U.S. patent application number 16/772409 was filed with the patent office on 2021-03-11 for coolant-containing composition, use for same, refrigerator having same, and method for operating 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, Daisuke KARUBE, Kazuhiro TAKAHASHI, Yuuki YOTSUMOTO.
Application Number | 20210071055 16/772409 |
Document ID | / |
Family ID | 1000005253213 |
Filed Date | 2021-03-11 |
United States Patent
Application |
20210071055 |
Kind Code |
A1 |
ITANO; Mitsushi ; et
al. |
March 11, 2021 |
COOLANT-CONTAINING COMPOSITION, USE FOR SAME, REFRIGERATOR HAVING
SAME, AND METHOD FOR OPERATING REFRIGERATOR
Abstract
An object is to provide a mixed refrigerant having three types
of performance, i.e., a refrigerating capacity and a coefficient of
performance that are equivalent to those of R410A, and a
sufficiently low GWP. Provided as a means for achieving the object
is a composition comprising a refrigerant, the refrigerant
comprising trans-1,2-difluoroethylene (HFO-1132(E)),
trifluoroethylene (HFO-1123), and 2,3,3,3-tetrafluoro-1-propene
(R1234yf).
Inventors: |
ITANO; Mitsushi; (Osaka,
JP) ; KARUBE; Daisuke; (Osaka, JP) ;
YOTSUMOTO; Yuuki; (Osaka, JP) ; TAKAHASHI;
Kazuhiro; (Osaka, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DAIKIN INDUSTRIES, LTD. |
Osaka |
|
JP |
|
|
Assignee: |
DAIKIN INDUSTRIES, LTD.
Osaka
JP
|
Family ID: |
1000005253213 |
Appl. No.: |
16/772409 |
Filed: |
December 18, 2018 |
PCT Filed: |
December 18, 2018 |
PCT NO: |
PCT/JP2018/046640 |
371 Date: |
June 12, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 2205/40 20130101;
C09K 2205/22 20130101; C09K 2205/122 20130101; C09K 5/045 20130101;
C09K 2205/126 20130101; F25B 1/00 20130101 |
International
Class: |
C09K 5/04 20060101
C09K005/04; F25B 1/00 20060101 F25B001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 18, 2017 |
JP |
2017-242185 |
Claims
1. A composition comprising a refrigerant, the refrigerant
comprising trans-1,2-difluoroethylene (HFO-1132(E)),
trifluoroethylene (HFO-1123), and 2,3,3,3-tetrafluoro-1-propene
(R1234yf).
2. A composition comprising a refrigerant, the refrigerant
comprising trans-1,2-difluoroethylene (HFO-1132(E)) and
2,3,3,3-tetrafluoro-1-propene (R1234yf), and optionally further
comprising trifluoroethylene (HFO-1123), wherein when the mass % of
HFO-1132(E), HFO-1123, and R1234yf based on their sum in the
refrigerant 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), HFO-1123, and R1234yf is 100 mass % are within the
range of a figure surrounded by line segments OD, DG, GH, and HO
that connect the following 4 points: point D (87.6, 0.0, 12.4),
point G (18.2, 55.1, 26.7), point H (56.7, 43.3, 0.0), and point O
(100.0, 0.0, 0.0), or on the line segments OD, DG, and GH
(excluding the points O and H); the line segment DG is represented
by coordinates (0.0047y.sup.2-1.5177y+87.598, y,
-0.0047y.sup.2+0.5177y+12.402), the line segment GH is represented
by coordinates (-0.0134z.sup.2-1.0825z+56.692,
0.0134z.sup.2+0.0825z+43.308, z), and the line segments HO and OD
are straight lines.
3. The composition according to claim 1, wherein when the mass % of
HFO-1132(E), HFO-1123, and R1234yf based on their sum in the
refrigerant 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), HFO-1123, and R1234yf is 100 mass % are within the
range of a figure surrounded by line segments LG, GH, HI, and IL
that connect the following 4 points: point L (72.5, 10.2, 17.3),
point G (18.2, 55.1, 26.7), point H (56.7, 43.3, 0.0), and point I
(72.5, 27.5, 0.0), or on the line segments LG, GH, and IL
(excluding the points H and I); the line segment LG is represented
by coordinates (0.0047y.sup.2-1.5177y+87.598, y,
-0.0047y.sup.2+0.5177y+12.402), the line segment GH is represented
by coordinates (-0.0134z.sup.2-1.0825z+56.692,
0.0134z.sup.2+0.0825z+43.308, z), and the line segments HI and IL
are straight lines.
4. The composition according to claim 1, further comprising
R32.
5. The composition according to claim 4, wherein when the mass % of
HFO-1132(E), HFO-1123, R1234yf, and R32 based on their sum in the
refrigerant is respectively represented by x, y, z, and a, if
0<a.ltoreq.10.0, coordinates (x,y,z) in a ternary composition
diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is
(100-a) mass % are within the range of a figure surrounded by
straight lines that connect the following 4 points: point A
(0.02a.sup.2-2.46a+93.4, 0, -0.02a.sup.2+1.46a+6.6), point
B'(-0.008a.sup.2-1.38a+56, 0.018a.sup.2-0.53a+26.3,
-0.01a.sup.2+0.91a+17.7), point C (-0.016a.sup.2+0.02a+77.6,
0.016a.sup.2-1.02a+22.4, 0), and point O (100.0-a, 0.0, 0.0), or on
the straight lines OA, AB', and B'C (excluding the points O and C);
if 10.0<a.ltoreq.16.5, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points: point A
(0.0244a.sup.2-2.5695a+94.056, 0, -0.0244a.sup.2+1.5695a+5.944),
point B'(0.0161a.sup.2-1.9959a+59.749, 0.014a.sup.2-0.3399a+24.8,
-0.0301a.sup.2+1.3358a+15.451), point C
(-0.0161a.sup.2-0.0041a+77.851, 0.0161a.sup.2-0.9959a+22.149, 0),
and point O (100.0-a, 0.0, 0.0), or on the straight lines OA, AB',
and B'C (excluding the points O and C); or if
16.5<a.ltoreq.21.8, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points: point A
(0.0161a.sup.2-2.3535a+92.742, 0, -0.0161a.sup.2+1.3535a+7.258),
point B'(-0.0435a.sup.2-0.4456a+50.406,
-0.0304a.sup.2+1.8991a-0.0661, 0.0739a.sup.2-2.4535a+49.6601),
point C (-0.0263a.sup.2+0.3107a+75.444,
0.0263a.sup.2-1.3107a+24.556, 0), and point O (100.0-a, 0.0, 0.0),
or on the straight lines OA, AB', and B'C (excluding the points O
and C).
6. The composition according to claim 1, for use as a working fluid
for a refrigerating machine, wherein the composition further
comprises a refrigeration oil.
7. The composition according to claim 1, for use as an alternative
refrigerant for R410A.
8. Use of the composition according to claim 1 as an alternative
refrigerant for R410A.
9. A refrigerating machine comprising the composition according to
claim 1 as a working fluid.
10. A method for operating a refrigerating machine, comprising the
step of circulating the composition according to claim 1 as a
working fluid in a refrigerating machine.
11. The composition according to claim 2, further comprising
R32.
12. The composition according to claim 11, wherein when the mass %
of HFO-1132(E), HFO-1123, R1234yf, and R32 based on their sum in
the refrigerant is respectively represented by x, y, z, and a, if
0<a.ltoreq.10.0, coordinates (x,y,z) in a ternary composition
diagram in which the sum of HFO-1132(E), HFO-1123, and R1234yf is
(100-a) mass % are within the range of a figure surrounded by
straight lines that connect the following 4 points: point A
(0.02a.sup.2-2.46a+93.4, 0, -0.02a.sup.2+1.46a+6.6), point
B'(-0.008a.sup.2-1.38a+56, 0.018a.sup.2-0.53a+26.3,
-0.01a.sup.2+0.91a+17.7), point C (-0.016a.sup.2+0.02a+77.6,
0.016a.sup.2-1.02a+22.4, 0), and point O (100.0-a, 0.0, 0.0), or on
the straight lines OA, AB', and B'C (excluding the points O and C);
if 10.0<a.ltoreq.16.5, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points: point A
(0.0244a.sup.2-2.5695a+94.056, 0, -0.0244a.sup.2+1.5695a+5.944),
point B'(0.0161a.sup.2-1.9959a+59.749, 0.014a.sup.2-0.3399a+24.8,
-0.0301a.sup.2+1.3358a+15.451), point C
(-0.0161a.sup.2-0.0041a+77.851, 0.0161a.sup.2-0.9959a+22.149, 0),
and point O (100.0-a, 0.0, 0.0), or on the straight lines OA, AB',
and B'C (excluding the points O and C); or if
16.5<a.ltoreq.21.8, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points: point A
(0.0161a.sup.2-2.3535a+92.742, 0, -0.0161a.sup.2+1.3535a+7.258),
point B'(-0.0435a.sup.2-0.4456a+50.406,
-0.0304a.sup.2+1.8991a-0.0661, 0.0739a.sup.2-2.4535a+49.6601),
point C (-0.0263a.sup.2+0.3107a+75.444,
0.0263a.sup.2-1.3107a+24.556, 0), and point O (100.0-a, 0.0, 0.0),
or on the straight lines OA, AB', and B'C (excluding the points O
and C).
13. The composition according to claim 2, for use as a working
fluid for a refrigerating machine, wherein the composition further
comprises a refrigeration oil.
14. The composition according to claim 2, for use as an alternative
refrigerant for R410A.
15. Use of the composition according to claim 2 as an alternative
refrigerant for R410A.
16. A refrigerating machine comprising the composition according to
claim 2 as a working fluid.
17. A method for operating a refrigerating machine, comprising the
step of circulating the composition according to claim 2 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: HFC-32 or R32) and
pentafluoroethane (C.sub.2HF.sub.5: HFC-125 or R125), and is a
pseudo-azeotropic composition.
[0003] However, the global warming potential (GWP) of R410A is
2088. Due to growing concerns about global warming, R32, which has
a GWP of 675, has been increasingly used.
[0004] For this reason, various low-GWP mixed refrigerants that can
replace R410A have been proposed (PTL 1).
CITATION LIST
Patent Literature
PTL 1: WO2015/141678
SUMMARY OF INVENTION
Technical Problem
[0005] The present inventors performed independent examination, and
conceived of the idea that no prior art had developed refrigerant
compositions having three types of performance, i.e., a
refrigerating capacity (also referred to as "cooling capacity" or
"capacity") and a coefficient of performance (COP) that are
equivalent to those of R410A, and a sufficiently low GWP. An object
of the present disclosure is to solve this unique problem.
Solution to Problem
Item 1
[0006] A composition comprising a refrigerant, the refrigerant
comprising trans-1,2-difluoroethylene (HFO-1132(E)),
trifluoroethylene (HFO-1123), and 2,3,3,3-tetrafluoro-1-propene
(R1234yf).
Item 2
[0007] A composition comprising a refrigerant, the refrigerant
comprising trans-1,2-difluoroethylene (HFO-1132(E)) and
2,3,3,3-tetrafluoro-1-propene (R1234yf), and optionally further
comprising trifluoroethylene HFO-1123),
wherein
[0008] when the mass % of HFO-1132(E), HFO-1123, and R1234yf based
on their sum in the refrigerant 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), HFO-1123, and R1234yf is 100 mass %
are within the range of a figure surrounded by line segments OD,
DG, GH, and HO that connect the following 4 points:
point D (87.6, 0.0, 12.4), point G (18.2, 55.1, 26.7), point H
(56.7, 43.3, 0.0), and point O (100.0, 0.0, 0.0), or on the line
segments OD, DG, and GH (excluding the points O and H);
[0009] the line segment DG is represented by coordinates
(0.0047y.sup.2-1.5177y+87.598, y,
-0.0047y.sup.2+0.5177y+12.402),
[0010] the line segment GH is represented by coordinates
(-0.0134z.sup.2-1.0825z+56.692, 0.0134z.sup.2+0.0825z+43.308, z),
and
[0011] the line segments HO and OD are straight lines.
Item 3
[0012] The composition according to Item 1,
wherein
[0013] when the mass % of HFO-1132(E), HFO-1123, and R1234yf based
on their sum in the refrigerant 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), HFO-1123, and R1234yf is 100 mass %
are within the range of a figure surrounded by line segments LG,
GH, HI, and IL that connect the following 4 points:
point L (72.5, 10.2, 17.3), point G (18.2, 55.1, 26.7), point H
(56.7, 43.3, 0.0), and point I (72.5, 27.5, 0.0), or on the line
segments LG, GH, and IL (excluding the points H and I);
[0014] the line segment LG is represented by coordinates
(0.0047y.sup.2-1.5177y+87.598, y,
-0.0047y.sup.2+0.5177y+12.402),
[0015] the line segment GH is represented by coordinates (-0.0134
z.sup.2-1.0825z+56.692, 0.0134z.sup.2+0.0825z+43.308, z), and
[0016] the line segments HI and IL are straight lines.
Item 4
[0017] The composition according to any one of Items 1 to 3,
further comprising R32.
Item 5
[0018] The composition according to Item 4,
wherein
[0019] when the mass % of HFO-1132(E), HFO-1123, R1234yf, and R32
based on their sum in the refrigerant is respectively represented
by x, y, z, and a,
[0020] if 0<a.ltoreq.10.0, coordinates (x,y,z) in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is (100-a) mass % are within the range of a figure
surrounded by straight lines that connect the following 4
points:
point A (0.02a.sup.2-2.46a+93.4, 0, -0.02a.sup.2+1.46a+6.6), point
B'(-0.008a.sup.2-1.38a+56, 0.018a.sup.2-0.53a+26.3,
-0.01a.sup.2+0.91a+17.7), point C (-0.016a.sup.2+0.02a+77.6,
0.016a.sup.2-1.02a+22.4, 0), and point O (100.0-a, 0.0, 0.0), or on
the straight lines OA, AB', and B'C (excluding the points O and
C);
[0021] if 10.0<a.ltoreq.16.5, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points:
point A (0.0244a.sup.2-2.5695a+94.056, 0,
-0.0244a.sup.2+1.5695a+5.944), point
B'(0.0161a.sup.2-1.9959a+59.749, 0.014a.sup.2-0.3399a+24.8,
-0.0301a.sup.2+1.3358a+15.451), point C
(-0.0161a.sup.2-0.0041a+77.851, 0.0161a.sup.2-0.9959a+22.149, 0),
and point O (100.0-a, 0.0, 0.0), or on the straight lines OA, AB',
and B'C (excluding the points O and C); or
[0022] if 16.5<a.ltoreq.21.8, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points:
point A (0.0161a.sup.2-2.3535a+92.742, 0,
-0.0161a.sup.2+1.3535a+7.258), point
B'(-0.0435a.sup.2-0.4456a+50.406, -0.0304a.sup.2+1.8991a-0.0661,
0.0739a.sup.2-2.4535a+49.6601), point C
(-0.0263a.sup.2+0.3107a+75.444, 0.0263a.sup.2-1.3107a+24.556, 0),
and point O (100.0-a, 0.0, 0.0), or on the straight lines OA, AB',
and B'C (excluding the points O and C).
Item 6
[0023] The composition according to any one of Items 1 to 5, for
use as a working fluid for a refrigerating machine, wherein the
composition further comprises a refrigeration oil.
Item 7
[0024] The composition according to any one of Items 1 to 6, for
use as an alternative refrigerant for R410A.
Item 8
[0025] Use of the composition according to any one of Items 1 to 6
as an alternative refrigerant for R410A.
Item 9
[0026] A refrigerating machine comprising the composition according
to any one of Items 1 to 6 as a working fluid.
Item 10
[0027] A method for operating a refrigerating machine, comprising
the step of circulating the composition according to any one of
Items 1 to 6 as a working fluid in a refrigerating machine.
Advantageous Effects of Invention
[0028] The refrigerant according to the present disclosure has
three types of performance, i.e., a refrigerating capacity and a
coefficient of performance that are equivalent to those of R410A,
and a sufficiently low GWP.
BRIEF DESCRIPTION OF DRAWING
[0029] FIG. 1 is a schematic view of an apparatus used in a
flammability test.
[0030] FIG. 2 is a diagram showing points A to M and O, and line
segments that connect these points to each other in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is 100 mass %.
[0031] FIG. 3 is a diagram showing points A to C, B' and O, and
line segments that connect these points to each other in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is 100 mass %.
[0032] FIG. 4 is a diagram showing points A to C, B' and O, and
line segments that connect these points to each other in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is 95 mass % (R32 content is 5 mass %).
[0033] FIG. 5 is a diagram showing points A to C, B' and O, and
line segments that connect these points to each other in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is 90 mass % (R32 content is 10 mass %).
[0034] FIG. 6 is a diagram showing points A to C, B' and O, and
line segments that connect these points to each other in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is 85.7 mass % (R32 content is 14.3 mass %).
[0035] FIG. 7 is a diagram showing points A to C, B' and O, and
line segments that connect these points to each other in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is 83.5 mass % (R32 content is 16.5 mass %).
[0036] FIG. 8 is a diagram showing points A to C, B' and O, and
line segments that connect these points to each other in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is 80.8 mass % (R32 content is 19.2 mass %).
[0037] FIG. 9 is a diagram showing points A to C, B' and O, and
line segments that connect these points to each other in a ternary
composition diagram in which the sum of HFO-1132(E), HFO-1123, and
R1234yf is 78.2 mass % (R32 content is 21.8 mass %).
DESCRIPTION OF EMBODIMENTS
[0038] The present inventors conducted intensive study to solve the
above problem, and consequently found that a mixed refrigerant
comprising trans-1,2-difluoroethylene (HFO-1132(E)) and
2,3,3,3-tetrafluoro-1-propene (R1234yf), and optionally further
comprising trifluoroethylene (HFO-1123) has the above
properties.
[0039] 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
[0040] In the present specification, 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 cf the
compounds. Fluorocarbon compounds include chlorofluorocarbons
(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.
[0041] In the present specification, 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."
[0042] In the present specification, 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.
[0043] 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.
[0044] In the present specification, the term "refrigerating
machine" refers to machines in general that draw heat from an
object or space to make its temperature 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.
[0045] In the present specification, a refrigerant having a "lower
flammability" means that it is determined to be "Class 2L"
according to the US ANSI/ASHRAE Standard 34-2013.
1. Refrigerant
1.1 Refrigerant Component
[0046] The refrigerant according to the present disclosure is a
mixed refrigerant comprising trans-1,2-difluoroethylene
(HFO-1132(E)), trifluoroethylene (HFO-1123), and
2,3,3,3-tetrafluoro-1-propene (R1234yf).
[0047] The refrigerant according to the present disclosure has
various properties that are desirable as an R410A-alternative
refrigerant, i.e., a refrigerating capacity and a coefficient of
performance that are equivalent to those of R410A, and a
sufficiently low GWP.
[0048] The refrigerant according to the present disclosure is a
composition comprising HFO-1132(E) and R1234yf, and optionally
further comprising HFO-1123, and may further satisfy the following
requirements. This refrigerant also has various properties
desirable as an alternative refrigerant for R410A; i.e., it has a
refrigerating capacity and a coefficient of performance that are
equivalent to those of R410A, and a sufficiently low GWP.
Requirements
[0049] When the mass % of HFO-1132(E), HFO-1123, and R1234yf based
on their sum is respectively represented by x, y, and z,
[0050] coordinates (x,y,z) in a ternary composition diagram in
which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass %
are within the range of a figure surrounded by line segments OD,
DG, GH, and HO that connect the following 4 points:
point D (87.6, 0.0, 12.4), point G (18.2, 55.1, 26.7), point H
(56.7, 43.3, 0.0), and point O (100.0, 0.0, 0.0), or on the line
segments OD, DG, and GH (excluding the points O and H);
[0051] the line segment DG is represented by coordinates
(0.0047y.sup.2-1.5177y+87.598, y,
-0.0047y.sup.2+0.5177y+12.402),
[0052] the line segment GH is represented by coordinates
(-0.0134z.sup.2-1.0825z+56.692, 0.0134z.sup.2+0.0825z+43.308, z),
and
[0053] the lines HO and OD are straight lines.
When the requirements above are satisfied, the refrigerant
according to the present disclosure has a refrigerating capacity
ratio of 92.5% or more relative to that of R410A, and a COP ratio
of 92.5% or more relative to that of R410A.
[0054] The refrigerant according to the present disclosure is
preferably a refrigerant wherein
[0055] when the mass % of HFO-1132(E), HFO-1123, and R1234yf 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), HFO-1123, and R1234yf is 100 mass % are within
the range of a figure surrounded by line segments LG, GH, HI, and
IL that connect the following 4 points:
point L (72.5, 10.2, 17.3), point G (18.2, 55.1, 26.7), point H
(56.7, 43.3, 0.0), and point I (72.5, 27.5, 0.0), or on the line
segments LG, GH, and IL (excluding the points H and I);
[0056] the line segment LG is represented by coordinates
(0.0047y.sup.2-1.5177y+87.598, y,
-0.0047y.sup.2+0.5177y+12.402),
[0057] the line segment GH is represented by coordinates
(-0.0134z.sup.2-1.0825z+56.692, 0.0134z.sup.2+0.0825z+43.308, z),
and
[0058] the line segments HI and IL are straight lines.
When the requirements above are satisfied, the refrigerant
according to the present disclosure has a refrigerating capacity
ratio of 92.5% or more relative to that of R410A, and a COP ratio
of 92.5% or more relative to that of R410A; furthermore, the
refrigerant has a lower flammability (Class 2L) according to the
ASHRAE standard.
[0059] The refrigerant according to the present disclosure is
preferably a refrigerant wherein
[0060] when the mass % of HFO-1132(E), HFO-1123, and R1234yf 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), HFO-1123, and R1234yf is 100 mass % are within
the range of a figure surrounded by line segments OD, DE, EF, and
FO that connect the following 4 points:
point D (87.6, 0.0, 12.4), point E (31.1, 42.9, 26.0), point F
(65.5, 34.5, 0.0), and point O (100.0, 0.0, 0.0), or on the line
segments OD, DE, and EF (excluding the points O and F);
[0061] the line segment DE is represented by coordinates
(0.0047y.sup.2-1.5177y+87.598, y,
-0.0047y.sup.2+0.5177y+12.402),
[0062] the line segment EF is represented by coordinates
(-0.0064z.sup.2-1.1565z+65.501, 0.0064z.sup.2+0.1565z+34.499, z),
and
[0063] the line segments FO and OD are straight lines.
When the requirements above are satisfied, the refrigerant
according to the present disclosure has a refrigerating capacity
ratio of 93.5% or more relative to that of R410A, and a COP ratio
of 93.5% or more relative to that of R410A.
[0064] The refrigerant according to the present disclosure is
preferably a refrigerant wherein
[0065] when the mass % of HFO-1132(E), HFO-1123, and R1234yf based
on their sum is respectively represented by x, y, and z,
[0066] coordinates (x,y,z) in a ternary composition diagram in
which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass %
are within the range of a figure surrounded by line segments LE,
EF, FI, and IL that connect the following 4 points:
point L (72.5, 10.2, 17.3), point E (31.1, 42.9, 26.0), point F
(65.5, 34.5, 0.0), and point I (72.5, 27.5, 0.0), or on the line
segments LE, EF, and IL (excluding the points F and I);
[0067] the line segment LE is represented by coordinates
(0.0047y.sup.2-1.5177y+87.598, y,
-0.0047y.sup.2+0.5177y+12.402),
[0068] the line segment EF is represented by coordinates
(-0.0134z.sup.2-1.0825z+56.692, 0.0134z.sup.2+0.0825z+43.308, z),
and
[0069] the line segments FI and IL are straight lines.
When the requirements above are satisfied, the refrigerant
according to the present disclosure has a refrigerating capacity
ratio of 93.5% or more relative to that of R410A, and a COP ratio
of 93.5% or more relative to that of R410A; furthermore, the
refrigerant has a lower flammability (Class 2L) according to the
ASHRAE standard.
[0070] The refrigerant according to the present disclosure is
preferably a refrigerant wherein
[0071] when the mass % of HFO-1132(E), HFO-1123, and R1234yf based
on their sum is respectively represented by x, y, and z,
[0072] coordinates (x,y,z) in a ternary composition diagram in
which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass %
are within a figure surrounded by line segments CA, AB, BC, and CO
that connect the following 4 points:
point A (93.4, 0.0, 6.6), point B (55.6, 26.6, 17.8), point C
(77.6, 22.4, 0.0), and point O (100.0, 0.0, 0.0), or on the line
segments OA, AB, and BC (excluding the points O and C);
[0073] the line segment AB is represented by coordinates
(0.0052y.sup.2-1.5588y+93.385, y,
-0.0052y.sup.2+0.5588y+6.615),
[0074] the line segment BC is represented by coordinates
(-0.0032z.sup.2-1.1791z+77.593, 0.0032z.sup.2+0.1791z+22.407, z),
and
[0075] the line segments CO and OA are straight lines.
When the requirements above are satisfied, the refrigerant
according to the present disclosure has a refrigerating capacity
ratio of 95% or more relative to that of R410A, and a COP ratio of
95% or more relative to that of R410A.
[0076] The refrigerant according to the present disclosure is
preferably a refrigerant wherein
[0077] when the mass % of HFO-1132(E), HFO-1123, and R1234yf based
on their sum is respectively represented by x, y, and z,
[0078] coordinates (x,y,z) in a ternary composition diagram in
which the sum of HFO-1132(E), HFO-1123, and R1234yf is 100 mass %
are within a figure surrounded by line segments KB, BJ, and JK that
connect the following 3 points:
point K (72.5, 14.1, 13.4), point B (55.6, 26.6, 17.8), and point J
(72.5, 23.2, 4.3), or on the line segments KB, BJ, and JK;
[0079] the line segment KB is represented by coordinates
(0.0052y.sup.2-1.5588y+93.385, y, and
-0.0052y.sup.2+0.5588y+6.615),
[0080] the line segment BJ is represented by coordinates
(-0.0032z.sup.2-1.1791z+77.593, 0.0032z.sup.2+0.1791z+22.407, z),
and
[0081] the line segment JK is a straight line.
When the requirements above are satisfied, the refrigerant
according to the present disclosure has a refrigerating capacity
ratio of 95% or more relative to that of R410A, and a COP ratio of
95% or more relative to that of R410A; furthermore, the refrigerant
has a lower flammability (Class 2L) according to the ASHRAE
standard.
[0082] The refrigerant according to the present disclosure may
further comprise difluoromethane (R32) in addition to HFO-1132(E),
HFO-1123, and R1234yf as long as the above properties and effects
are not impaired. The content of R32 based on the entire
refrigerant according to the present disclosure is not particularly
limited and can be selected from a wide range. For example, when
the R32 content of the refrigerant according to the present
disclosure is 21.8 mass %, the mixed refrigerant has a GWP of 150.
Therefore, the R32 content can be 21.8 mass % or less. The R32
content of the refrigerant according to the present disclosure may
be, for example, 5 mass % or more, based on the entire
refrigerant.
[0083] When the refrigerant according to the present disclosure
further contains R32 in addition to HFO-1132(E), HFO-1123, and
R1234yf, the refrigerant may be a refrigerant wherein
[0084] when the mass % of HFO-1132(E), HFO-1123, R1234yf, and R32
based on their sum is respectively represented by x, y, z, and
a,
[0085] if 0<a.ltoreq.10.0, coordinates (x,y,z) in a ternary
composition diagram (FIGS. 3 to 9) in which the sum of HFO-1132(E),
HFO-1123, and R1234yf is (100-a) mass % are within the range of a
figure surrounded by straight lines that connect the following 4
points:
point A (0.02a.sup.2-2.46a+93.4, 0, -0.02a.sup.2+1.46a+6.6), point
B'(-0.008a.sup.2-1.38a+56, 0.018a.sup.2-0.53a+26.3,
-0.01a.sup.2+0.91a+17.7), point C (-0.016a.sup.2+0.02a+77.6,
0.016a.sup.2-1.02a+22.4, 0), and point O (100.0-a, 0.0, 0.0), or on
the straight lines OA, AB', and B'C (excluding the points O and
C);
[0086] if 10.0<a.ltoreq.16.5, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points:
point A (0.0244a.sup.2-2.5695a+94.056, 0,
-0.0244a.sup.2+1.5695a+5.944), point
B'(0.0161a.sup.2-1.9959a+59.749, 0.014a.sup.2-0.3399a+24.8,
-0.0301a.sup.2+1.3358a+15.451), point C
(-0.0161a.sup.2-0.0041a+77.851, 0.0161a.sup.2-0.9959a+22.149, 0),
and point O (100.0-a, 0.0, 0.0), or on the straight lines OA, AB',
and B'C (excluding the points O and C); or
[0087] if 16.5<a.ltoreq.21.8, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points:
point A (0.0161a.sup.2-2.3535a+92.742, 0,
-0.0161a.sup.2+1.3535a+7.258), point
B'(-0.0435a.sup.2-0.4456a+50.406, -0.0304a.sup.2+1.8991a-0.0661,
0.0739a.sup.2-2.4535a+49.6601), point C
(-0.0263a.sup.2+0.3107a+75.444, 0.0263a.sup.2-1.3107a+24.556, 0),
and point O (100.0-a, 0.0, 0.0), or on the straight lines OA, AB',
and B'C (excluding the points O and C). Note that when point B in
the ternary composition diagram is defined as a point where a
refrigerating capacity ratio of 95% relative to that of R410A and a
COP ratio of 95% relative to that of R410A are both achieved, point
B' is the intersection of straight line AB and an approximate line
formed by connecting the points where the COP ratio relative to
that of R410A is 95%. When the requirements above are satisfied,
the refrigerant according to the present disclosure has a
refrigerating capacity ratio of 95% or more relative to that of
R410A, and a COP ratio of 95% or more relative to that of
R410A.
[0088] The refrigerant according to the present disclosure may
further comprise other additional refrigerants in addition to
HFO-1132(E), HFO-1123, R1234yf, and R32 as long as the above
properties and effects are not impaired. In this respect, the
refrigerant according to the present disclosure preferably
comprises HFO-1132(E), HFO-1123, R1234yf, and R32 in a total amount
of 99.5 mass % or more, more preferably 99.75 mass % or more, and
still more preferably 99.9 mass % or more, based on the entire
refrigerant.
[0089] The refrigerant according to the present disclosure may
comprise HFO-1132(E), HFO-1123, and R1234yf in a total amount of
99.5 mass % or more, 99.75 mass % or more, or 99.9 mass % or more,
based on the entire refrigerant.
[0090] The refrigerant according to the present disclosure may
comprise HFO-1132(E), HFO-1123, R1234yf, and R32 in a total amount
of 99.5 mass % or more, 99.75 mass % or more, or 99.9 mass % or
more, based on the entire refrigerant.
[0091] Additional refrigerants are not particularly limited and can
be widely selected. The mixed refrigerant may contain one
additional refrigerant, or two or more additional refrigerants.
1.2. Use
[0092] The refrigerant according to the present disclosure can be
preferably used as a working fluid in a refrigerating machine.
[0093] The composition according to the present disclosure is
suitable for use as an alternative refrigerant for R410A.
2. Refrigerant Composition
[0094] 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.
[0095] 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
[0096] The refrigerant composition according to the present
disclosure may contain a small amount of water. The water content
of the refrigerant composition is preferably 0.1 mass % or less
based on the entire refrigerant. 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.
2.2. Tracer
[0097] 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.
[0098] The refrigerant composition according to the present
disclosure may comprise a single tracer, or two or more
tracers.
[0099] The tracer is not limited, and can be suitably selected from
commonly used tracers.
[0100] 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.
[0101] 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-161 (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)
[0102] The refrigerant composition according to the present
disclosure may contain one or more tracers at a total concentration
of about 10 parts per million by weight (ppm) to about 1000 ppm
based on the entire refrigerant composition. The refrigerant
composition according to the present disclosure may preferably
contain one or more tracers at a total concentration of about 30
ppm to about 500 ppm, and more preferably about 50 ppm to about 300
ppm, based on the entire refrigerant composition.
2.3. Ultraviolet Fluorescent Dye
[0103] The refrigerant composition according to the present
disclosure may comprise a single ultraviolet fluorescent dye, or
two or more ultraviolet fluorescent dyes.
[0104] The ultraviolet fluorescent dye is not limited, and can be
suitably selected from commonly used ultraviolet fluorescent
dyes.
[0105] 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
[0106] The refrigerant composition according to the present
disclosure may comprise a single stabilizer, or two or more
stabilizers.
[0107] The stabilizer is not limited, and can be suitably selected
from commonly used stabilizers.
[0108] Examples of stabilizers include nitro compounds, ethers, and
amines.
[0109] Examples of nitro compounds include aliphatic nitro
compounds, such as nitromethane and nitroethane; and aromatic nitro
compounds, such as nitro benzene and nitro styrene.
[0110] Examples of ethers include 1,4-dioxane.
[0111] Examples of amines include 2,2,3,3,3-pentafluoropropylamine
and diphenylamine.
[0112] Examples of stabilizers also include butylhydroxyxylene and
benzotriazole.
[0113] 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
[0114] The refrigerant composition according to the present
disclosure may comprise a single polymerization inhibitor, or two
or more polymerization inhibitors.
[0115] The polymerization inhibitor is not limited, and can be
suitably selected from commonly used polymerization inhibitors.
[0116] 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.
[0117] 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
[0118] 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
[0119] The composition according to the present disclosure may
comprise a single refrigeration oil, or two or more refrigeration
oils.
[0120] 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.
[0121] 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).
[0122] 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.
[0123] A refrigeration oil with a kinematic viscosity of 5 to 400
cSt at 40.degree. C. is preferable from the standpoint of
lubrication.
[0124] The refrigeration oil-containing working fluid according to
the present disclosure may further optionally contain at least one
additive. Examples of additives include compatibilizing agents
described below.
3.2. Compatibilizing Agent
[0125] The refrigeration oil-containing working fluid according to
the present disclosure may comprise a single compatibilizing agent,
or two or more compatibilizing agents.
[0126] The compatibilizing agent is not limited, and can be
suitably selected from commonly used compatibilizing agents.
[0127] 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
[0128] 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.
[0129] Specifically, the method for operating a refrigerating
machine according to the present disclosure comprises the step of
circulating the refrigerant according to the present disclosure in
a refrigerating machine.
[0130] 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
[0131] The present disclosure is described in more detail below
with reference to Examples. However, the present disclosure is not
limited to the Examples.
[0132] Mixed refrigerants were prepared by mixing HFO-1132(E),
HFO-1123, and R1234yf at mass % based on their sum shown in Tables
1 to 5.
[0133] The COP ratio and the refrigerating capacity ratio of the
mixed refrigerants relative to those of R410 were determined. The
calculation conditions were as follows.
[0134] Evaporating temperature: 5.degree. C.
[0135] Condensation temperature: 45.degree. C.
[0136] Degree of superheating: 1 K
[0137] Degree of subcooling: 5 K
[0138] E.sub.comp (compressive modulus): 0.7 kWh
[0139] Tables 1 to 5 show these values together with the GWP of
each mixed refrigerant.
TABLE-US-00001 TABLE 1 Comp. Example Example Example Example
Example Example Item Unit Ex. 1 1 A 2 3 4 5 6 B HFO-1132(E) mass %
R410A 93.4 85.7 78.3 71.2 64.3 55.6 HFO-1123 mass % 0.0 5.0 10.0
15.0 20.0 26.6 R1234yf mass % 6.6 9.3 11.7 13.8 15.7 17.8 GWP --
2088 1 1 1 1 1 2 COP ratio % (relative 100 98.0 97.5 96.9 96.3 95.8
95.0 to R410A) Refrigerating % (relative 100 95.0 95.0 95.0 95.0
95.0 95.0 capacity ratio to R410A)
TABLE-US-00002 TABLE 2 Comp. Ex. 2 Example Example Example item
Unit C 7 8 9 HFO-1132(E) mass % 77.6 71.6 65.5 59.2 HFO-1123 mass %
22.4 23.4 24.5 25.8 R1234yf mass % 0.0 5.0 10.0 15.0 GWP -- 1 1 1 1
COP ratio % (relative 95.0 95.0 95.0 95.0 to R410A) Refrigerating %
(relative 102.5 100.5 98.4 96.3 capacity ratio to R410A)
TABLE-US-00003 TABLE 3 Example Example Example Example Example
Example Example Item Unit 10 D 11 12 13 14 15 16 G HFO-1132(E) mass
% 87.6 72.9 59.1 46.3 34.4 23.5 18.2 HFO-1123 mass % 0.0 10.0 20.0
30.0 40.0 50.0 55.1 R1234yf mass % 12.4 17.1 20.9 23.7 25.6 26.5
26.7 GWP -- 1 2 2 2 2 2 2 COP ratio % (relative 98.2 97.1 95.9 94.8
93.8 92.9 92.5 to R410A) Refrigerating % (relative 92.5 92.5 92.5
92.5 92.5 92.5 92.5 capacity ratio to R410A)
TABLE-US-00004 TABLE 4 Comp. Example Example Comp. Example Example
Example Item Unit Ex. 3 H 17 18 Ex. 4 F 19 20 21 E HFO-1132(E) mass
% 56.7 44.5 29.7 65.5 53.3 39.8 31.1 HFO-1123 mass % 43.3 45.5 50.3
34.5 36.7 40.2 42.9 R1234yf mass % 0.0 10.0 20.0 0.0 10.0 20.0 26.0
GWP -- 1 1 2 1 1 2 2 COP ratio % (relative 92.5 92.5 92.5 93.5 93.5
93.5 93.5 to R410A) Refrigerating % (relative 105.8 101.2 96.2
104.5 100.2 95.5 92.5 capacity ratio to R410A)
TABLE-US-00005 TABLE 5 Comp. Example Example Example Comp. Ex. 5 22
23 24 Ex. 6 Item Unit I J K L M HFO-1132(E) mass % 72.5 72.5 72.5
72.5 72.5 HFO-1123 mass % 27.5 23.2 14.1 10.2 0.0 R1234yf mass %
0.0 4.3 13.4 17.3 27.5 GWP -- 1 1 1 2 2 COP ratio % (relative 94.4
95.0 96.4 97.1 98.8 to R410A) Refrigerating % (relative 103.5.
100.8 95.0 92.5 85.7 capacity ratio to R410A)
[0140] These results indicate that under the condition that the
mass % of HFO-1132(E), HFO-1123, and R1234yf based on their sum is
respectively represented by x, y, and z, when coordinates (x,y,z)
in a ternary composition diagram in which the sum of HFO-1132(E),
HFO-1123, and R1234yf is 100 mass % are within the range of a
figure (FIG. 2) surrounded by line segments OD, DG, GH, and HO that
connect the following 4 points:
point D (87.6, 0.0, 12.4), point G (18.2, 55.1, 26.7), point H
(56.7, 43.3, 0.0), and point O (100.0, 0.0, 0.0), or on the line
segments OD, DG, and GH (excluding the points O and H), the
refrigerant has a refrigerating capacity ratio of 92.5% or more
relative to that of R410A, and a COP ratio of 92.5% or more
relative to that of R410A.
[0141] Likewise, the results indicate that when coordinates (x,y,z)
are within the range of a figure (FIG. 2) surrounded by line
segments OD, DE, EF, and FO that connect the following 4
points:
point D (87.6, 0.0, 12.4), point E (31.1, 42.9, 26.0), point F
(65.5, 34.5, 0.0), and point O (100.0, 0.0, 0.0), or on the line
segments OD, DE, and EF (excluding the points O and F), the
refrigerant has a refrigerating capacity ratio of 93.5% or more
relative to that of R410A, and a COP ratio of 93.5% or more
relative to that of R410A.
[0142] Likewise, the results indicate that when coordinates (x,y,z)
are within the range of a figure (FIG. 2) surrounded by line
segments OA, AB, BC, and CO that connect the following 4
points:
point A (93.4, 0.0, 6.6), point B (55.6, 26.6, 17.8), point C
(77.6, 22.4, 0.0), and point O (100.0, 0.0, 0.0), or on the line
segments OA, AB, and BC (excluding the points O and C), the
refrigerant has a refrigerating capacity ratio of 95% or more
relative to that of R410A, and a COP ratio of 95% or more relative
to that of R410A.
[0143] R1234yf contributes to reduction of flammability and
deterioration of polymerization etc. in these compositions.
Therefore, the composition according to the present disclosure
preferably contains R1234yf.
[0144] Further, the burning velocity of these mixed refrigerants
was measured according to the ANSI/ASHRAE Standard 34-2013.
Compositions that showed a burning velocity cf 10 cm/s or less were
determined to be Class 2L (lower flammability). These results
clearly indicate that when the content cf HFO-1132(E) in a mixed
refrigerant of HFO-1132(E), HFO-1123, and R1234yf is 72.5 mass % or
less based on their sum, the refrigerant can be determined to be
Class 2L (lower flammability).
[0145] A burning velocity test was performed using the apparatus
shown in FIG. 1 in the following manner. First, the mixed
refrigerants used had a purity of 99.5% or more, and were degassed
by repeating a cycle of freezing, pumping, and thawing until no
traces of air were observed on the vacuum gauge. The burning
velocity was measured by the closed method. The initial temperature
was ambient temperature. Ignition was performed by generating an
electric spark between the electrodes in the center of a sample
cell. The duration of the discharge was 1.0 to 9.9 ms, and the
ignition energy was typically about 0.1 to 1.0 J. The spread of the
flame was visualized using schlieren photographs. A cylindrical
container (inner diameter: 155 mm, length: 198 mm) equipped with
two light transmission acrylic windows was used as the sample cell,
and a xenon lamp was used as the light source. Schlieren images of
the flame were recorded by a high-speed digital video camera at a
frame rate of 600 fps and stored on a PC.
[0146] Mixed refrigerants were prepared by mixing HFO-1132(E),
HFO-1123, R1234yf, and R32 in amounts shown in Tables 6 to 12, in
terms of mass %, based on their sum.
[0147] The COP ratio and the refrigerating capacity ratio of these
mixed refrigerants relative to those of R410A were determined. The
calculation conditions were the same as described above. Tables 6
to 12 show these values together with the GWP of each mixed
refrigerant.
TABLE-US-00006 TABLE 6 Comp. Comp. Comp. Comp. Example Comp.
Example Example Comp. Ex. Item Unit Ex. 1 Ex. 7 A Ex. 8 Ex. 9 25 B'
Ex. 10 B 26 27 11 C HFO-1132(E) mass % R410A 93.4 78.3 64.3 56.0
55.6 60.0 70.0 77.6 HFO-1123 mass % 0.0 10.0 20.0 26.3 26.6 25.6
23.7 22.4 R1234yf mass % 6.6 11.7 15.7 17.7 17.8 14.4 6.3 0.0 R32
mass % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 GWP -- 2088 1.2 1.4 1.5 1.5
1.5 1.4 1.2 1.0 COP ratio % (relative 100 98.0 96.9 95.8 95.0 95.0
95.0 95.0 95.0 to R410A) Refrigerating % (relative 100 95.0 95.0
95.0 95.0 95.0 96.5 100.0 102.5 capacity ratio to R410A)
TABLE-US-00007 TABLE 7 Comp. Comp. Comp. Example Comp. Example
Example Comp. Ex. Item Unit Ex. 12 A Ex. 13 Ex. 14 28 B' Ex. 15 B
29 30 16 C HFO-1132(E) mass % 81.6 67.3 53.9 48.9 47.2 60.0 70.0
77.3 HFO-1123 mass % 0.0 10.0 20.0 24.1 25.3 21.6 19.2 17.7 R1234yf
mass % 13.4 17.7 21.1 22.0 22.5 13.4 5.8 0.0 R32 mass % 5.0 5.0 5.0
5.0 5.0 5.0 5.0 5.0 GWP -- 35 35 35 35 35 35 35 35 COP ratio %
(relative 97.6 96.6 95.5 95.0 95.0 95.0 95.0 95.0 to R410A)
Refrigerating % (relative 95.0 95.0 95.0 104.4 95.0 99.0 102.1
104.4 capacity ratio to R410A)
TABLE-US-00008 TABLE 8 Comp. Comp. Comp. Example Comp. Example
Example Comp. Ex. Item Unit Ex. 17 A Ex. 18 Ex. 19 31 B' Ex. 20 B
32 33 21 C HFO-1132(E) mass % 70.8 57.2 44.5 41.4 36.4 60.0 70.0
76.2 HFO-1123 mass % 0.0 10.0 20.0 22.8 26.7 18.0 15.3 13.8 R1234yf
mass % 19.2 22.8 25.5 25.8 26.9 12.0 4.7 0.0 R32 mas s% 10.0 10.0
10.0 10.0 10.0 10.0 10.0 10.0 GWP -- 69 69 69 69 69 69 69 68 COP
ratio % (relative 97.4 96.5 95.6 95.0 95.0 95.0 95.0 95.0 to R4104)
Refrigerating % (relative 95.0 95.0 95.0 106.2 95.0 101.5 104.4
106.2 capacity ratio to R410A)
TABLE-US-00009 TABLE 9 Comp. Comp. Comp. Example Comp. Example
Example Comp. Ex Item Unit Ex. 22 A Ex. 23 Ex. 24 34 B' Ex. 25 B 35
36 26 C HFO-1132(E) mass % 62.3 49.3 37.1 34.5 24.9 60.0 70.0 74.5
HFO-1123 mass % 0.0 10.0 20.0 22.8 30.7 15.4 12.4 11.2 R1234yf mass
% 23.4 26.4 28.6 28.4 30.1 10.3 3.3 0.0 R32 mass % 14.3 14.3 14.3
14.3 14.3 14.3 14.3 14.3 GWP -- 98 98 98 98 98 98 97 97 COP ratio %
(relative 97.3 96.5 95.7 95.5 95.0 95.0 95.0 95.0 to R410A)
Refrigerating % (relative 95.0 95.0 95.0 95.4 95.0 103.7 106.5
107.7 capacity ratio to R410A)
TABLE-US-00010 TABLE 10 Comp. Comp. Comp. Example Comp. Example
Example Comp. Ex. Item Unit Ex. 27 A Ex. 28 Ex. 29 37 B' Ex. 30 B
38 39 31 C HFO-1132(E) mass % 58.3 45.5 33.5 31.2 16.5 60.0 70.0
73.4 HFO-1123 mass % 0.0 10.0 20.0 23.0 35.5 14.2 11.1 10.1 R1234yf
mass % 25.2 28.0 30.0 29.3 31.5 9.3 2.4 0.0 R32 mass % 16.5 16.5
16.5 16.5 16.5 16.5 16.5 16.5 GWP -- 113.0 113.1 113.1 113.1 113.2
112.5 112.3 112.2 COP ratio % (relative 97.4 96.6 95.9 95.6 95.0
95.0 95.0 95.0 to R410A) Refrigerating % (relative 95.0 95.0 95.0
95.7 95.0 104.9 107.6 108.5 capacity ratio to R410A)
TABLE-US-00011 TABLE 11 Comp. Comp. Comp. Example Comp. Example
Example Comp. Ex. Item Unit Ex. 32 A Ex. 33 Ex. 34 40 B' Ex. 35 B
41 42 36 C HFO-1132(E) mass % 53.5 41.0 29.3 25.8 0.0 50.0 60.0
71.7 HFO-1123 mass % 0.0 10.0 20.0 25.2 48.8 16.8 12.9 9.1 R1234yf
mass % 27.3 29.8 31.5 29.8 32.0 14.0 7.9 0.0 R32 mass % 19.2 19.2
19.2 19.2 19.2 19.2 19.2 19.2 GWP -- 131.2 131.3 131.4 131.3 131.4
130.8 130.6 130.4 COP ratio % (relative 97.4 96.7 96.1 97.8 95.0
95.0 95.0 95.0 to R410) Refrigerating % (relative 95.0 95.0 95.0
96.3 95.0 104.0 106.4 109.4 capacity ratio to R410A)
TABLE-US-00012 TABLE 12 Comp. Comp. Comp. Example Comp. Example
Example Comp. Ex. Item Unit Ex. 37 A Ex. 38 Ex. 39 43 B' Ex. 40 B
44 45 41 C HFO-1132(E) mass % 49.1 36.9 25.5 20.0 0.0 50.0 60.0
69.7 HFO-1123 mass % 0.0 10.0 20.0 26.9 45.3 15.8 11.9 8.5 R1234yf
mass % 29.1 31.3 20.0 31.3 32.9 12.4 63 0.0 R32 mass % 21.8 21.8
21.8 21.8 21.8 21.8 21.8 21.8 GWP -- 148.8 148.9 148.9 148.9 148.9
148.3 148.1 147.9 COP ratio % (relative 97.6 96.9 96.4 95.9 95.5
95.0 95.0 95.0 to R410 Refrigerating % (relative 95.0 95.0 95.0
98.4 95.0 105.6 108.0 110.3 capacity ratio to R410A)
[0148] These results indicate that the refrigerants according to
the present disclosure that satisfy the following conditions have a
refrigerating capacity ratio of 95% or more relative to that of
R410A, and a COP ratio of 95% or more relative to that of
R410A:
[0149] when the mass % of HFO-1132(E), HFO-1123, R1234yf, and R32
based on their sum is respectively represented by x, y, z, and
a,
[0150] if 0<a.ltoreq.1.0.0, coordinates (x,y,z) in a ternary
composition diagram (FIGS. 3 to 9) in which the sum of HFO-1132(E),
HFO-1123, and R1234yf is (100-a) mass % are within the range of a
figure surrounded by straight lines that connect the following 4
points:
point A (0.02a.sup.2-2.46a+93.4, 0, -0.02a.sup.2+1.46a+6.6), point
B'(-0.008a.sup.2-1.38a+56, 0.018a.sup.2-0.53a+26.3,
-0.01a.sup.2+0.91a+17.7), point C (-0.016a.sup.2+0.02a+77.6,
0.016a.sup.2-1.02a+22.4, 0), and point O (100.0-a, 0.0, 0.0), or on
the straight lines OA, AB', and B'C (excluding the points O and
C);
[0151] if 10.0<a.ltoreq.16.5, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points:
point A (0.0244a.sup.2-2.5695a+94.056, 0,
-0.0244a.sup.2+1.5695a+5.944), point
B'(0.0161a.sup.2-1.9959a+59.749, 0.014a.sup.2-0.3399a+24.8,
-0.0301a.sup.2+1.3358a+15.451), point C
(-0.0161a.sup.2-0.0041a+77.851, 0.0161a.sup.2-0.9959a+22.149, 0),
and point O (100.0-a, 0.0, 0.0), or on the straight lines OA, AB',
and B'C (excluding the points O and C); or
[0152] if 16.5<a.ltoreq.21.8, coordinates (x,y,z) in the ternary
composition diagram are within the range of a figure surrounded by
straight lines that connect the following 4 points:
point A (0.0161a.sup.2-2.3535a+92.742, 0,
-0.0161a.sup.2+1.3535a+7.258), point
B'(-0.0435a.sup.2-0.4456a+50.406, -0.0304a.sup.2+1.8991a-0.0661,
0.0739a.sup.2-2.4535a+49.6601), point C
(-0.0263a.sup.2+0.3107a+75.444, 0.0263a.sup.2-1.3107a+24.556, 0),
and point O (100.0-a, 0.0, 0.0), or on the straight lines OA, AB',
and B'C (excluding the points O and C).
[0153] FIGS. 3 to 9 show compositions whose R32 content a (mass %)
is 0 mass %, 5 mass %, 10 mass %, 14.3 mass %, 16.5 mass %, 19.2
mass %, and 21.8 mass %, respectively.
[0154] Note that when point B in the ternary composition diagram is
defined as a point where a refrigerating capacity ratio of 95%
relative to that of R410A and a COP ratio of 95% relative to that
of R410A are both achieved, point B' is the intersection of
straight line AB and an approximate line formed by connecting three
points, including point C, where the COP ratio relative to that of
R410A is 95%.
[0155] Points A, B', and C were individually obtained by
approximate calculation in the following manner.
[0156] Point A is a point where the HFO-1123 content is 0 mass %
and a refrigerating capacity ratio of 95% relative to that of R410A
is achieved. Three points corresponding to point A were obtained in
each of the following three ranges by calculation, and their
approximate expressions were obtained.
TABLE-US-00013 TABLE 13 Item 10.0 .gtoreq. R32 .gtoreq. 0 16.5
.gtoreq. R32 .gtoreq. 10.0 21.8 .gtoreq. R32 .gtoreq. 16.5 R32 0.0
5.0 10.0 10.0 14.3 16.5 16.5 19.2 21.8 HFO-1132(E) 93.4 81.6 70.8
70.8 62.3 58.3 58.3 53.5 49.1 HFO-1123 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 R1234yf 6.6 13.4 19.2 192 23.4 25.2 25.2 27.3 29.1 R32 A a
a HFO-1132(E) 0.02a2 - 2.46a + 93.4 0.0244a2 - 2.5695a + 94.056
0.0161a2 - 2.3535a + 92.742 approximate expression HFO-1123 0 0 0
approximate expression R1234yf 100 - R32 - HFO - 1132(E) 100 - R32
- HFO - 1132(E) 100 - R32 - HFO - 1132(E) approximate
expression
[0157] Point C is a point where the R1234yf content is 0 mass % and
a COP ratio of 95% relative to that of R410A is achieved. Three
points corresponding to point C were obtained in each of the
following three ranges by calculation, and their approximate
expressions were obtained.
TABLE-US-00014 TABLE 14 Item 10.0 .gtoreq. R32 .gtoreq. 0 16.5
.gtoreq. R32 .gtoreq. 10.0 21.8 .gtoreq. R32 .gtoreq. 16.5 R32 0 5
10 10 14.3 16.5 16.5 19.2 21.8 HFO-1132(E) 77.6 77.3 76.2 76.2 74.5
73.4 73.4 71.7 69.7 HFO-1123 22.4 17.7 13.8 13.8 11.2 10.1 10.1 9.1
8.5 R1234yf 0 0 0 0 0 0 0 0 0 R32 A a A HFO-1132(E) 100 - R32 - HFO
- 1123 100 - R32 - HFO - 1123 100 - R32 - HFO - 1123 approximate
expression HFO-1123 0.016a2 - 1.02a + 22.4 0.0161a2 - 0.9959a +
22.149 0.0263a2 - 1.3107a + 24.556 approximate expression R1234yf 0
0 0 approximate expression
[0158] Three points corresponding to point B' were obtained in each
of the following three ranges by calculation, and their approximate
expressions were obtained.
TABLE-US-00015 TABLE 15 Item 10.0 .gtoreq. R32 .gtoreq. 0 16.5
.gtoreq. R32 .gtoreq. 10.0 21.8 .gtoreq. R32 .gtoreq. 16.5 R32 0 5
10 10 14.3 16.5 16.5 19.2 21.8 HFO-1132(E) 56 48.9 41.4 41.4 34.5
31.2 31.2 25.8 20 HFO-1123 26.3 24.1 22.8 22.8 22.8 23 23 25.2 26.9
R1234yf 17.7 22 25.8 25.8 28.4 29.3 29.3 29.8 31.3 R32 a a a
HFO-1132(E) -0.008a2 - 1.38a + 56 0.0161a2 - 1.9959a + 59.749
-0.0435a2 - 0.4456a + 50.406 approximate expression HFO-1123
0.018a2 - 0.53a + 26.3 0.014a2 - 0.3399a + 24.8 -0.0304a2 + 1.8991a
- 0.0661 approximate expression R1234yf 100 - R32 - HFO - 1132(E) -
HFO - 1123 100 - R32 - HFO - 1132(E) - HFO - 1123 100 - R32 - HFO -
1132(E) - HFO - 1123 approximate expression
DESCRIPTION OF REFERENCE NUMERALS
[0159] 1: Sample cell [0160] 2: High-speed camera [0161] 3: Xenon
lamp [0162] 4: Collimating lens [0163] 5: Collimating lens [0164]
6: Ring filter
* * * * *