WO2020096347A1 - Non-flammable environment-friendly refrigerant - Google Patents

Abstract

The present invention relates to a non-flammable environment-friendly refrigerant which may be used for a vehicle air conditioner, a home refrigerator, a water purifier, a commercial refrigerator, etc., may be used so as to be safe for a user by being non-flammable, and may be used as a drop-in type without having to refurbish or alter a refrigerating mechanism using a conventional CFC-12, HFC-134a and HFO-1234yf refrigeration cycle refrigerant. The non-flammable environment-friendly refrigerant comprises 75-86 parts by volume of trifluoroiodomethane (CF3I), 14-25 parts by volume of propane (C₃H₈), and 0.1-0.5 parts by volume of a hexamethyl silicone oil, or comprises a further addition of isobutene (C4H10).

Description

Non-flammable eco-friendly refrigerant

The present invention can replace commercial CFC-based, HCFC-based, HFC-based, and HFO-based refrigerants without any technical design changes to refrigeration appliances such as automobile air conditioners, home refrigerators, and refrigerators. It has no corrosion of metals and is stable in a refrigeration system, and can be used without any harmful effects on human body. At room temperature, it is used as gases trifluoroiodmethane (CF ₃ I), propane (C ₃ H8) and isobutane (C4H ₁₀ ). It is related to the azeotropic non-combustible eco-friendly refrigerant.

Refrigerants currently in use include CFC (Chloro-Fluoro-Carbon), HFC (Hydro-Fluoro-Carbon), HCFC (Hydro-Chloro-Fluoro-Carbon), HFO (Hydro-Fluoro-Propene), HC (Hydrocarbon), and the like. . CFCs and HCFCs, when released into the atmosphere, do not easily decompose, so they move into the atmosphere, combine with ozone and destroy the ozone layer, and the CFC was already banned from use by the world in 1996 under the Montreal Convention. We are negotiating to ban use and reducing usage. Although they have used different HFC and HFC mixed refrigerants to replace these refrigerants, these refrigerants also have a high global warming index, so they are prohibited for use in new cooling systems of all vehicles produced in Europe and around 2017, and instead use HFO refrigerants or HFO mixed refrigerants. I am using However, these refrigerants have a great impact on the industry, but their price competitiveness is so low that consumers avoid using them.

   Small refrigerators such as home refrigerators and water purifiers have been using HC (Hydrocarbon) refrigerants R-600a (Isobutane) in the past two or three years ago, and small air conditioners have used R-290 (Propane). HC natural refrigerant does not affect the ozone layer destruction and global warming, but because it is flammable in a limited area as it is released into the atmosphere, there is a risk of explosion, limiting its use.

     Under the Montreal Protocol or the Kyoto Agreement, the Paris Kigali Agreement, HCFC and HFC will face a crisis of use in the near future, and the HC blend refrigerant is flammable, and due to flammability, the provisions of ISO 817-2014-5-15 and the United States The use of SNAP (Significant New Alternative Policy) has been restricted to less than 57g, but it is expected to be recognized for commercial use soon. Refrigerant researchers are currently interested in non-combustible HC mixed refrigerants. However, a selective azeotropic non-flammable mixed refrigerant (R-400 series) made with a proper percentage of mixed volume ratio has not yet been developed, and general mixed refrigerants with a global warming index of GWP = 600 or higher have been developed, but have a large temperature gradient to freeze. 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 through an expansion valve in an evaporator and evaporates to set the ambient temperature. After absorbing (endothermic reaction), the evaporated refrigerant 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 are ammonia, carbon dioxide, and chlorofluorocarbons (hereinafter referred to as “CFC” systems), which condense and vaporize well at low pressure and small temperature difference. That is, as carbon compounds containing fluorine, Freon-based gas and HFC (Hydrofluorocarbon) -based gas 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) are used (where R is derived from 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 solves them has good refrigeration ability, and has no toxicity, explosiveness, corrosiveness to metal, and no harmfulness to the human body. It has been developed and used as an excellent refrigerant. However, it has recently been discovered that CFC-based refrigerants destroy the stratospheric ozone (O3), which has been completely banned since 1996 and has been banned for use. Certain Freon R-11 (CCl ₃ F), R 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 In addition to -500 (R12 / R152a) and R-502 (R22 / R115), HFC (Hydrofluorocarbon) R-134a (CF ₃ CFH ₂ ) or R-22 (HCFC Hydrochloro fluorocarbon) systems are also subject to use restrictions. It has been reducing since. Among these refrigerants, R-134a is mainly used in relatively small refrigerators such as automobile air conditioners and household electric refrigerators, and R-22 (referred to as “HCFC” system) has a larger refrigeration capacity per volume than R-134a. Used in compressors, and is used in home and industrial air conditioners.

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

   In addition, when air and moisture are mixed with the Freon refrigerant, hydrofluoric acid is generated, and there is a defect that causes corrosion in compressors and pipes. For this reason, the conventional Freon freezer must adopt a method of removing moisture by using a drying agent such as silica gel. In addition, refrigeration oil is used as a lubricant to protect compressors from mechanical abrasion, etc. The refrigeration oil must be obtained to be able to stably share with a refrigerant without losing lubricity even at low temperatures. In the case of a Freon-based refrigerant, the refrigeration oil is melted to a certain temperature, and the refrigerant is melted and combined.

In Korean Patent Registration No. 1009764490000 (2010.08.11), ethane-based 1,1-difluoroethane (R-152a) 55-65 kg, trifluoromethyl iodine (CF ₃ I) 10-25 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 nuclear methyl silicone oil, destroying the ozone layer A refrigerant composition with an index of 0 (ODP) and a global warming index (GWP) of 79 is disclosed,

   In Korean Patent Registration No. 1009764480000 (2010.08.11), hydrocarbon-based propane (R-290) 50-56 kg and isobutane (R-600a) 40-49 kg are based on normal butane (R-600) 2 ~ The ozone layer destruction index (ODP) is 0 with 5 to 1 kg of propylene (R-1270) added and 0.5 to 1 kg of nuclear methyl methyl oil as an additive to make the azeotrope, and the global warming index (GWP) is 3 Phosphorus mixed refrigerant composition is described,

   In Korean Patent Registration No. 1011393770000 (2012.04.17.), 80 to 99 kg of propane (R-290) and 1 to 20 kg of dimethyl ether (R-E170) are added, and nuclear methyl is used to make azeotropic refrigerant mixtures. A refrigerant composition with an ozone depletion index (ODP) of 0, and a global warming index (GWP) of 3, in which 0.5 to 1 kg of silicone oil is added as an additive, is disclosed,

   In Korean Patent Registration No. 1009692570000 (2010.07.02), ethane-based 1,1-difluoroethane (R-152a) 85 ~ 98kg, 1,1,1,2-tetrafluoroethane (R-134a) ) 1 ~ 5kg, propylene (R-1270) 0.5 ~ 5kg, propane (R-290) 1 ~ 5kg and nuclear methyl silicone oil 0.1 ~ 0.5kg, ozone depletion index (ODP) is 0, global warming It can be seen that a refrigerant composition having an index (GWP) of 128.2 is disclosed.

[Advanced technical literature]

[Patent Document]

(Patent Document 1) 1. Domestic Registered Patent Publication No. 1009764490000 (2010.08.11)

(Patent Document 2) 2. Domestic Registered Patent Publication No. 1009764480000 (2010.08.11)

(Patent Document 3) 3. Korean Registered Patent Publication No. 1011393770000 (2012.04.17)

(Patent Document 4) 4. Domestic Registered Patent Publication No. 1009692570000 (2010.07.02)

Conventional refrigerants have ammonia among refrigerants, and there are problems of toxicity, metal corrosion, deliquescent, and harmfulness to the human body. The refrigerant of the Freon-based gas that solves these problems has good refrigeration ability, toxicity and explosiveness, metallic corrosion and harmfulness to the human body. It has been developed and used as a very good refrigerant, but it has recently been discovered that CFC-based refrigerants destroy ozone (O3) in the stratosphere, and has been completely banned since 1996, and is a substance that causes global warming. Freon 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 ), and R-404A, R-407A, R-407C, R-410A, etc. as mixed refrigerants. However, these refrigerants have a large temperature gradient (Temperature Grade), so the evaporator has a large amount of freezing, so it is inconvenient to use and has a problem to be solved. There are also azeotropic mixed refrigerants such as R-500 (R12 / R152a) and R-502 (R22 / R115), but these refrigerants are still regulated for use with high warming index, and HFC (Hydrofluorocarbon) R-134a (CF ₃ CFH) ₂ ) or R-22 (HCFC Hydrochloro fluorocarbon) system is also subject to use restrictions and has been reducing since 2017.

   In addition, when air and moisture are mixed with Freon refrigerant, hydrofluoric acid is generated, which causes corrosion in compressors and pipes. For this reason, conventional Freon freezers must adopt a method of removing moisture by using a drying agent such as silica gel.

   As a refrigerant other than Freon, hydrocarbon-based isobutane, propane, etc. are used, but because flammability and explosiveness are necessary, a safety device for this is required, and a problem that a separate design must be made to be used to use in a Freon freezer such as an existing household refrigerator and car air conditioner This is a solution to be achieved by the present invention.

In order to solve the above object, the present invention is an improved refrigerant composition of Patent Registration No. 1009764480000 (2010.08.11) filed by the present inventor, and is used in automobile air conditioners, household refrigerators, water purifiers, commercial refrigerators, etc. Because it is flexible, it can be safely used by users, and it is a mixed refrigerant, but it has been modified with existing refrigerant cycles such as CFC-12, HFC-134a, HFO-1234yf, etc., which minimize the temperature grade using additives. As a drop-in type without modification or change, 74 to 86 parts by volume of trifluoroiodine methane (CF3I), 14.5 to 25 parts by volume of propane (C ₃ H ₈ ), and 0.1 to 0.5 parts by volume of hexamethyl silicone oil It relates to a non-combustible eco-friendly refrigerant that is added or further added isobutane (C4H10).

The present invention can be used to replace conventional CFC-based, HCFC-based, HFC-based, HFO-based refrigerants without any technical design changes to common automotive air conditioners, home refrigerators, freezers, etc., non-combustible, non-explosive safety and compressors, etc. There is no corrosion of metal, it is safe in refrigeration system, and it is effective to use a new refrigerant that has no harmful effect on human body.

A non-flammable eco-friendly refrigerant was prepared by mixing 76 L of trifluoroiodine methane (CF3I), 24 L of propane (R290), and 0.1 L of nuclear tetramethyl silicone oil (HMSO).

The present invention is used in automobile air conditioners, household refrigerators, water purifiers, commercial refrigerators, and the like, and can be safely used by users because it is non-combustible, and is a mixed refrigerant, but is an existing refrigeration cycle CFC that minimizes temperature grade using additives. Trifluoro iodine methane (CF3I) 74 ~ 86 volume propane (C ₃ ) that can be used as a drop-in type without modifying or changing a refrigeration mechanism using refrigerants such as -12, HFC-134a, HFO-1234yf, etc. H ₈ ) 14.5 to 25 parts by volume, hexamethyl silicone oil is composed of 0.1 to 0.5 parts by volume, or isobutane (C4H10) is further added to the non-combustible eco-friendly refrigerant.

   The present invention is a refrigerant that provides a method for selecting and mixing a proportion of a mixed volume part having non-flammable properties. The selection of the mixing volume fraction 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, starting from 74 parts by volume of trifluoroiodmethane starting from a material having a low BP (Boiling Point), propane (C3H8) (R290) After gradually mixing 14.5 to 25 parts by volume, the non-flammable eco-friendly refrigerant was tested for the flammability test under the worst-case composition of the compositions of Examples 1, 4, 5, and 8, and Table 11 shows the performance test of the automotive air conditioner. Table 2 shows the oil compatibility test of the household refrigerator in Table 2. 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 experiment (RAPID & ON-OFF CYCLE LIFE TEST) of the home refrigerator.

   However, it is characterized by applying more additives than other prior art additives. The reason is to supplement the disadvantages of trifluoroiodmethane (CF3I) to improve heat resistance, cold resistance, abrasion resistance, and the mixing property of refrigerant and refrigeration oil. The non-combustible eco-friendly refrigerant in the volume fraction ratio obtained by these experiments is as follows.

   Hereinafter, embodiments of the present invention are as follows.

    Example 1

    A non-flammable eco-friendly refrigerant was prepared by mixing 76 L of trifluoroiodine methane (CF3I), 24 L of propane (R290), and 0.1 L of nuclear tetramethyl silicone oil (HMSO).

    Example 2

    A non-flammable eco-friendly refrigerant was prepared by mixing 77 liters of trifluoroiodine methane (CF3I), 23 liters of propane (R290), and 0.1 liters of nuclear tetramethyl silicone oil (HMSO).

    Example 3

    Non-flammable eco-friendly refrigerants were prepared by mixing 78L of trifluoroiodinemethane (CF3I), 22L of propane (R290), and 0.1L of nuclear tetramethyl silicone oil (HMSO).

    Example 4

    A non-flammable eco-friendly refrigerant was prepared by mixing 79 L of trifluoroiodine methane (CF3I), 21 L of propane (R290), and 0.1 L of nuclear tetramethyl silicone oil (HMSO).

   Example 5

   Non-flammable eco-friendly refrigerants were prepared by mixing 76 l of trifluoroiodine methane (CF3I), 12 l of propane (R290), 12 l of isobutane (R600a), and 0.1 l of nuclear tetramethyl silicone oil (HMSO).

    Example 6

    A non-flammable eco-friendly refrigerant was prepared by mixing 77 l of trifluoroiodine methane (CF3I), 12 l of propane (R290), 11 l of isobutane (R600a), and 0.1 l of nuclear tetramethyl silicone oil (HMSO).

    Example 7

    Non-flammable eco-friendly refrigerants were prepared by mixing 78 l of trifluoroiodine methane (CF3I), 11 l of propane (R290), 11 l of isobutane (R600a), and 0.1 l of nuclear tetramethyl silicone oil (HMSO).

    Example 8

    A non-flammable eco-friendly refrigerant was prepared by mixing 79 l of trifluoroiodine methane (CF3I), 11 l of propane (R290), 10 l of isobutane (R600a), and 0.1 l of nuclear tetramethyl silicone oil (HMSO).

   Additive nucleated methyl silicone oil used in the present invention 0.1 ~ 0.5ℓ (HMSO) is an amount used to induce the colloidal phenomenon during ultrasonic mixing.

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

Table 2 takes the American Refrigeration and Air Conditioning Association (ASHRAE) LBP conditions These are experimental values that measured the performance (COP) of a Korean G company Reso car air conditioner. When the conventional mixing method (agitation method) was selected, the temperature gradients of the condensation unit and the compression unit were many, 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-combustible eco-friendly refrigerant of the present invention is a non-flammable and safe near azeotropic refrigerant in a refrigeration system.

   For the flammability test, the results of the flammability test for the compositions up to Examples 1 to 8 of the worst filling composition according to the standards of ASTM E 681 or ISO 817 2014 are shown in Table 11. Therefore, it was found that the non-flammable eco-friendly refrigerant of the present invention is a non-flammable near-azeotropic mixed refrigerant.

   Table 12 shows the results of the overload experiment (HEAVY LOAD LIFE TEST) of the D-Model-BHRB51H 510 liter household refrigerator.

This experiment is to verify the compatibility of frozen oil with non-flammable mixed refrigerants based on CF ₃ I.

   Table 1. Temperature gradient between the mixing method by an argon laser (wavelength: 514.15 mm) and the general mixing method The amount of nuclear tetramethyl silicone oil used is the same, so it is not described in the mixing ratio.

Experiment	Mixing ratio (by 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. Experimental results of measuring the performance (COP) of a Korean G company's Reso vehicle air conditioner by taking ASHRAE LBP conditions.

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
Ambient 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

  The results of the composition separation tests (Fractionation Testing) conducted to show that the refrigerant of the present invention is near azeotropic even in the worst condition composition are Tables 3-10.

   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 the event of a gas or liquid leak. The UL2182 standard requires the determination of the worst conditions through compositional separation analysis for cases where the liquid refrigerant is 90% filled and 15% filled 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).

When charging at 90% (CHARGING): 25.0 ℃

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

CHARGING COMPOSITION: The composition of the refrigerant sold at the first mix (MIXTURE). The amount of flammable refrigerant is usually about 1 part by volume more than the filling composition, and the worst filling composition is determined and tested.

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

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

                   2) 76 volume CF3I / 24 volume R290

                   3) 77 volume CF3 I / 23 volume R290

                   4) 78 volume CF3I / 22 volume R290

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

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

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

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

   After setting these conditions, the worst-case leak composition was determined using the REFPROP 9.1 program. The REFLEAK program calculated the worst leak composition without any temperature condition for 15% fill, but tested composition separation under 90% fill at a temperature of 25.0 ° C for 90% fill.

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

   Table 4 shows the proportion of the remaining composition when the gas and the liquid leaked by 10% at the worst filling composition of Example 2).

   Table 5 shows the remaining composition ratio when the gas and liquid leaked by 10% at the worst filling composition of Example 3).

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

   Table 7 shows the proportion of the remaining composition when the gas and the liquid leaked by 10% at the worst filling composition of Example 5).

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

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

   Table 3 Non-flammable eco-friendly refrigerant Composition ratio analyzed by Gas Chromatograph of the remaining refrigerant after emitting 10% of gas and liquid refrigerant by Example 1 at 25 ℃

Experiment temperature (℃)		25
Initial charging%		60% charge
Starting composition		75.0 / 25.0
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 residual composition (volume) in each composition, the names of the trifluoroiodmethane (CF3I) and propane (R290) of the composition of Example 1 were deleted. The volume part of was described in order, and the nuclear methyl methyl silicone oil was not described.

   Table 4. Non-flammable eco-friendly refrigerant composition ratio of the worst filling composition of Example 2 after analyzing gas and liquid refrigerant by 10% at 25 ℃ and analyzing the remaining refrigerant in the Gas Chromatograph

Experiment temperature ℃		25
Initial charging%		60% charge
Starting composition		76.0 / 24.0
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

   The initial composition of the composition of Table 4 and the remaining composition of each composition (in the description of the skin part, the names of the composition components of the composition of Example 2, trifluoroiodmethane (CF3I) and propane (R290) have been deleted. The volume parts of the raw materials were described in order, and the nuclear tetramethyl silicone oil was not described.

   Table 5. Non-flammable eco-friendly refrigerant composition ratio analyzed by gas chromatograph of the remaining refrigerant after discharging the filling composition of Example 3 by 10% of gas and liquid refrigerant at 25 ℃

Experiment temperature (℃)		25
Initial charging%		60% charge
Starting composition		77.0 / 23.0
Every composition	Leakage%	Residual composition (volume skin)
	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 residual composition (volume) of each composition, trifluoroiodmethane (CF3I), propane (R290), and isobutane (C4H10), which are the components of Example 3 The names of the components are described in order of the volume parts of the components, and the nuclear methyl methyl silicone oil is not described.

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

Experiment temperature (℃)		25
Initial charging%		60% charge
Starting composition		78.0 / 22.0
Every composition	Leakage%	Residual composition (volume skin)
	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 residual composition (volume) of each composition,

The components of the composition of Example 4, trifluoroiodmethane (CF3I), and the names of propane (R290) were deleted, and the volumes of the components were described in order, and the nuclear tetramethyl silicone oil was not described.

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

Experiment temperature ℃		25
Initial charging%		60% charge
Starting composition		75.0 / 13.0 / 12.0
Every Composition	Leakage%	Residual composition (volume skin)
	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 residual composition (volume) of each composition,

Trifluoroiodine methane (CF3I), propane (R290), and isobutane (C4H10), which are the compositional components of Example 5, were deleted, and the volume parts of the components were sequentially described, and nuclear methyl methyl silicone oil was not described. Did.

   Table 8. Non-flammable eco-friendly refrigerant Composition ratio of the worst filling composition of Example 6 after 25% of gas and liquid refrigerant was released by 10%, and the remaining refrigerant was analyzed by Gas Chromatograph

Experiment temperature (℃)		25
Initial charging%		60% charge
Starting composition		76.0 / 13.0 / 11.0
Every composition	Leakage%	Residual composition (volume skin)
	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 residual composition (volume) of each composition, trifluoroiodmethane (CF3I), propane (R290), and isobutane (C4H10), which are the compositional components of Example 6 The names of the components are described in order of the volume parts of the components, and the nuclear methyl methyl silicone oil is not described.

    Table 9. Non-flammable eco-friendly refrigerant The composition ratio analyzed by the gas chromatograph of the remaining refrigerant after emitting the worst filling composition of Example 7 by 10% of gas and liquid refrigerant at 25 ℃

Experiment temperature (℃)		25
Initial charging%		60% charge
Starting composition		77.0 / 12.0 / 11.0
Every composition	Leakage%	Residual composition (volume skin)
	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, trifluoroiodmethane (CF3I), propane (R290), and isobutane (C4H10), which are the compositional components of Example 7 The names of the components are described in order of the volume parts of the components, and the nuclear methyl methyl silicone oil is not described.

   Table 10. Non-flammable eco-friendly refrigerant The composition ratio analyzed by gas chromatograph of the remaining refrigerant after discharging the worst filling composition of Example 8 by 10% of gas and liquid refrigerant at 25 ℃

Experiment temperature (℃)		25
Initial charging%		60% charge
Starting composition		78.0 / 12.0 / 10.0
Every composition	Leakage%	Residual composition (volume skin)
	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 residual composition (volume) of each composition, trifluoroiodmethane (CF3I), propane (R290), and isobutane (C4H10), which are the compositional components of Example 8 The names of the components are described in order of the volume parts of the components, and the nuclear methyl methyl silicone oil is not described.

   Table 11. Combustibility test results of Examples 1 to 8 at worst filling conditions at 23 ° C. according to the specifications 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 non-flammable refrigerant and is a non-flammable refrigerant. have.

   In addition, the refrigerant mixed with CF3I is compatible with refrigeration oil and overload test (HEAVY LOAD LIFE TEST) and capillary block test (CAPILLARY BLOCKAGE TEST) to see the compatibility of materials used in refrigeration equipment under the worst conditions that contain more than 50 ppm of moisture. , Repeated instantaneous operation-stop experiment (RAPID & ON-OFF CYCLE LIFE TEST) was performed.

   The result is the overload test (HEAVY LOAD LIFE TEST) in Table 12, the capillary block test (CAPILLARY BLOCKAGE TEST) in Table 13, and the repeated instantaneous operation-stop test (RAPID & ON-OFF CYCLE LIFE TEST) results in Table 14. It was shown.

   Table 12. HEAVY LOAD LIFE TEST

    1) TEST CONDITIONS: (Nikkei, American cold, Toshiba standards)

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

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

       RUNNING TIME: 1,000 hours

       Compressor: for D company's R-134a

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

 2) Experiment result

Applied parts		Example 1	Example 4	Example 5	Example 8
Suction 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 (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) 20 or less	2	3	3	2
L / SHELL ASS’Y		good	good	good	good

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

   Table 13. CAPILLARY BLOCKAGE TEST

     1) Test conditions (TEST CONDITIONS): (G.E standard)

        Condensing temperature (CONDENSING TEMP): 54.4 ℃

        CAPILLARY OUTLET TEMP: -29 ℃

        Motor wind temperature (MOTOR WINDING TEMP): 140 ℃

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

        RUNNING TIME: 4 weeks (672 hours)

        Compressor (Company D)

        Frozen Oil (REF.OIL): S-22T Japan Energy

CAP-TUBE:

0.75 × 2.12 m

        Dryer: XH-5 (R-134a only)

      2) Experiment result (TEST RESULT)

Applied parts		Example 1	Example 4	Example 5	Example 8
Suction 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 (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
CAPILLARYWAITE	FLOW CHANGEABLE	3.3%	3.0%	2.0%	3.5%
	INNETT TUBE	good	good	good	good
	OUTLET TUBE	good	good	good	good

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

   Table 14. RAPID & ON-OFF CYCLE LIFE TEST

    1) Repeated momentary operation-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 / ㎠

          Operating time (ON-TIME): 15 sec

          OFF-TIME: 15 sec

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

          RUNNING TIME: 1,000hr

          Compressor (Company D)

          Frozen 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 / ㎠

        Operating time (ON-TIME): 15 min

        OFF-TIME: 15 min

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

        RUNNING TIME: 1,000hr

        Compressor (Company D)

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

      3) Experiment result

Applied parts			Example 1	Example 4	Example 5	Example 8
Suction 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 (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) 20 or less	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: Light yellow

The refrigerant of the present invention is used for refrigerants used in household air conditioners, commercial air conditioners and freezers, and other industries such as showcases, non-combustion, non-explosive safety, corrosion of metals such as compressors, stable in refrigeration systems, and harmful to humans The present invention relates to a near-azeotropic non-combustible eco-friendly refrigerant composed of trifluoroiodmethane (CF ₃ I), propane (C ₃ H8), and isobutane (C4H ₁₀ ), which are gases at room temperature that can be used without any of these.

Claims (2)

1. In the non-flammable eco-friendly refrigerant,

   Trifluoro iodine methane (CF3I) 75 to 86 parts by volume, propane (C ₃ H ₈ ) 14 to 25 parts by volume, hexamethyl silicone oil 0.1 to 0.5 parts by volume non-flammable eco-friendly refrigerant.
2. Claim 1 is isobutane (C4H10) is further added to the composition

          Trifluoro iodine methane (CF3I) 75 ~ 86 volume, propane (C3H8) 8-13 volume, isobutane (C4H10) 6-12 volume, hexamethyl silicone oil 0.1 ~ 0.5 volume Non-flammable eco-friendly refrigerant.