KR102254272B1 - Environment-friendly, non-flammable refrigerant mixture - Google Patents

Abstract

The present invention is used in automobile air conditioners, household refrigerators, water purifiers, commercial refrigerators, etc., and because it is non-flammable, it can be safely used by users, and refrigerants using refrigerants such as existing refrigeration cycles CFC-12, HFC-134a, HFO-1234yf, etc. Trifluoroiodomethane (CF3I) 75 to 86 parts by volume, propane (C ₃ H ₈ ) 8 to 13 parts by volume, hexamethyl silicone oil 0.1 to 0.5 It relates to a non-flammable eco-friendly refrigerant composed of a volume part or to which isobutane (C4H10) is further added.

Description

Non-flammable eco-friendly refrigerant {ENVIRONMENT-FRIENDLY, NON-FLAMMABLE REFRIGERANT MIXTURE}

In general, the present invention can replace conventional CFC-based, HCFC-based, HFC-based, and HFO-based refrigerants without technical design changes in refrigeration devices such as automobile air conditioners, household refrigerators, and freezers, and non-combustible, non-explosive safety and compressor _{It is made of trifluoroiodomethane (CF 3} I), propane (C ₃ H8) and isobutane (C4H ₁₀ ), which are gases at room temperature, which are free from corrosion of metal such as, and are stable even in refrigeration systems and can be used without any harm to the human body. The present invention relates to a non-flammable eco-friendly refrigerant with near azeotrope.

Refrigerants currently in use include Chloro-Fluoro-Carbon (CFC), Hydro-Fluoro-Carbon (HFC), Hydro-Chloro-Fluoro-Carbon (HCFC), Hydro-Fluoro-Propene (HFO), and Hydrocarbon (HC). . When CFC and HCFC are released into the atmosphere, compounds are not easily decomposed, so they move to the atmosphere, bind to ozone, and destroy the ozone layer. It has been negotiated to ban its use and is reducing its use. Different HFC and HFC mixed refrigerants have been used in place of these refrigerants, but these refrigerants also have a high global warming index, prohibiting their use in the new cooling system of all vehicles produced from 2017, mainly in Europe, instead of HFO refrigerants or HFO mixed refrigerants. I am using However, these refrigerants have a very large impact on the industry, but their price competitiveness is low, so consumers are avoiding using them.

For the last two to three years, small freezers such as refrigerators and water purifiers for home use, mainly in Europe, use R-600a (Isobutane), a hydrocarbon (HC) refrigerant, and R-290 (Propane), for small air conditioners. HC natural refrigerant does not affect ozone depletion and global warming, but it is flammable within a limited area as it is ejected into the atmosphere, so it has a risk of explosion and limits its use.

According to the Montreal Protocol, the Kyoto Agreement, or the Paris Kigali Agreement, HCFC and HFC will face a risk of deprecation in the near future, and the HCFC blend is flammable, so the regulations of ISO 817-2014-5-15 and the US Although its use is restricted to less than 57g in SNAP (Significant New Alternative Policy), it is expected to be recognized for commercial use in the near future. Currently, refrigerant researchers are interested in non-flammable HC mixed refrigerants. However, selectively made near-azeotropic non-flammable mixed refrigerants (R-400 series) with an appropriate mixed volume% ratio have not yet been developed, and general mixed refrigerants with a global warming index of GWP = 600 or higher have been developed. There is a problem that causes irregular operation in the system.

As is well known, in general, a refrigerator is composed of a compressor, a condenser, a receiver, an expansion valve, an evaporator, and an oil-water separator to perform a refrigeration cycle operation.At this time, the refrigerant is sprayed from the evaporator through the expansion valve and evaporated to reduce the ambient temperature. The refrigerant absorbed (endothermic reaction) and evaporated is compressed by a compressor, sent to a condenser through an oil-water separator, condensed (exothermic reaction), and then refrigerated by repeating a refrigeration cycle operation that is returned to the receiver. Typical refrigerants used at this time include ammonia, carbon dioxide, and chlorofluorocarbons (hereinafter referred to as “CFC” systems) that are well condensed and evaporated under a small pressure and a small temperature difference. That is, as a carbon compound containing fluorine, Freon gas and HFC (hydrofluorocarbon) gas such as R-11 (CCl ₃ F), R-12 (CCl ₂ F ₂ ), R-13 (CClF ₃ ), R-22 (CHClF) ₂ ), R-113 (Cl ₂ FC-CClF ₂ ), R-114 (ClF ₂ C-CClF ₂ ), R-134a (CF ₃ CFH ₂ ), R-500 (R12/R152a) and R-502 ( R22/R115), etc. are used (where R is derived from the abbreviation Refrigerant for refrigerant).

Among these refrigerants, ammonia has problems of toxicity, metal corrosion, deliquescent, and harmfulness to the human body, but the refrigerant of the freon-based gas that has solved these problems has good refrigeration ability, and is very toxic, explosive, metal corrosive, and no harm to the human body. It has been developed and used as an excellent refrigerant. However, it was recently discovered that CFC-based refrigerants destroy ozone (O3) in the stratosphere, and since 1996 it has been completely abolished, prohibiting its use, and certain Freon R-11 (CCl ₃ F), R, which are substances that cause global warming. -12 (CCl ₂ F ₂ ), R-13 (CClF ₃ ), R-22 (CHClF ₂ ), R-113 (Cl ₂ FC-CClF ₂ ), R-114 (ClF ₂ C-CClF ₂ ), R -500 (R12/R152a) and R-502 (R22/R115), as well as HFC (hydrofluorocarbon), R-134a (CF ₃ CFH ₂ ) or R-22 (HCFC Hydrochloro fluorocarbon), are also subject to restrictions on use in 2017. From the beginning. Among these refrigerants, R-134a is mainly used in relatively small freezers such as automobile air conditioners and household electric refrigerators, and R-22 (referred to as “HCFC” system) has a higher refrigeration capacity per volume than R-134a. It is used in compressors and used in household and industrial air conditioners.

Freon R-113 (Cl ₂ FC-CClF ₂ ) and R-114 (ClF ₂ C-CClF ₂ ) of “CFC” series are mainly used in turbo chillers, and azeotropic mixed refrigerants by mixing R-115 and R-22 R-502 is used as a low-temperature refrigerant.

In addition, when air and moisture are mixed in the freon refrigerant, hydrofluoric acid is generated, which causes corrosion in compressors and pipes. For this reason, the conventional Freon refrigerator had to adopt a method of removing moisture by using a drying agent such as silica gel. In addition, refrigeration oil is used as a lubricating oil to protect the compressor, etc. from mechanical wear. This refrigeration oil must be obtained that can be reliably shared with the refrigerant without losing its lubricity even at low temperatures. In the case of a freon-based refrigerant, the refrigerant oil and refrigerant melt until a certain temperature and are combined.

In Korean Patent Publication No. 10-0976449 (2010.08.11), an ethane-based 1,1-difluoroethane (R-152a) of 55 to 65 kg and trifluoromethyl iodine (CF ₃ I) from 10 to It is composed of 25 kg, 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 HEXA methyl silicone oil. A refrigerant composition with an ozone layer destruction index (ODP) of 0 and a global warming index (GWP) of 79 has been disclosed,

In Korean Patent Publication No. 10-0976448 (2010.08.11), 50-56 kg of propane (R-290) and 40-49 kg of isobutane (R-600a) are used as a base, and normal butane (R-600). 2~5kg and 1~3kg of propylene (R-1270) are added, and 0.5~1kg of hexamethyl silicone oil is added as an additive to make muscle azeotrope, and the ozone layer destruction index (ODP) is 0, and the global warming index (GWP) A mixed refrigerant composition having 3 is described,

To make azeotropic Refrigerant Mixtures by adding 80-99 kg of propane (R-290) and 1-20 kg of dimethyl ether (R-E170) to Korean Patent Publication No. 10-1139377 (2012.04.17) A refrigerant composition with an ozone layer destruction index (ODP) of 0 and a global warming index (GWP) of 3, in which 0.5 to 1 kg is added as an additive, has been disclosed.

In Korean Patent Publication No. 10-0969257 (2010.07.02), ethane-based 1,1-difluoroethane (R-152a) 85-98kg, 1,1,1,2-tetrafluoroethane (R -134a) It is composed of 1~5kg, 0.5~5kg of propylene (R-1270), 1~5kg of propane (R-290) and 0.1~0.5kg of hexamethyl silicone oil, and the ozone layer destruction index (ODP) is 0, It can be seen that a refrigerant composition with a global warming potential (GWP) of 128.2 has been disclosed.

1. Domestic Patent Publication No. 1009764490000 (2010.08.11) 2. Domestic Patent Publication No. 1009764480000 (2010.08.11) 3. Domestic Patent Publication No. 1011393770000 (2012.04.17) 4. Domestic Patent Publication No. 1009692570000 (2010.07.02)

In conventional refrigerants, ammonia among the refrigerants has problems of toxicity, metal corrosion, deliquescent, and harmfulness to the human body, and the refrigerant of the freon-based gas that has solved these problems has good refrigeration capacity and has no toxicity, explosiveness, metal corrosiveness, and no harmfulness to the human body. It has been developed and used as a very excellent refrigerant, but it was recently discovered that CFC-based refrigerants destroy ozone (O3) in the stratosphere. -11 (CCl ₃ F), R-12 (CCl ₂ F ₂ ), R-13 (CClF ₃ ), R-22 (CHClF ₂ ), R-113 (Cl ₂ FC-CClF ₂ ), R-114 ( ClF ₂ C-CClF ₂ ), and mixed refrigerants include R-404A, R-407A, R-407C, and R-410A. However, these refrigerants are inconvenient to use because they have a large temperature grade and have a large freezing phenomenon in the evaporator, which has a problem to be solved. In addition, there are R-500 (R12/R152a) and R-502 (R22/R115) as azeotropic mixed refrigerants, but these refrigerants are still subject to regulation due to their high warming potential, and R-134a (CF ₃ CFH), which is a hydrofluorocarbon (HFC) system. ₂ ) and R-22 (HCFC Hydrochloro fluorocarbon) are also subject to restrictions on use and are being reduced from 2017.

In addition, when air and moisture are mixed in the freon refrigerant, hydrofluoric acid is generated, which causes corrosion in compressors and pipes. For this reason, a method using a desiccant such as silica gel and the conventional freon refrigerator must adopt a method of removing moisture.

Hydrocarbon-based isobutane, propane, etc. are used as refrigerants other than freon, but they are flammable and explosive, so a safety device is required, and a separate design is required to be used for freon refrigerators such as existing home refrigerators and automobile air conditioners. That is the problem to be achieved by the present invention.

In order to solve the above object, the present invention is an improvement of the refrigerant composition of Patent Registration No. 1009764480000 (2010.08.11) previously filed by the present inventor, and is used in automobile air conditioners, household refrigerators, water purifiers, commercial refrigerators, etc. Because it is ductile, it can be used safely for users.Although it is a mixed refrigerant, refrigeration equipment using refrigerants such as CFC-12, HFC-134a, HFO-1234yf, etc., which have minimized the temperature grade by using additives, has been modified. Trifluoroiodomethane (CF ₃ I) 74 to 86 parts by volume, propane (C ₃ H ₈ ) 11 to 25 parts by volume, 0.1 to 0.5 parts of hexamethyl silicone oil It relates to a non-flammable eco-friendly refrigerant composed of skin or isobutane (C ₄ H _{10) is further added.}

The present invention can replace conventional CFC-based, HCFC-based, HFC-based, and HFO-based refrigerants without technical design changes in refrigeration appliances such as general automobile air conditioners, household refrigerators, and freezers, and non-combustible, non-explosive safety and compressors, etc. There is no corrosion of the metal in the refrigeration system, it is safe in the refrigeration system, and there is an effect that a new refrigerant that is not harmful to the human body can be usefully used.

The present invention is used in automobile air conditioners, household refrigerators, water purifiers, commercial refrigerators, etc., and it is non-flammable, so it can be safely used for users. In particular, although it is a mixed refrigerant, it is a conventional refrigeration cycle CFC that minimizes the temperature grade by using additives. _{Trifluoroiodomethane (CF3I) 74 to 86 volumes of propane (C 3} ) that can be used as a drop-in type without modifying or changing refrigerants using refrigerants such as -12, HFC-134a, HFO-1234yf, etc. H ₈ ) It relates to a non-flammable eco-friendly refrigerant composed of 11 to 25 parts by volume, 0.1 to 0.5 parts by volume of hexamethyl silicone oil, or to which isobutane (C4H10) is further added.

The present invention is a refrigerant that provides a method of selecting and mixing a mixing volume part ratio having a non-flammable property. The selection of the mixing volume part ratio proceeded as follows.

As a more preferable manufacturing method, for example, starting from 0.1 to 0.5 parts by volume of hexamethyl silicone oil, from a material having a low BP (Boiling Point) to 74 to 86 parts by volume of trifluoroiodomethane and propane (C3H8) (R290) After gradually mixing 11 to 25 parts by volume, the composition of Examples 1, 4, 5, and 8 was mixed with this non-flammable eco-friendly refrigerant. In Table 2, an oil compatibility test of a household refrigerator was performed, and it is shown in Table 12. Table 13 shows the results of the capillary block test (CAPILLARY BLOCKAGE TEST) of the home refrigerator, and Table 14 shows the results of the repeated instantaneous operation-stop test (RAPID & ON-OFF CYCLE LIFE TEST) of the home refrigerator.

However, the additive is characterized in that the content of other additives is applied more than the conventional prior art. The reason is to compensate for the disadvantages of trifluoroiodomethane (CF3I) to improve heat resistance, cold resistance, abrasion resistance, and refrigerant and refrigerant oil mixing properties. The non-flammable eco-friendly refrigerant in the proportion by volume obtained by this experiment is as follows.

Hereinafter, an embodiment of the present invention is as follows.

Example 1

Trifluoroiodomethane (CF ₃ I) 76 liters, propane (R290) 24 liters, and hexamethyl silicon oil (HMSO) 0.1 liters were mixed to prepare a non-flammable eco-friendly refrigerant.

Example 2

Trifluoroiodomethane (CF3I) 77ℓ, propane (R290) 23ℓ, and hexamethyl silicon oil (HMSO) 0.1ℓ were mixed to prepare a non-flammable eco-friendly refrigerant.

Example 3

Trifluoroiodomethane (CF3I) 78L, propane (R290) 22L, and hexamethyl silicon oil (HMSO) 0.1L were mixed to prepare a non-flammable eco-friendly refrigerant.

Example 4

Trifluoroiodomethane (CF3I) 79L, propane (R290) 21L, and hexamethyl silicon oil (HMSO) 0.1L were mixed to prepare a non-flammable eco-friendly refrigerant.

Example 5

Trifluoroiodomethane (CF3I) 76ℓ, propane (R290) 12ℓ, isobutane (R600a) 12ℓ, and hexamethyl silicon oil (HMSO) 0.1ℓ were mixed to prepare a non-flammable eco-friendly refrigerant.

Example 6

Trifluoroiodomethane (CF3I) 77ℓ, propane (R290) 12ℓ, isobutane (R600a) 11ℓ, and hexamethyl silicon oil (HMSO) 0.1ℓ were mixed to prepare a non-flammable eco-friendly refrigerant.

Example 7

Trifluoroiodomethane (CF3I) 78L, propane (R290) 11L, isobutane (R600a) 11L, and hexamethyl silicon oil (HMSO) 0.1L were mixed to prepare a non-flammable eco-friendly refrigerant.

Example 8

Trifluoroiodomethane (CF3I) 79ℓ, propane (R290) 11ℓ, isobutane (R600a) 10ℓ, and hexamethyl silicon oil (HMSO) 0.1ℓ were mixed to prepare a non-flammable eco-friendly refrigerant.

0.1~0.5ℓ (HMSO) of the additive used in the present invention is an amount used to induce a colloidal phenomenon during ultrasonic mixing.

If the additive is used above this range, agglomeration occurs, and if the following is used, colloidal phenomenon does not occur. This was confirmed by a scattering experiment with an argon laser (wavelength: 514.15 mm), and the temperature gradient when the refrigerant was prepared by the NIST REFPROP 9.1 (National Institute of Standards and Technology) program of the mixing method of the present invention and the general mixing method ( Temperature Gradient) is shown in Table 1.

Table 2 takes the American Refrigeration and Air Conditioning Association (ASHRAE) LBP conditions These are the experimental values that measured the performance (COP) of the air conditioner of the Rezo vehicle of Korea Company G. When the conventional mixing method (the agitation method) was selected, there were many temperature gradients in the condensing part and the compression part, but it was found that the temperature gradient did not occur when the mixing method of the present invention was selected. As a result of this, it can be seen that the non-flammable eco-friendly refrigerant of the present invention is non-flammable and is a safe near-azeotropic refrigerant in a refrigeration system.

For the flammability test, Table 11 shows the flammability test results for the worst filling composition examples 1 to 8 according to the standards of ASTM E 681 or ISO 817 2014. Therefore, it can be seen that the non-flammable eco-friendly refrigerant of the present invention is a non-flammable near-azeotropic mixed refrigerant.

Table 12 is the result of an overload test (HEAVY LOAD LIFE TEST) of the D's model-BHRB51H 510 liter household refrigerator.

This experiment is to verify the compatibility of the refrigerated oil with the non-flammable mixed refrigerant based on _{CF 3 I.}

Table 1. Temperature gradient between the mixing method using an argon laser (wavelength: 514.15㎜) and the general mixing method (Temperature Gradient) Since the amount of hexamyl silicon oil used was the same, it was not described in the mixing ratio.

Experiment Mixing ratio (volume) Temperature gradient mixed by the mixing method of the present invention Temperature gradient mixed with NIST Refprop 9.1 program Example 1 CF ₃ I/R290 (76/24) 0.22℃ 2.9℃ Example 2 CF ₃ I/R290 (77/234) 0.22℃ 3.1℃ Example 3 CF ₃ I/R290 (78/22) 0.23℃ 2.3℃ Example 4 CF ₃ I/R290 (79/21) 0.23℃ 2.3℃ Example 5 CF ₃ I/R290/600a (76/12/12) 0.18℃ 2.3℃ Example 6 CF ₃ I/R290/600a (77/12/11) 0.19℃ 2.4℃ Example 7 CF ₃ I/R290/600a (78/11/11) 0.18℃ 2.3℃ Example 8 CF ₃ I/R290/600a (79/11/10) 0.18℃ 2.3℃

Table 2. This is an experiment result of measuring the performance (COP) of the air conditioner of Korea G's leisure vehicle by taking the ASHRAE LBP condition.

Refrigerant R134a Example 1 Example 4 Example 5 Example 8 Injection volume (g) 465 300 350 400 200 300 360 200 300 360 310 360 400 Cold air temperature (C) 12.8 14.7 12.1 10.6 17.9 14.4 12.4 17.9 14.4 12.4 14.4 12.7 13.4 Power consumption (W) 770 674 675 866 534 704 762 534 704 752 708 577 732 Pressure (barg) 11.8 10.8 11.3 12.9 9.2 11.3 11.7 9.2 11.3 11.7 10.5 10.9 11.4 Discharge temperature (C) 55.6 70.7 63.9 73.8 72.4 67.4 53.6 72.4 67.4 55.6 65.3 55.5 59.2 Suction temperature(C) 12.9 22.0 12.0 21.0 26.2 21.6 12.5 26.2 21.6 11.5 19.9 12.7 16.4 Outside temperature (C) 29.2 26.3 27.5 28.7 26.5 26.9 27.3 26.5 26.9 27.3 29.5 29.1 29.1

Tables 3-10 are the results of the Fractionation Testing conducted to show that the refrigerant of the present invention is a near azeotrope even in the worst condition composition.

In this experiment, the worst case formulation composition was determined using the REFLEAK program developed by the American Standards Institute. REFLEAK is a program that uses the REFPROP 9.1 program described above to determine the worst composition in case of leakage in gaseous or liquid state. The UL2182 standard requires the determination of the worst case conditions through compositional separation analysis for 90% and 15% liquid refrigerant filling in a container under some temperature conditions. So, in the case of the non-flammable eco-friendly refrigerant of the present invention, composition separation analysis was performed under the following room temperature conditions (25.0° C.).

90% charging (CHARGING): 25.0℃

In order to analyze the composition separation, the following definitions should be made for the composition.

CHARGING COMPOSITION: Composition of refrigerant sold after mixing at first Worst filling composition: Since there is inevitably an error (RANGE) when mixing, it depends on the composition of the most combustible refrigerant and the error of the refrigerant mixing machine. The worst filling composition was determined as the worst filling composition and the amount of combustible refrigerant was usually 1 part by volume more than the filling composition.

According to this definition, the filling composition and the worst filling composition in the non-flammable eco-friendly refrigerant of the present invention are determined as follows.

Worst filling composition: 1) 75 volume CF3I / 25 volume R290

2) 76 vol. CF3I / 24 vol. R290

3) 77 vol. CF3 I / 23 vol. R290

4) 78 vol. CF3I / 22 vol. R290

5) 75 vol CF3I / 13 vol R290 / 12 vol R600a

6) 76 vol CF3I / 13 vol R290 / 11 vol R600a

7) 77 volume CF3I / 12 volume R290 / 11 volume R600a

8) 78 volume CF3I / 12 volume R290 / 10 volume R600a

After these conditions were established, the worst-case leakage composition was determined using the REFPROP 9.1 program. The REFLEAK program calculated the worst leak composition without any temperature conditions for 15% filling, but for 90% filling, composition separation experiments were conducted at a temperature of 25.0°C and less than 90% filling.

Table 3 shows the ratio of the remaining composition when the gas and the liquid leaked by 10% in the worst filling composition of the composition of Example 1),

Table 4 shows the ratio of the remaining composition when the gas and the liquid leaked each 10% in the worst filling composition of the composition of Example 2),

Table 5 shows the ratio of the remaining composition when the gas and the liquid leaked each 10% in the worst filling composition of the composition of Example 3),

Table 6 shows the ratio of the remaining composition when the gas and the liquid leaked by 10% in the worst filling composition of the composition of Example 4),

Table 7 shows the ratio of the remaining composition when the gas and the liquid leaked by 10% in the worst filling composition of the composition of Example 5),

Table 8 shows the ratio of the remaining composition when the gas and liquid leaked out by 10% in the worst filling composition of the composition of Example 4),

Table 9 shows the ratio of the remaining composition when the gas and liquid leaked by 10% in the worst filling composition of the composition of Example 4),

Table 3 Composition ratio of the remaining refrigerant analyzed by Gas Chromatograph after discharging the gas and liquid refrigerant by 10% at 25° C. in Example 1 of non-flammable eco-friendly refrigerant

Experiment temperature (℃) 25 Starting percent 60% charge Starting composition 75.0/25.0 Each composition
(Every composition) Leakage% Residual composition (volume) 10 75.1342/24.8658 20 75.2494/24.7506 30 75.3626/24.6374 40 75.3968/24.6032 50 75.5510/24.4490 60 75.7294/24.2706 70 75.7694/24.2306 80 75.7936/24.2064 90 75.0178/24.9822

In the description of the initial composition of the composition of Table 3 and the remaining composition (volume) of each composition, the names of trifluoroiodomethane (CF3I) and propane (R290) of the composition of Example 1 are omitted. The volume parts of were described in order, and the hexamethyl silicone oil was not described.

Table 4. The worst filling composition of the non-flammable eco-friendly refrigerant Example 2 was analyzed by Gas Chromatograph for the remaining refrigerant after releasing 10% of gas and liquid refrigerant at 25°C.

Experiment temperature ℃ 25 Starting percent 60% charge Starting composition 76.0/24.0 Each composition
(Every composition) Leakage% Residual composition (volume) 10 76.4812/23.5188 20 76.5019/23.4981 30 76.5112/23.4888 40 76.2047/23.7953 50 76.1163/23.8837 60 76.5801/23.4199 70 76.1028/23.8972 80 76.4231/23.5769 90 76.5350/23.4650

In the initial composition of the composition of Table 4 and the remaining composition of each composition (description of the volume), the names of the composition components of the composition of Example 2, trifluoroiodomethane (CF3I) and propane (R290) were deleted. The volume parts of the components were described in order, and hexamethyl silicone oil was not described.

Table 5. Composition ratio of the filling composition of the non-flammable eco-friendly refrigerant Example 3 analyzed by Gas Chromatograph of the remaining refrigerant after 10% of gas and liquid refrigerants were released at 25°C

Experiment temperature (℃) 25 Starting percent 60% charge Starting composition 77.0/23.0 Each composition
(Every composition) Leakage% Residual composition (volume) 10 77.1342/22.8658 20 77.2494/22.7506 30 77.3626/22.6374 40 77.3968/22.6032 50 77.5510/22.4490 60 77.7294/22.2706 70 77.7694/22.2306 80 77.7936/22.2064 90 77.0178/22.9822

In the description of the initial composition of the composition of Table 5 and the remaining composition (volume) of each composition, trifluoroiodomethane (CF3I), propane (R290), isobutane (C4H10), which are the composition components of Example 3 The names of the components are omitted in order, and the volume parts of the components are described in order, and hexamethyl silicone oil is not described.

Table 6. Non-flammable eco-friendly refrigerant Composition ratio analyzed by Gas Chromatograph for the remaining refrigerant after releasing 10% of gas and liquid refrigerant at 25°C for the worst filling composition of Example 4

Experiment temperature (℃) 25 Starting percent 60% charge Starting composition 78.0/22.0 Each composition
(Every composition) Leakage% Residual composition (volume) 10 78.1432/21.8568 20 78.2449/21.7551 30 78.6326/21.3674 40 78.9367/21.0633 50 78.5003/21.4997 60 78.2795/21.7205 70 78.6794/21.7606 80 78.7546/21.2454 90 78.3778/21.6222

In the description of the initial composition of the composition of Table 6 and the remaining composition (volume) of each composition,

The names of trifluoroiodomethane (CF3I) and propane (R290), which are the components of the composition of Example 4, are described in order, with the names of the components omitted, and hexamethyl silicone oil is not described.

Table 7. Non-flammable eco-friendly refrigerant Composition ratio of the worst filling composition of Example 5 analyzed by Gas Chromatograph of the remaining refrigerant after 10% of gas and liquid refrigerants were released at 25°C

Experiment temperature ℃ 25 Starting percent 60% charge Starting composition 75.0/13.0/12.0 Each composition
(Every Composition) Leakage% Residual composition (volume) 10 75.0958/12.3421/12.5621 20 75.5986/12.2070/12.1944 30 75.1596/12.7321/12.1083 40 75.1276/12.6910/12.1814 50 75.0200/12.9691/12.0109 60 75.1639/12.5716/12.2645 70 75.7022/12.1844/12.1134 80 75.2822/12.5591/12.1587 90 75.3482/12.4127/12.2391

In the description of the initial composition of the composition of Table 7 and the remaining composition (volume) of each composition,

The names of the composition components of Example 5, trifluoroiodomethane (CF3I), propane (R290), and isobutane (C4H10) were omitted, and the volume parts of the components were sequentially described, and hexamethyl silicone oil was not described. Did.

Table 8. Composition ratio of the worst filling composition of the non-flammable eco-friendly refrigerant Example 6 analyzed by Gas Chromatograph of the remaining refrigerant after releasing 10% of gas and liquid refrigerants at 25°C

Experiment temperature (℃) 25 Starting percent 60% charge Starting composition 76.0/13.0/11.0 Each composition
(Every composition) Leakage% Residual composition (volume) 10 76.0968/12.8812/11.0220 20 76.0896/12.8700/11.0404 30 76.1569/12.8021/11.0410 40 76.1726/12.7019/11.1255 50 76.0020/12.9961/11.0019 60 76.1358/12.7516/11.1126 70 76.0722/12.8846/11.0432 80 76.2482/12.5549/11.1969 90 76.3082/12.4110/11.2808

In the description of the initial composition of the composition of Table 8 and the remaining composition (volume) of each composition, trifluoroiodomethane (CF3I), propane (R290), isobutane (C4H10), which are the composition components of Example 6 The names of the components are omitted in order, and the volume parts of the components are described in order, and hexamethyl silicone oil is not described.

Table 9. Composition ratio of the worst filling composition of the non-flammable eco-friendly refrigerant Example 7 analyzed by Gas Chromatograph of the remaining refrigerant after 10% of gas and liquid refrigerants were released at 25°C

Experiment temperature (℃) 25 Starting percent 60% charge Starting composition 77.0/12.0/11.0 Each composition
(Every composition) Leakage% Residual composition (volume) 10 77.1256/11.7812/11.0932 20 77.2456/11.3511/11.4033 30 77.0357/11.8175/11.1468 40 77.3856/11.5119/11.1025 50 77.4320/11.1235/11.4445 60 77.5701/11.3411/11.0888 70 77.6822/11.3115/11.0063 80 77.2482/11.2455/11.5063 90 77.7053/11.2110/11.0847

In the description of the initial composition of the composition of Table 9 and the remaining composition (volume) of each composition, the composition components of Example 7 trifluoroiodomethane (CF3I), propane (R290), isobutane (C4H10) The names of the components are omitted in order, and the volume parts of the components are described in order, and hexamethyl silicone oil is not described.

Table 10. Non-flammable eco-friendly refrigerant Composition ratio analyzed by Gas Chromatograph for the remaining refrigerant after 10% of gas and liquid refrigerants were released at 25° C. for the worst filling composition of Example 8

Experiment temperature (℃) 25 Starting percent 60% charge Starting composition 78.0/12.0/10.0 Each composition
(Every composition) Leakage% Residual composition (volume) 10 78.1235/11.5744/10.3021 20 78.3457/11.3004/10.3539 30 78.2574/11.3500/10.3926 40 78.7126/11.2119/10.0755 50 78.5520/11.1922/10.0019 60 78.1588/11.6616/10.2558 70 78.4882/11.0057/10.5061 80 78.6211/11.1755/10.2034 90 78.8102/11.0910/10.0988

In the description of the initial composition of the composition of Table 10 and the remaining composition (volume) of each composition, the composition components of Example 8, trifluoroiodomethane (CF3I), propane (R290), isobutane (C4H10) The names of the components are omitted in order, and the volume parts of the components are described in order, and hexamethyl silicone oil is not described.

Table 11. Flammability test results of Examples 1 to 8 under the worst charging conditions at 23°C according to the standards of ASTM E 681 or ISO 817 2014

Experiment Flammability test General mixing method Mixing method of the present invention Lower limit Upper limit Lower limit Upper limit Example 1 Non-stick Non-stick Non-stick Non-stick Example 2 Non-stick Non-stick Non-stick Non-stick Example 3 Non-stick Non-stick Non-stick Non-stick Example 4 Non-stick Non-stick Non-stick Non-stick Example 5 Non-stick Non-stick Non-stick Non-stick Example 6 Non-stick Non-stick Non-stick Non-stick Example 7 Non-stick Non-stick Non-stick Non-stick Example 8 Non-stick Non-stick Non-stick Non-stick

Therefore, in the case of this refrigerant, the worst leakage composition that can occur in the worst filling composition is a near-azeotropic refrigerant and a non-combustible refrigerant as it is considered that CF3I, which is a non-flammable composition, remains in the same ratio even in the case of the most flammable composition. have.

In addition, the refrigerant mixed with CF3I is an overload test (HEAVY LOAD LIFE TEST) and a capillary block test (CAPILLARY BLOCKAGE TEST) to see the compatibility with refrigeration oil and the suitability of materials used in refrigeration equipment under the worst conditions in which more than 50 ppm of moisture is contained. , Repetitive instantaneous operation-stop experiments (RAPID & ON-OFF CYCLE LIFE TEST) were performed.

The results are shown in Table 12 for HEAVY LOAD LIFE TEST, Table 13 for Capillary BLOCKAGE TEST, and Table 14 for repeated instantaneous operation-stop tests (RAPID & ON-OFF CYCLE LIFE TEST) results. Is shown.

Table 12. HEAVY LOAD LIFE TEST

1) TEST CONDITIONS: (Nikkei, Americold, Toshiba standard)

Suction pressure (SUC. PRESS.): 1 Kg _f /㎠

Discharge pressure (DIS. PRESS.): 25~30 Kg _f /㎠

RUNNING TIME: 1,000 hours

Compressor: For R-134a of D company

Compressor case temperature (COMP. CASE TEMP): 100±5℃

2) Experiment result

Applicable parts Example 1 Example 4 Example 5 Example 8 Intake valve (SUC. VALVE) good good good good Discharge valve assembly (DIS. VALVE ASS'Y) good good good good Circulation silencer assembly (DEL. MUFF. ASS’Y) good good good good Piston good good good good Block good good good good PAG-
105
oil Color＊ L0.5 L0.5 L0.5 L0.5 TAN(mgKOH/g) 0.10 or less 0.0754 0.0733 0.0741 0.0723 Moisture (PPM) less than 20 2 3 3 2 L/SHELL ASS’Y good good good good

＊ Color <COLOR> L0.5: Very pale pale yellow

Table 13. CAPILLARY BLOCKAGE TEST

1) TEST CONDITIONS: (G.E standard)

CONDENSING TEMP: 54.4℃

Capillary Outlet Temperature (CAPILLARY OUTLET TEMP): -29℃

MOTOR WINDING TEMP: 140℃

Compressor case temperature (COMP. CASE TEMP): 110℃

RUNNING TIME: 4 weeks (672 hours)

Compressor: D company

Refrigeration oil (REF.OIL): S-22T Japan Energy

0.75 × 2.12 mCAP-TUBE:

0.75 × 2.12 m

Dryer: XH-5 (R-134a only)

2) Experiment result (TEST RESULT)

Applicable parts Example 1 Example 4 Example 5 Example 8 Intake valve (SUC. VALVE) good good good good Discharge valve assembly (DIS. VALVE ASS'Y) good good good good Circulation silencer assembly (DEL. MUFF. ASS’Y) good good good good Piston good good good good Block good good good good oil Color＊ L1.5 L1.5 L1.5 L1.5 TAN(mgKOH/g) 0.10 or less 0.0366 0.0457 0.0422 0.0453 Moisture (PPM) 20 or less 0 One One 0 L/SHELL ASS’Y good good good good CAPILLARY
WAITE FLOW CHANGEABLE 3.3% 3.0% 2.0% 3.5% INLET TUBE good good good good OUTLET TUBE good good good good

＊ Color <COLOR> L1.5: Yellow, L3.0 Brown

Table 14. Repetitive instantaneous run-stop experiment (RAPID & ON-OFF CYCLE LIFE TEST)

1) Repetitive instantaneous run-stop test conditions (RAPID CYCLE TEST CONDITIONS): (G.E standard)

Suction pressure (SUC. PRESS): 1.0 ± 0.5kgf/㎠

Discharge pressure (DIS. PRESS): 23 ± 2 kgf/㎠

ON-TIME: 15 sec

Stop time (OFF-TIME): 15 sec

Compressor case temperature (COMP CASE TEMP): 90 ± 5℃

RUNNING TIME: 1,000hr

Compressor: D company

Refrigeration oil (REF.OIL): FREOL S-22T (Japan Energy)

2) ON-OFF TEST CONDITIONS: (AMERICOLD SPEC.)

Suction pressure (SUC. PRESS): 1.0 ± 0.5kgf/㎠

Discharge pressure (DIS. PRESS): 23 ± 2 kgf/㎠

ON-TIME: 15 min

OFF-TIME: 15 min

Compressor case temperature (COMP CASE TEMP): 90 ± 5℃

RUNNING TIME: 1,000hr

Compressor: D company

Refrigeration oil (REF.OIL): FREOL S-22T (Japan Energy)

3) Experiment result

Applicable parts Example 1 Example 4 Example 5 Example 8 Intake valve (SUC. VALVE) good good good good Discharge valve assembly (DIS. VALVE ASS'Y) good good good good Circulation silencer assembly (DEL. MUFF. ASS’Y) good good good good Piston good good good good Block good good good good oil Color＊ RAPI D L1.0 L1.0 L1.0 L1.0 ON-OFFCYCLE L1.0 L1.0 L1.0 L1.0 TAN(mgKOH/g)
0.10 or less RAPI D 0.0405 0.0522 0.0521 0.0431 ON-OFFCYCLE 0.0439 0.0548 0.0493 0.0374 Moisture (PPM) less than 20 RAPI D 16.3 16.5 17.1 16.4 ON-OFFCYCLE 15.3 14.3 15.1 15.6 L/SHELL ASS’Y good good good good

＊Color <COLOR> L1.0: Pale yellow

Claims (2)

_{Drop-in type trifluoroiodomethane (CF 3} I) with low BP (Boiling Point) 75 to 86 parts by volume, propane (C ₃ H ₈ ) 11 to 25 parts by volume, 0.1 to 0.5 parts of hexamethyl silicone oil Skin and isobutane (C ₄ H ₁₀ ) Non-flammable eco-friendly refrigerant, characterized in that formed by gradually mixing 10 to 12 volumes of the skin. delete