U.S. patent application number 17/254425 was filed with the patent office on 2021-04-29 for composition containing refrigerant, use thereof, refrigerator having same, and operation method for said refrigerator.
This patent application is currently assigned to DAIKIN INDUSTRIES, LTD.. The applicant listed for this patent is DAIKIN INDUSTRIES, LTD.. Invention is credited to Mitsushi ITANO, Hitomi KUROKI, Kazuhiro TAKAHASHI.
Application Number | 20210122960 17/254425 |
Document ID | / |
Family ID | 1000005371211 |
Filed Date | 2021-04-29 |
United States Patent
Application |
20210122960 |
Kind Code |
A1 |
ITANO; Mitsushi ; et
al. |
April 29, 2021 |
COMPOSITION CONTAINING REFRIGERANT, USE THEREOF, REFRIGERATOR
HAVING SAME, AND OPERATION METHOD FOR SAID REFRIGERATOR
Abstract
The present disclosure provides a mixed refrigerant having four
types of performance, i.e., an excellent coefficient of performance
and refrigerating capacity that allow it to serve as an alternative
refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, the present disclosure provides a
composition comprising a refrigerant, the refrigerant comprising
trifluoroiodomethane (CF.sub.3I) and difluoromethane (R32), wherein
the contents of CF.sub.3I and R32 in the refrigerant are
respectively 48 mass %.gtoreq.CF.sub.3.gtoreq.46 mass % and 54 mass
%.gtoreq.R32.gtoreq.52 mass %, based on the total amount of
CF.sub.3I and R32 taken as 100 mass %.
Inventors: |
ITANO; Mitsushi; (Osaka,
JP) ; TAKAHASHI; Kazuhiro; (Osaka, JP) ;
KUROKI; Hitomi; (Osaka, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DAIKIN INDUSTRIES, LTD. |
Osaka |
|
JP |
|
|
Assignee: |
DAIKIN INDUSTRIES, LTD.
Osaka
JP
|
Family ID: |
1000005371211 |
Appl. No.: |
17/254425 |
Filed: |
June 21, 2019 |
PCT Filed: |
June 21, 2019 |
PCT NO: |
PCT/JP2019/024822 |
371 Date: |
December 21, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 2205/126 20130101;
F25B 9/006 20130101; C09K 5/044 20130101; C09K 2205/40 20130101;
C09K 2205/122 20130101 |
International
Class: |
C09K 5/04 20060101
C09K005/04; F25B 9/00 20060101 F25B009/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 22, 2018 |
JP |
2018-119328 |
Claims
1. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I) and difluoromethane
(R32), wherein the contents of CF.sub.3I and R32 in the refrigerant
are respectively 48 mass %.gtoreq.CF.sub.3I.gtoreq.46 mass % and 54
mass %.gtoreq.R32.gtoreq.52 mass %, based on the total amount of
CF.sub.3I and R32 taken as 100 mass %.
2. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I), difluoromethane (R32),
and pentafluoroethane (R125), wherein when the mass % of R32, R125,
and CF.sub.3I based on their sum is respectively represented by x,
y, and z, coordinates (x,y,z) in a ternary composition diagram in
which the sum of R32, R125, and CF.sub.3I is 100 mass % are within
the range of a figure surrounded by line segments EF, FD, DX, and
XE that connect the following 4 points: point E (53.7, 11.0, 35.3),
point F (51.6, 0.0, 48.4) point D (65.0. 0.0, 35.0), and point X
(64.6. 8.9, 26.5), excluding the line segment FD, the line segment
EF is represented by coordinates (x, -1.1255x.sup.2+123.76x-3389.3,
1.1255x.sup.2-124.76x+3489.3), and the line segments FD, DX, and XE
are straight lines.
3. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I) and
trans-1,2-difluoroethylene (HFO-1132(E)), wherein the contents of
CF.sub.3I and HFO-1132(E) in the refrigerant are respectively 68
mass %.gtoreq.CF.sub.3I.gtoreq.62 mass % and 38 mass
%.gtoreq.HFO-1132(E).gtoreq.32 mass %, based on the total amount of
CF.sub.3I and HFO-1132(E) taken as 100 mass %.
4. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I), difluoromethane (R32),
and trans-1,2-difluoroethylene (HFO-1132(E)), wherein when the mass
% of HFO-1132(E), CF.sub.3I, and R32 based on their sum is
respectively represented by x, y, and z, coordinates (x,y,z) in a
ternary composition diagram in which the sum of HFO-1132(E),
CF.sub.3I, and R32 is 100 mass % are within the range of a figure
surrounded by line segments JH, HY, and YJ that connect the
following 3 points: point Y (32.5, 58.1, 9.4), point J (0.0. 77.2,
22.8), and point H (0.0. 35.0, 65.0), excluding the line segment
JH, the line segment YJ is represented by coordinates (x,
-0.0027x.sup.2-0.5002x+77.2, 0.0027x.sup.2-0.4998x+22.8), and the
line segments JH and HY are straight lines.
5. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I), difluoromethane (R32),
and trifluoroethylene (HFO-1123), wherein when the mass % of
HFO-1123, CF.sub.3I, and R32 based on their sum is respectively
represented by x, y, and z, coordinates (x,y,z) in a ternary
composition diagram in which the sum of HFO-1123, CF.sub.3I, and
R32 is 100 mass % are within the range of a figure surrounded by
line segments ZN, NL, and LZ that connect the following 3 points:
point Z (41.6, 53.5, 4.9), point N (0.0. 77.2, 22.8), and point L
(0.0. 35.0, 65.0), excluding the line segment NL, the line segment
ZN is represented by coordinates (x, -0.0007x.sup.2-0.5402x+77.2,
0.0007x.sup.2-0.4598x+22.8), and the line segments NL and LZ are
straight lines.
6. A composition comprising a refrigerant, the refrigerant
comprising difluoromethane (R32), pentafluoroethane (R125),
trifluoroiodomethane (CF.sub.3I), and 2,3,3,3-tetrafluoroethylene
(HFO-1234yf), and the refrigerant comprising one of the following
refrigerants A and B: in a ternary composition diagram in which the
total concentration of R32, R123, CF.sub.3I, and HFO-1234yf is 100
mass %, the concentration of HFO-1234yf is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %, refrigerant A having a composition ratio in which (1)-1.
11.7 mass %.gtoreq.x.gtoreq.6.0 mass %, and (1)-2. the
concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R123 (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a quadrilateral or triangle
having, as vertices, point C
(1.1753x+41.14/-0.2282x+13.464/100-R1234yf-R32-R125), point D
(0.0247x.sup.2+0.563x+43.733/0.0/100-R1234yf-R32-R125), point F
(-0.8069x+64.948/0.0/100-R1234yf-R32-R125), and point E
(-0.8247x+64.54/0.1581x+8.96/100-R1234yf-R32-R125), excluding the
line segment DF; and refrigerant B having a composition ratio in
which (2)-1. 12.6 mass %.gtoreq.x.gtoreq.11.7 mass %, and (2)-2.
the concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R12S (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a triangle having, as vertices,
point G
(-1.2222x.sup.2+29.589x-123.98/20.5x.sup.2-510.15x+3173.3/100-R1234yf-R32-
-R125), point D (1.2213x+39.415/0.0/100-R1234yf-R32-R125), and
point F (0.7787x+64.615/0.0/100-R1234yf-R32-R125), excluding the
line segment DF.
7. A composition comprising a refrigerant, the refrigerant
comprising difluoromethane (R32), pentafluoroethane (R125),
trifluoroiodomethane (CF.sub.3I), and 1,3,3,3-tetrafluoropropene
(HFO-1234ze), and the refrigerant comprising one of the following
refrigerants A and B: in a ternary composition diagram in which the
total concentration of R32, R123, CF.sub.3I, and HFO-1234ze is 100
mass %, the concentration of HFO-1234ze is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %, refrigerant A having a composition ratio in which (1)-1.
8.3 mass %.gtoreq.x.gtoreq.4.0 mass %, and (1)-2. the concentration
of R32, R125, and CF.sub.3I (concentration of R32 (mass
%)/concentration of R123 (mass %)/concentration of CF.sub.3I (mass
%)) is within the range of a quadrilateral or triangle having, as
vertices, point C
(0.0435x.sup.2+1.4652x+42.543/-0.3726x+13.406/100-R1234ze-R32-R125),
point D (0.097x.sup.2+0.6802x+44.628/0.0/100-R1234ze-R32-R125),
point F (-0.8143x+64.967/0.0/100-R1234ze-R32-R125), and point E
(-0.0061x.sup.2-0.7393x+64.254/0.1631x+8.9386/100-R1234ze-R32-R125),
excluding the line segment DF; and refrigerant B having a
composition ratio in which (2)-1. 8.9 mass %.gtoreq.x.gtoreq.8.3
mass %, and (2)-2. the concentration of R32, R125, and CF.sub.3I
(concentration of R32 (mass %)/concentration of R123 (mass
%)/concentration of CF.sub.3I (mass %)) is within the range of a
triangle having, as vertices, point G
(0.1667x+56.3/2.7778x.sup.2-64.944x+357.98/100-R1234ze-R32-R125),
point D (1.5625x.sup.2-24.938x+155.98/0.0/100-R1234ze-R32-R125),
and point F (-0.6667x+63.733/0.0/100-R1234ze-R32-R125), excluding
the line segment DF.
8. The composition according to claim 1, for use as a working fluid
for a refrigerating machine, wherein the composition further
comprises a refrigeration oil.
9. The composition according to claim 1, for use as an alternative
refrigerant for R410A.
10. Use of the composition according to claim 1 as an alternative
refrigerant for R410A.
11. A refrigerating machine comprising the composition according to
claim 1 as a working fluid.
12. A method for operating a refrigerating machine, comprising
circulating the composition according to claim 1 as a working fluid
in a refrigerating machine.
Description
TECHNICAL FIELD
[0001] The present disclosure relates to a composition comprising a
refrigerant, use of the composition, a refrigerating machine having
the composition, and a method for operating the refrigerating
machine.
BACKGROUND ART
[0002] R410A is currently used as an air conditioning refrigerant
for home air conditioners etc. R410A is a two-component mixed
refrigerant of difluoromethane (CH.sub.2F.sub.2: R32) and
pentafluoroethane (C.sub.2HF.sub.5: R125), and is a
pseudo-azeotropic composition.
[0003] However, R410A has a global warming potential (GWP) of 2088.
Due to the growing concerns about global warming, R32, which has a
GWP of 675, has been increasingly used. For this reason, various
low-GWP mixed refrigerants that can replace R410A have been
proposed (PTL 1).
[0004] Further, as the prior art related to the present disclosure,
PTL 2, PTL 3, and the like disclose refrigerant compositions
comprising trifluoroiodomethane (CF.sub.3I).
CITATION LIST
Patent Literature
[0005] PTL 1: WO2015/141678
[0006] PTL 2: JP2009-24152A
[0007] PTL 3: JPH08-277389A
SUMMARY OF INVENTION
Technical Problem
[0008] The present inventors performed independent examination, and
conceived of the idea that no prior art had developed refrigerant
compositions having four types of performance, i.e., an excellent
coefficient of performance (COP) and refrigerating capacity (also
referred to as "cooling capacity" and "capacity") that allow them
to serve as alternative refrigerants for R410A, a sufficiently low
GWP, and non-flammability. An object of the present disclosure is
to solve this unique problem.
Solution to Problem
[0009] 1. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I) and difluoromethane
(R32), wherein the contents of CF.sub.3I and R32 in the refrigerant
are respectively 48 mass %.gtoreq.CF.sub.3I.gtoreq.46 mass % and 54
mass %.gtoreq.R32.gtoreq.52 mass %, based on the total amount of
CF.sub.3I and R32 taken as 100 mass %.
[0010] 2. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I), difluoromethane (R32),
and pentafluoroethane (R125), wherein
[0011] when the mass % of R32, R125, and CF.sub.3I based on their
sum is respectively represented by x, y, and z, coordinates (x,y,z)
in a ternary composition diagram in which the sum of R32, R125, and
CF.sub.3I is 100 mass % are within the range of a figure surrounded
by line segments EF, FD, DX, and XE that connect the following 4
points:
point E (53.7, 11.0, 35.3), point F (51.6, 0.0, 48.4) point D
(65.0. 0.0, 35.0), and point X (64.6. 8.9, 26.5), excluding the
line segment FD,
[0012] the line segment EF is represented by coordinates (x,
-1.1255x.sup.2+123.76x-3389.3, 1.1255x.sup.2-124.76x+3489.3), and
the line segments FD, DX, and XE are straight lines.
[0013] 3. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I) and
trans-1,2-difluoroethylene (HFO-1132(E)), wherein the contents of
CF.sub.3I and HFO-1132(E) in the refrigerant are respectively 68
mass %.gtoreq.CF.sub.2I.gtoreq.62 mass % and 38 mass
%.gtoreq.HFO-1132(E).gtoreq.32 mass %, based on the total amount of
CF.sub.3I and HFO-1132 (E) taken as 100 mass %.
[0014] 4. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I), difluoromethane (R32),
and trans-1,2-difluoroethylene (HFO-1132 (E)),
wherein
[0015] when the mass % of HFO-1132(E), CF.sub.3I, and R32 based on
their sum is respectively represented by x, y, and z, coordinates
(x,y,z) in a ternary composition diagram in which the sum of
HFO-1132 (E), CF.sub.3I, and R32 is 100 mass % are within the range
of a figure surrounded by line segments JH, HY, and YJ that connect
the following 3 points:
point Y (32.5, 58.1, 9.4), point J (0.0. 77.2, 22.8), and point H
(0.0. 35.0, 65.0), excluding the line segment JH,
[0016] the line segment YJ is represented by coordinates (x,
-0.0027x.sup.2-0.5002x+77.2, 0.0027x.sup.2-0.4998x+22.8), and
[0017] the line segments JH and HY are straight lines.
[0018] 5. A composition comprising a refrigerant, the refrigerant
comprising trifluoroiodomethane (CF.sub.3I)/difluoromethane (R32),
and trifluoroethylene (HFO-1123),
wherein
[0019] when the mass % of HFO-1123, CF.sub.3I, and R32 based on
their sum is respectively represented by x, y, and z, coordinates
(x,y,z) in a ternary composition diagram in which the sum of
HFO-1123, CF.sub.3I, and R32 is 100 mass % are within the range of
a figure surrounded by line segments ZN, NL, and LZ that connect
the following 3 points:
point Z (41.6, 53.5, 4.9), point N (0.0. 77.2, 22.8), and point L
(0.0. 35.0, 65.0), excluding the line segment NL,
[0020] the line segment ZN is represented by coordinates (x,
-0.0007x.sup.2-0.5402x+77.2, 0.0007x.sup.2-0.4598x+22.8), and the
line segments NL and LZ are straight lines.
[0021] 6. A composition comprising a refrigerant, the refrigerant
comprising difluoromethane (R32), pentafluoroethane (R125),
trifluoroiodomethane (CF.sub.3I), and 2,3,3,3-tetrafluoroethylene
(HFO-1234yf), and the refrigerant comprising one of the following
refrigerants A and B:
[0022] in a ternary composition diagram in which the total
concentration of R32, R125, CF.sub.3I, and HFO-1234yf is 100 mass
%, the concentration of HFO-1234yf is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %,
[0023] refrigerant A having a composition ratio in which
(1)-1. 11.7 mass %.gtoreq.x.gtoreq.6.0 mass %, and (1)-2. the
concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a quadrilateral or triangle
having, as vertices, point C
(1.1753x+41.14/-0.2282x+13.464/100-R1234yf-R32-R125), point D
(0.0247x.sup.2+0.563x+43.733/0.0/100-R1234yf-R32-R125), point F
(-0.8069x+64.948/0.0/100-R1234yf-R32-R125), and point E
(-0.8247x+64.54/0.1581x+8.96/100-R1234yf-R32-R125), excluding the
line segment DF; and
[0024] refrigerant B having a composition ratio in which
(2)-1. 12.6 mass %>x>11.7 mass %, and (2)-2. the
concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a triangle having, as vertices,
point G
(-1.2222x.sup.2+29.589x-123.98/20.5x.sup.2-510.15x+3173.3/100-R1234yf-R32-
-R125), point D (1.2213x+39.415/0.0/100-R1234yf-R32-R125), and
point F (0.7787x+64.615/0.0/100-R1234yf-R32-R125), excluding the
line segment DF.
[0025] 7. A composition comprising a refrigerant, the refrigerant
comprising difluoromethane (R32), pentafluoroethane (R125),
trifluoroiodomethane (CF.sub.3I), and 1,3,3,3-tetrafluoropropene
(HFO-1234ze), and the refrigerant comprising one of the following
refrigerants A and B:
[0026] in a ternary composition diagram in which the total
concentration of R32, R125, CF.sub.3I, and HFO-1234ze is 100 mass
%, the concentration of HFO-1234ze is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %,
[0027] refrigerant A having a composition ratio in which
(1)-1. 8.3 mass %.gtoreq.x.gtoreq.4.0 mass %, and (1)-2. the
concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a quadrilateral or triangle
having, as vertices, point C
(0.0435x.sup.2+1.4652x+42.543/-0.3726x+13.406/100-R1234ze-R32-R12-
5), point D (0.097x.sup.2+0.6802x+44.628/0.0/100-R1234ze-R32-R125),
point F (-0.8143x+64.967/0.0/100-R1234ze-R32-R125), and point E
(-0.0061x.sup.2-0.7393x+64.254/0.1631x+8.9386/100-R1234ze-R32-R125),
excluding the line segment DF; and
[0028] refrigerant B having a composition ratio in which
(2)-1. 8.9 mass %>x>8.3 mass %, and (2)-2. the concentration
of R32, R125, and CF.sub.3I (concentration of R32 (mass
%)/concentration of R125 (mass %)/concentration of CF.sub.3I (mass
%)) is within the range of a triangle having, as vertices, point G
(0.1667x+56.3/2.7778x.sup.2-64.944x+357.98/100-R1234ze-R32-R125),
point D (1.5625x.sup.2-24.938x+155.98/0.0/100-R1234ze-R32-R125),
and point F (-0.6667x+63.733/0.0/100-R1234ze-R32-R125), excluding
the line segment DF.
[0029] 8. The composition according to any one of Items 1 to 7, for
use as a working fluid for a refrigerating machine, wherein the
composition further comprises a refrigeration oil.
[0030] 9. The composition according to any one of Items 1 to 8, for
use as an alternative refrigerant for R410A.
[0031] 10. Use of the composition according to any one of Items 1
to 8 as an alternative refrigerant for R410A.
[0032] 11. A refrigerating machine comprising the composition
according to any one of Items 1 to 9 as a working fluid.
[0033] 12. A method for operating a refrigerating machine,
comprising circulating the composition according to any one of
Items 1 to 9 as a working fluid in a refrigerating machine.
Advantageous Effects of Invention
[0034] The refrigerant according to the present disclosure has four
types of performance, i.e., an excellent coefficient of performance
(COP) and refrigerating capacity that allow it to serve as an
alternative refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Therefore, the refrigerant and composition
comprising the same according to the present disclosure are useful,
for example, as working fluids for refrigerating machines.
BRIEF DESCRIPTION OF DRAWINGS
[0035] FIG. 1 is a schematic diagram of an apparatus used for a
non-flammability test of refrigerants.
[0036] FIG. 2 is a view showing the formulation of refrigerant 2 of
the present invention in a ternary composition diagram in which the
sum of R32, R125, and CF.sub.3I is 100 mass % falling within the
range of a figure surrounded by line segments EF, FD, DX, and XE
that connect 4 points E, F, D, and X (excluding the line segment
FD).
[0037] FIG. 3 is a view showing the formulation of refrigerant A of
the present invention in a ternary composition diagram in which the
sum of HFO-1132(E), CF.sub.3I, and R32 is 100 mass % falling within
the range of a figure surrounded by line segments JH, HY, and YJ
that connect 3 points Y, J, and H (excluding the line segment
JH).
[0038] FIG. 4 is a view showing the formulation of refrigerant of
the present invention in a ternary composition diagram in which the
sum of HFO-1123, CF.sub.3I, and R32 is 100 mass % falling within
the range of a figure surrounded by line segments ZN, NL, and LZ
that connect 3 points Z, N, and L (excluding the line segment
NL).
[0039] FIG. 5 is a view showing the formulation of refrigerant 6 of
the present invention in a ternary composition diagram in which the
total concentration of R32, R125, CF.sub.3I, and HFO-1234yf is 100
mass %, the concentration of HFO-1234yf is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %, when x=6 mass %; that is, the formulation falls within the
range of a quadrilateral having, as vertices, points C, D, F, and E
(excluding the line segment DF).
[0040] FIG. 6 is a view showing the formulation of refrigerant 6 of
the present invention in a ternary composition diagram in which the
total concentration of R32, R125, CF.sub.3I, and HFO-1234yf is 100
mass %, the concentration of HFO-1234yf is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %, when x=9 mass %; that is, the formulation falls within the
range of a quadrilateral having, as vertices, points C, D, F, and E
(excluding the line segment DF).
[0041] FIG. 7 is a view showing the formulation of refrigerant 6 of
the present invention in a ternary composition diagram in which the
total concentration of R32, R125, CF.sub.3I, and HFO-1234yf is 100
mass %, the concentration of HFO-1234yf is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %, when x=11.7 mass %; that is, the formulation falls within
the range of a triangle having, as vertices, points C (=E=G), D,
and F (excluding the line segment DF).
[0042] FIG. 8 is a view showing the formulation of refrigerant 6 of
the present invention in a ternary composition diagram in which the
total concentration of R32, R125, CF.sub.3I, and HFO-1234yf is 100
mass %, the concentration of HFO-1234yf is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %, when x=12.1 mass %; that is, the formulation falls within
the range of a triangle having, as vertices, points G, D, and F
(excluding the line segment DF).
[0043] FIG. 9 is a view showing that in a ternary composition
diagram in which the total concentration of R32, R125, CF.sub.3I,
and HFO-1234yf is 100 mass %, the concentration of HFO-1234yf is x
mass %, and the total concentration of R32, R125, and CF.sub.3I is
represented by (100-x) mass %, when x=12.6 mass %, the formulation
converges to point D (=F=G). Here, point D does not correspond to
refrigerant 6 of the present invention.
[0044] FIG. 10 is a view showing the formulation of refrigerant 7
of the present invention in a ternary composition diagram in which
the total concentration of R32, R125, CF.sub.3I, and HFO-1234ze is
100 mass %, the concentration of HFO-1234ze is x mass %, and the
total concentration of R32, R125, and CF.sub.3I is represented by
(100-x) mass %, when x=4 mass %; that is, the formulation falls
within the range of a quadrilateral having, as vertices, points C,
D, F, and E (excluding the line segment DF).
[0045] FIG. 11 is a view showing the formulation of refrigerant 7
of the present invention in a ternary composition diagram in which
the total concentration of R32, R125, CF.sub.3I, and HFO-1234ze is
100 mass %, the concentration of HFO-1234ze is x mass %, and the
total concentration of R32, R125, and CF.sub.3I is represented by
(100-x) mass %, when x=6 mass %; that is, the formulation falls
within the range of a quadrilateral having, as vertices, points C,
D, F, and E (excluding the line segment DF).
[0046] FIG. 12 is a view showing the formulation of refrigerant 7
of the present invention in a ternary composition diagram in which
the total concentration of R32, R125, CF.sub.3I, and HFO-1234ze is
100 mass %, the concentration of HFO-1234ze is x mass %, and the
total concentration of R32, R125, and CF.sub.3I is represented by
(100-x) mass %, when x=8.3 mass %; that is, the formulation falls
within the range of a triangle having, as vertices, points C
(=E=G), D, and F (excluding the line segment DF).
[0047] FIG. 13 is a view showing the formulation of refrigerant 7
of the present invention in a ternary composition diagram in which
the total concentration of R32, R125, CF.sub.3I, and HFO-1234ze is
100 mass %, the concentration of HFO-1234ze is x mass %, and the
total concentration of R32, R125, and CF.sub.3I is represented by
(100-x) mass %, when x=8.6 mass %; that is, the formulation falls
within the range of a triangle having, as vertices, points G, D,
and F (excluding the line segment DF).
[0048] FIG. 14 is a view showing that in a ternary composition
diagram in which the total concentration of R32, R125, CF.sub.3I,
and HFO-1234ze is 100 mass %, the concentration of HFO-1234ze is x
mass %, and the total concentration of R32, R125, and CF.sub.3I is
represented by (100-x) mass %, when x=8.9 mass %, the formulation
converges to point D (=F=G). Here, point D does not correspond to
refrigerant 7 of the present invention.
DESCRIPTION OF EMBODIMENTS
[0049] The present inventors conducted intensive studies to solve
the above problem, and consequently found that a refrigerant having
a specific formulation comprising trifluoroiodomethane (CF.sub.3I)
has the properties described above.
[0050] The present disclosure has been completed as a result of
further research based on this finding. The present disclosure
includes the following embodiments.
DEFINITION OF TERMS
[0051] In the present disclosure, the term "refrigerant" includes
at least compounds that are specified in ISO 817 (International
Organization for Standardization), and that are given a refrigerant
number (ASHRAE number) representing the type of refrigerant with
"R" at the beginning; and further includes refrigerants that have
properties equivalent to those of such refrigerants, even though a
refrigerant number is not yet given. Refrigerants are broadly
divided into fluorocarbon compounds and non-fluorocarbon compounds
in terms of the structure of the compounds. Fluorocarbon compounds
include chlorofluorccarbons (CFC), hydrochlorofluorocarbons (HCFC),
and hydrofluorocarbons (HFC). Non-fluorocarbon compounds include
propane (R290), propylene (R1270), butane (R600), isobutane
(R600a), carbon dioxide (R744), ammonia (R717), and the like.
[0052] In the present disclosure, the phrase "composition
comprising a refrigerant" at least includes (1) a refrigerant
itself (including a mixture of refrigerants), (2) a composition
that further comprises other components and that can be mixed with
at least a refrigeration oil to obtain a working fluid for a
refrigerating machine, and (3) a working fluid for a refrigerating
machine containing a refrigeration oil. In the present
specification, of these three embodiments, the composition (2) is
referred to as a "refrigerant composition" so as to distinguish it
from a refrigerant itself (including a mixture of refrigerants).
Further, the working fluid for a refrigerating machine (3) is
referred to as a "refrigeration oil-containing working fluid" so as
to distinguish it from the "refrigerant composition."
[0053] In the present disclosure, when the term "alternative" is
used in a context in which the first refrigerant is replaced with
the second refrigerant, the first type of "alternative" means that
equipment designed for operation using the first refrigerant can be
operated using the second refrigerant under optimum conditions,
optionally with changes of only a few parts (at least one of the
following: refrigeration oil, gasket, packing, expansion valve,
dryer, and other parts) and equipment adjustment. In other words,
this type of alternative means that the same equipment is operated
with an alternative refrigerant. Embodiments of this type of
"alternative" include "drop-in alternative," "nearly drop-in
alternative," and "retrofit," in the order in which the extent of
changes and adjustment necessary for replacing the first
refrigerant with the second refrigerant is smaller.
[0054] The term "alternative" also includes a second type of
"alternative," which means that equipment designed for operation
using the second refrigerant is operated for the same use as the
existing use with the first refrigerant by using the second
refrigerant. This type of alternative means that the same use is
achieved with an alternative refrigerant.
[0055] In the present disclosure, the term "refrigerating machine"
refers to machines in general that draw heat from an object or
space to make the temperature thereof lower than the temperature of
ambient air, and maintain a low temperature. In other words,
refrigerating machines refer to conversion machines that gain
energy from the outside to do work, and that perform energy
conversion, in order to transfer heat from where the temperature is
lower to where the temperature is higher.
[0056] In the present disclosure, the term "non-flammable" means
that, among refrigerant allowable concentrations, the worst case of
formulation for flammability (WCF) is determined to be classified
as "Class 1 (i.e., WCF non-flammable)" or ASHRAE non-flammable
according to the US ANSI/ASHRAE Standard 34-2013.
[0057] The non-flammability is determined based on the measurement
equipment and measurement method of the flammability test according
to ASTM E681-2009. The measurement is specifically carried out in
the following manner.
[0058] A spherical glass flask with an internal volume of 12 liters
shown in FIG. 1 is used so that the state of combustion can be
visually observed and video-recorded. The glass flask is configured
so that gas is released from the upper lid when excessive pressure
is generated by combustion. Ignition is generated by discharge from
electrodes held at a height of 1/3 from the bottom. The test
conditions are as follows.
Test Conditions
[0059] Test container: 280 mm-diameter spherical shape (internal
volume: 12 liters) Test temperature: 60.degree. C..+-.3.degree. C.
Pressure: 101.3 kPa.+-.0.7 kPa Water content: 0.0088 g.+-.0.0005 g
per gram of dry air Binary refrigerant composition/air mixture
ratio: 1 vol. % increment .+-.0.2 vol. % Binary refrigerant
composition mixture: .+-.0.1 mass % Ignition method: AC discharge,
voltage 15 kV, current 30 mA, neon transformer Electrode spacing:
6.4 mm (1/4 inch) Spark: 0.4 seconds.+-.0.05 seconds Determination
criteria: [0060] When the flame spreads at 90 degrees or more
around the ignition point=flammable (propagation) [0061] When the
flame spreads at less than 90 degrees around the ignition point=no
flame propagation (non-flammable)
1. Refrigerant
1.1 Refrigerant Component
[0062] The refrigerants according to the present disclosure can be
roughly classified into Embodiments 1 to 7 (also referred to as
refrigerants 1 to 7, respectively). All of refrigerants 1 to 7 have
four types of performance, i.e., an excellent coefficient of
performance and refrigerating capacity that allow them to serve as
alternative refrigerants for R410A, a sufficiently low GWP, and
non-flammability. Therefore, refrigerants 1 to 7 and the
compositions comprising the same according to the present
disclosure are useful, for example, as working fluids for
refrigerating machines. Refrigerants 1 to 7 are described
below.
Embodiment 1: Refrigerant 1
[0063] Refrigerant 1 according to the present disclosure comprises
trifluoroiodomethane (CF.sub.3I) and difluoromethane (R32), wherein
the contents of CF.sub.3I and R32 in the refrigerant are
respectively 48 mass %.gtoreq.CF.sub.3I.gtoreq.46 mass % and 54
mass %.gtoreq.R32.gtoreq.52 mass %, based on the total amount of
CF.sub.3I and R32 taken as 100 mass %. That is, refrigerant 1 is a
mixed refrigerant.
[0064] Refrigerant 1 has four types of performance, i.e., an
excellent coefficient of performance and refrigerating capacity
that allow it to serve as an alternative refrigerant for R410A, a
sufficiently low GWP, and non-flammability. Specifically,
refrigerant 1 has a coefficient of performance of 98% or more
relative to R32, a refrigerating capacity of 95% or mere relative
to R32, a GWP of 750 or less (particularly 400 or less), and ASHRAE
non-flammability performance.
[0065] Refrigerant 1 comprises CF.sub.3I and R32, and the contents
of CF.sub.3I and R32 in the refrigerant are respectively 48 mass
%.gtoreq.CF.sub.3I.gtoreq.46 mass % and 54 mass
%.gtoreq.R32.gtoreq.52 mass % based on the total amount of
CF.sub.3I and R32 taken as 100 mass %. Further, the total amount of
CF.sub.3I and R32 in the entire refrigerant is preferably 99.5 mass
% or more, more preferably 99.7 mass % or more, and most preferably
99.9 mass % or more. Examples of components other than CF.sub.3I
and R32 in the entire refrigerant include by-products that may be
inevitably contained during the production of CF.sub.3I and
R32.
[0066] The ASHRAE non-flammability limit of CF.sub.3I and R32 was
confirmed by the following procedure.
[0067] A leak test during storage, shipping, and use was simulated
based on ANSI/ASHRAE Standard 34-2013 using Refprop 9.0 to
determine the initial mixture formulation in which the worst case
of fractionation for flammability (WCFF) became the
non-flammability limit formulation of CF.sub.3I and R32
(CF.sub.3I/R32)=(35 mass %/65 mass %); the method for determination
thereof is described in Embodiment 6. As a result, the initial
mixture formulation was (CF.sub.3I/R32)=(46 mass %/54 mass %). This
mixture formulation is the ASHRAE non-flammability limit.
Embodiment 2: Refrigerant 2
[0068] Refrigerant 2 according to the present disclosure comprises
trifluoroiodomethane (CF.sub.3I), difluoromethane (R32), and
pentafluoroethane (R125), wherein when the mass % of R32, R125, and
CF.sub.3I based on their sum is respectively represented by x, y,
and z, coordinates (x,y,z) in a ternary composition diagram in
which the sum of R32, R125, and CF.sub.3I is 100 mass % are within
the range of a figure surrounded by line segments EF, FD, DX, and
XE that connect the following 4 points:
point E (53.7, 11.0, 35.3), point F (51.6, 0.0, 48.4) point D
(65.0. 0.0, 35.0), and point X (64.6. 8.9, 26.5), excluding the
line segment FD,
[0069] the line segment EF is represented by coordinates (x,
-1.1255x.sup.r+123.76x-3389.3, 1.1255x.sup.2-124.76x+3489.3),
and
[0070] the line segments FD, DX, and XE are straight lines.
That is, refrigerant 2 is a mixed refrigerant.
[0071] When the above requirements are satisfied, refrigerant 2 has
four types of performance, i.e., an excellent coefficient of
performance and refrigerating capacity that allow it to serve as an
alternative refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, refrigerant 2 has a coefficient of
performance of 98% or more relative to R32, a refrigerating
capacity of 95% or more relative to R32, a GWP of 750 or less
(particularly 600 or less), and WCF non-flammability
performance.
[0072] Refrigerant 2 comprises R32, R125, and CF.sub.3I. In
particular, the total amount of R32, R125, and CF.sub.3I in the
entire refrigerant is preferably 99.5 mass % or more, more
preferably 99.7 mass % or more, and most preferably 99.9 mass % or
more. Examples of components other than R32, R125, and CF.sub.3I in
the entire refrigerant include by-products that may be inevitably
contained during the production of R32, R125, and CF.sub.3I.
Embodiment 3: Refrigerant 3
[0073] Refrigerant 3 according to the present disclosure comprises
trifluoroiodomethane (CF.sub.3I) and trans-1,2-difluoroethylene
(HFO-1132(E)), wherein the contents of CF.sub.3I and HFO-1132(E) in
the refrigerant are respectively 68 mass
%.gtoreq.CF.sub.3I.gtoreq.62 mass % and 38 mass
%.gtoreq.HFO-1132(E).gtoreq.32 mass %, based on the total amount of
CF.sub.3I and HFO-1132 (E) taken as 100 mass %. That is,
refrigerant 3 is a mixed refrigerant.
[0074] Refrigerant 3 has four types of performance, i.e., an
excellent coefficient of performance and refrigerating capacity
that allow it to serve as an alternative refrigerant for R410A, a
sufficiently low GWP, and non-flammability. Specifically,
refrigerant 3 has a coefficient of performance of 100% or more
(particularly 105% or more) relative to R410A, a refrigerating
capacity of 65% or more relative to R410A, a GWP of 1 or less, and
WCF non-flammability performance.
[0075] Refrigerant 3 comprises CF.sub.3I and HFO-1132(E), and the
contents of CF.sub.3I and HFO-1132(E) in the refrigerant are
respectively 68 mass %.gtoreq.CF.sub.3I.gtoreq.62 mass % and 38
mass %.gtoreq.HFO-1132(E).gtoreq.32 mass %, based on the total
amount of CF.sub.3I and HFO-1132(E) taken as 100 mass %. Further,
the total amount of CF.sub.3I and HFO-1132(E) in the entire
refrigerant is preferably 99.5 mass % or more, more preferably 99.7
mass % or more, and most preferably 99.9 mass % or more. Examples
of components other than CF.sub.3I and HFO-1132(E) in the entire
refrigerant include by-products that may be inevitably contained
during the production of CF.sub.3I and HFO-1132(E).
Embodiment 4: Refrigerant 4
[0076] Refrigerant 4 according to the present disclosure comprises
trifluoroiodomethane (CF.sub.3I), difluoromethane (R32), and
trans-1,2-difluoroethylene (HFO-1132(E)), wherein when the mass %
of HFO-1132 (E), CF.sub.3I, and R32 based on their sum is
respectively represented by x, y, and z, coordinates (x,y,z) in a
ternary composition diagram in which the sum of HFO-1132 (E),
CF.sub.3I, and R32 is 100 mass % are within the range of a figure
surrounded by line segments JH, HY, and YJ that connect the
following 3 points:
point Y (32.5, 58.1, 9.4), point J (0.0. 77.2, 22.8), and point H
(0.0. 35.0, 65.0), excluding the line segment JH,
[0077] the line segment YJ is represented by coordinates (x,
-0.0027x.sup.2-0.5002x+77.2, 0.0027x.sup.2-0.4998x+22.8), and
[0078] the line segments JH and HY are straight lines.
That is, refrigerant 4 is a mixed refrigerant.
[0079] When the above requirements are satisfied, refrigerant 4 has
four types of performance, i.e., an excellent coefficient of
performance and refrigerating capacity that allow it to serve as an
alternative refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, refrigerant 4 has a coefficient of
performance of 99% or more relative to R32, a refrigerating
capacity of 80% or more relative to R32, a GWP of 750 or less
(particularly 450 or less), and WCF non-flammability
performance.
[0080] Refrigerant 4 comprises HFO-1132 (E), CF.sub.3I, and R32. In
particular, the total amount of HFO-1132 (E), CF.sub.3I, and R32 in
the entire refrigerant is preferably 99.5 mass % or more, more
preferably 99.7 mass % or more, and most preferably 99.9 mass % or
more. Examples of components other than HFO-1132(E), CF.sub.3I, and
R32 in the entire refrigerant include by-products that may be
inevitably contained during the production of HFO-1132(E),
CF.sub.3I, and R32.
Embodiment 5: Refrigerant 5
[0081] Refrigerant 5 according to the present disclosure comprises
trifluoroiodomethane (CF.sub.3I), difluoromethane (R32), and
trifluoroethylene (HFO-1123), wherein when the mass % of HFO-1123,
CF.sub.3I, and R32 based on their sum is respectively represented
by x, y, and z, coordinates (x,y,z) in a ternary composition
diagram in which the sum of HFO-1123, CF.sub.3I, and R32 is 100
mass % are within the range of a figure surrounded by line segments
ZN, NL, and LZ that connect the following 3 points:
point Z (41.6, 53.5, 4.9), point N (0.0. 77.2, 22.8), and point L
(0.0. 35.0, 65.0), excluding the line segment NL,
[0082] the line segment ZN is represented by coordinates (x,
-0.0007x.sup.2-0.5402x+77.2, 0.0007x.sup.2-0.4598x+22.8), and
[0083] the line segments NL and LZ are straight lines.
That is, refrigerant 5 is a mixed refrigerant.
[0084] When the above requirements are satisfied, refrigerant has
four types of performance, i.e., an excellent coefficient of
performance and refrigerating capacity that allow it to serve as an
alternative refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, refrigerant 5 has a coefficient of
performance of 99% or more relative to R32, a refrigerating
capacity of 80% or more relative to R32, a GWP of 750 or less
(particularly 450 or less), and WCF non-flammability
performance.
[0085] Refrigerant 5 comprises HFO-1123, CF.sub.3I, and R32. In
particular, the total amount of HFO-1123, CF.sub.3I, and R32 in the
entire refrigerant is preferably 99.5 mass % or more, more
preferably 99.7 mass % or more, and most preferably 99.9 mass % or
more. Examples of components other than HFO-1123, CF.sub.3I, and
R32 in the entire refrigerant include by-products that may be
inevitably contained during the production of HFO-1123, CF.sub.3I,
and R32.
Embodiment 6: Refrigerant 6
[0086] Refrigerant 6 according to the present disclosure comprises
difluoromethane (R32), pentafluoroethane (R125),
trifluoroiodomethane (CF.sub.3I), and 2, 3,3,3-tetrafluoroethylene
(HFO-1234yf), and refrigerant 6 comprises one of the following
refrigerants A and B:
[0087] in a ternary composition diagram in which the total
concentration of R32, R125, CF.sub.3I, and HFO-1234yf is 100 mass
%, the concentration of HFO-1234yf is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %,
[0088] refrigerant A having a composition ratio in which
(1)-1-11.7 mass %.gtoreq.x.gtoreq.6.0 mass %, and (1)-2. the
concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a quadrilateral or triangle
having, as vertices, point C
(1.1753x+41.14/-0.2282x+13.464/100-R1234yf-R32-R125), point D
(0.0247x.sup.2+0.563x+43.733/0.0/100-R1234yf-R32-R125), point F
(-0.8069x+64.948/0.0/100-R1234yf-R32-R125), and point E
(-0.8247x+64.54/0.1581x+8.96/100-R1234yf-R32-R125), excluding the
line segment DF; and
[0089] refrigerant B having a composition ratio in which
(2)-1. 12.6 mass %.gtoreq.x.gtoreq.11.7 mass %, and (2)-2. the
concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a triangle having, as vertices,
point G
(-1.2222x.sup.2+29.589x-123.98/20.5x.sup.2-510.15x+3173.3/100-R1234yf-R32-
-R125), point D (1.2213x+39.415/0.0/100-R1234yf-R32-R125), and
point F (0.7787x+64.615/0.0/100-R1234yf-R32-R125), excluding the
line segment DF. That is, refrigerant 6 is a mixed refrigerant.
[0090] When the above requirements are satisfied in the case in
which the concentration x of HFO-1234yfx is (1) 11.7 mass
%.gtoreq.x.gtoreq.6.0 mass % or (2) 12.6 mass %>x.gtoreq.11.7
mass %, refrigerant 6 has four types of performance, i.e., an
excellent coefficient of performance and refrigerating capacity
that allow it to serve as an alternative refrigerant for R410A, a
sufficiently low GWP, and non-flammability. Specifically,
refrigerant 6 has a coefficient of performance of 100% or more
relative to R410A, a refrigerating capacity of 100% or more
relative to R410A, a GWP of 750 or less, and WCF non-flammability
performance.
[0091] Refrigerant 6 comprises R32, R125, CF.sub.3I, and
HFO-1234yf. In particular, the total amount of R32, R125,
CF.sub.3I, and HFO-1234yf in the entire refrigerant is preferably
99.5 mass % or more, more preferably 99.7 mass % or more, and most
preferably 99.9 mass % or more. Examples of components other than
R32, R125, CF.sub.3I, and HFO-1234yf in the entire refrigerant
include by-products that may be inevitably contained during the
production of R32, R125, CF.sub.3I, and HFO-1234yf.
[0092] The following describes the methods for determining points
A, B, C, D, E, F, and G, which are classified according to the
range of x. The technical meanings of points A, B, C, D, E, F, and
G are as follows. Further, the concentration at each point is a
value obtained in the Examples of Embodiment 6 (refrigerant 6)
described later.
A: a composition ratio in which GWP=750, and the concentration of
CF.sub.3I (mass %) is 0.0 mass % B: a composition ratio in which
GWP=750, and the concentration of R32 (mass %) is 0.0 mass % C: a
composition ratio in which the refrigerating capacity relative to
R410A is 100% (a refrigerating capacity of 100% relative to R410A),
and GWP=750 D: a composition ratio in which the refrigerating
capacity relative to R410A is 100% (a refrigerating capacity of
100% relative to R410A), and the concentration of R125 (mass %) is
0.0 mass % E: a WCF non-flammable composition ratio in which
GWP=750 F: a WCF non-flammable composition ratio in which the
concentration of R125 (mass %) is 0.0 mass % G: a WCF non-flammable
composition ratio in which the refrigerating capacity relative to
R410A is 100% (a refrigerating capacity of 100% relative to
R410A)
(1) Method for Determining Points C, D, E, F, and G
(1-1) Point C
[0093] 11.7 Mass %.gtoreq.x.gtoreq.6.0 Mass %
[0094] When the concentration of HFO-1234yf is 6.0 mass %, point C
on a ternary composition diagram in which the total concentration
of R32, R125, and CF.sub.3I is (100-x) mass % is concentration of
R32 (mass %)/concentration of R125 (mass %)/concentration of
CF.sub.3I (mass %)=(48.2/12.1/33.7);
[0095] when the concentration of HFO-1234yf is 9.0 mass %, point C
on the ternary composition diagram in which the total concentration
of R32, R125, and CF.sub.3I is (100-x) mass % is concentration of
R32 (mass %)/concentration of R125 (mass %)/concentration of
CF.sub.3I (mass %)=(51.7/11.4/27.9); and
[0096] when the concentration of HFO-1234yf is 11.7 mass %, point C
on the ternary composition diagram in which the total concentration
of R32, R125, and CF.sub.3I is (100-x) mass % is (concentration of
R32 (mass %)/concentration of R125 (mass %)/concentration of
CF.sub.3I (mass %))=(54.9/10.8/22.6).
[0097] Therefore, when the total concentration of R32, R125,
CF.sub.3I, and HFO-1234yf is 100 mass %, assuming that the
concentration of R32 is y mass %, the equation of the regression
line obtained from the above three points plotted in the xy
coordinates is represented by y=1.1753x+41.14.
[0098] Moreover, assuming that the concentration of R125 is y mass
%, the equation of the regression line obtained in the same manner
is represented by y=-0.2282x+13.464.
[0099] Therefore, the concentration of CF.sub.3I at point C is
(100-R1234yf-R32-R125).
[0100] Form the above, point C on the ternary composition diagram
in which the total concentration of R32, R125, and CF.sub.3I is
(100-x) (concentration of R32 (mass %)/concentration of R125 (mass
%)/concentration of CF.sub.3I (mass %)) is represented by
(1.1753x+41.14/-0.2282x+13.464/100-R1234yf-R32-R125).
12.6 Mass %.gtoreq.x>11.7 Mass %
[0101] The same calculation was performed for the above range of x.
Table 1 below shows the results of point C (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) for each concentration range of x.
TABLE-US-00001 TABLE 1 Point C Item 11.7 .gtoreq. R1234yf .gtoreq.
6.0 12.6 .gtoreq. R1234yf .gtoreq. 11.7 R1234yf 6.0 9.0 11.7 11.7
12.1 12.6 R32 48.2 51.7 54.9 54.9 55.5 56.4 R125 12.1 11.4 10.8
10.8 10.7 10.5 CF3I 33.7 27.9 22.6 22.6 21.7 20.4 R1234yf x x R32
approximate 1.1753x + 41.14 1.6721x + 35.311 expression R125
approximate -0.2282x + 13.464 -0.3361x + 14.744 expression CF3I
approximate 100-R1234yf-R32-R125 100-R1234yf-R32-R125
expression
(1-2) Points D, E, F, and G
[0102] Points D, E, F, and G were determined below in the same
manner as in the case of point C. The results are shown in Tables 2
to 5 below.
TABLE-US-00002 TABLE 2 Point D Item 11.7 .gtoreq. R1234yf .gtoreq.
6.0 12.6 .gtoreq. R1234yf .gtoreq. 11.7 R1234yf 6.0 9.0 11.7 11.7
12.1 12.6 R32 48.0 50.8 53.7 53.7 54.8 54.8 R125 0 0 0 0 0 0 CF3I
46.0 40.2 34.6 34.6 32.6 32.6 R1234yf x x R32 approximate 0.0247x2
+ 0.563x + 43.733 1.2213x + 39.415 expression R125 approximate 0 0
expression CF3I approximate 100-R1234yf-R32-R125
100-R1234yf-R32-R125 expression
TABLE-US-00003 TABLE 3 Point E Item 11.7 .gtoreq. R1234yf .gtoreq.
6.0 12.6 .gtoreq. R1234yf .gtoreq. 11.7 R1234yf 6.0 9.0 11.7 11.7
12.1 12.6 R32 59.6 57.1 54.9 54.9 54.6 54.2 R125 9.9 10.4 10.8 10.8
10.9 10.9 CF3I 24.5 23.5 22.6 22.6 22.4 22.3 R1234yf x x R32
approximate -0.8247x + 64.54 -0.7787x + 64.015 expression R125
approximate 0.1581x + 8.96 0.1066x + 9.5738 expression CF3I
approximate 100-R1234yf-R32-R125 100-R1234yf-R32-R125
expression
TABLE-US-00004 TABLE 4 Point F Item 11.7 .gtoreq. R1234yf .gtoreq.
6.0 12.6 .gtoreq. R1234yf .gtoreq. 11.7 R1234yf 6.0 9.0 11.7 11.7
12.1 12.6 R32 60.1 57.7 55.5 55.5 55.2 54.8 R125 0 0 0 0 0 0 CF3I
33.9 33.3 32.8 32.8 32.7 32.6 R1234yf x x R32 approximate -0.8069x
+ 64.948 -0.7787x + 64.615 expression R125 approximate 0 0
expression CF3I approximate 100-R1234yf-R32-R125
100-R1234yf-R32-R125 expression
TABLE-US-00005 TABLE 5 Point G Item 12.6 .gtoreq. R1234yf .gtoreq.
11.7 R1234yf 11.7 12.1 12.6 R32 54.9 55.1 54.8 R125 10.8 1.9 0 CF3I
22.6 30.9 32.6 R1234yf x R32 approximate -1.2222x2 + 29.589x -
123.98 expression R125 approximate 20.5x2 - 510.15x + 3173.3
expression CF3I approximate 100 - R1234ze - R32 - R125
expression
[0103] On the ternary composition diagram in which the total
concentration of R32, R125, and CF.sub.3I is (100-x), a set of
points with GWP=7500 is represented by a straight line connecting
points A and B, which are presented as functions of x when
HFO-1234yf=x. For example, on the ternary composition diagrams of
FIGS. 5 to 9, GWP is 750 or less in the regions on the vertex side
of CF.sub.3I with respect to the straight line.
[0104] Further, on the ternary composition diagram in which the
total concentration of R32, R125, and CF.sub.3I is (100-x), a set
of points with a refrigerating capacity of 100% relative to R410A
is approximated to a straight line connecting points C and D, which
are presented as functions of x when HFO-1234yf=x. For example, on
the ternary composition diagrams of FIGS. 5 to 9, the refrigerating
capacity relative to R410A is 100% or mere in the regions on the
vertex side of R32 with respect to the approximate line.
[0105] Moreover, on the ternary composition diagram in which the
total concentration of R32, R125, and CF.sub.3I is (100-x), a set
of points with WCF non-flammability is approximated to a straight
line connecting points E and F, which are presented as functions of
x when HFO-1234yf=x. For example, on the ternary composition
diagrams of FIGS. 5 to 9, it is WCF non-flammable in the regions on
the vertex side of CF.sub.3I with respect to the approximate
line.
Non-Flammability Limit (Identification of Line Segment EF)
[0106] First, the non-flammability limit of a binary mixed
refrigerant of a flammable refrigerant (R32, 1234yf) and a
non-flammable refrigerant (CF.sub.3I, R125) was identified.
[0107] The non-flammability limit of the binary mixed refrigerant
was determined based on the measurement equipment and measurement
method of the flammability test according to ASTM E681-2009
(details are as described above).
[0108] As a result, in the mixed refrigerant of flammable
refrigerant R32 and non-flammable refrigerant CF.sub.3I, no flame
propagation was observed from R32=65.0 wt % and CF.sub.3I=35.0 wt
%, and this formulation was regarded as the non-flammability limit.
Further, no flame propagation was observed from R32=63.0 wt % and
R125=37.0 wt % in the mixed refrigerant of flammable refrigerant
R32 and non-flammable refrigerant R125, from 1234yf=80.0 wt % and
CF.sub.3I=20.0 wt % in the mixed refrigerant of flammable
refrigerant 1234yf and non-flammable refrigerant CF.sub.3I, and
from 1234yf=79.0 wt % and R125=21.0 wt % in the mixed refrigerant
of flammable refrigerant 1234yf and non-flammable refrigerant R125.
These formulations were regarded as the non-flammability limits.
The results are summarized in Table 6.
TABLE-US-00006 TABLE 6 Flammable Non-flammable Item refrigerant
refrigerant Combination in binary mixed refrigerant R32 CF3I
Non-flammability limit (wt. %) 65.0 35.0 Combination in binary
mixed refrigerant R32 R125 Non-flammability limit (wt. %) 63.0 37.0
Combination in binary mixed refrigerant 1234yf CF3I
Non-flammability limit (wt. %) 80.0 20.0 Combination in binary
mixed refrigerant 1234yf R125 Non-flammability limit (wt. %) 79.0
21.0
[0109] Points E and F showing the non-flammability limit were
identified in such a manner that in the relationships of
R32-equivalent flammable refrigerant
concentration=R32+(63/37)*(21/79)*R1234yf and R32-equivalent
non-flammable refrigerant
concentration=(63/37)*R125+(65/35)*CF.sub.3I, a case in which
R32-equivalent flammable refrigerant concentration-non-flammable
refrigerant concentration<0 was determined to be non-flammable,
and a case in which R32-equivalent flammable refrigerant
concentration-non-flammable refrigerant concentration>0 was
determined to be flammable.
[0110] Table 7 shows the details of points E and F. Line segment EF
is a regression line connecting these two points E and F.
TABLE-US-00007 TABLE 7 Flammable Non-flammable refrigerant
refrigerant concentration concentration Flammability - in terms of
in terms of non- R32 R125 CF3I R1234yf R32 R32 flammability mass %
mass % mass % mass % mass % mass % mass % Determination Point E
59.6 9.9 24.5 6.0 62.316 62.357 -0.041 Non-flammable 59.7 9.9 24.4
6.0 62.416 62.171 0.245 Flammable 57.1 10.4 23.5 9.0 61.174 61.351
-0.177 Non-flammable 57.2 10.4 23.4 9.0 61.274 61.165 0.108
Flammable 54.9 10.8 22.6 11.7 60.196 60.361 -0.165 Non-flammable
55.0 10.8 22.5 11.7 60.296 60.175 0.121 Flammable 54.6 10.9 22.4
12.1 60.077 60.159 -0.083 Non-flammable 54.5 10.9 22.3 12.1 59.977
59.974 0.003 Flammable 54.2 10.9 22.3 12.6 59.903 59.974 -0.071
Non-flammable 54.3 10.9 22.2 12.6 60.003 59.788 0.215 Flammable
Point F 60.1 0 33.9 6 62.816 62.957 -0.141 Non-flammable 60.2 0
33.8 6 62.916 62.771 0.144 Flammable 57.7 0 33.3 9 61.774 61.843
-0.069 Non-flammable 57.8 0 33.2 9 61.874 61.657 0.216 Flammable
55.5 0 32.8 11.7 60.796 60.914 -0.119 Non-flammable 55.6 0 32.7
11.7 60.896 60.729 0.167 Flammable 55.2 0 32.7 12.1 60.677 60.729
-0.052 Non-flammable 55.3 0 32.6 12.1 60.777 60.543 0.234 Flammable
54.8 0 32.6 12.6 60.503 60.543 -0.040 Non-flammable 54.9 0 32.5
12.6 60.603 60.357 0.246 Flammable
Embodiment 7: Refrigerant 7
[0111] Refrigerant 7 according to the present disclosure comprises
difluoromethane (R32), pentafluoroethane (R125),
trifluoroiodomethane (CF.sub.3I), and 1,3,3,3-tetrafluoropropene
(HFO-1234ze), and refrigerant 7 comprises at least one of the
following refrigerants A and B:
[0112] in a ternary composition diagram in which the total
concentration of R32, R125, CF.sub.3I, and HFO-1234ze is 100 mass
%, the concentration of HFO-1234ze is x mass %, and the total
concentration of R32, R125, and CF.sub.3I is represented by (100-x)
mass %,
[0113] refrigerant A having a composition ratio in which
(1)-1. 8.3 mass %.gtoreq.x.gtoreq.4.0 mass %, and (1)-2. the
concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a quadrilateral or triangle
having, as vertices, point C
(0.0435x.sup.2+1.4652x+42.543/-0.3726x+13.406/100-R1234ze-R32-R12-
5), point D (0.097x.sup.2+0.6302x+44.628/0.0/100-R1234ze-R32-R125),
point F (-0.8143x+64.967/0.0/100-R1234ze-R32-R125), and point E
(-0.0061x.sup.2-0.7393x+64.254/0.1631x+8.9386/100-R1234ze-R32-R125),
excluding the line segment DF; and
[0114] refrigerant B having a composition ratio in which
(2)-1. 8.9 mass %>x.gtoreq.8.3 mass %, and (2)-2. the
concentration of R32, R125, and CF.sub.3I (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) is within the range of a triangle having, as vertices,
point G
(0.1667x+56.3/2.7778x.sup.2-64.944x+357.98/100-R1234ze-R32-R125),
point D (1.5625x.sup.2-24.938x+155.98/0.0/100-R1234ze-R32-R125),
and point F (-0.6667x+63.733/0.0/100-R1234ze-R32-R125), excluding
the line segment DF. That is, refrigerant 7 is a mixed
refrigerant.
[0115] When the above requirements are satisfied in the case in
which the concentration x of HFO-1234ze is (1) 8.3 mass
%.gtoreq.x.gtoreq.4.0 mass % or (2) 8.9 mass %>x.gtoreq.8.3 mass
%, refrigerant 7 has four types of performance, i.e., an excellent
coefficient of performance and refrigerating capacity that allow it
to serve as an alternative refrigerant for R410A, a sufficiently
low GWP, and non-flammability. Specifically, refrigerant 7 has a
coefficient of performance of 100% or more relative to R410A, a
refrigerating capacity of 100% or more relative to R410A, a GWP of
750 or less, and WCF non-flammability performance.
[0116] Refrigerant 7 comprises R32, R125, CF.sub.3I, and
HFO-1234ze. In particular, the total amount of R32, R125,
CF.sub.3I, and HFO-1234ze in the entire refrigerant is preferably
99.5 mass % or more, more preferably 99.7 mass % or more, and most
preferably 99.9 mass % or more. Examples of components other than
R32, R125, CF.sub.3I, and HFO-1234ze in the entire refrigerant
include by-products that may be inevitably contained during the
production of R32, R125, CF.sub.3I, and HFO-1234ze.
[0117] The following describes the methods for determining points
A, B, C, D, E, F, and G, which are classified according to the
range of x. The technical meanings of points A, B, C, D, E, F, and
G are as follows. Further, the concentration at each point is a
value obtained in the Examples of Embodiment 7 (refrigerant 7)
described later.
A: a composition ratio in which GWP=750, and the concentration of
CF.sub.3I (mass %) is 0.0 mass % B: a composition ratio in which
GWP=750, and the concentration of R32 (mass %) is 0.0 mass % C: a
composition ratio in which the refrigerating capacity relative to
R410A is 100% (a refrigerating capacity of 100% relative to R410A),
and GWP=750 D: a composition ratio in which the refrigerating
capacity relative to R410A is 100% (a refrigerating capacity of
100% relative to R410A), and the concentration of R125 (mass %) is
0.0 mass % E: a WCF non-flammable composition ratio in which
GWP=750 F: a WCF non-flammable composition ratio in which the
concentration of R125 (mass %) is 0.0 mass % G: a WCF non-flammable
composition ratio in which the refrigerating capacity relative to
R410A is 100% (a refrigerating capacity of 100% relative to
R410A)
(1) Method for Determining Points C, D, E, F, and G
(1-1) Point C
[0118] 8.3 Mass %.gtoreq.x.gtoreq.4.0 Mass %
[0119] When the concentration of HFO-1234ze is 4.0 mass %, point C
on a ternary composition diagram in which the total concentration
of R32, R125, and CF.sub.3I is (100-x) mass % is concentration of
R32 (mass %)/concentration of R125 (mass %)/concentration of
CF.sub.3I (mass %)=(49.1/11.9/35.0);
[0120] when the concentration of HFO-1234yf is 6.0 mass %, point C
on the ternary composition diagram in which the total concentration
of R32, R125, and CF.sub.3I is (100-x) mass % is concentration of
R32 (mass %)/concentration of R125 (mass %)/concentration of
CF.sub.3I (mass %)=(52.9/11.2/29.9); and
[0121] when the concentration of HFO-1234yf is 8.3 mass %, point C
on the ternary composition diagram in which the total concentration
of R32, R125, and CF.sub.3I is (100-x) mass % is (concentration of
R32 (mass %)/concentration of R125 (mass %)/concentration of
CF.sub.3I (mass %)=(57.7/10.3/23.7).
[0122] Therefore, when the total concentration of R32, R125,
CF.sub.3I, and HFO-1234ze is 100 mass %, assuming that the
concentration of R32 is y mass %, the equation of the regression
line obtained from the above three points plotted in the xy
coordinates is represented by y=0.0435x.sup.2+1.4652x+42.543.
[0123] Moreover, assuming that the concentration of R125 is y mass
%, the equation of the regression line obtained in the same manner
is represented by y=-0.3726x+13.462.
[0124] Therefore, the concentration of CF.sub.3I at point C is
(100-R1234ze-R32-R125).
[0125] From the above, point C on the ternary composition diagram
in which the total concentration of R32, R125, and CF.sub.3I is
(100-x) (concentration of R32 (mass %)/concentration of R125 (mass
%)/concentration of CF.sub.3I (mass %)) is represented by
(0.0435x.sup.2+1.4652x+42.543/-0.3726x+13.462/100-R1234ze-R32-R125).
8.9 Mass %.gtoreq.x>8.3 Mass %
[0126] The same calculation was performed for the above range of x.
Table 8 below shows the results of point C (concentration of R32
(mass %)/concentration of R125 (mass %)/concentration of CF.sub.3I
(mass %)) for each concentration range of x.
TABLE-US-00008 TABLE 8 Point C Item 8.3 .gtoreq. R1234ze .gtoreq.
4.0 8.9 .gtoreq. R1234ze .gtoreq. 8.3 R1234ze 4.0 6.0 8.3 8.3 8.6
8.9 R32 49.1 52.9 57.7 57.7 58.4 59.1 R125 11.9 11.2 10.3 10.3 10.1
10.0 CF3I 35.0 29.9 23.7 23.7 22.9 22.0 R1234ze x x R32 approximate
0.0435x2 + 1.4652x + 42.543 2.3333x + 38.333 expression R125
approximate -0.3726x + 13.406 -0.5x + 14.433 expression CF3I
approximate 100-R1234ze-R32-R125 100-R1234ze-R32-R125
expression
(1-2) Points D, E, F, and G
[0127] Points D, E, F, and G were determined below in the same
manner as in the case of point C. The results are shown in Tables 9
to 12 below.
TABLE-US-00009 TABLE 9 Point D Item 8.3 .gtoreq. R1234ze .gtoreq.
4.0 8.9 .gtoreq. R1234ze .gtoreq. 8.3 R1234ze 4.0 6.0 8.3 8.3 8.6
8.9 R32 48.9 52.2 56.5 56.5 57.1 57.8 R125 0 0 0 0 0 0 CF3I 47.1
41.8 35.4 35.4 34.3 33.3 R1234ze x x R32 approximate 0.097x2 +
0.6802x + 44.628 1.5625x2 - 24.938x + 155.98 expression R125
approximate 0 0 expression CF3I approximate 100-R1234ze-R32-R125
100-R1234ze-R32-R125 expression
TABLE-US-00010 TABLE 10 Point E Item 8.3 .gtoreq. R1234ze .gtoreq.
4.0 8.9 .gtoreq. R1234ze .gtoreq. 8.3 R1234ze 4.0 6.0 8.3 8.3 8.6
8.9 R32 61.2 59.6 57.7 57.7 57.4 57.2 R125 9.6 9.9 10.3 10.3 10.3
10.3 CF3I 25.2 24.5 23.7 23.7 23.7 23.6 R1234ze x x R32 approximate
-0.0061x2 - 0.7393x + 64.254 0.5556x2 - 10.389x + 105.66 expression
R125 approximate 0.1631x + 8.9386 10.3 expression CF3I approximate
100-R1234ZS-R32-R125 100-R1234ze-R32-R125 expression
TABLE-US-00011 TABLE 11 Point F Item 8.3 .gtoreq. R1234ze .gtoreq.
4.0 8.9 .gtoreq. R1234ze .gtoreq. 8.3 R1234ze 4.0 6.0 8.3 8.3 8.6
8.9 R32 61.7 60.1 58.2 58.2 58 57.8 R125 0 0 0 0 0 0 CF3I 34.3 33.9
33.5 33.5 33.4 33.3 R1234ze x x R32 approximate -0.8143X + 64.967
-0.6667x + 63.733 expression R125 approximate 0 0 expression CF3I
approximate 100-R1234ze-R32-R125 100-R1234ze-R32-R125
expression
TABLE-US-00012 TABLE 12 Point G Item 8.9 .gtoreq. R1234ze .gtoreq.
8.3 R1234ze 8.3 8.6 8.9 R32 57.7 57.7 57.8 R125 10.3 4.9 0 CF3I
23.7 28.8 33.3 R1234ze x R32 approximate 0.1667x + 56.3 expression
R125 approximate 2.7778x2 - 64.944x + 357.98 expression CF3I
approximate 100 - R1234ze - R32 - R125 expression
[0128] On the ternary composition diagram in which the total
concentration of R32, R125, and CF.sub.3I is (100-x), a set of
points with GWP=7500 is represented by a straight line connecting
points A and B, which are presented as functions of x when
HFO-1234ze=x. For example, on the ternary composition diagrams of
FIGS. 10 to 14, the GWP is 750 or less in the regions on the vertex
side of CF.sub.3I with respect to the straight line.
[0129] Further, on the ternary composition diagram in which the
total concentration of R32, R125, and CF.sub.3I is (100-x), a set
of points with a refrigerating capacity of 100% relative to R410A
is approximated to a straight line connecting points C and D, which
are presented as functions of x when HFO-1234ze=x. For example, on
the ternary composition diagrams of FIGS. 10 to 14, the
refrigerating capacity relative to R410A is 100% or more in the
regions on the vertex side of R32 with respect to the approximate
straight line.
[0130] Moreover, on the ternary composition diagram in which the
total concentration of R32, R125, and CF.sub.3I is (100-x), a set
of points with WCF non-flammability is approximated to a straight
line connecting points E and F, which are presented as functions of
x when HFO-1234ze=x. For example, on the ternary composition
diagrams of FIGS. 10 to 14, it is WCF non-flammable in the regions
on the vertex side of CF.sub.3I with respect to the approximate
line.
Non-Flammability Limit (Identification of Line Segment EF)
[0131] First, the non-flammability limit of a binary mixed
refrigerant of a flammable refrigerant (R32, 1234ze) and a
non-flammable refrigerant (CF.sub.3I, R125) was identified.
[0132] The non-flammability limit of the binary mixed refrigerant
was determined based on the measurement equipment and measurement
method of the flammability test according to ASTM E681-2009
(details are as described above).
[0133] As a result, in the mixed refrigerant of flammable
refrigerant R32 and non-flammable refrigerant CF.sub.3I, no flame
propagation was observed from R32=65.0 wt % and CF.sub.3I=35.0 wt
%, and this formulation was regarded as the non-flammability limit.
Further, no flame propagation was observed from R32=63.0 wt % and
R125=37.0 wt % in the mixed refrigerant of flammable refrigerant
R32 and non-flammable refrigerant R125, from 1234ze=80.0 wt % and
CF.sub.3I=20.0 wt % in the mixed refrigerant of flammable
refrigerant 1234ze and non-flammable refrigerant CF.sub.3I, and
from 1234yf=79.0 wt % and R125=21.0 wt % in the mixed refrigerant
of flammable refrigerant 1234ze and non-flammable refrigerant R125.
These formulations were regarded as the non-flammability limits.
The results are summarized in Table 13.
TABLE-US-00013 TABLE 13 Flammable Non-flammable Item refrigerant
refrigerant Combination in binary mixed refrigerant R32 CF3I
Non-flammability limit (wt. %) 65.0 35.0 Combination in binary
mixed refrigerant R32 R125 Non-flammability limit (wt. %) 63.0 37.0
Combination in binary mixed refrigerant 1234ze CF3I
Non-flammability limit (wt. %) 80.0 20.0 Combination in binary
mixed refrigerant 1234ze R125 Non-flammability limit (wt. %) 79.0
21.0
[0134] Points E and F showing the non-flammability limit were
identified in such a manner that in the relationships of
R32-equivalent flammable refrigerant=R32+(63/37)*(21/79)*R1234ze
and R32-equivalent non-flammable refrigerant
concentration=(63/37)*R125+(65/35)*CF.sub.3I, a case in which
R32-equivalent flammable refrigerant concentration-non-flammable
refrigerant concentration<0 was determined to be non-flammable,
and a case in which R32-equivalent flammable refrigerant
concentration-non-flammable refrigerant concentration>0 was
determined to be flammable.
[0135] Table 14 shows the details of points E and F. Line segment
EF is a regression line connecting these two points E and F.
TABLE-US-00014 TABLE 14 Flammable Non-flammable refrigerant
refrigerant concentration concentration Flammability - in terms of
in terms of non- R32 R125 CF3I R1234ze R32 R32 flammability mass %
mass % mass % mass % mass % mass % mass % Determination Point E
61.2 9.6 25.2 4.0 63.010 63.146 -0.135 Non-flammable 61.3 9.6 25.1
4.0 63.110 62.960 0.150 Flammable 59.6 9.9 24.5 6.0 62.316 62.357
-0.041 Non-flammable 59.7 9.9 24.4 6.0 62.416 62.171 0.245
Flammable 57.7 10.3 23.7 8.3 61.457 61.552 -0.095 Non-flammable
57.8 10.3 23.6 8.3 61.557 61.366 0.190 Flammable 57.4 10.3 23.7 8.6
61.293 61.552 -0.260 Non-flammable 57.5 10.3 23.6 8.6 61.393 61.366
0.026 Flammable 57.2 10.3 23.6 8.9 61.228 61.366 -0.138
Non-flammable 57.3 10.3 23.5 8.9 61.328 61.181 0.148 Flammable
Point F 61.7 0 34.3 4 63.510 63.700 -0.190 Non-flammable 61.8 0
34.2 4 63.610 63.514 0.096 Flammable 60.1 0 33.9 6 62.816 62.957
-0.141 Non-flammable 60.2 0 33.8 6 62.916 62.771 0.144 Flammable
58.2 0 33.5 8.3 61.957 62.214 -0.258 Non-flammable 58.3 0 33.4 8.3
62.057 62.029 0.028 Flammable 58 0 33.4 8.6 61.893 62.029 -0.136
Non-flammable 58.1 0 33.3 8.6 61.993 61.843 0.150 Flammable 57.8 0
33.4 8.9 61.828 62.029 -0.200 Non-flammable 57.9 0 33.3 8.9 61.928
61.843 0.085 Flammable
1.2. Use
[0136] The refrigerant according to the present disclosure can be
preferably used as a working fluid in a refrigerating machine.
[0137] The composition according to the present disclosure is
suitable for use as an alternative refrigerant for R410A.
2. Refrigerant Composition
[0138] The refrigerant composition according to the present
disclosure comprises at least the refrigerant according to the
present disclosure, and can be used for the same use as the
refrigerant according to the present disclosure. Moreover, the
refrigerant composition according to the present disclosure can be
further mixed with at least a refrigeration oil to thereby obtain a
working fluid for a refrigerating machine.
[0139] The refrigerant composition according to the present
disclosure further comprises at least one other component in
addition to the refrigerant according to the present disclosure.
The refrigerant composition according to the present disclosure may
comprise at least one of the following other components, if
necessary. As described above, when the refrigerant composition
according to the present disclosure is used as a working fluid in a
refrigerating machine, it is generally used as a mixture with at
least a refrigeration oil. Therefore, it is preferable that the
refrigerant composition according to the present disclosure does
not substantially comprise a refrigeration oil. Specifically, in
the refrigerant composition according to the present disclosure,
the content of the refrigeration oil based on the entire
refrigerant composition is preferably 0 to 1 mass %, and more
preferably 0 to 0.1 mass %.
2.1. Water
[0140] The refrigerant composition according to the present
disclosure may contain a small amount of water. The water content
of the refrigerant composition is preferably 0 to 0.1 mass %, more
preferably 0 to 0.075 mass %, even more preferably 0 to 0.05 mass
%, and particularly preferably 0 to 0.025 mass %, based on the
entire refrigerant.
[0141] A small amount of water contained in the refrigerant
composition stabilizes double bonds in the molecules of unsaturated
fluorocarbon compounds that can be present in the refrigerant, and
makes it less likely that the unsaturated fluorocarbon compounds
will be oxidized, thus increasing the stability of the refrigerant
composition. From the viewpoint of obtaining the above effect due
to inclusion of 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 %, or 0.001 to 0.025 mass %.
2.2. Tracer
[0142] A tracer is added to the refrigerant composition according
to the present disclosure at a detectable concentration such that
when the refrigerant composition has been diluted, contaminated, or
undergone other changes, the tracer can trace the changes.
[0143] The refrigerant composition according to the present
disclosure may comprise a single tracer, or two or more
tracers.
[0144] The tracer is not limited, and can be suitably selected from
commonly used tracers. It is preferable to select, as the tracer, a
compound that cannot become an impurity inevitably mixed in the
refrigerant according to the present disclosure.
[0145] Examples of tracers include hydrofluorocarbons,
hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons,
fluorocarbons, deuterated hydrocarbons, deuterated
hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated
compounds, iodinated compounds, alcohols, aldehydes, ketones, and
nitrous oxide (N.sub.2O). The tracer is particularly preferably a
hydrofluorocarbon, a hydrochlorofluorocarbon, a chlorofluorocarbon,
a hydrochlorocarbon, a fluorocarbon, or a fluoroether.
[0146] Specifically, the following compounds are preferable as the
tracer.
FC-14 (tetrafluoromethane, CF.sub.4) HCC-40 (chloromethane,
CH.sub.3Cl) HFC-23 (trifluoromethane, CHF.sub.3) HFC-41
(fluoromethane, CH.sub.3Cl) HFC-125 (pentafluoroethane,
CF.sub.3CHF.sub.2) HFC-134a (1,1,1,2-tetrafluoroethane,
CF.sub.3CH.sub.2F) HFC-134 (1,1,2,2-tetrafluoroethane,
CHF.sub.2CHF.sub.2) HFC-143a (1,1,1-trifluoroethane,
CF.sub.3CH.sub.3) HFC-143 (1,1,2-trifluoroethane,
CHF.sub.2CH.sub.2F) HFC-152a (1,1-difluoroethane,
CHF.sub.2CH.sub.3) HFC-152 (1,2-difluoroethane, CH.sub.2FCH.sub.2F)
HFC-lol (fluoroethane, CH.sub.3CH.sub.2F) HFC-245fa
(1,1,1,3,3-pentafluoropropane, CF.sub.3CH.sub.2CHF.sub.2) HFC-236fa
(1,1,1,3,3,3-hexafluoropropane, CF.sub.3CH.sub.2CF.sub.3) HFC-236ea
(1,1,1,2,3,3-hexafluoropropane, CF.sub.3CHFCHF.sub.2) HFC-227ea
(1,1,1,2,3,3,3-heptafluoropropane, CF.sub.3CHFCF.sub.3) HCFC-22
(chlorodifluoromethane, CHClF.sub.2) HCFC-31 (chlorofluoromethane,
CH.sub.2ClF) CFC-1113 (chlorotrifluoroethylene, CF.sub.2.dbd.CClF)
HFE-125 (trifluoromethyl-difluoromethyl ether, CF.sub.3OCHF.sub.2)
HFE-134a (trifluoromethyl-fluoromethyl ether, CF.sub.3OCH.sub.2F)
HFE-143a (trifluoromethyl-methyl ether, CF.sub.3OCH.sub.3)
HFE-227ea (trifluoromethyl-tetrafluoroethyl ether,
CF.sub.3OCHFCF.sub.3) HFE-236fa (trifluoromethyl-trifluoroethyl
ether, CF.sub.3OCH.sub.2CF.sub.3)
[0147] The tracer compound may be present at a total concentration
of about 10 parts per million by weight (ppm) to about 1000 ppm in
the refrigerant composition. The tracer compound is preferably
present at a total concentration of about ppm to about 500 ppm, and
most preferably about 50 ppm to about 300 ppm, in the refrigerant
composition.
2.3. Ultraviolet Fluorescent Dye
[0148] The refrigerant composition according to the present
disclosure may comprise a single ultraviolet fluorescent dye, or
two or more ultraviolet fluorescent dyes.
[0149] The ultraviolet fluorescent dye is not limited, and can be
suitably selected from commonly used ultraviolet fluorescent
dyes.
[0150] Examples of ultraviolet fluorescent dyes include
naphthalimide, coumarin, anthracene, phenanthrene, xanthene,
thioxanthene, naphthoxanthene, fluorescein, and derivatives
thereof. The ultraviolet fluorescent dye is particularly preferably
either naphthalimide or coumarin, or both.
2.4. Stabilizer
[0151] The refrigerant composition according to the present
disclosure may comprise a single stabilizer, or two or more
stabilizers.
[0152] The stabilizer is not limited, and can be suitably selected
from commonly used stabilizers.
[0153] Examples of stabilizers include nitro compounds, ethers, and
amines.
[0154] Examples of nitro compounds include aliphatic nitro
compounds, such as nitronethane and nitroethane; and aromatic nitro
compounds, such as nitro benzene and nitro styrene.
[0155] Examples of ethers include 1,4-dioxane.
[0156] Examples of amines include 2,2,3,3,3-pentafluoropropylamine
and diphenylamine.
[0157] Examples of stabilizers also include butylhydroxyxylene and
benzotriazole.
[0158] The content of the stabilizer is not limited. Generally, the
content of the stabilizer is preferably 0.01 to 5 mass %, and more
preferably 0.05 to 2 mass %, based on the entire refrigerant.
2.5. Polymerization Inhibitor
[0159] The refrigerant composition according to the present
disclosure may comprise a single polymerization inhibitor, or two
or more polymerization inhibitors.
[0160] The polymerization inhibitor is not limited, and can be
suitably selected from commonly used polymerization inhibitors.
[0161] Examples of polymerization inhibitors include
4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether,
dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and
benzotriazole.
[0162] The content of the polymerization inhibitor is not limited.
Generally, the content of the polymerization inhibitor is
preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %,
based on the entire refrigerant.
3. Refrigeration Oil-Containing Working Fluid
[0163] The refrigeration oil-containing working fluid according to
the present disclosure comprises at least the refrigerant or
refrigerant composition according to the present disclosure and a
refrigeration oil, for use as a working fluid in a refrigerating
machine. Specifically, the refrigeration oil-containing working
fluid according to the present disclosure is obtained by mixing a
refrigeration oil used in a compressor of a refrigerating machine
with the refrigerant or the refrigerant composition. The
refrigeration oil-containing working fluid generally comprises 10
to 50 mass % of refrigeration oil.
3.1. Refrigeration Oil
[0164] The composition according to the present disclosure may
comprise a single refrigeration oil, or two or more refrigeration
oils.
[0165] The refrigeration oil is not limited, and can be suitably
selected from commonly used refrigeration oils. In this case,
refrigeration oils that are superior in the action of increasing
the miscibility with the mixture and the stability of the mixture,
for example, are suitably selected as necessary.
[0166] The base oil of the refrigeration oil is preferably, for
example, at least one member selected from the group consisting of
polyalkylene glycols (PAG), polyol esters (POE), and polyvinyl
ethers (PVE).
[0167] The refrigeration oil may further contain additives in
addition to the base oil. The additive may be at least one member
selected from the group consisting of antioxidants,
extreme-pressure agents, acid scavengers, oxygen scavengers, copper
deactivators, rust inhibitors, oil agents, and antifoaming
agents.
[0168] A refrigeration oil with a kinematic viscosity of 5 to 400
cSt at 40.degree. C. is preferable from the standpoint of
lubrication.
[0169] The refrigeration oil-containing working fluid according to
the present disclosure may further optionally contain at least one
additive. Examples of additives include the compatibilizing agents
described below.
3.2. Compatibilizing Agent
[0170] The refrigeration oil-containing working fluid according to
the present disclosure may comprise a single compatibilizing agent,
or two or more compatibilizing agents.
[0171] The compatibilizing agent is not limited, and can be
suitably selected from commonly used compatibilizing agents.
[0172] Examples of compatibilizing agents include polyoxyalkylene
glycol ethers, amides, nitriles, ketones, chlorocarbons, esters,
lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes.
The compatibilizing agent is particularly preferably a
polyoxyalkylene glycol ether.
4. Method for Operating Refrigerating Machine
[0173] The method for operating a refrigerating machine according
to the present disclosure is a method for operating a refrigerating
machine using the refrigerant according to the present
disclosure.
[0174] Specifically, the method for operating a refrigerating
machine according to the present disclosure comprises circulating
the refrigerant according to the present disclosure in a
refrigerating machine.
[0175] The embodiments are described above; however, it will be
understood that various changes in forms and details can be made
without departing from the spirit and scope of the claims.
EXAMPLES
[0176] The present disclosure is described in more detail below
with reference to Examples. However, the present disclosure is not
limited to the Examples.
[0177] In the Examples and Comparative Examples, the GWP of mixed
refrigerants was evaluated based on the values stated in the
Intergovernmental Panel on Climate Change (IPCC), fourth report.
The GWP of HFO-1132(E), which was not stated therein, was assumed
to be 1 from HFO-1132a (GWP=1 or less) and HFO-1123 (GWP=0.3,
described in PTL 1). The refrigerating capacity of the mixed
refrigerants was determined by performing theoretical refrigeration
cycle calculations for the mixed refrigerants using the National
Institute of Science and Technology (NIST) and Reference Fluid
Thermodynamic and Transport Properties Database (Refprop 9.0) under
the following conditions.
Evaporating temperature: 5.degree. C. Condensation temperature:
45.degree. C. Superheating temperature: 5K Subcooling temperature:
5K Compressor efficiency: 70%
[0178] Further, the coefficient of performance (COP) of the mixed
refrigerants was calculated according to the following
equation.
COP=(refrigerating capacity or heating capacity)/amount of
electrical power consumed
Examples and Comparative Examples of Embodiment 1 (Refrigerant
1)
[0179] Mixed refrigerants were prepared by mixing R32 and CF.sub.3I
at mass % shown in Table 15 based on the sum of them.
TABLE-US-00015 TABLE 15 Evaluation results COP Temper- Flammable/
Example/ Composition ratio (%) Refrigerating ature non- Comparative
ratio (mass %) (relative capacity ratio (%) glide flammable Example
CF3I HFC-32 GWP to R32) (relative to R32) (K) (ASHRAE) Comparative
0 100 675 100 100 0 Slightly Example 1 flammable Comparative 40 60
405 98.3 97.1 0.2 Slightly Example 2 flammable Comparative 41 59
399 98.3 96.9 0.2 Slightly Example 3 flammable Comparative 42 58
392 98.3 96.7 0.2 Slightly Example 4 flammable Comparative 43 57
385 98.2 96.5 0.3 Slightly Example5 flammable Comparative 44 56 378
98.2 96.2 0.3 Slightly Example 6 flammable Comparative 45 55 372
98.2 96.0 0.4 Slightly Example 7 flammable Example 1 46 54 365 98.1
95.7 0.4 Non- flammable Example 2 47 53 358 98.1 95.4 0.5 Non-
flammable Example 3 48 52 351 98.1 95.1 0.6 Non- flammable
Comparative 49 51 345 98.0 94.8 0.7 Non- Example8 flammable
Comparative 50 50 338 98.0 94.4 0.8 Non- Example 9 flammable
Comparative 100 0 1 109.5 31.1 0.0 Non- Example 10 flammable
[0180] Due to the predetermined formulation, refrigerant 1 has four
types of performance, i.e., an excellent coefficient of performance
and refrigerating capacity that allow it to serve as an alternative
refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, it was revealed that the mixed
refrigerants of Examples 1 to 3, which were specific examples of
refrigerant 1, had a coefficient of performance of 98% or more
relative to R32, a refrigerating capacity of 95% or more relative
to R32, a GWP of 750 or less (particularly 400 or less), and ASHRAE
non-flammability performance.
Examples and Comparative Examples of Embodiment 2 (Refrigerant
2)
[0181] Mixed refrigerants were prepared by mixing R32, R125, and
CF.sub.3I at mass % shown in Table 16 based on the sum of them.
TABLE-US-00016 TABLE 16 Evaluation results COP Temper- Flammable/
Example/ Composition ratio (%) Refrigerating ature non- Comparative
ratio (mass %) (relative capacity ratio (%) glide flammable Example
Point CF3I HFC-32 HFC-125 GWP to R32) (relative to R32) (K) (WCF)
Comparative 0 100 0 675 100 100 0 Slightly Example 1 flammable
Comparative A 2.6 97.4 0 750 99.9 99.7 0.0 Slightly Example 11
flammable Comparative B 0 21.4 78.6 750 105.6 45.9 11.0 Non-
Example 12 flammable Comparative C 0 63.0 37.0 1720 98.5 94.3 1.0
Non- Example 13 flammable Example 4 D 35.0 65.0 0 439 98.5 97.9 0.1
Non- flammable Example 5 X 26.5 64.6 8.9 750 98.4 97.1 0.1 Non-
flammable Example 6 E 35.3 53.7 11.0 750 98.0 95.0 0.2 Non-
flammable Example 7 40.3 52.7 7.0 601 98.0 95.0 0.3 Non- flammable
Example 8 F 48.4 51.6 0 349 98.1 95.0 0.6 Non- flammable Example 9
36.5 53.5 10.0 711 98.0 95.0 0.3 Non- flammable Comparative 20.0
70.0 10.0 823 98.7 97.6 0.0 Slightly Example 14 flammable
[0182] Due to the predetermined formulation, refrigerant 2 has four
types of performance, i.e., an excellent coefficient of performance
and refrigerating capacity that allow it to serve as an alternative
refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, it was revealed that the mixed
refrigerants of Examples 4 to 9, which were specific examples of
refrigerant 2, had a coefficient of performance of 98% or more
relative to R32, a refrigerating capacity of 95% or more relative
to R32, a GWP of 750 or less (particularly 600 or less), and WCF
non-flammability performance.
Examples and Comparative Examples of Embodiment 3 (Refrigerant
3)
[0183] Mixed refrigerants were prepared by mixing HFO-1132(E) and
CF.sub.3I at mass % shown in Table 17 based on the sum of them.
TABLE-US-00017 TABLE 17 Evaluation results Composition COP Temper-
Flammable/ Example/ ratio (mass %) ratio (%) Refrigerating ature
non- Comparative E-HFO- (relative capacity ratio (%) glide
flammable Example CF3I 1132 GWP to R410A) (relative to R410A) (K)
(WCF) Comparative HFC-32 = 100 675 102.4 109.8 0 Slightly Example 1
flammable Comparative R410A 2088 100 100 0.1 Non- Example 15
flammable Comparative 0 100 1 97.8 97.6 0 Weakly Example 15
flammable Comparative 60 40 1 105.6 69.0 1.0 Slightly Example 16
flammable Comparative 61 39 1 105.7 68.4 9.6 Slightly Example 17
flammable Example 10 62 38 1 105.9 67.7 9.7 Non- flammable Example
11 63 37 1 106.1 67.1 9.8 Non- flammable Comparative 64 36 1 106.2
66.4 9.9 Non- Example 12 flammable Example 13 65 35 1 106.4 65.7
10.0 Non- flammable Example 14 66 34 1 106.6 65.0 10.0 Non-
flammable Comparative 67 33 1 106.8 64.4 10.1 Non- Example 18
flammable Comparative 68 32 1 106.9 63.6 10.2 Non- Example 19
flammable Comparative 69 31 1 107.1 62.9 10.2 Non- Example 20
flammable Comparative 70 30 1 107.3 62.2 10.3 Non- Example 21
flammable Comparative 100 0 1 112.1 34.1 0.0 Non- Example 10
flammable
[0184] Due to the predetermined formulation, refrigerant 3 has four
types of performance, i.e., an excellent coefficient of performance
and refrigerating capacity that allow it to serve as an alternative
refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, it was revealed that the mixed
refrigerants of Examples 10 to 14, which were specific examples of
refrigerant 3, had a coefficient of performance of 100% or more
(particularly 105% or more) relative to R410A, a refrigerating
capacity of 65% or more relative to R410A, a GWP of 1 or less, and
WCF non-flammability performance.
Examples and Comparative Examples of Embodiment 4 (Refrigerant
4)
[0185] Mixed refrigerants were prepared by mixing R32, HFO-1132(E),
and CF.sub.3I at mass % shown in Table 18 based on the sum of
them.
TABLE-US-00018 TABLE 18 Evaluation results Composition COP Temper-
Flammable/ Example/ ratio (mass %) ratio (%) Refrigerating ature
non- Comparative E-HFO- (relative capacity ratio (%) glide
flammable Example Point CF3I 1132 HFC-32 GWP to R32) (relative to
R32) (K) (WCF) Comparative 0 0 100 675 100 100 0 Slightly Example 1
flammable Comparative 0 100 0 1 97.8 97.6 0 Weakly Example 15
flammable Comparative G 62 38 0 1 105.9 67.7 9.7 Non- Example 22
flammable Example 15 H 35 0 65 439 100.8 107.5 0.1 Non- flammable
Comparative I 40.6 59.4 0 1 102.4 80.0 6.6 Slightly Example 23
flammable Example 16 Y 58.1 32.5 9.4 64 102.6 80.0 11.7 Non-
flammable Example 17 67.8 17.2 15 102 102.6 80.0 13.7 Non-
flammable Example 18 J 77.2 0 22.8 155 100.2 80.0 13.1 Non-
flammable Example 19 55 25 20 136 99.4 88.6 9.0 Non- flammable
Comparative 70 20 10 68 104.6 74.9 15.2 Non- Example 24 flammable
Comparative 40 30 30 203 97.5 99.7 4.1 Slightly Example 25
flammable
[0186] Due to the predetermined formulation, refrigerant 4 has four
types of performance, i.e., an excellent coefficient of performance
and refrigerating capacity that allow it to serve as an alternative
refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, it was revealed that the mixed
refrigerants of Examples 15 to 19, which were specific examples of
refrigerant 4, had a coefficient of performance of 99% or more
relative to R32, a refrigerating capacity of 80% or more relative
to R32, a GWP of 750 or less (particularly 450 or less), and WCF
non-flammability performance.
Examples and Comparative Examples of Embodiment 5 (Refrigerant
5)
[0187] Mixed refrigerants were prepared by mixing R32, HFO-1123,
and CF.sub.3I at mass % shown in Table 19 based on the sum of
them.
TABLE-US-00019 TABLE 19 Evaluation results COP Temper- Flammable/
Example/ Composition ratio (%) Refrigerating ature non- Comparative
ratio (mass %) (relative capacity ratio (%) glide flammable Example
Point CF3I HFO-1123 HFC-32 GWP to R32) (relative to R32) (K) (WCF)
Comparative 0 0 100 675 100 100 0 Slightly Example 1 flammable
Comparative 0 100 0 0.3 90.6 108.0 0 Slightly Example 26 flammable
Comparative K 45 55 0 0.7 103.0 73.9 12.8 Non- Example 27 flammable
Example 20 L 35 0 65 439 100.8 107.5 0.1 Non- flammable Comparative
M 46.5 53.5 0 0.6 101.0 80.0 11.4 Slightly Example 28 flammable
Example 21 Z 53.5 41.6 4.9 34 101.6 80.0 12.7 Non- flammable
Example 22 65.6 20.9 13.5 92 102.1 80.0 13.9 Non- flammable Example
23 N 77.2 0 22.8 155 100.2 80.0 13.1 Non- flammable Example 24 55
30 15 102 99.5 86.3 10.5 Non- flammable Comparative 70 20 10 68
104.3 75.0 16.2 Non- Example 29 flammable Comparative 40 40 20 136
96.8 96.6 5.8 Slightly Example 30 flammable
[0188] Due to the predetermined formulation, refrigerant 5 has four
types of performance, i.e., an excellent coefficient of performance
and refrigerating capacity that allow it to serve as an alternative
refrigerant for R410A, a sufficiently low GWP, and
non-flammability. Specifically, it was revealed that the mixed
refrigerants of Examples 20 to 24, which were specific examples of
refrigerant 5, had a coefficient of performance of 99% or more
relative to R32, a refrigerating capacity of 80% or more relative
to R32, a GWP of 750 or less (particularly 450 or less), and WCF
non-flammability performance.
Examples and Comparative Examples of Embodiment 6 (Refrigerant
6)
[0189] Mixed refrigerants were prepared by mixing R32, R125,
HFO-1234yf, and CF.sub.3I at mass % shown in Table 20 (R1234yf=6
mass %), Table 21 (R1234yf=9 mass %), Table 22 (R1234yf=11.7 mass
%), Table 23 (R1234yf=12.1 mass %), and Table 24 (R1234yf=12.6 mass
%) based on the sum of them.
TABLE-US-00020 TABLE 20 Comparative Comparative Comparative
Comparative Comparative Example 1 Example Example Example Example
Example Example Item Unit R410A A B C D E F R32 mass % 50 90.0 0.0
48.2 48.0 59.6 60.1 R125 mass % 50 4.0 21.4 12.1 0.0 9.9 0.0 CF3I
mass % 0 0.0 72.6 33.7 46.0 24.5 33.9 R1234yf mass % 0 6.0 6.0 6.0
6.0 6.0 6.0 COP ratio % 100 102 108 100 100 101 101 (relative to
R410A) Refrigerating % 100 107 50 100 100 103 104 capacity ratio
(relative to R410A) GWP -- 2088 750 750 750 325 750 406
Flammability Non- Flammable Non- Non- Non- Non- Non- flammable
flammable flammable flammable flammable flammable
TABLE-US-00021 TABLE 21 Comparative Comparative Comparative
Comparative Comparative Example 1 Example Example Example Example
Example Example Item Unit R410A A B C D E F R32 mass % 50 86.2 0.0
51.7 50.8 57.1 57.7 R125 mass % 50 4.8 21.4 11.4 0.0 10.4 0.0 CF3I
mass % 0 0.0 69.6 27.9 40.2 23.5 33.3 R1234yf mass % 0 9.0 9.0 9.0
9.0 9.0 9.0 COP ratio % 100 102 107 101 101 101 101 (relative to
R410A) Refrigerating % 100 106 50 100 100 102 102 capacity ratio
(relative to R410A) GWP -- 2088 750 750 750 344 750 390
Flammability Non- Flammable Non- Non- Non- Non- Non- flammable
flammable flammable flammable flammable flammable
TABLE-US-00022 TABLE 22 Comparative Comparative Comparative
Comparative Comparative Example 1 Example Example Example Example
Example Item Unit R410A A B C = E = G D F R32 mass % 50 82.9 0.0
54.9 537 55.5 R125 mass % 50 5.4 21.4 10.8 0.0 0.0 CF3I mass % 0
0.0 66.9 22.6 34.6 32.8 R1234yf mass % 0 11.7 11.7 11.7 11.7 117
COP ratio % 100 102 107 101 101 101 (relative to R410A)
Refrigerating % 100 105 49 100 100 101 capacity ratio (relative to
R410A) GWP -- 2088 750 750 750 363 375 Flammability Non- Flammable
Non- Non- Non- Non- flammable flammable flammable flammable
flammable
TABLE-US-00023 TABLE 23 Comparative Comparative Comparative
Comparative Comparative Example 1 Example Example Example Example
Example Example Example Item Unit R410A A B C D E F G R32 mass % 50
82.4 0.0 55.5 54.3 54.6 55.2 54.9 R125 mass % 50 5.5 21.4 10.7 0.0
10.9 0.0 5.4 CF3I mass % 0 0.0 65.9 21.7 33.6 22.4 32.7 27.6
R1234yf mass % 0 12.1 12.1 12.1 12.1 12.1 12.1 12.1 COP ratio % 100
102 107 101 101 101 101 101 (relative to R410A) Refrigerating % 100
105 49 100 100 100 100 100 capacity ratio (relative to R410A) GWP
-- 2088 750 750 750 367 750 373 560 Flammability Non- Flammable
Non- Non- Non- Non- Non- Non- flammable flammable flammable
flammable flammable flammable flammable
TABLE-US-00024 TABLE 24 Comparative Comparative Comparative
Comparative Example 1 Example Example Example Example Example Item
Unit R410A A B C D = F = G E R32 mass % 50 81.8 0.0 56.4 54.8 54.2
R125 mass % 50 5.6 21.4 10.5 0.0 10.9 CF3I mass % 0 0.0 65.9 20.5
326 22.3 R1234yf mass % 0 12.6 12.6 12.6 12.6 12.6 COP ratio % 100
102 107 101 101 101 (relative to R410A) Refrigerating % 100 105 49
100 100 99 capacity ratio (relative to R410A) GWP -- 2088 750 750
750 371 750 Flammability Non- Flammable Non- Non- Non- Non-
flammable flammable flammable flammable flammable
[0190] When the above requirements are satisfied in the case in
which the concentration x of HFO-1234yfx is (1) 11.7 mass
%.gtoreq.x.gtoreq.6.0 mass % or (2) 12.6 mass %>x.gtoreq.11.7
mass %, refrigerant 6 has four types of performance, i.e., an
excellent coefficient of performance and refrigerating capacity
that allow it to serve as an alternative refrigerant for R410A, a
sufficiently low GWP, and non-flammability. Specifically, it was
revealed that the mixed refrigerants of the Examples in the above
tables, which were specific examples of refrigerant 6, had a
coefficient of performance of 100% or more relative to R410A, a
refrigerating capacity of 100% or more relative to R410A, a GWP of
750 or less, and WCF non-flammability performance.
Examples and Comparative Examples of Embodiment 7 (Refrigerant
7)
[0191] Mixed refrigerants were prepared by mixing R32, R125,
HFO-1234ze, and CF.sub.3I at mass % shown in Table 25 (R1234ze=4
mass %), Table 26 (R1234ze=6 mass %), Table 27 (R1234ze=8.3 mass
%), Table 28 (R1234ze=8.6 mass %), and Table 29 (R1234ze=8.9 mass
%) based on the sum of them.
TABLE-US-00025 TABLE 25 Comparative Comparative Comparative
Comparative Comparative Example 1 Example Example Example Example
Example Example Item Unit R410A A B C D E F R32 mass % 50 92.4 0.0
49.1 48.9 61.2 61.7 R125 mass % 50 3.6 21.4 11.9 0.0 9.6 0.0 CF3I
mass % 0 0.0 74.6 35.0 47.1 25.2 34.3 R1234ze mass % 0 4.0 4.0 4.0
4.0 4.0 4.0 COP ratio (relative to % 100 102 108 100 100 101 101
R410A) Refrigerating % 100 107 49 100 100 103 104 capacity ratio
(relative to R41QA) GWP -- 2088 750 750 750 331 750 417
Flammability Non- Flammable Non- Non- Non- Non- Non- flammable
flammable flammable flammable flammable flammable
TABLE-US-00026 TABLE 26 Comparative Comparative Comparative
Comparative Comparative Example 1 Example Example Example Example
Example Example Item Unit R410A A B C D E F R32 mass % 50 90.0 0.0
52.9 52.2 59.6 60.1 R125 mass % 50 4.0 21.4 11.2 0.0 9.9 0.0 CF3I
mass % 0 0.0 72.6 29.9 41.8 24.5 33.9 R1234ze mass % 0 6.0 6.0 6.0
6.0 6.0 6.0 COP ratio % 100 102 108 101 101 101 101 (relative to
R410A) Refrigerating % 100 106 49 100 100 102 102 capacity ratio
(relative to R41QA) GWP -- 2088 750 750 750 353 750 406
Flammability Non- Flammable Non- Non- Non- Non- Non- flammable
flammable flammable flammable flammable flammable
TABLE-US-00027 TABLE 27 Comparative Comparative Comparative
Comparative Comparative Example 1 Example Example Example Example
Example fem Unit R410A A 8 C = E = G D F R32 mass % 50 87.4 0.0
57.5 56.5 58.2 R125 mass % 50 4.5 21.4 10.3 0.0 0.0 CF3I mass % 0
0.0 70.5 24.1 35.4 33.5 R1234ze mass % 0 8.3 8.3 8.3 8.3 8.3 COP
ratio % 100 102 108 101 101 101 (relative to R41QA) Refrigerating %
100 105 49 100 100 101 capacity ratio (relative to R410A) GWP --
2088 750 750 750 382 394 Flammability Non- Flammable Non- Non- Non-
Non- flammable flammable flammable flammable flammable
TABLE-US-00028 TABLE 28 Comparative Comparative Comparative
Comparative Comparative Example Example Example Example Example
Example Example Example Item Unit R410A A B C D E F G R32 mass % 50
86.7 0.0 58.4 57.1 57.4 58.0 57.7 R125 mass % 50 4.7 21.4 10.1 0.0
10.3 0.0 4.9 CF3I mass % 0 0.0 70.0 22.9 34.3 23.7 33.4 28.8
R1234ze mass % 0 8.6 8.6 8.6 8.6 8.6 8.6 8.6 COP ratio % 100 102
108 101 101 101 101 101 (relative to R410A) Refrigerating % 100 104
49 100 100 100 100 100 capacity ratio (relative to R410A) GWP --
2088 750 750 748 386 750 392 562 Flammability Non- Flammable Non-
Non- Non- Non- Non- Non- flammable flammable flammable flammable
flammable flammable flammable
TABLE-US-00029 TABLE 29 Comparative Comparative Comparative
Comparative Example 1 Example Example Example Example Example Item
Unit R410A A B C D = F = G E R32 mass % 50 86.4 0.0 59.1 57.8 57.2
R125 mass % 50 4.7 21.4 10.0 0.0 10.3 CF3I mass % 0 0.0 70.5 22.0
33.3 23.6 R1234ze mass % 0 8.9 8.1 8.9 8.9 8.9 COP ratio % 100 102
108 101 101 101 (relative to R410A) Refrigerating % 100 104 49 100
100 100 capacity ratio (relative to R410A) GWP -- 2088 750 750 750
391 750 Flammability Non- Flammable Non- Non- Non- Non- flammable
flammable flammable flammable flammable
[0192] When the above requirements are satisfied in the case in
which the concentration x of HFO-1234ze is (1) 8.3 mass
%.gtoreq.x.gtoreq.4.0 mass % or (2) 8.9 mass %>x.gtoreq.8.3 mass
%, refrigerant 7 has four types of performance, i.e., an excellent
coefficient of performance and refrigerating capacity that allow it
to serve as an alternative refrigerant for R410A, a sufficiently
low GWP, and non-flammability. Specifically, it was revealed that
the mixed refrigerants of the Examples in the above tables, which
were specific examples of refrigerant 7, had a coefficient of
performance of 100% or more relative to R410A, a refrigerating
capacity of 100% or more relative to R410A, a GWP of 750 or less,
and WCF non-flammability performance.
REFERENCE SIGNS LIST
[0193] 1: Ignition source [0194] 2: Sample inlet [0195] 3: Springs
[0196] 4: 12-liter glass flask [0197] 5: Electrodes [0198] 6:
Stirrer [0199] 7: Insulated chamber [0200] A: A composition ratio
in which GWP=750, and the concentration of CF.sub.3I (mass %) is
0.0 mass % [0201] B: A composition ratio in which GWP=750, and the
concentration of R32 (mass %) is 0.0 mass % [0202] C: A composition
ratio in which the refrigerating capacity relative to R410A is 100%
(a refrigerating capacity of 100% relative to R410A), and GWP=750
[0203] D: A composition ratio in which the refrigerating capacity
relative to R410A is 100% (a refrigerating capacity of 100%
relative to R410A), and the concentration of R125 (mass %) is 0.0
mass % [0204] E: A WCF non-flammable composition ratio in which
GWP=750 [0205] F: A WCF non-flammable composition ratio in which
the concentration of R125 (mass %) is 0.0 mass % [0206] G: A WCF
non-flammable composition ratio in which the refrigerating capacity
relative to R410A is 100% (a refrigerating capacity of 100%
relative to R410A)
* * * * *