KR20120080289A - Near azeotropic refrigerant mixtures - Google Patents

Abstract

PURPOSE: An environment-friendly coolant composition is provided to prevent ozone layer destruction at discharging or wasting coolant, because the ozone depletion potential of the coolant composition is 0, and to able to stably use refreezing system because composition change according to phase change is not occurred. CONSTITUTION: An environment-friendly coolant composition comprises 1-50 kg of difluoromethane(R-32), 50-99 kg of 1,1-difluoroethane(R-152a), and 0.5-1 kg of hexamethyl silicon oil as additives. The ozone depletion potential(ODP) is 0, and the global warming potential(GWP) is 332. More specifically the coolant composition comprises 37.9 kg of difluoromethane(R-32), 62 kg of 1,1-difluoroethane(R-152a), and 0.1 kg of hexamethyl silicon oil.

Description

R-22 Alternative Environmentally Friendly Refrigerant Compositions {Near Azeotropic Refrigerant Mixtures}

The present invention is to replace the Freon refrigerant R-22 or R-410A, R-407C mainly used in home air conditioner or industrial air conditioner in the environment-friendly refrigerant composition that can be used to adjust the amount of refrigerant without changing the structure of the conventional refrigerator system 1 to 50 kg of difluoromethane (R-32) and 50 to 99 kg of 1,1, -difluoro ethane (R-152a) are added and 0.5 to 0.5% nucleated methyl silicone oil is added as an additive to achieve muscle azeotropy. It relates to a refrigerant composition having an ozone depletion index (ODP = 0) added to ˜1 kg and a global warming index (GWP = 332).

Refrigerant is the working fluid of the refrigeration cycle. It refers to a medium that takes heat away from a low temperature object and transfers heat to a high temperature object. It is an inexpensive, chemically stable and efficient Chlorofluo rocarbon, '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 addition, HFCs with a global ozone depletion index of zero in the Kyoto Protocol protocol are now regulated as global warming substances (GWP = 1,430).

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 HFC-134a for automobiles and refrigerators without causing ozone depletion (ODP = 0) and with a relatively low warming index (GWP = 1,430), but this also does not become a long-term alternative. It is also subject to the regulation of the correctional protocol. Recently, DuPont, USA, has developed a product called HFO-1234yf and introduced it at a high price. This refrigerant is also a refrigerant recommended for use in automobiles or refrigerators as the A2 grade like the flammability of the present invention.

In addition, the HFC-134a refrigerant, which is restricted in the Kyoto Protocol, is not a suitable substitute in the long term due to its high global warming index.

AllaidSignal Inc. has developed and sold a binary mixture refrigerant (50% by weight R-32 / 50% by weight R-125) called R-410A, but this refrigerant is essential because its vapor pressure is about 60% higher than that of conventional HCFCs. As a result, the compressor needs to be modified and the pressure of the system is high, so the strength of the material used for the condenser must be increased.

Recently, the characteristics of the effects of global warming (GWP) and temperature gradient (GTD) among the patents on the composition of the new mixed refrigerant for R-22 replacement invented in Korea are as follows.

In Korea, 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) in a mixture of 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, hereinafter referred to as' HFC-227ea') It is called 'R-600a'). 1,1,1,2,3,3-hexafluoropropane (CHF2CHFCF3, hereinafter referred to as 'HFC-236ea') and butane (C4H10, hereinafter referred to as 'R-600') Or a component selected from 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. As a mixed four-way refrigerant composition, it is used as an alternative refrigerant of chlorodifluoromethane (CHClF2: hereafter referred to as 'HCFC-22') and has no ozone depleting ability, and is used for household refrigerators and automobile air conditioners. Mixed refrigerant compositions which can be used as refrigerant materials for

Publication No. 10-305080 includes difluoro methane (CH3F2, HFC-32) as the first component and 1,1,1-trifluouroethane (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,

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) is a refrigerant composition consisting of a compound selected from the group consisting of It is

Publication No. 10-305905 discloses difluoromethane (CH 3 F 2, HFC-32) as the first component, and perfluoropropane (C 3 F 8, PFC- as the second and third components). 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-pentafluuropropane (CH 3 CF 2 CF 3, HFC-245cb), or HCFC-22 replacement refrigerant containing butane (C 4 H 10, R-600) and bis (difluoromethyl) ether (CHF 2 OCHF 2, HFE-134) 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, difluuromethane (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', trifluoroiodo methane (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-tetra fluoroethane, 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 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,

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

However, the mixed refrigerant composition of the patent can not only reduce the cooling effect because the temperature difference (GTD) in the evaporator is more than 5 to 7 degrees Celsius, the warming index is 'HFC-32' is 675, 'HFC-134a' is 1,430 , 'HFC-227ea' is 3,320, 'HFC-236ea' is 9,810, 'HFC-152a'124 is selected by mixing either the lowest refrigerant material warming index of R-600 or R-600a of 3 However, since the GWP, which has been recently agreed around the world, does not become a refrigerant of 400 or less, this refrigerant is also a regulated invention patent.

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-tetrafluoroethane) 1 to 70 parts by weight of a mixed refrigerant 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 (CH3 CF2CF2, 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 bis (difluoromethyl) ether (CHF 2 OCHF 2, HFE-134), respectively,

Publication No. 10-0540284 discloses a mixed refrigerant comprising a combination of propane, 1,1,1,2-tetrafluoethane, 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 Publication No. 10-540280 discloses a mixed refrigerant composed by selectively combining propylene, 1,1,1,2-tetrafluoethane, 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% by weight of R-1270 (propylene), 1 to 69% by weight of R-134A (1,1,1,2-tetrafluoroethane), R-152a ( 1,1-difluoroethane) is described in a refrigerant composition consisting of 1 to 69% by weight.

The conventional techniques have a relatively low global warming index (GWP) but a temperature difference (GTD) of 5-7 degrees Celsius, which creates ice in the evaporator, which can drastically reduce the cooling effect and similar volumetric capacity (VC). As it is a non-azeotropic mixed refrigerant, it is inevitable to change the compressor or to greatly modify the existing condenser or evaporator, and it is very difficult to obtain a performance coefficient similar to that of the existing refrigerant. Have.

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.

The present invention to solve the problem as described above,

Patent Application Nos. 10-2009-63299 (Registration No. 10-976449), 10-2009-63300 (Registration No. 10-957043) filed by the present applicant,

No. 10-2009 63302 (Registration No. 10-976448),

No. 10-2009-90999 (Registration No. 10-969258),

No. 10-2009-91005 (Registration No. 10-969257),

10-2009-91008 (Registration No. 10-969256), title of the invention; Refrigerant composition was improved by adding 1 to 50 kg of difluoromethane (R-32) and 50 to 99 kg of ethane-based 1,1, -difluoro ethane (R-152a) and making aerosols. It is an object of the present invention to provide a refrigerant composition having an ozone layer destruction index (ODP = 0) and a global warming index (GWP = 332) added with methyl silicone oil as an additive of 0.5 to 1 kg. will be.

The present invention

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) can be lowered to (GWP) 332, which is much lower than the global warming index of existing R-22 (10,060), R-410A (2,100), R-407C (1,700) and R-134a (1,430).

3) As it is a mixed refrigerant that forms near azeotropes, there is no change of composition due to phase change, so that the refrigeration system can be used stably as in the case of using pure refrigerant.

4) Since the mixed refrigerant forming near azeotropy, the temperature difference in the evaporator was minimized to 0.3 ℃.

5) There is no change in the refrigerating effect due to the composition separation phenomenon when the refrigerant composition flows out, and it can be used only by replenishment when it flows out.

6) not only can improve the thermal efficiency of refrigeration / air conditioning, but also has the advantage of being compatible with the oil of mineral oil, which is the existing lubricating oil,

7) The freezing effect is more than 5 ~ 10%, which saves energy.

1 is a block diagram of a general refrigeration / air conditioner used in the present invention
Fig. 2 Binary mixture obtained by the program of REFPROP 9.0 of the present invention
Temperature gradient diagram of refrigerant composition
Figure 3 Ph diagram of a typical mixed refrigerant composition
Figure 4 Ph diagram of the near azeotropic mixed refrigerant composition
Figure 5 R-22 Ph diagram
Fig. 6 "SC-47D" Ph diagram
Fig. 7 "SC-47D1" Ph diagram
Fig. 8 "SC-47D" First Best Condition When the Worst Composition of the Refrigerant Composition is Filled at 60%
Result of composition separation in case of liquid leakage at -18.28 ℃
Figure 9 "SC-47D1" second best condition when the worst composition of the refrigerant composition 60% charge
Result of composition separation experiment at liquid leakage at -18.28 ℃
Figure 10 "SC-47D" first best condition when the worst composition 15% charge of the refrigerant composition
Result of composition separation experiment at liquid leakage at -18.28 ℃
Figure 11 "SC-47D1" second best condition when the worst composition 15% charge of the refrigerant composition
Result of composition separation experiment at liquid leakage at -18.28 ℃

In order to achieve the above object, the present invention adds 1 to 50 kg of difluoromethane (R-32) and 50 to 99 kg of ethane-based 1,1, -difluoro ethane (R-152a) and the muscle azeotropy. It relates to a refrigerant composition having an ozone layer destruction index (ODP = 0) and a global warming index (GWP = 332) added with 0.5-1 kg of nucleated methyl silicone oil as an additive.

'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, refrigerant compositions are different from each other due to different boiling points, so they are separated from each other, resulting in temperature gradients.Near Azeotropic Refrigerant Mixtures Is very difficult to develop.

In the present invention, in order to solve the problem of the temperature gradient, the core azeotropic mixed refrigerant composition (Near Azeotropic Refrigerant Mixtures) is minimized by adding the nucleated methyl silicone oil as an additive to the mixed refrigerant selected and combined by the present inventors. ) Can be obtained.

The mixed refrigerant composition according to the present invention is an azeotropic mixed refrigerant composition having an ozone depletion index (ODP) of 0.0 and a temperature gradient of 0.3 ° C. or less when evaporated, and thus can be used like a conventional pure refrigerant, and R-22 or R Its value is close to the coefficient of performance (COP) and volumetric capacity (VC) of the -410A and R-407C, so there is no need to change any parts of the refrigeration system, so the R-22 or R-410A and R-407C that have been used previously It is possible to substitute refrigerants such as these.

Moreover, in recent years environmental problems are calculated in TWEI. That is, (Total Worming Energy Indicate). In other words: equivalent CO2 emissions = power × operating time × operating life × CO ₂ emissions according to electricity generation

Power = System Power Used (Kw)

Uptime = Uptime per year with maximum load

Run life = Run life of the system (years)

CO ₂ emissions = CO ₂ per Kwh Is calculated by the expression amount (Kg) are equal, the degree of the combustible refrigerant matter because the regulation of CO ₂ emissions performance, or, yet more preferred the available power save refrigerant.

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 (Dew Point) was calculated to create the dew point, and the temperature gradient diagram of the near azeotropic binary 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, research institutes and universities worldwide for its proven accuracy and applicability. The actual data was used as possible as input data for the development and implementation of the Near Azeotropic Refrigerant Mixtures.

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. Near Azeotropic Refrigerant Mixtures, a mixed refrigerant composed of 1,1, -difluoroethane (R-152a) added with additive nucleated methyl silicone oil to form a near azeotropic mixed refrigerant composition. ).

That is, it is a near azeotropic mixed refrigerant composition with no fear of destroying the ozone layer, a temperature gradient (TG) within 0.3 ° C, and a global warming index (GWP) of 332.

Hereinafter, with reference to the accompanying drawings, 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.

Example  1 (first best condition)

37.9 kg of difluoro methane (R-32) and 62 kg of 1,1, -difluoro ethane (R-152a) were mixed, and then 0.1 kg of nucleated methyl silicone oil was added as an additive to implement a near azeotropic mixed refrigerant composition. A refrigerant composition prepared by adding was prepared .

Example  2 (second best condition)

40.9 kg of difluoro methane (R-32) and 59 kg of 1,1, -difluoro ethane (R-152a) are mixed, and then 0.1 kg of nucleated methyl silicone oil as an additive to implement a near azeotropic mixed refrigerant composition. Was added to prepare a refrigerant composition.

Example  3 (worst case in first best case)

36.9 kg of difluoro methane (R-32) and 63 kg of 1,1, -difluoro ethane (R-152a) were mixed, and then 0.1 kg of nucleated methyl silicone oil was added as an additive to implement a near azeotropic mixed refrigerant composition. A refrigerant composition prepared by adding was prepared .

Example  4 (worst case in second best case)

39.9 kg of difluoro methane (R-32) and 60 kg of 1,1, -difluoro ethane (R-152a) were mixed, and then 0.1 kg of nucleated methyl silicone oil as an additive to implement a near azeotropic mixed refrigerant composition. The refrigerant composition was prepared by the addition.

Refrigerant composition of the present invention prepared as described above, 1 ~ 50 kg of difluoro methane (R-32), 1 ~ 1, -difluoro ethane (R-152a) 50 ~ 99 kg, nucleated methyl silicone oil additives It is composed of 0.5 ~ 1 kg, ozone depletion index (ODP = 0), and global warming index (GWP = 332).

Experimental Example  1. Theoretical and actual temperature gradient  exam

2 and 3 show the temperature gradient diagram of the binary mixed refrigerant composition obtained by the program of REFPROP 9.0 of the present invention. However, it can be seen that the temperature gradient was minimized as shown in [Fig. 4] by the results of experimenting in the experimental apparatus of [Fig. 1] after adding an additive to form a near azeotropic refrigerant composition.

Experimental Example  Of two. 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 9.0 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 60% charged and 15% charged in a vessel under some temperature conditions. Thus, in the refrigerant composition of the present invention, the composition separation analysis was performed under the following two temperature conditions.

60% 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-32) 37.9 kg / (R-152a) 62 kg / (additive) 0.1 kg (hereinafter referred to as "SC-47D")

2) (R-32) 40.9 kg / (R-152a) 59 kg / (additive) 0.1 kg (hereinafter referred to as "SC-47D1")

Worst filling composition:

1) (R-32) 36.9 kg / (R-152a) 63 kg / (additive) 0.1 kg.

2) (R-32) 39.9 kg / (R-152a) 60 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 leak composition without any problem for 15% filling, but did not do harm due to its own convergence judgment problem at -18.28 ° C and 25 ° C for 60% filling, in which case less than 60% filling 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 R-152a has the lowest flammable lower limit and the worst filling composition The worst leakage composition of the refrigerant composition occurs when the amount of R-152a is the highest. This is because when the vapor leaks, the composition of the liquid phase R-152a is 63% at -18.28 ° C.

[Table 2] shows the composition separate experiments with "SC-47D", and "SC-47D1" best first condition and the second best of conditions, liquid and gas of the refrigerant composition. However, the additive was ignored because of its small amount.

Test temperature Gas leak Liquid leak -18.28 ℃
(60% filling) Case (1)
(L) 38.0032 / 61.9968
(V) 37.9925 / 62.0075 Case (2)
(L) 37.9828 / 62.0172
(V) 37.9323 / 62.0677 25 ℃
(85% filling) Case (3)
(L) 37.9244 / 62.0756
(V) 37.9330 / 62.0670 Case (4)
(L) 38.0015 / 61.9985
(V) 38.0220 / 61.9780 54.4 ℃
(90% filling)
Case (5)
(L) 37.9349 / 62.0651
(V) 38.0055 / 61.9945 Case (6)
(L) 38.0034 / 61.9966
(V) 37.9344 / 62.0656

Test temperature Gas leak Liquid leak -18.28 ℃
(60% filling) Case (1)
(L) 41.0012 / 58.9988
(V) 41.0020 / 58.9980 Case (2)
(L) 41.0759 / 58.9241
(V) 41.0077 / 58.9923 25 ℃
(85% filling) Case (3)
(L) 41.0294 / 589752
(V) 40.9785 / 59.0215 Case (4)
(L) 41.0125 / 58.9875
(V) 40.9765 / 59.0235 54.4 ℃
(90% filling)
Case (5)
(L) 40.8125 / 59.1875
(V) 41.0113 / 58.9887 Case (6)
(L) 41.0605 / 58.9395
(V) 40.9427 / 59.0573

[Table 3] shows the results of the composition separation experiment at the time of liquid leakage at -18.28 ℃ at 60% charge in the composition of the "SC-47D" first best condition refrigerant composition, it is shown in a graph [ Fig . .

Starting temperature (℃) -18.28 Start rate 60% filling Start subsidy 37.9 / 62 / 0.1


The furtherance ratio according to%






Leakage (%) Composition (% by weight) 10 37.9762 / 62.0238 20 38.0019 / 61.9981 30 37.9542 / 62.0458 40 37.9990 / 62.0010 50 37.9765 / 62.0235 60 37.9972 / 62.0028 70 38.0426 / 61.9574 80 38.0099 / 61.9906 90 38.0297 / 61.9703 99 38.0019 / 61.9981

[Table 4] shows the results of the composition separation experiment at the time of liquid leakage at -18.28 ℃ at 60% charge in the composition of the "SC-47D1" second best condition refrigerant composition, it is shown in a graph [Fig . .

Temperature (℃) -18.28 Start rate 60% filling Start subsidy 40.9 / 59.0 / 0.1



The furtherance ratio according to%





Leakage (%) Composition (% by weight) 10 40.9767 / 59.0233 20 41.0011 / 58.9989 30 40.9547 / 59.0453 40 40.9990 / 59.0011 50 40.9764 / 59.0236 60 40.9982 / 59.0018 70 41.0425 / 58.9575 80 41.0094 / 58.9906 90 41.0299 / 58.9701 99 41.0017 / 58.9983

[Table 5] shows the results of the composition separation experiment at the time of liquid leakage at -18.28 ℃ at 15% charge with the composition of the "SC-47D" first best condition refrigerant composition, it is shown in a graph [ Fig . .

Temperature (℃) -18.28 Start rate 15% filling Start subsidy 37.9 / 62.0 / 0.1



The furtherance ratio according to%





Leakage (%) Composition (% by weight) 10 37.9769 / 62.0231 20 38.0010 / 61.9990 30 37.9548 / 61.0452 40 37.9990 / 62.0011 50 37.9763 / 62.0237 60 37.9981 / 62.0019 70 38.0427 / 61.9573 80 38.0010 / 61.9900 90 38.0300 / 61.9700 99 38.0013 / 61.9987

[Table 6] shows the results of the composition separation experiment when the liquid leaked at -18.28 ℃ at 15% charge with the composition of the "SC-47D1" second best condition refrigerant composition, it is shown in a graph [Fig. .

Temperature (℃) -18.28 Start rate 15% filling Start subsidy 40.9 / 59.0 / 0.1



The furtherance ratio according to%





Leakage (%) Composition (% by weight) 10 40.9762 / 59.0238 20 41.0019 / 58.9981 30 40.9542 / 59.0458 40 40.9990 / 59.0010 50 40.9765 / 59.0235 60 40.9972 / 59.0028 70 41.0099 / 58.9906 80 41.0019 / 58.9981 90 41.0297 / 58.9703 99 41.0017 / 58.9983

Table 7 compares the "SC-47D" and "SC-47D 1" theoretical performance of the refrigerant composition of the present invention and its performance comparison with R-22 R-407C.

Item R-22 R-407C SC-47D SC-47D1 High pressure [bar] 15.34 17.37 15.25 16.17 Low pressure [bar] 4.981 4.56 4.96 5.65 Mass flow rate [kg / h] 89.57 92.62 88.24 89.95 Suction specific volume [㎥ / kg] 0.04708 0.15264 0.0426 0.0546 Discharge specific volume [㎥ / kg] 0.01703 0.01464 0.0169 0.0172 Suction volume flow rate [㎥ / h] 4.217 4.875 4.113 4.345 Discharge volume flow rate [㎥ / h] 1.525 1.356 1.036 1.786 Compression ratio 3.08 3.81 3.04 3.09 Compressor [kW] 0.6964 0.858 0.648 0.716 Condenser
[kJ / h], [kW] 16407
4.55 16989
4.72 15292
4.41 15485
4.47 COP 5.544
(standard) 4.50
(81.1%) 5.963
(107.6%) 5.889
(106.2%) GWP 1,810 1,700 332 349 TG (℃) 0 7 0.2 0.3

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 ℃

 PEFPROP 9.0 (Based on NIST, PEFPROP 9.0 & New Developed Refrigerant Program)

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

GWP: 332

Experimental Example 3. Performance test

[ Fig. 5 ] R-22, [Fig. 6, 7] is shown the pressure-en stripping diagram of each refrigerant composition "SC-47D""SC-47D1",

[Table 7] , HCFC refrigerant composition of the existing R-22 and R-407C has a lower coefficient of performance (COP) than "" SC-47D "and" SC-47D1 ", the only It can be seen that only "" SC-47D "and" SC-47D1 "" showed 10% higher efficiency than R-22 and R-407C.

Based on TEWI (Total Equivalent Warming Index), "SC-47D" and "SC-47D 1" are most suitable as alternative refrigerant compositions because performance is more important than the refrigerant composition itself. In addition, the pressure ratio and the compressor discharge temperature can be seen that the two refrigerant compositions are almost the same. As a result, "" SC-47D "and" SC-47D1 "" have very low ozone depletion index (ODP) and GWP of 332, so they are used as replacement refrigerant composition of R-22, R-410A and R-407C in the long term. There is no problem.

Experimental Example 4 . Comparison of Performance and Additive Performance of R-22 Alternative Mixture Refrigerant Compositions by Component Ratios

As shown in Table 8, Examples 1 and 2 show the highest performance index (COP) of 12.9% and 13.3%. In particular, even though it is a mixed refrigerant composition, when the additive is not added, there is a large difference in temperature (GTD) from 5.0 to 7.2 ° C. However, when the additive is added as shown in Examples 1 and 2, the temperature difference (GTD) of the evaporator is 0.3 ° C. As shown by the near azeotropy, it can be seen that the additive is essential to make the refrigerant composition of the near azeotropy.

Refrigerant
Furtherance(%)
COPr
QE
(W)
Tdis
(℃)
COP _diff (%)
QE _diff (%)
Tdis
_diff (℃)
GTD
_diff
(℃)


R-32
R-152a Hexa methyl
Silicon oil R-22 1.97 3476 77.5 0
Example 1 37.9 62 0.1 2.38 3965 68.7 12.9 12.9 -12.8 0.3
Example 2 40.9 59 0.1 2.35 3975 69.3 13.1 13.1 -11.8 0.3
Comparative Example 1 30 70 2.0 3962 70.5 12.3 12.3 -9.9 5.0
Comparative Example 2 50 50 1.98 3487 71.0 0.01 8.8 -9.2 5.3

        Experimental conditions: evaporator refrigerant temperature: 7 ℃ 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 directly related to the freezing capacity. The larger the capacity, the greater the freezing effect.

  Tdis: Compressor discharge temperature

  COPrdiff: Difference in refrigeration performance coefficient compared to R-22

  QEdiff: Evaporator (cooling) capacity difference compared to R-22

  Tdisdiff: Difference in compressor discharge temperature compared to R-22

GTD: Difference between Glide Temperature Difference compared to R-22 In general, if the difference in ionicity is more than 3 ℃, freezing occurs on the surface of evaporator. Therefore, it is better to have no or no temperature gradient.

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

As shown in [ Table 9 ] , the global warming index is shown according to the composition of refrigerant composition. However, as shown in Comparative Example 1, when the amount of R-152a is large, the global warming index is low, but the performance is remarkably low, which is not a good composition ratio.

Refrigerant
Furtherance(%) GWP

R-32 R-152a Hexa methyl Silicon Oil R-22 1,810 Example 1 37.9 62 0.1 330 Example 2 40.9 59 0.1 349 Comparative Example 1 30 70 289 Comparative Example 2 50 50 399

Experimental Example . 6 Refrigerant composition of the present invention Lower limit limit ( LFL )

As shown in [ Table 10 ] , it can be seen that the risk of flammability is also secured by an average of 20% or more in the composition containing the additive that has been tested for flammability according to the composition (experimental standard ASTM-E-681 2008).

Refrigerant
Furtherance(%) LFL
( vol % in air )

R-32 R-152a Hexa methyl  Silicon Oil R-22 0 Example 1 37.9 62 0.1 13.7 Example 2 40.9 59 0.1 13.6 Comparative Example 1 30 70 11.8 Comparative Example 2 50 50 12.2

Claims (2)

In the refrigerant composition,
1 to 50 kg of difluoro methane (R-32), 50 to 99 kg of 1,1, -difluoro ethane (R-152a), and 0.5 to 1 kg of nucleated methyl silicone oil as additives, and ozone depletion index Is (ODP = 0) and the global warming index is (GWP = 332). The method according to claim 1,
37.9 kg of difluoro methane (R-32), 62 kg of 1,1, -difluoro ethane (R-152a), and 0.1 kg of nucleated methyl silicon oil, with an ozone layer destruction index (ODP = 0), Refrigerant composition, characterized in that the global warming index (GWP = 332).

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