroethene; C2F3H or R1123) and trifluoroiodomethane (Trifluoro iodomethane (TFIM); CF3I or R13I1).

[0033] In the refrigerant composition of the present invention, trifluoroethylene (R1123) is contained in the range of 25 - 35 wt%, and trifluoroiodomethane (R13I1) is contained in the range of 65 - 75 wt%. Preferably, the refrigerant composition contains 30 wt% of trifluoroethylene (R1123) and 70 wt% of trifluoroiodomethane (R13I1). Mix 25 - 35 wt% of the trifluoroethylene (R1123) and 65 - 75 wt% of the trifluoroiodomethane (R13I1), and propane (R290) or R32 can be added in a small amount (2 parts by weight or less relative to 100 parts by weight of the mixture of trifluoroethylene (R1123) and trifluoroiodomethane (R13I1)).

[0034] The refrigerant containing the refrigerant composition of the present invention may further contain additives such as lubricants in the refrigerant composition of the present invention.

[0035] The following Table 1 shows the physical properties of the trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) respectively.

[0036] [Table 1]

[0037] Physical Property Table of Trifluoroethylene (R1123) and Trifluoroiodomethane (R13I1)

[0038]

[0039]

[0040] Lower Flammability Limit (LFL)

[0041] Hereinafter, the refrigerant composition of the present invention will be described in more detail by way of examples. However, these examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the examples.

[0042] In the refrigerant composition of the present invention, a refrigerant composition composed of 30 wt% trifluoroethylene (R1123) and 70 wt% trifluoroiodomethane (R13I1) (hereinafter referred to as "the example of the refrigerant composition of the present invention") will be compared with R410A, R1234yf, and R134a for illustration.

[0043] Even if trifluoroethylene (R1123) and trifluoroiodomethane (R13I1) in the refrigerant composition are mixed at a specified ratio, its properties will not change, and as azeotropic composition that complements each other's disadvantages, the environmental protection characteristics are maintained.

[0044] The boiling point, saturation vapor pressure, flammability rating, global warming potential (GWP), and ozone depletion potential (ODP) value of the example of the refrigerant composition of the present invention are compared with R410A, R1234yf, and R134a, and the results are shown in Table 2 below.

[0045] [Table 2]

[0046] Physical property comparison table of the present invention

[0047] Differentiate R410A R1234yf R134a Example Molecular weight (g / mol) 72.6 114 102 138 Boiling point (°C) -51.4 -29.5 -26.1 -55 Vapor pressure (@60°C, MPa) 3.8 1.6 1.7 2.4 Flammability rating A1 A2L A1 A1 Global warming potential (GWP) 2088 4 1430 1 Ozone depletion potential (ODP) 0 0 0 0

[0048] As Figure 1 shown, in terms of the saturation vapor pressure at 60 °C, the saturation vapor pressure of the example of the refrigerant composition of the present invention is 2.4 MPa, that of R410A is 3.8 MPa, that of R1234yf is 1.6 MPa, and that of R134a is 1.7 MPa. Therefore, it can be seen that the saturation vapor pressure of the example is about 58% lower than that of R410A and about 50% higher than that of R1234yf and R134a. Looking at Figure 2 the boiling point curve shown, the boiling point of the example of the refrigerant composition of the present invention is -55 °C, that of R410A is -51.4 °C, that of R1234yf is -29.5 °C, and that of R134a is -26.1 °C. It can be seen that the boiling point of the example is 3.6 °C lower than that of R410A, 25.5 °C lower than that of R1234yf, and 28.9 °C lower than that of R134a.

[0049] Next, the safety of the refrigerant composition of the example of the present invention will be examined.

[0050] According to Refrigerants Safety Classification (ISO 817), with non-toxic and a combustion heat of 19 MJ / kg as the benchmark, it is classified into A1, A2L, A2 groups and A3 grades. The combustion heat of the refrigerant composition examples of the present invention is as shown in the combustion heat curve diagram Figure 5 shown, reaching below 19 MJ / kg, so the combustion heat belongs to the A1 grade.

[0051] And the standard for A2L in ASHREA34 is that the burning velocity reaches below 10 cm / s. As described in Table 1 above, the burning velocity of R1123 (100%) is 6.6 cm / s, and the burning velocity of R13I1 (100%) is A1. Therefore, the burning velocity of the refrigerant composition of the present invention examples reaches below 10 cm / s, and the safety grade is A1 grade.

[0052] As shown in Table 2, the refrigerant composition of the refrigerant composition examples of the present invention has the characteristics of being usable as a refrigerant. Compared with R410A, R1234yf, and R134a, the global warming potential (GWP) is 1, which is significantly low, and the ozone depletion potential (ODP) is 0, being environmentally friendly.

[0053] Hereinafter, in order to confirm whether the refrigerant composition [R1123 (30 wt%) + R13I1 (70 wt%)] of the present invention can replace R410A, R1234yf, and R134a refrigerants, a comparative experiment of R134a and the refrigerant of the present invention was conducted to verify the improvement degree of heating performance. Under the conditions of a cold region with an outdoor temperature of -15°C, heating performance, compressor power consumption, air blowing temperature, refrigerant pressure, and flow rate characteristics experiments were carried out, and the results are shown in Tables 3 to 5 below.

[0054] When applying the refrigerant of the present invention, especially when not using the electric heater used to improve the insufficient heating performance of R134a and R1234yf refrigerants, the refrigerant pressure and flow rate can be ensured. Therefore, when applying the refrigerant of the present invention, the heating performance can be ensured alone.

[0055] Therefore, it is expected to be effective for the xEV (BEV, PHEV) heat pump system in the automotive field.

[0056] Moreover, not only can it replace R410A, but also for commercial or household VRF system air conditioners that are applying the R410A substitute R32, the refrigerant of the present invention can be widely applied from small capacity to large capacity due to its non-flammability of A1 grade.

[0057] [Table 3]

[0058] Comparison results of heating capacity and power consumption

[0059] Heating capacity (kW) Power consumption (kW) R134a 2.2 1.0 Example 4.7 3.3

[0060] Results under the same rpm of the compressor in cold outdoor areas (-15°C).

[0061] [Table 4]

[0062] Comparison results of heating air outlet temperature

[0063]

[0064]

[0065] Results under the same rpm of the compressor in cold outdoor areas (-15°C).

[0066] [Table 5]

[0067] Characteristics of the circulating refrigerant under heating conditions

[0068] R134a Example Refrigerant high pressure (kPa) 455 1873 Refrigerant low pressure (kPa) 110 244 Refrigerant flow rate (kg / h) 19 104

[0069] Results under the same rpm of the compressor in cold outdoor areas (-15°C). For the refrigerant composition of the present invention [R1123 (30 wt%) + R13I1 (70 wt%)], the condensation pressure and evaporation pressure are lower compared to R410A, and higher compared to R1234yf and R134a.

[0070] Moreover, compared to R410A and R134a, the global warming potential (GWP) is 1, which is significantly lower (the global warming potential of R410A is 2088, and that of R134a is 1430), and the ozone depletion potential (ODP) is 0, having the advantage of environmental protection.

[0071] Therefore, the refrigerant composition of the embodiments of the present invention can be used as a substitute for R410A and R32, directly applicable to existing R410A and R32 systems in an environmentally friendly manner, and can be applicable to variable refrigerant flow (VRF) in household appliances.

[0072] Compared to R1234yf and R134a used in electric vehicles, the heating capacity is very excellent, so the driving range of electric vehicles in winter can be increased. Moreover, it also has the advantage of being easy to manufacture a binary mixed refrigerant.

[0073] Industrial applicability

[0074] The refrigerant composition for an air-conditioning apparatus according to the present invention has excellent heating capacity, a sufficiently small global warming potential (GWP), conforms to the specifications of ASHRAE, has non-flammability, non-toxicity (A1 grade), an ozone depletion potential (ODP) of 0, is simple to manufacture, and can be implemented as a substitute by performing minimal modifications such as optimizing the expansion device and heat exchanger of the air-conditioning apparatus using R410A, R1234yf, and R134a. Moreover, for electric vehicles, it has an additional effect of functioning as a fire extinguisher in case of a fire.

Claims

1. A refrigerant composition for an air-conditioning device, characterized in that, it contains trifluoroethylene (R1123) and trifluoroiodomethane (R13I1).

2. The refrigerant composition for an air-conditioning device according to claim 1, characterized in that, the trifluoroethylene (R1123) is 25 - 35 wt%, and the trifluoroiodomethane (R13I1) is 65 - 75 wt%.

3. The refrigerant composition for an air-conditioning device according to claim 1, characterized in that, the trifluoroethylene (R1123) is 25 - 35 wt%, the trifluoroiodomethane (R13I1) is 65 - 75 wt%, and propane (R290) or R32 is added in a small amount.

4. The refrigerant composition for an air-conditioning device according to claim 1, characterized in that, the trifluoroethylene (R1123) is 30 wt%, and the trifluoroiodomethane (R13I1) is 70 wt%.

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