WO2011007968A9

WO2011007968A9 - Refrigerant composition

Info

Publication number: WO2011007968A9
Application number: PCT/KR2010/004107
Authority: WO
Inventors: 오경화; 오석재
Original assignee: 주식회사 와이엠환경연구소
Priority date: 2009-07-13
Filing date: 2010-06-24
Publication date: 2011-06-16
Also published as: WO2011007968A3; KR100976448B1; WO2011007968A2

Abstract

The present invention relates to a refrigerant composition, in particular a mixed refrigerant composition with an ozone depletion potential (ODP) of 0 and a global warming potential (GWP) of 3, the refrigerant composition comprising 50 to 56 kg of hydrocarbon-based propane (R-290) and 40 to 49 kg of isobutane (R-600a) as a base, to which 2 to 5 kg of normal butane (R-600) and 1-3 kg of propylene (R-1270) are added, and 0.5 to 1 kg of hexamethyl silicone oil is added as an additive to form a near azeotrope.

Description

Refrigerant composition

The present invention is to replace the Freon refrigerant R-12 or R-134a mainly used in automobile air conditioners or refrigerators in the existing refrigeration system is a hydrocarbon-based propane as an environmentally friendly refrigerant composition that can be used to adjust only the amount of refrigerant without changing the structure (R-290) 50-56 kg, and isobutane (R-600a) 40-49 kg, based on normal butane (R-600) 2-5 kg, and propylene (R-1270) 1-3 kg A mixed refrigerant composition having an ozone layer destruction index (ODP = 0) and a global warming index (GWP = 3) added with 0.5 to 1 kg of nucleated methyl silicone oil as an additive in order to make a near-air azeotropy was added. will be.

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, HFC with a global ozone depletion index of zero was also defined as a global warming substance (GWP = 1,300) regulated item.

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.

Therefore, in recent years, 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 mixed refrigerants have been proposed for years as a replacement for 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 a low temperature (GWP = 1,300) HFC for automobiles and refrigerators without destroying the ozone layer (ODP = 0), but this is also not a long-term alternative and it is a bridge. The protocol is subject to regulation. Recently, DuPont, USA, developed HFO-1234yf, and it is very expensive. But this product is not a non-flammable product.

In addition, the Kyoto Protocol consists only of HFCs that restrict their use, making them a suitable substitute in the long term. In addition, AllaidSignal Inc. develops and sells a binary mixture refrigerant (50% by weight R32 / 50% by weight R125) called R-410A, but this refrigerant has a vapor pressure of about 60% higher than that of the existing HCFC. And the high pressure of the system has 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 no ozone depleting ability, and is a household refrigerator. As refrigerant material for automobiles and air conditioners Can be a mixed refrigerant composition is described in,

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 RE-170 (dimethyl ether) and R-600a ( Isobutane) 21 to 98% by weight of a mixed refrigerant and a refrigeration system using the same are described,

Publication No. 10-0571358 discloses dichloromethane (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,

Publication No. 10-400345 discloses difluoromethane (CH2F2, hereinafter HFC-32), 1,1,1-trifluoroethane (CH3CF3, hereinafter HFC-143a) and 1,1-difluoro. Ethane (CH3CHF2, hereinafter HFC-152a), 1,1,1,2,3,3,3-heptafluoropropane (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 R134A (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 | 1,1,1-trifluoroethane (CH3CF3, hereinafter referred to as HFC-143a) and | It can be seen that a refrigerant composition comprising one compound selected from cyclopropane (C3H6, hereinafter RC-270) or propane (C3H8, hereinafter R-290) is disclosed.

Refrigerant effect should be similar to that of conventional refrigerant compositions, and also have similar vapor pressures to conventional refrigerants and ultimately provide similar volumetric capacity (VC). Looking at conventional refrigerant compositions, pure materials In the case of replacing the existing refrigerant, the volumetric capacity of the replacement refrigerant is different, so it is necessary to change the compressor or to remodel the existing condenser or evaporator, and to solve the problem that it is very difficult to obtain a performance coefficient similar to that of the existing refrigerant. The invention is to be solved.

In order to solve the above problems, the present invention is based on hydrocarbon propane (R-290) 50-56 kg, and isobutane (R-600a) 40-49 kg, and normal butane (R-600) 2 ~ 5 kg, and 1 to 3 kg of propylene (R-1270) were added, and the ozone layer destruction index (ODP = 0) was added with 0.5-1 kg of nucleated methyl silicone oil as an additive to make muscle azeotropy. The present invention relates to a mixed refrigerant composition having a warming index (GWP = 3).

According to the mixed refrigerant composition and the refrigeration system using the same according to the present invention having the above configuration

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

2) The global warming potential of the existing R-12 (10,060) R-134a (1,300) could be lowered to (GWP) 3.

3) Since the mixed refrigerant composition according to the present invention is a mixed refrigerant having a near azeotropy, there is no change in composition due to phase change, and thus a refrigeration system can be stably used as in the case of using pure refrigerant.

4) There is no change in the freezing effect due to the composition separation phenomenon when the refrigerant composition flows out.

5) Using the mixed refrigerant composition according to the present invention can not only improve the thermal efficiency of the refrigeration / air conditioner, but also has the advantage of good compatibility with the oil of the existing lubricating oil PAG.

6) When the refrigerant composition according to the present invention is used, the refrigeration effect is 5 to 10% or more, resulting in 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

P-h diagram of a typical mixed refrigerant

P-h diagram of near-azeotropic mixed refrigerant

Figure 5 R-134a P-h diagram

Figure 6 C-134A P-h diagram

Figure 7 SC-134A First Best Condition At Worst Composition 60% Charge of the Refrigerant

Result of composition separation experiment at liquid leakage at -18.28 ℃

8 SC-134A1 Second Best Condition At Worst Composition 60% Charge of Refrigerant

Result of composition separation experiment at liquid leakage at -18.28 ℃

Figure 9 SC-134A First Best Condition During Worst Composition 15% Charge of Refrigerant

Result of composition separation experiment at liquid leakage at -18.28 ℃

Figure 10 SC-134A1 Second Best Condition During Worst Composition 15% Charge of Refrigerant

Result of composition separation experiment at liquid leakage at -18.28 ℃

A refrigerant composition was prepared by mixing 53 kg of propane (R-290) and 46.9 kg of isobutane (R-600a), and then adding 0.1 kg of nucleated methyl silicone oil as an additive to produce a near azeotropic mixed refrigerant composition .

In order to achieve the above object, the present invention is based on the hydrocarbon-based propane (R-290) 50-56 kg, and isobutane (R-600a) 40-49 kg, and normal butane (R-600) 2 ~ 5 kg, and 1 to 3 kg of propylene (R-1270) were added, and the ozone layer destruction index (ODP = 0) was added with 0.5-1 kg of nucleated methyl silicone oil as an additive to make muscle azeotropy. The present invention relates to a mixed refrigerant composition having a warming index (GWP = 3).

'Refrigerant composition' of the present invention means that two or more different types of refrigerants are combined, and include additives other than the refrigerant composition.

In general, the refrigerant composition is different from each other because the boiling point between the refrigerant is different from each other, so it is difficult to develop a near azeotropic mixed refrigerant composition having a ionic gradient within at least 1 ° C. There is this.

In the present invention, in order to solve the problem of the temperature gradient, by adding the core yarn methyl silicone oil as an additive to the mixed refrigerant selected by the present inventors, it is possible to obtain a near azeotropic mixed refrigerant composition which minimizes the temperature gradient. .

The mixed refrigerant composition according to the present invention is a near azeotropic mixed refrigerant composition having an ozone depletion index (ODP) of 0.0 and a temperature gradient of less than 1 ° C. upon evaporation, and thus can be used like a conventional pure refrigerant, and R-12, As it has a value close to the coefficient of performance (COP) and volume capacity (VC) of R-134a, no parts of the refrigeration system need to be changed, and it is a replacement refrigerant of R-12 or R-134a. It is possible.

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 the standard in the United States and Japan, to condense bubbles and bubbles. The dew point was calculated to create the dew point, and the temperature gradient diagram of the near azeotropic ternary refrigerant composition was made. The CSD Refrigerant Condition Equation was developed by the National Institute of Standards and Technology and is the most widely used program in leading refrigeration and air conditioning companies, laboratories, and universities around the world for their proven accuracy and applicability. The actual data was used as input data for the development and execution of the mixed refrigerant composition.

Using the above program, the inventors have determined that the ozone depletion index (ODP) of the alternative refrigerant composition must be 0.0 and the global warming index (GWP) should be as low as possible. A mixed refrigerant composition in which additive nucleated methyl silicone oil is added to make a near azeotropic mixed refrigerant composition as a mixed refrigerant composed of R-600a) is developed.

That is, it 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 3.

Hereinafter, a near azeotropic mixed refrigerant composition 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.

실시예 1 (제 1 최선의 조건)Example 1 (First Best Condition)

실시예 2 (제 2 최선의 조건)Example 2 (second best condition)

52 kg of propane (R-290), 43.9 kg of isobutane (R-600a), followed by additives to make 2 kg of normal butane (R-600), 1 kg of propylene (R-1270) and azeotropic mixed refrigerant composition The refrigerant composition was prepared by adding 0.1 kg of nucleated methyl silicon oil.

The refrigerant composition of the present invention is 50 to 56 kg of propane (R-290), 40 to 49 kg of isobutane (R-600a), 0.1 to 0.5 kg of nucleated methyl silicone oil, or hydrocarbon based propane (R- 290) 50-56 kg, 40-49 kg of isobutane (R-600a), 2-5 kg of normal butane (R-600), 1-3 kg of propylene (R-1270), nucleated methyl silicone oil It can be seen that the composition is 0.1 ~ 0.5kg.

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

Figure 3 shows the temperature gradient diagram of the four-way 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 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 Filling Composition: Combination of most flammable refrigerants due to errors 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 composition of the present invention were determined as follows.

The best filling composition is: 1) (R-290) 53 kg / (R-600a) 46.9 kg / (additive) 0.1 kg (hereinafter referred to as "SC-134A")

2) (R-290) 52 kg / (R-600a) 43.9 kg / (R-600) 2 kg / (R-1270) 1 kg / (additive) 0.1 kg. (Hereinafter referred to as "SC-134A1")

Worst filling composition: 1) (R-290) 54 kg / (R-600a) 45.9 kg / (additive) 0.1 kg.

2) (R-290) 52 kg / (R-600a) 44.9 kg / (R-600) 2 kg / (R-1270) 1 kg / (additive) 0.1 kg.

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.

In the case of the refrigerant composition of the present invention, only the lower flammable lower limit of R-600a causes the worst filling composition. The worst leakage composition of the refrigerant composition occurs when the amount of R-600a is the highest. This is because when the vapor leaks, the composition of the liquid phase R-600a is 46.9% at -18.28 ° C.

Tables 1 and 2 show liquid and gas composition separation experiments of the "" SC-134A "and" SC-134A1 "" first best conditions and second best conditions refrigerants, and Tables 3 and 4 show "SC-134A" and "SC-134A1". 134A "and" SC-134A1 "" The first and second best conditions shows the results of the composition separation experiment when liquid and gas leak 15% at the worst condition for the liquid and gas composition of the refrigerant. . However, the additive was ignored because of its small amount.

Table 1

"SC-134A" First best condition liquid and gas composition separation experiment result of refrigerant

Test temperature	Gas leak	Liquid leak
-18.28 ℃ (60% filling)	Case (1) (L) 53.9943 / 46.0057 (V) 53.9978 / 46.0022	Case (2) (L) 54.0023 / 45.9977 (V) 53.9979 / 46.0021
25 ℃ (85% filling)	Case (3) (L) 53.9965 / 46.0035 (V) 54.0056 / 45.9944	(4) (L) 54.0049 / 45.9951 (V) 54.0064 / 45.9936
54.4 ℃ (90% filling)	Case (5) (L) 53.9954 / 46.0046 (V) 53.9986 / 46.0014	Case (6) (L) 54.0077 / 45.9923 (V) 54.0074 / 45.9926

TABLE 2

"SC-134A1" Second best condition liquid and gas composition separation experiment result of refrigerant

Test temperature	Gas leak	Liquid leak
-18.28 ℃ (60% filling)	Case (1) (L) 52.9274 / 43.9763 / 2.0963 / 1 (V) 53.0020 / 43.9248 / 2.0732 / 1	Case (2) (L) 53.0729 / 44.0049 / 1.9222 / 1 (V) 53.0077 / 44.0021 / 1.9902 / 1
25 ℃ (85% filling)	Case (3) (L) 53.0142 / 43.9972 / 1.9886 / 1 (V) 52.9871 / 44.0820 / 1.9309 / 1	(4) (L) 53.0205 / 43.9727 / 2.0077 / 1 (V) 52.9956 / 44.0057 / 1.9987 / 1
54.4 ℃ (90% filling)	Case (5) (L) 53.0309 / 44.0620 / 1.9071 / 1 (V) 53.0113 / 44.0243 / 1.9644 / 1	(6) (L) 53.0506 / 44.0248 / 1.9246 / 1 (V) 52.9487 / 43.9907 / 2.0606 / 1

TABLE 3

"SC-134A" First best condition Composition separation test results when liquid and gas leak 15% at worst condition for liquid and gas composition of refrigerant

Test temperature	Gas leak	Liquid leak
-18.28 ℃ (60% filling)	Case (1) (L) 52.9969 / 47.0031 (V) 52.9990 / 47.0001	Case (2) (L) 53.0009 / 46.9991 (V) 52.9989 / 47.0011
25 ℃ (85% filling)	Case (3) (L) 52.9987 / 47.0013 (V) 53.0099 / 46.9901	Case (4) (L) 53.0209 / 46.9791 (V) 53.0024 / 46.9976
54.4 ℃ (90% filling)	Case (5) (L) 52.9989 / 47.0011 (V) 52.9907 / 47.0093	Case (6) (L) 53.0049 / 46.9951 (V) 53.0079 / 46.9921

Table 4

"SC-134A1" Second best condition The composition separation test result when liquid and gas leak 15% at the worst condition for the liquid and gas refrigerant composition of the refrigerant.

Test temperature	Gas leak	Liquid leak
-18.28 ℃ (60% filling)	Case (1) (L) 52.0247 / 45.9928 / 1.9825 / 1 (V) 51.9737 / 46.0721 / 1.9542 / 1	(2) (L) 52.0119 / 45.9424 / 2.0457 / 1 (V) 51.9414 / 45.9987 / 1.9059 / 1
25 ℃ (85% filling)	(3) (L) 52.0173 / 45.9211 / 1.9059 / 1 (V) 52.0154 / 46.0015 / 1.9831 / 1	(4) (L) 52.0018 / 46.0002 / 1.9818 / 1 (V) 51.9633 / 46.0740 / 1.9627 / 1
54.4 ℃ (90% filling)	Case (5) (L) 52.0029 / 46.0144 / 1.9827 / 1 (V) 51.9945 / 45.9927 / 2.0128 / 1	(6) (L) 52.0040 / 45.9676 / 2.0284 / 1 (V) 51.9489 / 46.0023 / 2.0488 / 1

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 "SC-134A" first best condition refrigerant, Figure 7 is a graph .

Table 5

"SC-134A" 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% filling
Start subsidy		53.0 / 46.9 / 0.1
The furtherance ratio according to%	Leakage (%)	Composition (% by weight)
	10	52.9869 / 47.0131
	20	53.0019 / 46.9981
	30	52.9899 / 47.0101
	40	52.9990 / 47.0010
	50	52.9889 / 47.0111
	60	52.9967 / 47.0033
	70	53.0279 / 46.9703
	80	53.0099 / 46.9901
	90	53.0299 / 46.9701
	99	53.0019 / 46.9981

Table 6

"SC-134A1" Second best condition Composition separation test result in liquid leakage at -18.28 ℃ when 60% filling with worst composition of refrigerant

Temperature (℃)		-18.28
Start rate		60% filling
Start subsidy
		52 start .0 / 45.0 / 2.0 / 1.0
The furtherance ratio according to%	Leakage (%)	Composition (% by weight)
	10	52.0742 / 45.0041 / 1.9217 / 1.0
	20	51.9249 / 45.0024 / 2.0727 / 1.0
	30	52.0079 / 44.9929 / 1.9992 / 1.0
	40	52.0094 / 45.0810 / 1.9096 / 1.0
	50	51.9627 / 45.0143 / 2.0230 / 1.0
	60	52.0742 / 44.9951 / 1.9307 / 1.0
	70	52.0621 / 45.0090 / 1.9266 / 1.0
	80	52.0035 / 45.0090 / 1.9875 / 1.0
	90	51.9728 / 45.0126 / 2.0146 / 1.0
	99	52.0032 / 44.9274 / 2.0694 / 1.0

In addition, Table 6 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 "SC-134A1" second best condition refrigerant, Figure 8 is a graph.

TABLE 7

"SC-134A" 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

Starting temperature (℃)		-18.28
Start rate		15% filling
Start subsidy		53.0 / 46.9 / 0.1
The furtherance ratio according to%	Leakage (%)	Composition (% by weight)
	10	52.9989 / 47.0011
	20	53.0119 / 46.9881
	30	52.9969 / 47.0031
	40	52.9900 / 47.0010
	50	52.9899 / 47.0100
	60	52.9997 / 47.0033
	70	53.0258 / 46.9003
	80	53.0019 / 46.9981
	90	53.0223 / 46.9777
	99	53.0044 / 46.9956

In addition, Table 7 shows the results of the composition separation experiment when the liquid leaked at -18.28 ℃ at 15% charge with the worst composition of the "SC-134A" second best condition refrigerant, Figure 9 shows a graph.

Table 8

"SC-134A1" 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% filling
Start subsidy		53.0 / 44.0 / 2.0 / 1.0
The furtherance ratio according to%	Leakage (%)	Furtherance(%)
	10	51.9892 / 44.9929 / 2.0179 / 1.0
	20	52.0078 / 44.9243 / 2.0677 / 1.0
	30	51.9694 / 45.0024 / 2.0282 / 1.0
	40	52.0011 / 45.0008 / 1.9981 / 1.0
	50	51.9688 / 45.0900 / 1.9412 / 1.0
	60	52.0019 / 44.9487 / 2.0494 / 1.0
	70	51.9799 / 45.0021 / 2.0180 / 1.0
	80	52.0602 / 44.9872 / 1.9526 / 1.0
	90	52.0122 / 44.9241 / 2.0637 / 1.0
	99	52.0037 / 44.9767 / 2.0196 / 1.0

In addition, Table 8 shows the results of the composition separation experiment when the liquid leakage at -18.28 ℃ at 15% charge with the worst composition of the "SC-134A1" second best condition refrigerant, Figure 10 is a graph.

실시 예 3. 성능 시험Example 3. Performance Test

Table 9 compares the "SC-134A" and "SC-134A1" theoretical performance of the refrigerant of the present invention and the performance comparison with R-12 R-134a.

91R-12 and R-134a refrigerants have been widely used in air conditioners for home refrigerators and automobiles, but their 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%. Therefore, 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. . 5, R-134a and FIG. 6 "SC-134A" show pressure-enthalpy diagrams of the respective refrigerants.

Table 9

Comparison table of R-12, R-134a, "SC-134A" and "SC-134A1" alternative refrigerants

Type of refrigerant Item	unit	R-12	"SC-134A"	SC-134A1	R-134a
Condenser Medium Temperature	℃℃	40.0	40.0	40.0	40.0
Condenser medium pressure	㎪	950.7	969.5	979.5	1016
Liquid pressure P.	㎪	950.7	969.5	979.5	1016
Gas pressure P.	㎪	950.7	959.5	979.5	1016
Inlet temperature (gas) T.	℃℃	40.0	40.1	40.2	40.0
Outlet temperature (liquid) T.	℃℃	40.0	39.9	40.1	40.0
Δt condenser temperature difference	℃℃		0	0.2	0.1	0
Evaporator medium temperature	℃℃	-30.0	-30.0	-30.2	-30.0
Evaporator medium pressure	㎪	99.0	98.5	97.5	84.36
Gas pressure P.	㎪	99.0	92.4	94.5	84.36
Liquid pressure P.	㎪	99.0	92.4	94.5	84.36
Inlet temperature (liquid + gas) T.	℃℃	-30.0	-30.2	-31.1	-30.0
Outlet temperature (gas) T.	℃℃	-30.0	-30.1	-31.0	-30.0
△ t evaporator temperature difference	℃℃		0	0.1	0.1	0
Pressure ratio		9.60	11.79	11.79	12.04
Outlet side temperature	℃℃	119.6	106.4	110.4	112.3
P1 (suction side density)	Kg / ㎥	4.849	1.966	1.986	3.47
Volumetric capacity	Kcal / ㎥	166.9	163.9	169.7	155.4
Δh (condensation) capacity.	Kcal / kg	34.4	83.37	87.35	44.8
COP	(w / w)	2.81	2.97	2.90	2.81
Molecular Weight	(g / mol)	120.9	50.55	50.53	102.0

NOTE) REF. APL. Con. : Means Low Back Pressure Conditions

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: 3

Through Table 9, the conventional R-12 and R-134a, which is a refrigerant of the HFC series, showed a lower coefficient of performance (COP) than the "SC-134A" and "SC-134A1", and the only "SC-134A". It can be seen that only "and" SC-134A1 "showed 10% higher efficiency than R-134a.

Based on TEWI (Total Equivalent Warming Index), "SC-134A" and "SC-134A1" are the best alternative refrigerants because performance is more important than the refrigerant's own effect. In addition, the pressure ratio and the compressor discharge temperature can be seen that the two refrigerant compositions are almost the same. Therefore, "SC-134A" and "SC-134A1" have no ozone depletion index (ODP) and GWP of 3, so there is no problem in using R-134a as an alternative refrigerant in the long run.

Experimental Example 4 Performance Comparison of R134a Alternative Mixed Refrigerant and Additive Performance

조건: 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 indexes (COP) of 12.9% and 13.3%.

Particularly, when the additive is not added despite the mixed refrigerant, the difference in temperature (GTD) is 5.0 ~ 7.2 ° C., but 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

As shown above, the global warming index is shown according to the refrigerant composition. However, all hydrocarbon-based refrigerants did not make a big difference because of their low global warming potential.

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

As described above, it can be seen that the risk of flammability is also more than 50% secured in the composition of the composition containing additives that have 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 = 3).

Claims

In the refrigerant composition,

50 to 56 kg of propane (R-290), 40 to 49 kg of isobutane (R-600a), 0.1 to 0.5 kg of nucleated methyl silicone oil, ozone layer destruction index (ODP = 0), global warming Refrigerant composition, characterized in that the index (GWP = 3).
The refrigerant composition according to claim 1, comprising 54 kg of propane (R-290), 45.9 kg of isobutane (R-600a), and 0.1 kg of nucleated methyl silicone oil.
In the refrigerant composition,

50-56 kg of propane (R-290), 40-49 kg of isobutane (R-600a), 2-5 kg of normal butane (R-600), 1-3 kg of propylene (R-1270), nucleated methyl silicon Refrigerant composition, characterized in that the oil is composed of 0.1 ~ 0.5 kg, the ozone layer destruction index (ODP = 0), the global warming index is (GWP = 3).
The method of claim 3, 52 kg of propane (R-290), 43.9 kg of isobutane (R-600a), 2 kg of normal butane (R-600), 1 kg of propylene (R-1270), 0.1 kg of nucleated methyl silicone oil Refrigerant composition, characterized in that the composition.