Refrigerant-containing composition, heat transfer medium, and heat cycle system
阅读说明：本技术 含有制冷剂的组合物、热传递介质和热循环系统 (Refrigerant-containing composition, heat transfer medium, and heat cycle system ) 是由 板野充司 大久保瞬 黑木眸 山田康夫 土屋立美 午坊健司 于 2019-07-08 设计创作，主要内容包括：本发明提供一种含有兼具具有与R404A和/或R410A同等以上的性能系数(COP)和冷冻能力(Cap)并且GWP充分小这样的三种性能的制冷剂(混合制冷剂)的组合物。具体而言,本发明提供一种含有制冷剂的组合物,上述制冷剂中含有二氟甲烷(HFC－32)、2,3,3,3－四氟丙烯(HFO－1234yf)、以及1,1－二氟乙烯(HFO－1132a)和四氟乙烯(FO－1114)中的至少一种。(Disclosed is a composition containing a refrigerant (mixed refrigerant) having three properties, namely a coefficient of performance (COP) and a freezing capacity (Cap) which are both equal to or higher than those of R404A and/or R410A, and having sufficiently low GWP. Specifically, the present invention provides a composition containing a refrigerant containing difluoromethane (HFC-32), 2,3,3, 3-tetrafluoropropene (HFO-1234 yf), and at least one of 1, 1-difluoroethylene (HFO-1132 a) and tetrafluoroethylene (FO-1114).)
1. A refrigerant-containing composition characterized by:
the refrigerant contains:
difluoromethane (HFC-32),
2,3,3, 3-tetrafluoropropene (HFO-1234 yf), and
at least one of 1, 1-difluoroethylene (HFO-1132 a) and tetrafluoroethylene (FO-1114).
2. The composition of claim 1, wherein:
the refrigerant contains HFO-1132 a.
3. The composition of claim 2, wherein:
the refrigerant contains 15.0 to 24.0 mass% of HFC-32 and 1.0 to 7.0 mass% of HFO-1132 a, where the total amount of HFC-32, HFO-1234 yf and HFO-1132 a is 100 mass%.
4. The composition of claim 2, wherein:
the refrigerant contains 19.5 to 23.5 mass% of HFC-32 and 3.1 to 3.7 mass% of HFO-1132 a, where the total amount of HFC-32, HFO-1234 yf and HFO-1132 a is 100 mass%.
5. The composition of claim 1, wherein:
the refrigerant contains HFC-32, HFO-1234 yf and HFO-1132 a, wherein when mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum thereof is defined as x, y and z, respectively, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within or on a triangle surrounded by connecting lines RS, ST and TR of 3 points which are connected,
point R (21.80,3.95,74.25),
Point S (21.80,3.05,75.15), and
point T (20.95,75.30, 3.75).
6. The composition of any one of claims 1 to 5, wherein:
used as a replacement refrigerant for R404A.
7. The composition of claim 1, wherein:
the refrigerant contains HFC-32, HFO-1234 yf and HFO-1132 a, and in the refrigerant, when mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum thereof is x, y and z, respectively, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within or on a graph surrounded by lines LF, FG, GO, OB and BL respectively connecting the following 5 points, except for the lines on OB and lines on FG,
point L (74.0,19.9,6.1),
Point F (49.1,25.9,25.0),
Point G (0.0,48.6,51.4),
Point O (0.0,0.0,100), and
point B (73.9,0.0,26.1),
the connection line LF is defined by a coordinate (y is 0.0021 x)2-0.4975 x +45.264) in a single file,
the connection FG is given by the coordinate (y ═ 0.0031 x)2-0.6144 x +48.6), and
the connecting lines GO, OB and BL are straight lines.
8. The composition of claim 1, wherein:
the refrigerant contains HFC-32, HFO-1234 yf and HFO-1132 a, wherein when mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum thereof is x, y and z, respectively, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a pattern surrounded by or on a line PF, FG, GO, OB ' and B ' P connecting 5 points, respectively, except for lines GO and OB ',
a point P (59.1,23.2,17.7),
Point F (49.1,25.9,25.0),
Point G (0.0,48.6,51.4),
Point O (0.0,0.0,100), and
point B' (59.0,0.0,40.2),
the connection line PF is defined by the coordinates (y ═ 0.0021 x)2-0.4975 x +45.264) in a single file,
the connection FG is given by the coordinate (y ═ 0.0031 x)2-0.6144 x +48.6), and
the connecting lines GO, OB 'and B' P are straight lines.
9. The composition of claim 1, wherein:
the refrigerant contains HFC-32, HFO-1234 yf and HFO-1132 a, wherein when mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum thereof is x, y and z, respectively, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within or on a graph surrounded by connecting lines MI, IJ, JB and BM of 4 points, respectively, except on the connecting line JB,
point M (74.0,19.5,6.5),
Point I (62.9,15.5,21.6),
Point J (33.5,0.0,66.5), and
point B (73.9,0.0,26.1),
the connecting line MI is composed of a coordinate (y is 0.006 x)2+1.1837 x-35.264) indicates,
the connecting line IJ is composed of a coordinate (y is 0.0083 x)2-0.2719 x-0.1953), and
the connecting lines JB and BM are straight lines.
10. The composition of claim 1, wherein:
the refrigerant contains HFC-32, HFO-1234 yf and HFO-1132 a, wherein when mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum thereof is defined as x, y and z, respectively, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within or on a graph surrounded by connecting lines QJ, JB ' and B ' Q of 3 points, respectively, except for the connecting line JB ',
point Q (59.1,12.7,28.2),
Point J (33.5,0.0,66.5), and
point B' (59.0,0.0,40.2),
the connecting line QJ is composed of a coordinate (y is 0.0083 x)2-0.2719 x-0.1953), and
the connecting lines JB 'and B' Q are straight lines.
11. The composition of claim 1, wherein:
the refrigerant contains HFC-32, HFO-1234 yf and HFO-1132 a, and in the refrigerant, when mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum thereof is x, y and z, respectively, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of or on a graph surrounded by a line QU, UV and VQ connecting 3 points, respectively, as follows:
point Q (59.1,12.7,28.2),
Points U (59.0,5.5,35.5), and
point V (52.5,8.4,39.1),
the connecting line VQ is defined by a coordinate (y ═ 0.0083 x)2-0.2719 x-0.1953), and
the connecting line UV is defined by the coordinate (y ═ 0.0026 x)2-0.7385 x +39.946) in a single file,
the connecting line QU is a straight line.
12. The composition according to any one of claims 7 to 11, wherein:
used as a replacement refrigerant for R410A.
13. The composition of any one of claims 1 to 5, wherein:
as a replacement refrigerant for R, R134, R407, R410, R413, R417, R422, R423, R424, R426, R427, R430, R434, R437, R438, R448, R449, R452, R454, R455, R459, R465, R502, R507, or R513.
14. The composition according to any one of claims 7 to 11, wherein:
as a replacement refrigerant for R, R134, R404, R407, R413, R417, R422, R423, R424, R426, R427, R430, R434, R437, R438, R448, R449, R452, R454, R455, R459, R465, R502, R507, or R513.
15. The composition of any one of claims 1 to 14, wherein:
also contains a refrigerator oil, and the composition is used as a working fluid for refrigerators.
16. A freezer, characterized by:
a working fluid comprising a composition as claimed in any one of claims 1 to 14.
17. A heat transfer medium, characterized by:
comprising a composition according to any one of claims 1 to 14.
18. A heat cycle system, characterized by:
use of the heat transfer medium of claim 17.
19. A refrigerant-containing composition characterized by:
the refrigerant contains 1, 1-difluoroethylene (HFO-1132 a), and the composition is used as a substitute refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R454A, R36455, R459A, R465, R502, R507, or R A.
Technical Field
The invention relates to a refrigerant-containing composition, a heat transfer medium and a heat cycle system.
Background
In recent years, difluoromethane (CH) has been used as a refrigerant for air conditioners, refrigerators, and the like2F2R32, boiling point-52 ℃), pentafluoroethane (CF)3CHF2R125, boiling point-48 ℃), 1,1, 1-trifluoroethane (CF)3CH3R143a, boiling point-47 deg.C), 1,1,1, 2-tetrafluoroethane (CF)3CH2F. R134a, boiling point-26 ℃), 1-difluoroethane (CHF)2CH3R152a, boiling point-24 ℃), 2,3,3, 3-tetrafluoropropene (CF)3CF＝CH21234yf, boiling point-29 ℃), and the like.
Among the above fluorocarbons, 3-component mixed refrigerants composed of R32/R125/R134a, having a composition of 23/25/52 wt% (R407C); a 3-component mixed refrigerant composed of R125/143a/R134a has a composition of 44/52/4 wt% (R404A) and the like, and patent documents 1,2 and the like describe that R404A is used as a refrigerant for freezing and refrigerating.
However, R404A is known to have a very high Global Warming Potential (GWP) of 3922, compared to CHClF, which is one of the chlorofluorocarbons2(R22、GWP＝1810) But is also high. Therefore, development of an alternative refrigerant of R404A having a reduced GWP is desired, and for example, in patent documents 3 and 4, a refrigerant composition containing difluoromethane (R32), pentafluoroethane (R125), 2,3,3, 3-tetrafluoropropene (1234yf), and 1,1,1, 2-tetrafluoroethane (R134a) is disclosed as an alternative refrigerant of R404A.
Further, R410A (GWP 2088) is widely known together with R404A, and as an alternative refrigerant, patent document 5 proposes R454B (labeled as "DR-5A" in patent document 5) with reduced GWP (68.9 wt% R32/31.1 wt% R1234yf, GWP466, 102% COP (with respect to R410A), 97% Cap. (with respect to R410A)). However, 466 is the limit of GWP even with R454B.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 9-324175
Patent document 2: specification of U.S. Pat. No. 8,168,077
Patent document 3: international publication No. 2010/059677
Patent document 4: international publication No. 2011/163117
Patent document 5; international publication No. 2016/075541
Disclosure of Invention
Technical problem to be solved by the invention
The technical problem to be solved by the invention is as follows: provided is a refrigerant composition (mixed refrigerant) which can be used as a substitute refrigerant for R404A and/or R410A and has three properties of a Coefficient of Performance of Performance (COP) and a freezing Capacity (Refrigeration Capacity) that are equal to or higher than R404A and/or R410A, and which has sufficiently low GWP.
Technical solution for solving technical problem
1. A composition containing a refrigerant, wherein the refrigerant contains difluoromethane (HFC-32), 2,3,3, 3-tetrafluoropropene (HFO-1234 yf), and at least one of 1, 1-difluoroethylene (HFO-1132 a) and tetrafluoroethylene (FO-1114).
2. The composition according to item 1, wherein said refrigerant contains HFO-1132 a.
3. The composition according to item 2 above, wherein the refrigerant contains 15.0 to 24.0 mass% of HFC-32 and 1.0 to 7.0 mass% of HFO-1132 a, based on 100 mass% of the total amount of HFC-32, HFO-1234 yf and HFO-1132 a.
4. The composition according to item 2 above, wherein the refrigerant contains 19.5 to 23.5 mass% of HFC-32 and 3.1 to 3.7 mass% of HFO-1132 a, based on 100 mass% of the total amount of HFC-32, HFO-1234 yf and HFO-1132 a.
5. The composition according to item 1 above, wherein the refrigerant contains HFC-32, HFO-1234 yf, and HFO-1132 a, and wherein when x, y, and z are mass% of HFC-32, HFO-1132 a, and HFO-1234 yf, respectively, based on the total of them, in the refrigerant, in a 3-component composition diagram in which the total of HFC-32, HFO-1132 a, and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a triangle surrounded by or on a connecting line RS, ST, and TR connecting 3 points, respectively,
point R (21.80,3.95,74.25),
Point S (21.80,3.05,75.15), and
point T (20.95,75.30, 3.75).
6. The composition as set forth in any one of items 1 to 5 above, which is used as a substitute refrigerant for R404A.
7. The composition according to item 1 above, wherein the refrigerant contains HFC-32, HFO-1234 yf, and HFO-1132 a, and wherein when x, y, and z are mass% of HFC-32, HFO-1132 a, and HFO-1234 yf, respectively, based on the total of them, in the refrigerant, in a 3-component composition diagram in which the total of HFC-32, HFO-1132 a, and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a pattern surrounded by or on the lines LF, FG, GO, OB, and BL, respectively, which are the 5 points that are connected, respectively (except for the lines GO and OB),
point L (74.0,19.9,6.1),
Point F (49.1,25.9,25.0),
Point G (0.0,48.6,51.4),
Point O (0.0,0.0,100), and
point B (73.9,0.0,26.1),
the connection line LF is defined by a coordinate (y is 0.0021 x)2-0.4975 x +45.264) in a single file,
the connection line FG is defined by a coordinate (y is 0.0031 ×)2-0.6144 x +48.6), and
the connecting lines GO, OB and BL are straight lines.
8. The composition according to item 1 above, wherein the refrigerant contains HFC-32, HFO-1234 yf, and HFO-1132 a, and wherein when x, y, and z are mass% of HFC-32, HFO-1132 a, and HFO-1234 yf, respectively, based on the total of them, in the refrigerant, in a 3-component composition diagram in which the total of HFC-32, HFO-1132 a, and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a pattern surrounded by connecting lines PF, FG, GO, OB ', and B ' P that respectively connect the following 5 points or on the connecting lines (except for the connecting lines GO and OB '),
a point P (59.1,23.2,17.7),
Point F (49.1,25.9,25.0),
Point G (0.0,48.6,51.4),
Point O (0.0,0.0,100), and
point B' (59.0,0.0,40.2),
the connection PF is defined by the coordinates (y is 0.0021 x)2-0.4975 x +45.264) in a single file,
the connection line FG is defined by a coordinate (y is 0.0031 ×)2-0.6144 x +48.6), and
the connecting lines GO, OB 'and B' P are straight lines.
9. The composition according to item 1 above, wherein the refrigerant contains HFC-32, HFO-1234 yf, and HFO-1132 a, and wherein when x, y, and z are mass% of HFC-32, HFO-1132 a, and HFO-1234 yf, respectively, based on the total of them, in the refrigerant, in a 3-component composition diagram in which the total of HFC-32, HFO-1132 a, and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a pattern surrounded by a line, IJ, JB, and JB, respectively, connecting 4 points MI as follows or on the line (except for the line):
point M (74.0,19.5,6.5),
Point I (62.9,15.5,21.6),
Point J (33.5,0.0,66.5), and
point B (73.9,0.0,26.1),
the connecting line MI is defined by a coordinate (y is 0.006 x)2+1.1837 x-35.264) indicates,
the connecting line IJ is defined by a coordinate (y is 0.0083 x)2-0.2719 x-0.1953), and
the connecting lines JB and BM are straight lines.
10. The composition according to item 1 above, wherein the refrigerant contains HFC-32, HFO-1234 yf, and HFO-1132 a, and wherein when x, y, and z are mass% of HFC-32, HFO-1132 a, and HFO-1234 yf, respectively, based on the total of these components, in a 3-component composition diagram in which 100 mass% is the total of HFC-32, HFO-1132 a, and HFO-1234 yf, the coordinates (x, y, z) are within the range of a pattern defined by a line QJ, JB ', and B ' Q connecting 3 points, respectively, or on the line (except for the line JB '),
point Q (59.1,12.7,28.2),
Point J (33.5,0.0,66.5), and
point B' (59.0,0.0,40.2),
the connecting line QJ is defined by a coordinate (y is 0.0083 x)2-0.2719 x-0.1953), and
the connecting lines JB 'and B' Q are straight lines.
11. The composition according to item 1 above, wherein the refrigerant contains HFC-32, HFO-1234 yf and HFO-1132 a, and wherein when x, y and z are mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total of them in the refrigerant, respectively, coordinates (x, y, z) are within a range of a pattern surrounded by a line QU, UV and VQ connecting the following 3 points in a 3-component composition diagram in which the total of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, or on the line,
point Q (59.1,12.7,28.2),
Points U (59.0,5.5,35.5), and
point V (52.5,8.4,39.1),
the line VQ is defined by a coordinate (y is 0.0083 x)2-0.2719 x-0.1953), and
the connecting line UV is defined by the coordinate (y is 0.0026 x)2-0.7385 x +39.946) in a single file,
the above-mentioned connecting line QU is a straight line.
12. The composition as set forth in any one of the above items 7 to 11, which is used as a substitute refrigerant for R410A.
13. The composition of any one of items 1 to 5 above for use as a replacement refrigerant for R, R134, R407, R410, R413, R417, R422, R423, R424, R426, R427, R430, R434, R437, R438, R448, R449, R452, R454, R455, R459, R465, R502, R507, or R513.
14. The composition of any of the above items 7-11 for use as a replacement refrigerant for R, R134, R404, R407, R413, R417, R422, R423, R424, R426, R427, R430, R434, R437, R438, R448, R449, R452, R454, R455, R459, R465, R502, R507, or R513.
15. The composition as set forth in any one of the above items 1 to 14, which further contains a refrigerator oil, and the above composition is used as a working fluid for a refrigerator.
16. A refrigerator comprising the composition as set forth in any one of items 1 to 14 as a working fluid.
17. A heat transfer medium comprising the composition as set forth in any one of items 1 to 14 above.
18. A heat cycle system using the heat transfer medium according to item 17 above.
19. A refrigerant-containing composition, wherein the refrigerant contains 1, 1-difluoroethylene (HFO-1132 a), and the composition is used as a substitute refrigerant for R, R134, R404, R407, R410, R413, R417, R422, R423, R424, R426, R427, R430, R434, R437, R438, R448, R449, R452, R454, R455, R459, R465, R502, R507, or R513.
Effects of the invention
The refrigerant (mixed refrigerant) of the present invention has three types of performances including a coefficient of performance (COP) and a freezing capacity (Cap) which are equal to or higher than those of R404A and/or R410A and sufficiently low GWP.
Drawings
Fig. 1 is a 3-component composition diagram for explaining the compositions of the refrigerants of the first and second embodiments of the present invention. In the enlarged view of fig. 1, the maximum composition of the refrigerant of the first embodiment is within the range of the quadrangle indicated by X or on the line connecting the quadrangles. In the enlarged view of fig. 1, the composition of the refrigerant according to the first embodiment is preferably within the range of a quadrangle indicated by Y or on the line connecting the quadrangles. In the enlarged view of fig. 1, the composition of the refrigerant of the second embodiment is within the range of the triangle surrounded by the connecting lines RS, ST, and TR or on the connecting lines.
Fig. 2 is a 3-component composition diagram for explaining the compositions of the refrigerants in the third to seventh embodiments of the present invention.
Detailed Description
As a result of intensive studies by the inventors of the present invention in order to solve the above-described technical problems, it was found that a refrigerant (mixed refrigerant) containing difluoromethane (HFC-32), 2,3,3, 3-tetrafluoropropene (HFO-1234 yf), and at least one of 1, 1-difluoroethylene (HFO-1132 a) and tetrafluoroethylene (FO-1114) has the above-described properties.
Further, the present invention has been completed as a result of further and repeated studies based on such findings. The present invention includes the following embodiments.
< definition of term >
In the present specification, the term "refrigerant" includes at least a compound specified by ISO817 (international standardization organization) and labeled with a refrigerant number (ASHRAE number) beginning with R indicating the kind of refrigerant, and also includes a compound having refrigerant properties equivalent to those of the above without labeling the refrigerant number.
In view of the structure of the compound, refrigerants are roughly classified into "fluorocarbon-based compounds" and "non-fluorocarbon-based compounds". "fluorocarbon-based compounds" include chlorofluorocarbons (CFCs), Hydrochlorofluorocarbons (HCFCs), and Hydrofluorocarbons (HFCs). Examples of the "non-fluorocarbon compound" include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), and ammonia (R717).
In the present specification, the term "refrigerant-containing composition" comprises at least: (1) the refrigerant itself (including mixtures of refrigerants); (2) a composition which contains other components and can be used for mixing with at least refrigerator oil to obtain a working fluid for a refrigerator; (3) a working fluid for a refrigerator contains a refrigerator oil.
In the present specification, the composition of (2) is distinguished from the refrigerant itself (including a mixture of refrigerants) and is labeled as a "refrigerant composition" in the three modes. The working fluid for a refrigerator in (3) is distinguished from the "refrigerant composition" and is labeled as "working fluid containing refrigerator oil".
In the present specification, the term "substitute" means that, when used in the context of "substituting" a first refrigerant with a second refrigerant, in a first type of equipment designed to operate using the first refrigerant, operation can be performed under optimum conditions using the second refrigerant only through modification of minute components (at least one of a refrigerator oil, a gasket, a packing, an expansion valve, a dryer, and other components) and equipment adjustment, as necessary. That is, this type refers to operating the same equipment "instead of" the refrigerant. As a method of "replacement" of this type, there may be "simple (drop in) replacement", "approximately simple (neutral drop in) replacement", and "update (refresh)" in order of the degree of change and adjustment required for replacement with the second refrigerant.
As a second type, equipment designed to operate using a second refrigerant, which is carried with the second refrigerant and used for the same purpose as the existing purpose of the first refrigerant, is also encompassed within the term "alternative". This type is meant to "replace" the refrigerant to provide the same purpose.
In the present specification, the term "refrigerating machine" refers to all devices that take away heat from an object or space to have a temperature lower than that of the surrounding outside air and maintain the low temperature. In other words, a refrigerator is a conversion device that obtains energy from the outside to convert energy in order to transfer heat from a low-temperature object to a high-temperature object.
In other words, in the present specification, the temperature glide (temperature glide) refers to an absolute value of a difference between a start temperature and an end temperature of a phase change process of a composition containing the refrigerant of the present invention in a component of a heat cycle system.
1.Refrigerant
1－1.Refrigerant composition
The refrigerant of the present invention is characterized in that: contains difluoromethane (HFC-32), 2,3,3, 3-tetrafluoropropene (HFO-1234 yf), and at least one of 1, 1-difluoroethylene (HFO-1132 a) and tetrafluoroethylene (FO-1114). The refrigerant of the present invention having the above-described characteristics has three types of performances including a coefficient of performance (COP) and a refrigerating capacity (Cap) which are equal to or higher than those of R404A and/or R410A, and a sufficiently small GWP.
In the present invention, the coefficient of performance (COP) equal to or higher than R404A means that the COP ratio with respect to R404A is 100% or more (preferably 103% or more, more preferably 105% or more), and the freezing capacity (Cap) equal to or higher than R404A means that the Cap ratio with respect to R404A is 80% or more (preferably 90% or more, more preferably 95% or more, and most preferably 100% or more).
The coefficient of performance (COP) equal to or greater than R410A means that the COP ratio with respect to R410A is 90% or more (preferably 93% or more, more preferably 95% or more, and most preferably 100% or more), and the freezing capacity (Cap) equal to or greater than R410A means that the Cap ratio with respect to R410A is 80% or more (preferably 95% or more, more preferably 99% or more, and most preferably 100% or more).
Further, a sufficiently low GWP means a GWP of 500 or less, preferably 400 or less, more preferably 300 or less, and in the case of a refrigerant of the first embodiment described below, a GWP of 200 or less, preferably 170 or less, more preferably 150 or less, and even more preferably 130 or less.
The refrigerant of the present invention is not particularly limited as long as it contains HFC-32, HFO-1234 yf and at least one of HFO-1132 a and FO-1114 and can exhibit the above-described performance, and the composition thereof is preferably one having a GWP of 500 or less (particularly 170 or less in the case of the refrigerant of the first embodiment described later). With respect to at least one of HFO-1132 a and FO-1114, either one or two may be contained, and in the present invention, HFO-1132 a is preferably contained.
Specifically, the refrigerant of the present invention preferably contains HFC-32, HFO-1234 yf and HFO-1132 a, and when the total amount of these three components is 100 mass%, a mixed refrigerant containing HFO-1234 yf and containing 15.0 to 24.0 mass% of HFC-32 and 1.0 to 7.0 mass% of HFO-1132 a is preferred (the refrigerant of the first embodiment; in the enlarged view of FIG. 1, the range of the quadrangle indicated by X or the line connecting the quadrangles). Among them, a mixed refrigerant containing HFO-1234 yf, 19.5 to 23.5 mass% of HFC-32 and 3.1 to 3.7 mass% of HFO-1132 a is preferable (a preferable refrigerant of the first embodiment; in an enlarged view of FIG. 1, in the range of a quadrangle represented by Y or on a line connecting the quadrangles). Within such a composition range, the effects specified in the present invention can be easily exhibited. The refrigerant of the first embodiment is particularly useful as a substitute refrigerant for R404A.
The condensation temperature glide of the refrigerant of the present invention (the refrigerant of the first embodiment) is preferably 12 ℃ or lower, more preferably 10 ℃ or lower, and further preferably 9 ℃ or lower. The compressor outlet pressure is preferably in the range of 1.60 to 2.00MPa, and more preferably in the range of 1.73 to 1.91 MPa. The refrigerant of the present invention has a characteristic of having good compatibility with a refrigerating machine oil when mixed with a known refrigerating machine oil described later.
The refrigerant of the first aspect includes the refrigerant of the second aspect within its composition range.
The refrigerant of the present invention (refrigerant of the second aspect) is characterized in that: HFC-32, HFO-1234 yf and HFO-1132 a are contained, and in the above-mentioned refrigerant, when x, y and z are respectively set as mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum thereof, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a triangle surrounded by connecting lines RS, ST and TR of 3 points R (21.80,3.95,74.25), S (21.80,3.05,75.15) and T (20.95,75.30,3.75), respectively, or on the above-mentioned connecting line (in the enlarged view of FIG. 1, within a range of a triangle surrounded by the connecting lines RS, ST and TR, or on the above-mentioned connecting line).
When the refrigerant of the present invention (the refrigerant of the second embodiment) satisfies the above conditions, it has a coefficient of performance (COP) equal to or higher than R404A and a freezing capacity (Cap) of 95% or higher, has a GWP of 150 or lower, and has a condensation temperature glide of 9 ℃ or lower.
The refrigerant of the present invention includes the refrigerants of the third to seventh aspects described below in addition to the refrigerants of the first and second aspects described above. These third to seventh mode refrigerants are particularly useful as a substitute refrigerant for R410A.
The refrigerant of the present invention (the refrigerant of the third aspect) is characterized in that: HFC-32, HFO-1234 yf and HFO-1132 a are contained, and in the above-mentioned refrigerant, when x, y and z are respectively set as mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum of them, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a pattern surrounded by connecting lines LF, FG, GO, OB and BL respectively connecting points L (74.0,19.9,6.1), F (49.1,25.9,25.0), G (0.0,48.6,51.4), O (0.0,0.0,100) B (73.9,0.0,26.1) or on the connecting lines LF, FG, GO and BL (except for the connecting lines and OB),
the connection line LF is defined by a coordinate (y is 0.0021 x)2-0.4975 x +45.264) in a single file,
the connection line FG is defined by a coordinate (y is 0.0031 ×)2-0.6144 x +48.6), and
the connecting lines GO, OB and BL are straight lines.
When the refrigerant of the present invention (the refrigerant of the third embodiment) satisfies the above conditions, the refrigerant has a coefficient of performance (COP) and a refrigerating capacity (Cap) equal to or higher than those of R410A, a GWP of 500 or less, and a compressor outlet pressure of 1.25 times or less based on R410A. Such a compressor outlet pressure is preferably 3.4MPa or less, more preferably 3.0MPa or less.
The connection line EF (including the connection line LF and the connection line PF) is an approximation curve obtained by the least square method from the 3 points of the table and fig. 2, example 24, and point F in the present specification, and the connection line FG is an approximation curve obtained by the least square method from the 3 points of the point F, example 26, and point G.
The refrigerant of the present invention (the refrigerant of the fourth aspect) is characterized in that: HFC-32, HFO-1234 yf and HFO-1132 a are contained, and in the above-mentioned refrigerant, when mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum thereof is x, y and z, respectively, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a pattern surrounded by 5 points of connection PF, FG, GO, OB 'and B' P, respectively, point P (59.1,23.2,17.7), point F (49.1,25.9,25.0), point G (0.0,48.6,51.4), point O (0.0,0.0,100) and B '(59.0, 0,40.2), or on the above-mentioned connection (except for the connection points GO and OB',
the connection PF is defined by the coordinates (y is 0.0021 x)2-0.4975 x +45.264) in a single file,
the connection line FG is defined by a coordinate (y is 0.0031 ×)2-0.6144 x +48.6), and
the connecting lines GO, OB 'and B' P are straight lines.
When the refrigerant of the present invention (the refrigerant of the fourth embodiment) satisfies the above conditions, the refrigerant has a coefficient of performance (COP) and a refrigerating capacity (Cap) equal to or higher than those of R410A, a GWP of 400 or less, and a compressor outlet pressure of 1.25 times or less based on R410A. Such a compressor outlet pressure is preferably 3.4MPa or less, more preferably 3.0MPa or less.
The refrigerant of the present invention (the refrigerant of the fifth aspect) is characterized in that: HFC-32, HFO-1234 yf and HFO-1132 a are contained in the refrigerant, and when x, y and z are respectively set as mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum of them, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are within a range of a diagram surrounded by or on a connecting line MI, IJ, JB and BM of 4 points respectively connecting points M (74.0,19.5,6.5), I (62.9,15.5,21.6), J (33.5,0.0,66.5) and B (73.9,0.0,26.1) (except for the connecting line on JB),
the connecting line MI is defined by a coordinate (y is 0.006 x)2+1.1837 x-35.264) indicates,
the connecting line IJ is defined by a coordinate (y is 0.0083 x)2-0.2719 x-0.1953), and
the connecting lines JB and BM are straight lines.
When the refrigerant of the present invention (the refrigerant of the fifth embodiment) satisfies the above conditions, the refrigerant has a coefficient of performance (COP) and a refrigerating capacity (Cap) equal to or higher than those of R410A, a GWP of 500 or less, and a compressor outlet pressure of 1.25 times or less based on R410A, and such a compressor outlet pressure is preferably 3.4MPa or less, more preferably 3.0MPa or less. In addition, the condensation temperature slippage and the evaporation temperature slippage are both less than 5 ℃, and the evaporator is particularly suitable for replacing R410A.
The link HI (including the link MI) is an approximate curve obtained by the least square method from the points H, example 21, and 3 points I in the table and fig. 2 in the present specification, and the link IJ is an approximate curve obtained by the least square method from the points I, example 23, and 3 points J.
The refrigerant of the present invention (the refrigerant of the sixth aspect) is characterized in that: HFC-32, HFO-1234 yf and HFO-1132 a are contained, and in the above-mentioned refrigerant, when x, y and z are respectively set as mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum of them, in a 3-component composition diagram in which the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, coordinates (x, y, z) are in a range of a graph surrounded by connecting lines QJ, JB 'and B' Q of 3 points of respectively points Q (59.1,12.7,28.2), J (33.5,0.0,66.5) and B '(59.0, 0.0,40.2) or on the above-mentioned connecting lines (except for the connecting line JB's),
the connecting line QJ is defined by a coordinate (y is 0.0083 x)2-0.2719 x-0.1953), and
the connecting lines JB 'and B' Q are straight lines.
When the refrigerant of the present invention (the refrigerant of the sixth embodiment) satisfies the above conditions, the refrigerant has a coefficient of performance (COP) and a refrigerating capacity (Cap) equal to or higher than those of R410A, a GWP of 400 or less, and a compressor outlet pressure of 1.25 times or less based on R410A, and such a compressor outlet pressure is preferably 3.4MPa or less, more preferably 3.0MPa or less. The evaporation temperature glide is as low as 5 ℃ or lower, preferably 4 ℃ or lower, more preferably 3.5 ℃ or lower, and is particularly suitable in place of R410A.
The refrigerant of the present invention (the refrigerant of the seventh aspect) is characterized in that: HFC-32, HFO-1234 yf and HFO-1132 a are contained, in the above-mentioned refrigerant, when the mass% of HFC-32, HFO-1132 a and HFO-1234 yf based on the total sum of them is x, y and z respectively, in the 3 component composition diagram that the total sum of HFC-32, HFO-1132 a and HFO-1234 yf is 100 mass%, the coordinate (x, y, z) is in the scope of the graph enclosed by the connecting line QU, UV and VQ of the 3 points of the connecting point Q (59.1,12.7,28.2), point U (59.0,5.5,35.5) and point V (52.5,8.4,39.1) respectively or on the above-mentioned connecting line,
the line VQ is defined by a coordinate (y is 0.0083 x)2-0.2719 x-0.1953), and
the connecting line UV is defined by the coordinate (y is 0.0026 x)2-0.7385 x +39.946) in a single file,
the above-mentioned connecting line QU is a straight line.
When the refrigerant of the present invention (the refrigerant of the seventh aspect) satisfies the above conditions, the refrigerant has a coefficient of performance (COP) and a refrigerating capacity (Cap) (99% or more of refrigerating capacity R410A) which are equal to or higher than R410A, a GWP of 400 or less, and a compressor outlet pressure of 1.25 times or less based on R410A, and such a compressor outlet pressure is preferably 3.4MPa or less, more preferably 3.0MPa or less. The evaporation temperature glide is as low as 5 ℃ or lower, preferably 4 ℃ or lower, more preferably 3.5 ℃ or lower, and is particularly suitable in place of R410A.
The connecting line UV is an approximate curve obtained by the least square method from the 3 points of point U, example 28 and point V in the table and fig. 2 in the present specification.
As exemplified in the refrigerants of the first to seventh aspects, the present invention has been proposed for the first time as a substitute refrigerant using an existing refrigerant such as R, R134, R404, R407, R410, R413, R417, R422, R423, R424, R426, R427, R430, R434, R437, R438, R448, R449, R452, R454, R455, R459, R465, R502, R507, R513, and in the broadest sense, the present invention includes the following inventions: "a refrigerant-containing composition comprising 1, 1-difluoroethylene (HFO-1132 a) as a substitute refrigerant for R, R134, R404, R407, R410, R413, R417, R422, R423, R424, R426, R427, R430, R434, R437, R438, R448, R449, R452, R454, R455, R459, R465, R502, R507, or R513". ". Among them, the invention preferably includes: "a composition comprising a refrigerant comprising 1, 1-difluoroethylene (HFO-1132 a) as a substitute refrigerant for R410A. "
< Mixed refrigerant containing additional refrigerant
The refrigerant of the present invention may be a mixed refrigerant containing other additional refrigerants in addition to at least one of HFC-32, HFO-1234 yf and HFO-1132 a and FO-1114, within a range not impairing the above-described characteristics and effects. In this case, the total amount of HFC-32, HFO-1234 yf and at least one of HFO-1132 a and FO-1114 is preferably 99.5% by mass or more and less than 100% by mass, more preferably 99.75% by mass or more and less than 100% by mass, and still more preferably 99.9% by mass or more and less than 100% by mass, based on the entire refrigerant of the present invention.
The additional refrigerant is not particularly limited, and can be selected from a wide range of known refrigerants widely used in this field. The mixed refrigerant may contain the additional refrigerant alone, or may contain 2 or more additional refrigerants.
1－2.Use of
The refrigerant of the present invention can be preferably used as a working fluid for refrigerators.
The composition containing the refrigerant of the present invention is suitably used as a substitute refrigerant for existing refrigerants such as R, R134, R404, R407, R410, R413, R417, R422, R423, R424, R426, R427, R430, R434, R437, R438, R448, R449, R452, R454, R455, R459, R465, R502, R507, R513, and the like.
Of these, the composition containing the refrigerant of the present invention (particularly, the refrigerant of the first embodiment and the refrigerant of the second embodiment) is particularly suitable as an alternative refrigerant for R404A. Further, conventionally, as alternative refrigerants of R404A having a reduced GWP, a refrigerant (R454C) having a composition of 21.5/78.5% of R32/R1234yf and a refrigerant (R457A) having a composition of 18/70/12% of R32/R1234yf/R152a are known, but the refrigerant of the present invention (particularly, the refrigerant of the first and second embodiments) is superior to the conventional alternative refrigerant of R404A in terms of freezing capacity.
The composition containing the refrigerant of the present invention (particularly, the third to seventh embodiments) is particularly suitable as an alternative refrigerant for R410A. In particular, the refrigerant of the fifth embodiment is also suitable as an alternative refrigerant for R410A, from the viewpoint of COP, Cap, and GWP, in that both the condensation temperature glide and the evaporation temperature glide are as low as 5 ℃ or lower; the refrigerants of the sixth and seventh modes are suitable as the alternative refrigerant for R410A from the viewpoint of the evaporation temperature glide as small as 5 ℃ or less, in addition to the COP, Cap and GWP.
2.Refrigerant composition
The refrigerant composition of the present invention contains at least the refrigerant of the present invention, and can be used for the same purpose as the refrigerant of the present invention.
The refrigerant composition of the present invention can be used for obtaining a working fluid for a refrigerator by mixing at least a refrigerator oil.
The refrigerant composition of the present invention contains at least one other component in addition to the refrigerant of the present invention. The refrigerant composition of the present invention may contain at least one of the following other components as necessary.
As described above, when the refrigerant composition of the present invention is used as a working fluid for a refrigerator, it is usually used in a mixture with at least a refrigerator oil.
Therefore, the refrigerant composition of the present invention preferably contains substantially no refrigerating machine oil. Specifically, in the refrigerant composition of the present invention, the content of the refrigerator oil relative to the entire refrigerant composition is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, even more preferably 0 to 0.25% by mass, and particularly preferably 0 to 0.1% by mass.
2－1.Water (W)
The refrigerant composition of the present invention may contain a trace amount of water. The water content in the refrigerant composition is preferably 0 to 0.1% by mass, more preferably 0 to 0.075% by mass, even more preferably 0 to 0.05% by mass, and particularly preferably 0 to 0.025% by mass, based on the entire refrigerant.
When the refrigerant composition contains a small amount of water, the unsaturated fluorocarbon compound that can be contained in the refrigerant is stabilized in terms of intramolecular double bonds, and the unsaturated fluorocarbon compound is less likely to be oxidized, thereby improving the stability of the refrigerant composition. From the viewpoint of obtaining the above-described effects by containing water, the lower limit of the water content is about 0.001 mass%. For example, the water content can be adjusted within the range of 0.001 to 0.1 mass%, 0.001 to 0.075 mass%, 0.001 to 0.05 mass%, 0.001 to 0.025 mass%.
2－2.Tracer agent
When the refrigerant composition of the present invention is diluted, contaminated, or otherwise altered, a tracer may be added to the refrigerant composition of the present invention at a detectable concentration so that the alteration can be tracked.
The refrigerant composition of the present invention may contain one kind of the above tracer alone, or may contain two or more kinds.
The tracer is not particularly limited, and may be appropriately selected from conventional tracers. It is preferred to select as the tracer a compound that does not form impurities that are inevitably mixed into the refrigerant of the present invention.
Examples of the tracer include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, bromides, iodides, alcohols, aldehydes, ketones, and dinitrogen monoxide (N)2O), and the like. Of these, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers are preferred.
Specifically, the following compounds (hereinafter, also referred to as tracer compounds) are more preferable as the above tracer.
HCC-40 (chloromethane, CH)3Cl)
HFC-41 (fluoromethane, CH)3F)
HFC-161 (fluoroethane, CH)3CH2F)
HFC-245 fa (1,1,1,3, 3-pentafluoropropane, CF)3CH2CHF2)
HFC-236 fa (1,1,1,3,3, 3-hexafluoropropane, CF)3CH2CF3)
HFC-236 ea (1,1,1,2,3, 3-hexafluoropropane, CF)3CHFCHF2)
HCFC-22 (chlorodifluoromethane, CHClF)2)
HCFC-31 (chlorofluoromethane, CH)2ClF)
CFC-1113 (chlorotrifluoroethylene, CF)2＝CClF)
HFE-125 (trifluoromethyl-difluoromethyl ether, CF)3OCHF2)
HFE-134 a (trifluoromethyl-fluoromethyl ether, CF)3OCH2F)
HFE-143 a (trifluoromethyl-methyl ether, CF)3OCH3)
HFE-227 ea (trifluoromethyl-tetrafluoroethyl ether, CF)3OCHFCF3)
HFE-236 fa (trifluoromethyl-trifluoroethyl ether, CF)3OCH2CF3)
The tracer compounds may be present in the refrigerant composition at a total concentration of from 10 parts per million (ppm) by weight to 1000ppm by weight. The tracer compound is preferably present in the refrigerant composition at a total concentration of 30ppm to 500ppm, more preferably at a total concentration of 50ppm to 300ppm, even more preferably at a total concentration of 75ppm to 250ppm, and even more preferably at a total concentration of 100ppm to 200 ppm.
2－3.Ultraviolet fluorescent dye
The refrigerant composition of the present invention may contain one kind of ultraviolet fluorescent dye alone or two or more kinds thereof.
The ultraviolet fluorescent dye is not particularly limited, and may be appropriately selected from commonly used ultraviolet fluorescent dyes.
Examples of the ultraviolet fluorescent dye include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thiaanthracene, benzoxanthene, fluorescein, and derivatives thereof. Of these, naphthalimide and coumarin are preferred.
2－4.Stabilizer
The refrigerant composition of the present invention may contain one kind of stabilizer alone, or may contain two or more kinds.
The stabilizer is not particularly limited, and may be appropriately selected from conventional stabilizers.
Examples of the stabilizer include nitro compounds, ethers, and amines.
Examples of the nitro compound include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.
Examples of the ethers include 1, 4-dioxane and the like.
Examples of the amines include 2,2,3,3, 3-pentafluoropropylamine and diphenylamine.
Examples of the stabilizer include butylhydroxyxylene, benzotriazole, and the like, in addition to the nitro compound, ether, and amine.
The content of the stabilizer is not particularly limited, and is usually 0.01 to 5% by mass, preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, still more preferably 0.25 to 1.5% by mass, and particularly preferably 0.5 to 1% by mass, based on the entire refrigerant.
The method for evaluating the stability of the refrigerant composition of the present invention is not particularly limited, and the evaluation can be carried out by a general method. Examples of such a method include a method of evaluating the amount of free fluoride ion as an index according to ASHRAE standard 97-2007. Further, a method of evaluating with a total acid number (total acid number) as an index may be mentioned. The method can be carried out, for example, according to ASTM D974-06.
2－5.Polymerization inhibitor
The refrigerant composition of the present invention may contain one kind of polymerization inhibitor alone, or may contain two or more kinds.
The polymerization inhibitor is not particularly limited, and may be appropriately selected from conventional polymerization inhibitors.
Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone methyl ether, dimethyl-t-butylphenol, 2, 6-di-t-butyl-p-cresol, and benzotriazole.
The content of the polymerization inhibitor is not particularly limited, but is usually 0.01 to 5% by mass, preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, still more preferably 0.25 to 1.5% by mass, and particularly preferably 0.5 to 1% by mass, based on the entire refrigerant.
3.Working fluid containing refrigerator oil
The refrigerating machine oil-containing working fluid of the present invention contains at least the refrigerant or the refrigerant composition of the present invention and a refrigerating machine oil, and is used as a working fluid for a refrigerating machine. Specifically, the refrigerating machine oil-containing working fluid of the present invention is obtained by mixing a refrigerating machine oil used in a compressor of a refrigerating machine and a refrigerant or a refrigerant composition.
The content of the refrigerating machine oil is not particularly limited, and is usually 10 to 50% by mass, preferably 12.5 to 45% by mass, more preferably 15 to 40% by mass, still more preferably 17.5 to 35% by mass, and particularly preferably 20 to 30% by mass, based on the entire working fluid containing the refrigerating machine oil.
3－1.Refrigerating machine oil
The composition of the present invention may contain one kind of refrigerator oil alone, or may contain two or more kinds.
The refrigerating machine oil is not particularly limited, and may be appropriately selected from conventional refrigerating machine oils. In this case, if necessary, a more excellent refrigerating machine oil can be appropriately selected from the viewpoint of improving the compatibility (misflexibility) with the mixture of the refrigerant of the present invention (the mixed refrigerant of the present invention), improving the stability of the mixed refrigerant of the present invention, and the like.
The base oil of the refrigerator oil is preferably at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE), for example.
The refrigerator oil may contain an additive in addition to the base oil.
The additive may be at least one selected from the group consisting of an antioxidant, an extreme pressure agent, an acid scavenger, an oxygen scavenger, a copper deactivator, a rust preventive, an oiliness agent, and an antifoaming agent.
The refrigerator oil preferably has a kinematic viscosity of 5 to 400cSt at 40 ℃ from the viewpoint of lubrication.
The refrigerating machine oil-containing working fluid of the present invention may further contain at least one additive, as required. Examples of the additives include the following compatibilizers.
3－2.Compatibilizer
The working fluid containing the refrigerating machine oil of the present invention may contain one kind of the compatibilizer alone or two or more kinds thereof.
The compatibilizer is not particularly limited, and may be appropriately selected from commonly used compatibilizers.
Examples of the compatibilizer include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorinated hydrocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1, 1-trifluoroalkanes. Among these, polyoxyalkylene glycol ethers are preferred.
4.Method for operating refrigerator
The method for operating a refrigerator of the present invention is a method for operating a refrigerator using the refrigerant of the present invention.
Specifically, the method for operating a refrigerator according to the present invention includes a step of circulating a composition containing the refrigerant according to the present invention as a working fluid in the refrigerator.
5.Heat transfer medium and heat cycle system using the same
The heat transfer medium of the present invention comprises a composition comprising the refrigerant of the present invention.
The heat transfer medium of the present invention can be applied to various heat cycle systems. The heat cycle system having the heat transfer medium of the present invention can be a heat cycle system having a high cooling capacity.
Further, since the refrigerant of the present invention has a sufficiently low GWP, it is possible to provide a high safety to the heat cycle system by including the heat transfer medium of the present invention, as compared with the case of using a conventional refrigerant.
Further, the heat transfer medium of the present invention has low temperature slip, and therefore, a heat cycle system having high stability can be provided.
The kind of the heat cycle system is not particularly limited. Examples of the heat cycle system include an indoor air conditioner, an air conditioning cabinet for stores, an air conditioning cabinet for buildings, an air conditioning cabinet for equipment, a split air conditioner in which one or more indoor units and outdoor units are connected by refrigerant piping, a window air conditioner, a portable air conditioner, a ceiling type or central air conditioner that blows hot and cold air by using ventilation ducts, a gas engine heat pump, an air conditioner for trains, an air conditioner for automobiles, a built-in showcase, an independent showcase, a freezer refrigerator for business use, an ice maker, an integrated freezer, an automatic vending machine, an automobile air conditioner, a freezer for cooling containers or refrigerators for marine transportation, a turbo freezer, and a machine dedicated for room heating. Examples of the machine dedicated to the greenhouse circulation include a hot water supply device, a floor heating device, and a snow melting device.
The heat cycle system exemplified above is not particularly limited as long as it has the heat transfer medium of the present invention, and other configurations may be used, for example, the same configuration as a known heat cycle system.
While the embodiments have been described above, it should be understood that various changes in form and details may be made therein without departing from the spirit and scope of the invention as claimed.
Examples
The following will explain the present invention in more detail by way of examples. However, the present invention is not limited to these examples.
Examples 1 to 16 and comparative example 1 (corresponding to the refrigerants of the first and second embodiments)
Examples 17 to 87 and comparative examples 2 to 18 (corresponding to the refrigerants of the third to seventh aspects)
The GWP of the mixed refrigerants shown in the examples and comparative examples and the GWP of R404A (R125/143a/R134a ═ 44/52/4 wt%) and R410A (R32/R125 ═ 50/50 wt%) were evaluated based on the values in the 4 th report of IPCC (inter-government Climate Change special committee).
In addition, COP and freezing capacity of the mixed refrigerant and COP and freezing capacity of R404A shown in each of examples and comparative examples were determined using National Institute of Science and Technology (NIST), a Fluid Thermodynamic performance and Transport performance Reference Database (Reference Fluid Thermodynamic and Transport Properties Database) (Reference 9.0). Specifically, examples 1 to 16 and comparative example 1 (corresponding to the refrigerants of the first and second embodiments) were obtained by performing a theoretical calculation of the refrigeration cycle of the mixed refrigerant under the following conditions.
Examples 17 to 87 and comparative examples 2 to 18 (corresponding to the refrigerants of the third to seventh aspects) were obtained by performing theoretical calculation of the refrigeration cycle of the mixed refrigerant under the following conditions.
Further, the condensation temperature slip, the evaporation temperature slip, and the compressor outlet pressure when the mixed refrigerant shown in each of examples and comparative examples was used were also obtained using Refprop 9.0.
Further, the GWP, COP and freezing capacity calculated based on these results are shown in tables 1 and 2-1 to 2-12. Of these, examples 1 to 16 and comparative example 1 show the ratio (%) to R404A, and examples 17 to 87 and comparative examples 2 to 18 show the ratio (%) to R410A, with respect to the COP ratio and the freezing capacity ratio.
The coefficient of performance (COP) was determined by the following equation.
COP (freezing capacity or heating capacity)/power consumption
[ TABLE 1 ]
As is clear from the results in table 1, the refrigerant of the second embodiment has a coefficient of performance (COP) equal to or higher than R404A and a freezing capacity (Cap) of 95% or higher, has a GWP of 150 or lower and a condensing temperature glide of 9 ℃ or lower, and is particularly excellent as an alternative refrigerant of R404A.
[ TABLE 2-1 ]
[ TABLE 2-2 ]
[ TABLE 2-3 ]
[ tables 2-4 ]
Item
Unit of
Example 30
Example 31
Example 32
Example 33
Example 34
Comparative example 11
Example 35
Example 36
R32
Mass%
30.0
40.0
50.0
60.0
70.0
80.0
30.0
40.0
R1132a
Mass%
5.0
5.0
5.0
5.0
5.0
5.0
10.0
10.0
R1234yf
Mass%
65.0
55.0
45.0
35.0
25.0
15.0
60.0
50.0
GWP
-
205
272
339
406
474
541
205
272
Ratio of COP
% (relative to R410A)
101
101
101
101
101
101
100
99
Ratio of freezing capacities
% (relative to R410A)
79
86
93
99
104
109
86
93
Compressor discharge pressure ratio
% (relative to R410A)
80
87
93
97
101
105
88
95
Condensation slip
℃
7.6
5.9
4.5
3.5
2.8
2.2
8.9
7.0
Evaporation glide
℃
6.8
5.4
4.1
3.1
2.4
2.0
8.1
6.5
[ TABLE 2-5 ]
Item
Unit of
Example 37
Example 38
Example 39
Comparative example 12
Example 40
EXAMPLE 41
Example 42
Example 43
R32
Mass%
50.0
60.0
70.0
80.0
30.0
40.0
50.0
60.0
R1132a
Mass%
10.0
10.0
10.0
10.0
15.0
15.0
15.0
15.0
R1234yf
Mass%
40.0
30.0
20.0
10.0
55.0
45.0
35.0
25.0
GWP
-
339
406
473
541
205
272
339
406
Ratio of COP
% (relative to R410A)
99
99
99
100
98
98
98
98
Ratio of freezing capacities
% (relative to R410A)
100
105
110
115
92
99
106
112
Compressor discharge pressure ratio
% (relative to R410A)
101
105
109
112
96
103
108
113
Condensation slip
℃
5.6
4.6
3.8
3.3
9.7
7.7
6.2
5.2
Evaporation glide
℃
5.2
4.2
3.6
3.2
9.1
7.4
6.1
5.1
[ tables 2 to 6 ]
Item
Unit of
Example 44
Comparative example 13
Example 45
Example 46
Example 47
Example 48
Example 49
Example 50
R32
Mass%
70.0
80.0
30.0
40.0
50.0
60.0
70.0
30.0
R1132a
Mass%
15.0
15.0
20.0
20.0
20.0
20.0
20.0
25.0
R1234yf
Mass%
15.0
5.0
50.0
40.0
30.0
20.0
10.0
45.0
GWP
-
473
540
205
272
339
406
473
205
Ratio of COP
% (relative to R410A)
98
98
97
96
96
96
97
95
Ratio of freezing capacities
% (relative to R410A)
117
121
98
106
112
118
122
104
Compressor discharge pressure ratio
% (relative to R410A)
116
119
104
111
116
120
124
112
Condensation slip
℃
4.5
3.9
9.9
7.9
6.4
5.5
4.8
9.7
Evaporation glide
℃
4.5
4.1
9.8
8.0
6.7
5.8
5.2
10.2
[ tables 2 to 7 ]
Item
Unit of
Example 51
Example 52
Example 14
Example 15
Example 53
Comparative example 16
Comparative example 17
Comparative example 18
R32
Mass%
40.0
50.0
60.0
70.0
30.0
40.0
50.0
60.0
R1132a
Mass%
25.0
25.0
25.0
25.0
30.0
30.0
30.0
30.0
R1234yf
Mass%
35.0
25.0
15.0
5.0
40.0
30.0
20.0
10.0
GWP
-
272
339
406
473
204
272
339
406
Ratio of COP
% (relative to R410A)
95
95
95
95
93
93
93
93
Ratio of freezing capacities
% (relative to R410A)
112
118
123
128
110
117
123
129
Compressor discharge pressure ratio
% (relative to R410A)
119
124
128
131
120
127
132
136
Condensation slip
℃
7.7
6.3
5.4
4.8
9.2
7.3
6.0
5.1
Evaporation glide
℃
8.3
7.0
6.2
5.7
10.3
8.4
7.1
6.4
[ tables 2 to 8 ]
Item
Unit of
Example 54
Example 55
Example 56
Example 57
Example 58
Example 59
Example 60
Example 61
R32
Mass%
39.0
41.0
43.0
45.0
47.0
49.0
51.0
53.0
R1132a
Mass%
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
R1234yf
Mass%
60.0
58.0
56.0
54.0
52.0
50.0
48.0
46.0
GWP
-
266
279
293
306
319
333
346
360
Ratio of COP
% (relative to R410A)
102
102
102
102
102
102
102
102
Ratio of freezing capacities
% (relative to R410A)
80
82
83
85
86
87
88
90
Compressor discharge pressure ratio
% (relative to R410A)
80
81
83
84
85
86
87
88
Condensation slip
℃
4.6
4.3
4.1
3.8
3.6
3.3
3.1
2.9
Evaporation glide
℃
4.4
4.1
3.9
3.6
3.3
3.1
2.9
2.7
[ tables 2 to 9 ]
Item
Unit of
Example 62
Example 63
Example 64
Example 65
Example 66
Example 67
Example 68
Examples69
R32
Mass%
55.0
57.0
59.0
45.0
47.0
49.0
51.0
53.0
R1132a
Mass%
1.0
1.0
1.0
3.0
3.0
3.0
3.0
3.0
R1234yf
Mass%
44.0
42.0
40.0
52.0
50.0
48.0
46.0
44.0
GWP
-
373
386
400
306
319
333
346
360
Ratio of COP
% (relative to R410A)
102
102
102
101
101
101
101
101
Ratio of freezing capacities
% (relative to R410A)
91
92
93
87
89
90
91
92
Compressor discharge pressure ratio
% (relative to R410A)
89
90
91
87
88
89
90
91
Condensation slip
℃
2.7
2.5
2.3
4.5
4.3
4.0
3.8
3.6
Evaporation glide
℃
2.5
2.3
2.1
4.2
3.9
3.7
3.4
3.2
[ tables 2-10 ]
Item
Unit of
Example 70
Example 71
Example 72
Example 73
Example 74
Example 75
Example 76
Example 77
R32
Mass%
55.0
57.0
59.0
47.0
49.0
51.0
53.0
55.0
R1132a
Mass%
3.0
3.0
3.0
5.0
5.0
5.0
5.0
5.0
R1234yf
Mass%
42.0
40.0
38.0
48.0
46.0
44.0
42.0
40.0
GWP
-
373
386
400
319
333
346
359
373
Ratio of COP
% (relative to R410A)
101
101
101
101
101
101
101
101
Ratio of freezing capacities
% (relative to R410A)
93
95
96
91
92
94
95
96
Compressor discharge pressure ratio
% (relative to R410A)
92
93
94
91
92
93
94
95
Condensation slip
℃
3.4
3.2
3.0
4.9
4.6
4.4
4.2
3.9
Evaporation glide
℃
3.0
2.8
2.7
4.4
4.2
4.0
3.7
3.5
[ tables 2 to 11 ]
Item
Unit of
Example 78
Example 79
Example 80
Example 81
Example 82
Example 83
Example 84
Example 85
R32
Mass%
57.0
59.0
53.0
55.0
57.0
59.0
55.0
57.0
R1132a
Mass%
5.0
5.0
7.0
7.0
7.0
7.0
9.0
9.0
R1234yf
Mass%
38.0
36.0
40.0
38.0
36.0
34.0
36.0
34.0
GWP
-
386
400
359
373
386
400
373
386
Ratio of COP
% (relative to R410A)
101
101
100
100
100
100
100
100
Ratio of freezing capacities
% (relative to R410A)
97
98
98
99
100
101
101
102
Compressor discharge pressure ratio
% (relative to R410A)
96
97
97
98
99
100
101
102
Condensation slip
℃
3.8
3.6
4.7
4.4
4.2
4.1
4.9
4.7
Evaporation glide
℃
3.4
3.2
4.2
4.0
3.8
3.7
4.5
4.3
[ tables 2-12 ]
Item
Unit of
Example 86
Example 87
R32
Mass%
59.0
59.0
R1132a
Mass%
9.0
11.0
R1234yf
Mass%
32.0
30.0
GWP
-
400
400
Ratio of COP
% (relative to R410A)
100
99
Ratio of freezing capacities
% (relative to R410A)
104
106
Compressor discharge pressure ratio
% (relative to R410A)
103
106
Condensation slip
℃
4.5
4.8
Evaporation glide
℃
4.1
4.5
As is clear from the results of tables 2-1 to 2-12, the refrigerant of the third embodiment has a coefficient of performance (COP) and a refrigerating capacity (Cap) equal to or higher than those of R410A, a GWP of 500 or less, and a compressor outlet pressure of 1.25 times or less based on R410A, when satisfying the predetermined conditions. It is understood that the refrigerant of the fourth embodiment has a coefficient of performance (COP) and a refrigerating capacity (Cap) equal to or higher than those of R410A, a GWP of 400 or less, and a compressor outlet pressure of 1.25 times or less based on R410A, when satisfying predetermined conditions. It is understood that the refrigerant of the fifth aspect has a coefficient of performance (COP) and a refrigerating capacity (Cap) equal to or higher than those of R410A, a GWP of 500 or less, a compressor outlet pressure of 1.25 times or less based on R410A, and both a condensation temperature glide and an evaporation temperature glide are as low as 5 ℃ or less when the predetermined conditions are satisfied. It is also found that the refrigerant of the sixth aspect has a coefficient of performance (COP) and a refrigerating capacity (Cap) equal to or higher than those of R410A, a GWP of 400 or less, a compressor outlet pressure of 1.25 times or less based on R410A, and an evaporation temperature glide of 5 ℃ or less, when the predetermined conditions are satisfied. It is also found that the refrigerant of the seventh aspect has a coefficient of performance (COP) and a refrigerating capacity (Cap) (99% or more relative to R410A) which are equal to or higher than those of R410A, a GWP of 400 or less, a compressor outlet pressure of 1.25 times or less based on R410A, and an evaporation temperature glide of 5 ℃ or less, when the predetermined conditions are satisfied. These refrigerants of the third to seventh modes are suitable as the alternative refrigerant for R410A, and particularly, the refrigerant of the fifth mode or the sixth mode having a small condensation temperature slip and/or evaporation temperature slip is particularly suitable as the alternative refrigerant for R410A. Further, the refrigerant of the seventh aspect, in which the condensation temperature slip and/or the evaporation temperature slip are small and the coefficient of performance (COP) and the refrigerating capacity (Cap) (99% or more relative to R410A) are equal to or more than R410A, is more excellent as the substitute refrigerant for R410A.
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