WO2011007966A2

WO2011007966A2 - Refrigerant composition

Info

Publication number: WO2011007966A2
Application number: PCT/KR2010/004100
Authority: WO
Inventors: 오경화; 오석재
Original assignee: 주식회사 와이엠환경연구소
Priority date: 2009-07-13
Filing date: 2010-06-24
Publication date: 2011-01-20
Also published as: KR100976449B1; WO2011007966A3; WO2011007966A9

Abstract

The present invention relates to a refrigerant composition with an ozone depletion potential (ODP) of 0 and a global warming potential (GWP) of 79, the refrigerant composition comprising 55 to 65 kg of ethane-based 1,1-difluoroethane (R-152a), 10 to 25 kg of trifluoromethyl iodide (CF3I), 10 to 19 kg of propylene (R-1270), 3 to 5 kg of propane (R-290), 2 to 5 kg of ethane (R-170), and 0.1 to 1.5 kg of hexamethyl silicone oil.

Description

Refrigerant composition

The present invention is 55 to 65 kg of ethane 1,1-difluoroethane (R-152a), 10 to 25 kg of trifluoromethyl iodine (CF3I), 10 to 19 kg of propylene (R-1270), 3 to 5 kg of propane (R-290), 2 to 5 kg of ethane (R-170) and 0.1 to 1.5 kg of nucleated methyl silicone oil, and the ozone layer destruction index is (ODP = 0). The present invention relates to a refrigerant composition having a global warming index (GWP = 79).

Refrigerant is the working fluid of the refrigeration cycle, which refers to a medium that takes heat away from low-temperature objects and transfers heat to high-temperature objects. It is cheap, chemically stable, and efficient. 'CFC'), Hydrochlorofluorocarbons (HCFCs) and Hydrofluorofluorocarbons (HFCs) have been mainly used.

However, the destruction of the stratospheric ozone layer by CFCs and HCFCs has emerged as an important global environmental problem, and therefore the production and use of stratospheric ozone-depleting CFCs and HCFCs is regulated by the Montreal Protocol adopted in 1987. Therefore, most countries around the world are trying to use alternative refrigerants with an ozone depletion index (ODP) of 0.0.

In the Kyoto Protocol protocol, HFCs with a global ozone depletion index of zero were also regulated as global warming substances (GWP = 1,300).

In order to use any material as an alternative refrigerant to a conventional refrigerant, it must first have a coefficient of performance (COP) similar to that of a conventional refrigerant to exhibit a refrigerating effect similar to that of a conventional refrigerant, and also have a vapor pressure similar to that of a conventional refrigerant. You must provide a volumetric capacity (VC). However, in the case of replacing the existing refrigerant with pure material, the volumetric capacity of the replacement refrigerant is inevitably required to change the compressor or to greatly modify the existing condenser or evaporator, and it is very difficult to obtain a similar coefficient of performance as the existing refrigerant.

One way to solve this problem is to use a mixed refrigerant. The characteristic of mixed refrigerants is that the composition is well formulated to make the coefficient of performance (COP) similar to conventional refrigerants and at the same time to have a volumetric capacity (VC) similar to conventional refrigerants, so that the compressor does not need to be greatly modified. When these conditions are met, the manufacturer will not pay for the replacement of the compressor or any additional costs.

On the other hand, unlike azeotropes in which the evaporation temperature or condensation temperature is constant when evaporation or condensation occurs at isostatic pressure, such as pure refrigerant, the evaporation temperature increases when evaporation occurs, and condensation temperature increases when condensation occurs. There is a non-azeotropic Refrigerant Mixtures (NARMs). As such, the characteristics of the azeotropic mixed refrigerant are referred to as 'Gliding Temperature Phenomenon' and the temperature difference between the point at which evaporation starts and ends is called 'Gliding Temperature Difference' (GTD). The value varies greatly depending on the type and composition of pure materials constituting the mixed refrigerant.

Recently, many attempts have been made to develop Near Azeotropic Refrigerant Mixtures and use them as refrigerants in which GTD is less than about 3 ° C. among non-azeotropic Refrigerant Mixtures mixed refrigerants. Several types of mixed refrigerants have been proposed over the years as alternatives to CFCs, HFCs and HCFCs. However, some of them contain HCFCs, which are prohibited from use in the Montreal Protocol, and are not suitable alternatives in the long run.

So far, DuPont of the United States has developed and used HFCs with low warming index (GWP = 1,300) for automobiles and refrigerators without destroying the ozone layer (ODP = 0), but this is also not a long-term alternative material, The protocol is subject to regulation. Recently, DuPont in the US has developed a product called HFO-1234yf and it is being kept at a high price, but this product is a combustible product.

The Kyoto Protocol also prohibits the use of HFC-134a refrigerant, which is used as a CFC alternative refrigerant. Therefore, the refrigerant composed only of HFC is not a suitable substitute in the long term. And AllaidSignal Inc. The company developed and sells a binary mixture refrigerant (R-32 50% by weight / R-125 50% by weight) called R-410A, but this refrigerant also has a high global warming index and 60% higher vapor pressure than HCFC. Essentially, there is a problem in that the compressor needs to be modified and the system pressure is high to increase the strength of the material used in the condenser.

Korean Patent Publication No. 10-0405189 discloses difluoromethane (CH2F2, hereinafter referred to as 'HFC-32'), 1,1,1,2-tetrafluoroethane (CH2FCF3, hereinafter referred to as 'HFC-134a'). ) And isobutane (CH (CH3) 2CH3, hereinafter 'R-) in a mixture of 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, hereinafter referred to as' HFC-227ea'). 600a '), 1,1,1,2,3,3-hexafluoropropane (CHF2CHFCF3, hereinafter referred to as' HFC-236ea') and butane (C4H10, hereinafter referred to as' R-600 ') One component is mixed or R-600a, HFC-236ea and R-600 in a mixture of HFC-32, 1,1-difluoroethane (CH3CHF2, hereinafter referred to as 'HFC-152a') and HFC-227ea. It is a four-way mixed refrigerant composition in which one component is selected from among them, and it is used as an alternative refrigerant of chlorodifluoromethane (CHClF2: hereinafter referred to as 'HCFC-22') which has been used so far, and has no ozone depleting ability. And refrigerant materials for automobile air conditioners And the mixed refrigerant composition is described which may be,

Publication No. 10-0492169 discloses 1 to 99 parts by weight of R-1270 (propylene), 98 parts by weight or less of R-290 (propane), and R134a (1,1,1,2) in a mixed refrigerant for refrigeration / air conditioner. Tetrafluoroethane) mixed refrigerant consisting of 1 to 70 parts by weight is disclosed,

Publication No. 10-0540286 discloses 1 to 78% by weight of R-134a (1,1,1,2-tetrafluoroethane), 1 to 78% by weight of RE170 (dimethyl ether) and R-600a (isobutane). ) Is a mixed refrigerant composed of 21 to 98% by weight and a refrigeration system using the same,

Publication No. 10-0571358 discloses difluoromethane (CH2F2, hereinafter R-32), propane (CH3CH2CH3, hereinafter R-290), propylene (CH3CH = CH2, hereinafter R-1270), a methane refrigerant component. The mixture is composed of 5 to 40% by weight of dichloromethane (CH2F2), 35 to 70% by weight of propane (CH3CH2CH3), and 25 to 60% by weight of propylene (CH3CH = CH2). It is described a low-temperature alternative mixed refrigerant, characterized in that the composition is mixed with respect to the total 100% by weight,

Publication No. 10-0305079 contains difluoromethane (CH2F2, HFC-32) in the composition of a refrigerant mixture that can be used in place of HCFC-22, in a content of 40 to 96% by weight. Cyclopropane (C3F6, RC-270) and 1,1,1,2,2-pentafluoropropane (CH3CF2CF2, HFC-245cb), and butane (C4 H10, R-600) as the second and third components And a refrigerant mixture containing 1 to 40% by weight and 4 to 40% by weight of a fluorine compound selected from the group consisting of and bis (difluoromethyl) ether (CHF 2 OCHF 2, HFE-134), respectively, are disclosed.

Publication No. 10-400345 discloses difluoromethane (CH2F2, HFC-32), 1,1,1-trifluoroethane (CH3CF3, HFC-143a) and 1,1-difluoro. Ethane (CH3CHF2, hereinafter HFC-152a), 1,1,1,2,3,3,3-heptafluoro propane (CF3CHFCF3, hereinafter HFC-227ea), isobutane (CH (CH3) 2CH3, R-600a) , 1,1,1,2,3,3-hexafluoropropane (CHF2CHFCF3, hereinafter HFC-236ea) and butane (C4H10, hereinafter R-600) refrigerant composition consisting of a compound selected from the group consisting of It is

Publication No. 10-0540284 discloses a mixed refrigerant comprising a combination of propane, 1,1,1,2-tetrafluoroethane, dimethyl ether (hereinafter referred to as DME) and isobutane and a refrigeration system using the same. It is about. Mixed refrigerant according to a preferred embodiment of the present invention is 30 to 98% by weight of R-290 (propane), R-134a (1,1,1,2-tetrafluoroethane), 1 to 70% by weight, RE-170 A refrigerant mixture containing 1 to 70% by weight of (dimethyl ether) is disclosed.

Korean Patent No. 10-540280 discloses a mixed refrigerant composed of a selective combination of propylene, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, dimethyl ether and isobutane and It relates to a refrigeration system used. Mixed refrigerant according to a preferred embodiment of the present invention is 30 to 70% by weight of R-1270 (propylene), 1 to 69% by weight of R-134a (1,1,1,2-tetrafluoroethane), R-152a ( 1,1-difluoroethane) 1 to 69% by weight of a refrigerant composition is described,

Publication No. 10-305080 includes difluoromethane (CH3F2, HFC-32) as the first component and 1,1,1-trifluoroethane (CH3CF3, HFC-143a) as the second component. Cyclopropane (C3H6, RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea), 1,1,1,2,2 Pentafluoropropane (CH3CF2CF3, HFC-245cb), 1,1,1,2,3,3-hexafluoropropane (CHF2CHFCF3, HFC-236ea), butane (C4H10, R-600), bis (difluoro A refrigerant mixture containing HCFC-22 consisting of any one component selected from the group consisting of rhomethyl) ether (CHF 2 OCHF 2, HFE-134) and pentafluoroethylmethyl ether (CF 3 CF 2 OCH 3, HFE-245) is disclosed,

Korean Patent Publication No. 10-305905 includes difluoromethane (CH 3 F 2, HFC-32) as a first component, and perfluoropropane (C 3 F 8, 2) as a second component and a third component. PFC-218) and 1,1-difluoroethane (CH 3 CHF 2, HFC-152a), or cyclopropane (C 3 H 6, RC-270) and 1,1,1,2,2-pentafluoro HCFC comprising lopropanane (CH 3 CF 2 CF 3, HFC-245cb), or butane (C 4 H 10, R-600) and bis (difluoromethyl) ether (CHF 2 OCHF 2, HFE-134) -22 alternative refrigerant compositions are described,

Publication No. 10-0333503 discloses difluoromethane (CH 3 F 2, HFC-32) as the first component and 1,1,1-trifluoroethane (CH 3 CF 3, HFC as the second component. -143a), and as a third component cyclopropane (C 3 H 6, RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF 3 CHFCF 3, HFC- 227ea), 1,1,1,2,2-pentafluoropropane (CH 3 CF 2 CF 3, HFC-245cb), 1,1,1,2,3,3-hexafluoropropane (CHF 2 CHFCF 3, HFC-236ea), butane (C 4 H 10, R-600), bis (difluoromethyl) ether (CHF 2 OCHF 2, HFE-134) and pentafluoroethylmethylether (CF 3 CF 2 OCH 3, HFE-245) is disclosed a refrigerant mixture containing HCFC-22 consisting of any one component selected from the group consisting of,

Publication No. 10-0682828 discloses an alternative refrigerant to R-22, difluoromethane (CH2 F2, hereinafter referred to as 'HFC-32'), 1,1,1,2-tetrafluoroethane (CH2FCF3, hereinafter). Chlorodifluoromethane replacement (tertiary) azeotropic mixed refrigerant compositions composed of 'HFC-134a'), trifluoroiodomethane (CF3I, hereinafter referred to as "13I1"),

Korean Patent Publication No. 10-0492172 discloses a mixed refrigerant composed by selectively combining propylene, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, dimethylether and isobutane and It relates to a refrigeration system used. Mixed refrigerant according to a preferred embodiment of the present invention is 30 to 70 parts by weight of R-1270 (propylene), 1 to 69 parts by weight of R-134a (1,1,1,2-tetrafluoroethane), R-152a ( 1,1-difluoroethane) 1 to 69 parts by weight of a refrigerant mixture is disclosed,

Korean Patent Publication No. 10-2005-0057852 discloses difluoromethane (CH2F2, hereinafter HFC-32) and | Refrigerant consisting of 1,1,1-trifluoroethane (CH3CF3, hereinafter HFC-143a), cyclopropane (C3H6, rc-270) or propane (C3H8, hereinafter R-290) It can be seen that the composition is disclosed.

It should have a similar refrigerating effect as the refrigerant composition used in the past, and also have a similar vapor pressure as the existing refrigerant and ultimately provide a similar volumetric capacity (VC). Looking at the conventionally developed refrigerant composition, In case of replacing the existing refrigerant with pure material, it is necessary to change the compressor or greatly modify the existing condenser or evaporator because the volume of the replacement refrigerant is different, and to solve the problem that it is very difficult to obtain the performance coefficient similar to the existing refrigerant. It is a task to do.

In order to solve the above problems, the present invention is 55 to 65 kg of 1,1-difluoroethane (R-152a), 10 to 25 kg of trifluoromethyl iodine (CF3I), propylene (R-1270) 10 ~ 19 kg), propane (R-290) 3 ~ 5 kg, ethane (R-170) 2 ~ 5 kg, nucleated methyl silicone oil 0.1 ~ 1.5 kg, and the ozone layer destruction index The problem solving means is to provide a refrigerant composition having (ODP = 0) and a global warming index (GWP = 79).

The refrigerant composition of the invention

1) Since the ozone layer destruction index of the material constituting the mixed refrigerant is 0.0, there is a remarkable effect of preventing the destruction of the earth's ozone layer even when the refrigerant flows out or discards the refrigerant.

2) It can be lowered to GWP 79 which is much lower than the existing global warming index of 1,300 of R-134a.

3) Since the mixed refrigerant according to the present invention is a mixed refrigerant forming a near azeotropy, there is no change in composition due to the phase change, and thus it is possible to stably replace the refrigerant immediately without changing the refrigeration system as in the case of using pure refrigerant. .

4) There is no change in the freezing effect due to the composition separation during the outflow of the refrigerant, and it can be used only by replenishing the outflow of the refrigerant.

5) By using the mixed refrigerant according to the present invention can not only improve the thermal efficiency of the refrigerating / air conditioning, but also compatible with the oil of the existing lubricating oil PAG.

6) When the refrigerant according to the present invention is used, the refrigeration effect is 5 to 10% or more, which is an energy saving effect.

1 is a block diagram of a general refrigeration / air conditioner used in the present invention

Figure 2 Ternary mixture obtained by the program of REFPROP6.0 of the present invention

Temperature gradient diagram of refrigerant composition

Figure 3 is a pressure-en stripping diagram of the refrigerant composition

4 is a pressure-en stripping diagram minimized by the refrigerant composition of the present invention.

Figure 5 Pressure-En Stripping Diagram of R-134a

Fig. 6- Pressure stripping diagram of YM-1234A

7 is the worst composition of the first best condition refrigerant of YM-1234A, when 60% charge

Result of composition separation test in case of liquid leakage at -18.28 ℃

8 YM-1234A1 2nd best condition at the time of the worst composition 60% charge of the refrigerant

The result of composition separation experiment in case of liquid leakage at -18.28 ℃

9 YM-1234A first best condition worst composition at 15% charge

The result of composition separation experiment at the time of gas leakage at -18.28 ℃

Fig. 10 YM-1234A1 second best condition worst composition of refrigerant composition separation test result at the time of gas leakage at -18.28 ℃ when 15% filled

A refrigerant composition was prepared by mixing 65 kg of 1,1-difluoroethane (R-152a), 20 kg of trifluoromethyl iodide (CF3I), 14.9 kg of propylene (R-1270), and 0.1 kg of nucleated methyl silicone oil.

In order to achieve the above object, the present invention provides 55 to 65 kg of ethane-based 1,1-difluoroethane (R-152a), 10 to 25 kg of trifluoromethyl iodine (CF3I), and propylene (R- 1270) 10 ~ 19 kg, propane (R-290) 3 ~ 5 kg, ethane (R-170) 2 ~ 5 kg, nucleated methyl silicone oil 0.1 ~ 1.5 kg, the ozone layer destruction index Is (ODP = 0) and relates to a refrigerant composition having a global warming index (GWP = 79).

In general, mixed refrigerants have different boiling points (boiling points) between the refrigerants, so they are not mixed well and thus are separated from each other, resulting in a temperature gradient. Therefore, it is very difficult to develop a near azeotropic mixed refrigerant composition having an ionic gradient within at least 1 ° C. There is this.

In the present invention, in order to solve the problem of temperature gradient, nucleated methylsilicon oil is added as an additive to the mixed refrigerant selected and combined by the present inventors, thereby obtaining a near azeotropic mixed refrigerant composition which minimizes the temperature gradient. .

The refrigerant composition according to the present invention having the composition as described above is an azeotropic mixed refrigerant composition having an ozone depletion index (ODP) of 0.0 and a temperature gradient of 1 ° C. or less when evaporated, and thus can be used like a conventional pure refrigerant. It has a value close to or higher than the 134a coefficient of performance (COP) and the volumetric capacity (VC), so it is not necessary to change any parts of the refrigeration system, so it can be used as a replacement refrigerant of R-134a.

As described above, in order to develop a near azeotropic alternative mixed refrigerant composition according to the present invention, the present inventors have developed the CYCLE-D program developed by the National Institute of Standards and Technology to simulate the performance of the refrigeration / air conditioner Used. The program performed thermodynamic and heat transfer analyzes of the components that make up the refrigeration / air conditioner, such as heat exchangers and compressors, and finally all of them were used in combination.

One of the important factors that determine the accuracy of the program is the properties of the refrigerant composition. The program uses the Carnahan-Starling-De Santis (CSD) refrigerant state equation, which is based in the United States and Japan, as a bubble point for various refrigerants, and the dew point at which dew condenses as the gas condenses. Point) and a temperature gradient plot of the near azeotropic ternary refrigerant.

The CSD refrigerant state equation, known as REFPROP, was developed by the National Institute of Standards and Technology and is the most widely used program in leading refrigeration and air conditioning companies, research institutes, and universities worldwide for its proven accuracy and applicability. . The actual data was used as input data for the development and execution of the mixed refrigerant.

The present inventors have developed the present invention using the above program in the determination that the ozone depletion index (ODP) of the alternative refrigerant must be 0.0 and the global warming index (GWP) should be as low as possible.

The refrigerant composition of the present invention is a near azeotropic mixed refrigerant composition having no fear of destroying the ozone layer, having a temperature gradient (TG) of 1 ° C and a global warming index (GWP) of 79.

Hereinafter, a near azeotropic mixed refrigerant according to a preferred embodiment of the present invention will be described in detail. However, the following examples are illustrative of the present invention, and the content of the present invention is not limited by the examples.

실시예1(제1최선의 조건)Example 1 (First Best Condition)

실시예2(제2최선의 조건)Example 2 (second best condition)

60 kg 1,1-difluoroethane (R-152a), 20 kg trifluoromethyliodine (CF3I), 14.9 kg propylene (R-1270), 3 kg propane (R-290), ethane (R-170 2), 0.1 kg of nucleated methyl silicone oil, were mixed to prepare a refrigerant composition.

실시예3(제1최악의 조건)Example 3 (First Worst Condition)

A refrigerant composition was prepared by mixing 65 kg of 1,1-difluoroethane (R-152a), 19 kg of trifluoromethyl iodide (CF3I), 15.9 kg of propylene (R-1270), and 0.1 kg of nucleated methyl silicone oil. .

실시예4(제2최악의 조건)Example 4 (second worst condition)

60 kg of 1,1-difluoroethane (R-152a), 19 kg of trifluoromethyl iodine (CF3I), 15.9 kg of propylene (R-1270), 3 kg of propane (R-290), 2 kg of ethane (R-170), And 0.1 kg of nucleated methyl silicone oil were mixed to prepare a refrigerant composition.

The composition of the refrigerant composition of the present invention is 55 to 65 kg of ethane-based 1,1-difluoroethane (R-152a), 10 to 20 kg of trifluoromethyl iodide (CF3I), and 10 to 19 propylene (R-1270) kg, 0.1-1.5 kg of nucleated methyl silicone oil, or

Ethane-based 1,1-difluoroethane (R-152a) 55-65 kg, trifluoromethyl iodine (CF3I) 10-25 kg, propylene (R-1270) 10-19 kg, ethane (R-170) 2 ~ 5 kg, propane (R-290) 3 ~ 5 kg, nucleated methyl silicone oil 0.1 ~ 1.5 kg, ozone depletion index (ODP = 0), global warming potential (GWP = 79) Phosphorus refrigerant composition.

실험예 1 (이론적 및 실제 온도 구배 시험)Experimental Example 1 (Theoretical and Actual Temperature Gradient Test)

Figure 2 shows the temperature gradient diagram of the ternary mixed refrigerant composition obtained by the program of REFPROP6.0 of the present invention. However, it was found that the temperature gradient was minimized as shown in FIG. 4, after the additive was added to form a near azeotropic refrigerant composition, which is an object of the present invention.

실험예 2(조성 분리 실험)Experimental Example 2 (Composition Separation Experiment)

In order to confirm that the refrigerant composition of the present invention is near azeotropy, a composition separation experiment was performed. In this experiment, the worst composition (Example 3) was determined using the REFLEAK program developed by the US Standards Research Institute. REFLEAK is a program that uses the REFPROP program described above to determine the worst case composition in case of a leak in gas or liquid.

The UL2182 standard requires compositional analysis to determine the worst case for a case where a liquid refrigerant is 90% charged and 15% charged in a vessel under some temperature conditions. Thus, in the case of the refrigerant composition of the present invention, the composition separation analysis was performed under the following three temperature conditions.

90% charge: -18.28 ℃, 25.0 ℃, 54.4 ℃

15% charge: -18.28 ℃, 25.0 ℃, 60.0 ℃

For composition separation analysis, the following definitions were made for composition.

Filling composition: composition of the refrigerant that is initially formulated and sold

Worst-filled composition: The most mixed composition of flammable refrigerants due to the error in formulation. Depending on the error of the refrigerant blending machine, the amount of flammable refrigerant is usually 1% higher than that of the filling composition.

According to the above definition, the filling composition and the worst filling composition in the refrigerant of the present invention were determined as follows.

The best filling composition

1) 65% by weight of R-152a / 20% by weight of R-CF3I / 14.9% by weight of R-1270 / 0.1% by weight of additive.

2) 60% by weight R-152a / 20% by weight R-CF3I / 14.9% by weight R-1270 / 3% by weight R-290 / R-170

2 wt% / additive is 0.1 wt%.

Worst charge composition

1) 65% by weight of R-152a / 19% by weight of R-CF3I / 15.9% by weight of R-1270 / 0.1% by weight of additive.

2) 60 wt% of R-152a / 19 wt% of R-CF3I / 15.9 wt% of R-1270 / 3 wt% of R-290 / 2 wt% of R-170 / 0.1 wt% of the additive was used.

After setting the above conditions, the program was run at the temperature specified above to determine the worst leakage composition. The REFLEAK program calculated the worst leakage composition with no problem for 15% filling, but did not do harm due to its own convergence judgment problem at -18.28 ° C and 25 ° C for 90% charge, in which case less than 90% fill It is known that the value may be obtained by an external method after obtaining.

Best mixed refrigerant composition

65% by weight R-152a / 20% by weight R-CF3I / 14.9% by weight R-1270 / 0.1% by weight additives.

(Hereinafter "YM-1234A")

60% by weight R-152a / 20% by weight R-CF3I / 14.9% by weight R-1270 / 3% by weight R-290 / R-170

2 wt% / additive is 0.1 wt%.

(Hereinafter referred to as "YM-1234A1").

In the case of the refrigerant composition of the present invention, since R-1270 has the greatest flammability, the worst leakage composition of the worst-case filling composition refrigerant occurs when the amount of R-1270 is the highest. This is because the composition of the liquid R-1270 at -18.28 ° C is 15.9% when the vapor leaks.

Tables 1 and 2 show the liquid and gas composition separation experiments of the first " YM-1234A " and " YM-1234A1 " first second best condition refrigerants, and Tables 3 and 4 show " YM-1234A " The results of the composition separation experiments in which 15% of the liquid and gas leaked out under the worst conditions for the liquid and gas composition of the first second best condition refrigerant of YM-1234A1 "" are shown. However, the additive was ignored because of its small amount.

Table 1

"YM-1234A" first best condition liquid and gas composition separation experiment results of refrigerant

Test temperature	Gas leak (% by weight)	Liquid Leak (wt%)
-18.28 ℃ (60% charge)	Experiment (1) (L) 64.9857 / 19.9978 / 15.0165 (V) 65.0243 / 19,9922 / 14.9835	Experiment (2) (L) 64.9827 / 19.9988 / 15.0140 (V) 65.0043 / 19,9942 / 15.0015
25 ° C (85% charge)	Experiment (3) (L) 65.0150 / 19.9865 / 14.9985 (V) 65.0027 / 19,9938 / 15.0035	Experiment (4) (L) 65.0197 / 19.9838 / 14.9965 (V) 65.0243 / 19,9659 / 15.0098
54.4 ℃ (90% charge)	Experiment (5) (L) 64.9868 / 19.9987 / 15.0145 (V) 65.0113 / 19,9952 / 14.9935	Experiment (6) (L) 64.9968 / 19.9967 / 15.0047 (V) 65.0093 / 19,9972 / 14.9935

TABLE 2

"YM-1234A1" second best condition liquid and gas composition separation experiment results of refrigerant

Test temperature	Gas leak (% by weight)	Liquid Leak (wt%)
-18.28 ℃ (60% charge)	Experiment (1) (L) 60.0081 / 20.0191 / 14.8713 / 3.0626 / 2.0452 (V) 60.0224 / 20.0604 / 14.9076 / 3.0225 / 1.9871	Experiment (2) (L) 60.0194 / 20.0209 / 14.9001 / 3.0222 / 2.0374 (V) 59.9943 / 20.0542 / 14.9647 / 3.0094 / 1.9774
25 ° C (85% charge)	Experiment (3) (L) 60.0301 / 20.1900 / 14.8839 / 2.8981 / 1.9979 (V) 59.9987 / 20.2070 / 14.8732 / 2.9040 / 2.0171	Experiment (4) (L) 59.9799 / 20.0019 / 14.9020 / 3.0325 / 2.0837 (V) 60.0341 / 19.9898 / 14.9128 / 2.9697 / 2.0234
54.4 ° C (90% charge)	Experiment (5) (L) 60.0783 / 20.0011 / 14.9534 / 2.9705 / 1.9967 (V) 59.9809 / 19.9980 / 14.9011 / 3.1107 / 2.0093	Experiment (6) (L) 60.0474 / 19.9654 / 14.9298 / 3.0475 / 2.0099 (V) 59.9470 / 20.0921 / 14.8945 / 3.0391 / 2.0273

TABLE 3

"YM-1234A" First best condition Composition separation test result when liquid and gas leak 15% at worst condition for liquid and gas composition of refrigerant

Test temperature	Gas leak (% by weight)	Liquid Leak (wt%)
-18.28 ℃ (60% charge)	Experiment (1) (L) 65.0857 / 19.0098 / 15.9045 (V) 65.0943 / 18,9992 / 15.9065	Experiment (2) (L) 65.0327 / 18.9888 / 15.9785 (V) 65.0143 / 18,9842 / 16.0015
25 ° C (85% charge)	Experiment (3) (L) 65.0097 / 18.9975 / 15.9928 (V) 64.9827 / 19,0038 / 16.0135	Experiment (4) (L) 65.0997 / 18.9938 / 15.9065 (V) 64.9843 / 19,0059 / 16.0098
54.4 ° C (90% charge)	Experiment (5) (L) 64.9888 / 18.9967 / 16.0145 (V) 65.0133 / 19,0092 / 15.9775	Experiment (6) (L) 65.0038 / 18.9897 / 16.0065 (V) 65.0893 / 19,0092 / 15.9015

Table 4

"YM-1234A1" Second best condition Composition separation test result when liquid and gas leak 15% at worst condition for liquid and gas composition of refrigerant

Test temperature	Gas leak (% by weight)	Liquid Leak (wt%)
-18.28 ℃ (60% fill)	Experiment (1) (L) 60.0047 / 20.0043 / 14.9738 / 2.9680 / 2.0492 (V) 60.0077 / 20.0800 / 14.8099 / 0950 / 2.0074	Experiment (2) (L) 59.9949 / 19.9949 / 14.9001 / 3.1088 / 2.0013 (V) 60.0039 / 20.0021 / 14.8847 / 2.9820 / 2.1273
25 ℃ (85% fill)	Experiment (3) (L) 59.9878 / 19.9899 / 14.9098 / 3.0638 / 2.0738 (V) 60.0015 / 20.0070 / 14.9036 / 3.0815 / 2.0064	Experiment (4) (L) 60.0007 / 20.0131 / 14.8947 / 3.0910 / 2.0005 (V) 59.9876 / 20.0024 / 14.8895 / 3.0552 / 2.0437
54.4 ℃ (90% fill)	Experiment (5) (L) 60.0008 / 20.0013 / 14.9005 / 2.9979 / 2.1003 (V) 59.9799 / 19.9778 / 14.9231 / 3.0251 / 2.0941	Experiment (6) (L) 60.0021 / 20.0004 / 14.9077 / 3.0474 / 2.0424 (V) 59.9998 / 20.0045 / 14.8997 / 2.9890 / 2.1070

In addition, Table 5 below shows the results of the composition separation experiment at the time of liquid leakage at -18.28 ℃ at 60% charge with the worst composition of the "YM-1234A" first best condition refrigerant, Figure 7 is a graph .

Table 5

"YM-1234A" First best condition Composition separation test result in liquid leakage at -18.28 ℃ when 60% filling with worst composition of refrigerant

Starting temperature (℃)		-18.28
Start rate		60% charge
Start subsidy		65.0 / 19.0 / 15.9 / 0.1
The furtherance ratio according to%	Leakage (%)	Composition (wt%)
	10	65.0847 / 19.0098 / 15.9055
	20	65.0097 / 18.9975 / 15.9928
	30	65.0843 / 19.0058 / 15.9099
	40	64.9928 / 18.9967 / 16.0105
	50	65.0023 / 18.9975 / 16.0002
	60	65.0038 / 18.9827 / 16.0135
	70	65.0107 / 19.0028 / 15.9865
	80	65.0067 / 18.9985 / 15.9948
	90	65.0038 / 18.9897 / 15.9975
	99	65.0088 / 18.9847 / 16.0065

In addition, Table 6 below shows the results of the composition separation experiment at the time of liquid leakage at -18.28 ℃ at 15% charge with the worst composition of the "YM-1234A1" second best condition refrigerant, Figure 8 is a graph .

Table 6

"YM-1234A1" Second best condition Composition separation test result in liquid leakage at -18.28 ℃ when 60% filling with worst composition of refrigerant

Starting temperature (℃)		-18.28
Start rate		60% charge
Start subsidy		60.0 / 20.0 / 14.9 / 3.0 / 2.0
The furtherance ratio according to%	Leakage (%)	Composition (wt%)
	10	60.0249 / 20.0127 / 14.8831 / 3.0049 / 2.0744
	20	60.0125 / 20.0054 / 14.9013 / 3.0671 / 2.0137
	30	60.0044 / 20.0037 / 14.9009 / 3.0361 / 2.0549
	40	60.0308 / 20.0159 / 14.8974 / 3.0233 / 2.0326
	50	60.0237 / 20.0438 / 14.8279 / 3.0123 / 2.0923
	60	60.0190 / 20.0075 / 14.9047 / 2.9029 / 1.9949
	70	60.0284 / 20.0847 / 14.8949 / 3.0550 / 1.9370
	80	60.0980 / 20.0084 / 14.9043 / 2.9009 / 2.0803
	90	60.1070 / 20.1003 / 14.8792 / 2.9089 / 2.0046
	99	60.1049 / 20.0749 / 14.8648 / 2.9217 / 2.0337

In addition, Table 7 below shows the results of the composition separation experiment at the time of liquid leakage at -18.28 ℃ at 15% charge with the worst composition of the "YM-1234A" first best condition refrigerant, Figure 9 shows a graph.

TABLE 7

"YM-1234A" first best condition The composition of the composition separation at the time of gas leakage at -18.28 ℃ at 15% charge with the worst composition of the refrigerant

Start temperature (℃)		-18.28
Start rate		15% charge
Start subsidy		65.0 / 19.0 / 15.9 / 0.1
The furtherance ratio according to%	Leakage (%)	Composition (wt%)
	10	65.0357 / 19.0098 / 15.9545
	20	65.0297 / 18.9938 / 15.9605
	30	64.9938 / 18.9994 / 16.0068
	40	65.0012 / 19.0079 / 15.9909
	50	65.0128 / 18.9985 / 15.9887
	60	65.0092 / 18.9767 / 16.0141
	70	64.9967 / 19.0045 / 15.9988
	80	64.9996 / 18.9897 / 16.0107
	90	65.0093 / 19.0048 / 15.9859
	99	65.0088 / 18.9955 / 15.9957

In addition, Table 8 below shows the results of the composition separation experiment at the time of liquid leakage at -18.28 ℃ at 15% charge with the worst composition of the "YM-1234A1" second best condition refrigerant, Figure 10 is a graph.

Table 8

"YM-1234A1" The second best condition The composition of the composition separation at the time of gas leakage at -18.28 ℃ at 15% charge with the worst composition of the refrigerant

Starting temperature (℃)		-18.28
Start rate		15% fill
Start composition ratio		60.0 / 20.0 / 14.9 / 3.0 / 2.0
The furtherance ratio according to%	Leakage (%)	Composition ratio (wt%)
	10	60.0674 / 20.0433 / 14.9074 / 3.0020 / 1.9799
	20	60.0773 / 20.0076 / 14.8428 / 2.9891 / 2.0832
	30	60.0329 / 19.9939 / 14.9305 / 3.0328 / 2.0099
	40	60.0445 / 20.0308 / 14.8891 / 3.0049 / 2.0307
	50	60.0839 / 20.0177 / 14.8030 / 3.0231 / 2.0723
	60	60.0204 / 20.0644 / 14.8991 / 3.0144 / 2.0017
	70	60.0248 / 20.0733 / 14.9038 / 3.0108 / 1.9873
	80	60.0841 / 20.0092 / 14.8948 / 3.0115 / 2.0004
	90	60.0349 / 20.0249 / 14.9070 / 3.0102 / 2.0230
	99	60.0548 / 20.0073 / 14.8947 / 3.0221 / 2.02110

실험예 3 (성능 시험)Experimental Example 3 (Performance Test)

The theoretical performances of "YM-1234A" and "YM-1234A1" of the refrigerant composition of the present invention and the performance with R-134a were compared.

Refrigerant R-134a has been widely used in air conditioners for home refrigerators and automobiles, but its use is currently restricted. The impact of refrigerants on the global environment should be taken into account not only by the refrigerant itself, but also by the effects of carbon dioxide on the production of the power used to operate the system, which represents the total equivalent warming impact (TEWI). ). Based on this index, in the case of domestic refrigeration air conditioners, the direct effect of the refrigerant is 4% and the indirect effect is 96%, so the efficiency of the air conditioner is very important for selecting the refrigerant.

On the other hand, pure refrigerant having better performance than R-134a in freon series has not been developed yet.

In the following thermodynamic performance comparison, the evaporator temperature was 0 ° C and the condenser temperature was 40 ° C. There was no overheating and supercooling temperature at the evaporator outlet and the condenser outlet, and the compressor inlet outlet was an isotropic entropy process. .

FIG. 5 shows R-134a and FIG. 6 shows pressure-enthalpy diagrams of the refrigerants "YM-1234A".

Table 9

Comparison table of R-134a and "" YM-1234A "and" YM-1234A1 "" replacement refrigerants

Types of cold items	unit	YM-1234A	YM-1234A1	R-134a
Condenser Medium Temperature	℃℃	40.0	40.0	40.0
Condenser medium pressure	㎪	969.5	1012	1016
Liquid pressure P.	㎪	969.5	1012	1016
Gas pressure P.	㎪	959.5	1012	1016
Inlet temperature (gas) T.	℃℃	40.1	40.2	40.0
Outlet temperature (liquid) T.	℃℃	39.9	40.1	40.0
Δt condenser temperature difference	℃℃	0.2	0.1	0
Evaporator medium temperature	℃℃	-30.0	-30.0	-30.0
Evaporator medium pressure	㎪	98.5	99.5	84.36
Gas pressure P.	㎪	98.4	99.4	84.36
Liquid pressure P.	㎪	98.5	99.5	84.36
Inlet temperature (liquid + gas) T.	℃℃	-30.1	-31.1	-30.0
Outlet temperature (gas) T.	℃℃	-29.9	-31.0	-30.0
△ t evaporator temperature difference	℃℃	0.2	0.1	0
Pressure ratio		11.79	11.79	12.04
Outlet side temperature	℃℃	106.4	110.4	112.3
P1 (suction side density)	Kg / ㎥	1.966	1.986	3.47
Volumetric capacity	Kcal / ㎥	163.9	169.7	155.4
Δh (condensation) capacity.	Kcal / kg	83.37	87.35	44.8
COP	(w / w)	2.97	2.90	2.81
Molecular Weight	(g / mol)	88.35	87.1	102.0

Condenser Temperature: 40.0 ℃

Evaporator Temperature: -30.0 ℃

Sub cooled liquid temperature: 30.0 ℃

Superheated gas temperature: 30.0 ℃

The theoretical calculation was performed with the new version added by Technochem Co., Ltd. to the US Standards Institute PEFPROP 6.0 (Based on NIST, PEFPROP 6.0 & New Developed Refrigerant Program).

COP: coefficient of performance (Coefficient of performance, total refrigeration effect / work done on the compressor)

GWP: 85.4

Table 9 above Through the R-134a, which is a refrigerant of the HFC series, the coefficient of performance (COP) was lower than that of YM-1234A, and only YM-1234A showed that the efficiency was 9.4% higher than that of R-134a.

Based on TEWI (Total Equivalent Warming Index), YM-1234A is the best alternative refrigerant because performance is more important than the refrigerant itself. In addition, the pressure ratio or the compressor discharge temperature can be seen that the two refrigerants are almost the same.

Therefore, YM-1234A has no ozone depletion index (ODP) and GWP 79 is very low, so there is no problem in using it as a replacement refrigerant for R-134a in the long run.

Experimental Example 4 Comparison of Performance and Additive Performance of Refrigerant Compositions According to Component Ratios

실험 조건: Experimental condition:

증발기 냉매 온도: 7℃, Evaporator refrigerant temperature: 7 ℃,

응축기 냉매 온도: 45℃ Condenser Refrigerant Temperature: 45 ℃

COPr: Refrigeration performance coefficient (Coefficient of performance, evaporator capacity / work done on the compressor)

This coefficient of performance is the capacity of the work done by the evaporator divided by the work done on the compressor, the higher the energy savings.

QE: Evaporator capacity

The capacity of this evaporator is a value that is directly related to the freezing performance. The larger the capacity, the greater the freezing effect.

Tdis: Compressor discharge temperature

COPr _diff : Frozen performance coefficient difference compared to R134a

QE _diff : Evaporator (cooling) capacity difference compared to R134a

Tdis _diff : Compressor discharge temperature difference compared to R134a

GTD: difference between evaporator inlet and outlet temperature (Glide Temperature Difference)

In general, if the difference in ionicity is more than 3 ° C, freezing (also called freezing) appears on the surface of the evaporator, which degrades heat transfer and freezing performance. Therefore, it is better to have no or no temperature gradient.

As described above, the results of experiments with different composition ingredients and without adding additives showed that Examples 1 and 2 showed the highest performance index (COP) of 8.4% and 7.9%.

In particular, the temperature difference (GTD) is 6.0 ~ 7.3 ℃ when the additive is not added despite the mixed refrigerant. However, when the additive is added as shown in Examples 1 and 2, the temperature difference (GTD) of the evaporator is 0.1. As shown by the muscle azeotropes, it can be seen that additives are essential for making refrigerants of the aerosols.

Experimental Example 5 Global Warming Index (GWP) of Refrigerant Composition of the Present Invention

As shown above, the global warming index is shown according to the refrigerant composition. In the present invention, the global warming index is very important because it is necessary to develop a refrigerant of 150 or less because it is the purpose of developing an environmentally friendly refrigerant. As shown in the above table, it can be seen that Examples 1 and 2 show relatively low warming index.

Experimental Example 6 Lower Flammability Limit (LFL) of Refrigerant Composition of the Present Invention

As described above, it can be seen that the risk of flammability is also more than 15% secured in the composition containing the additive that has been tested for flammability according to the composition (experimental standard ASTM-E-681 2008).

The present invention is mainly used in automobile air conditioners or refrigerators, and the coefficient of performance (COP) of the mixed refrigerant to be similar to the existing refrigerant and at the same time have a volume capacity (VC) similar to the existing refrigerant, it is necessary to greatly modify the conventional compressor It does not pay for the replacement of the compressor or other additional costs, and provides a refrigerant composition with an ozone depletion index (ODP = 0) and a global warming index (GWP = 79).

Claims

In the refrigerant composition,

1,1-difluoroethane (R-152a) 55-65 kg, trifluoromethyliode

10 to 20 kg (CF3I), 10 to 19 kg of propylene (R-1270), 0.1 to 1.5 kg of nucleated methyl silicone oil, ozone depletion index (ODP = 0), global warming potential (GWP) 79) a refrigerant composition characterized in that.
In the refrigerant composition,

55 to 65 kg of 1,1-difluoroethane (R-152a), 10 to 25 kg of trifluoromethyl iodine (CF3I), 10 to 19 kg of propylene (R-1270), ethane (R-170) 2 to 5 kg, propane (R-290) 3 ~ 5 kg, nucleated methyl silicone oil 0.1 ~ 1.5 kg, ozone depletion index (ODP = 0), global warming potential (GWP = 79) Refrigerant composition.
According to claim 1,

65 kg of 1,1-difluoroethane (R-152a), 20 kg of trifluoromethyl iodide (CF3I), 14.9 kg of propylene (R-1270), and 0.1 kg of nucleated methyl silicone oil. Refrigerant composition.
The method according to claim 2,

60 kg of 1,1-difluoroethane (R-152a), 20 kg of trifluoromethyliode (CF3I), 14.9 kg of propylene (R-1270), 2 kg of ethane (R-170), propane (R-290 A refrigerant composition, characterized in that 3 kg, 0.1 kg of nucleated methyl silicon work.