U.S. patent application number 15/825975 was filed with the patent office on 2018-03-22 for working fluid for heat cycle, composition for heat cycle system and heat cycle system.
This patent application is currently assigned to ASAHI GLASS COMPANY, LIMITED. The applicant listed for this patent is ASAHI GLASS COMPANY, LIMITED. Invention is credited to Masato FUKUSHIMA, Hiroki HAYAMIZU, Hidekazu OKAMOTO, Hikaru ONO, Toshiyuki TANAKA, Mai TASAKA, Katsuya UENO.
Application Number | 20180079941 15/825975 |
Document ID | / |
Family ID | 57441077 |
Filed Date | 2018-03-22 |
United States Patent
Application |
20180079941 |
Kind Code |
A1 |
UENO; Katsuya ; et
al. |
March 22, 2018 |
WORKING FLUID FOR HEAT CYCLE, COMPOSITION FOR HEAT CYCLE SYSTEM AND
HEAT CYCLE SYSTEM
Abstract
A working fluid for a heat cycle, contains: trifluoroethylene;
and a first component consisting of at least one of substance
selected from carbon dioxide, fluoromethane, trifluoroiodomethane,
methane, ethane, propane, helium, neon, argon, krypton, xenon,
nitrogen and ammonia.
Inventors: |
UENO; Katsuya; (Chiyoda-ku,
JP) ; ONO; Hikaru; (Chiyoda-ku, JP) ; TANAKA;
Toshiyuki; (Chiyoda-ku, JP) ; OKAMOTO; Hidekazu;
(Chiyoda-ku, JP) ; HAYAMIZU; Hiroki; (Chiyoda-ku,
JP) ; FUKUSHIMA; Masato; (Chiyoda-ku, JP) ;
TASAKA; Mai; (Chiyoda-ku, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ASAHI GLASS COMPANY, LIMITED |
Chiyoda-ku |
|
JP |
|
|
Assignee: |
ASAHI GLASS COMPANY,
LIMITED
Chiyoda-ku
JP
|
Family ID: |
57441077 |
Appl. No.: |
15/825975 |
Filed: |
November 29, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2016/065818 |
May 27, 2016 |
|
|
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15825975 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 2205/13 20130101;
C09K 5/044 20130101; C09K 2205/126 20130101; C09K 5/04 20130101;
C09K 5/045 20130101; C09K 2205/132 20130101; C09K 2205/40 20130101;
C09K 2205/12 20130101; C09K 2205/106 20130101 |
International
Class: |
C09K 5/04 20060101
C09K005/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 1, 2015 |
JP |
2015-111614 |
Claims
1. A working fluid for a heat cycle, comprising: trifluoroethylene;
and a first component consisting of at least one of substance
selected from carbon dioxide, fluoromethane, trifluoroiodomethane,
methane, ethane, propane, helium, neon, argon, krypton, xenon,
nitrogen and ammonia.
2. The working fluid for the heat cycle according to claim 1,
wherein the first component is consisting of at least one of
substance selected from carbon dioxide, fluoromethane,
trifluoroiodomethane and propane.
3. The working fluid for the heat cycle according to claim 1,
wherein carbon dioxide is contained as the first component.
4. The working fluid for the heat cycle according to claim 1,
wherein fluoromethane is contained as the first component.
5. The working fluid for the heat cycle according to claim 1,
wherein trifluoroiodomethane is contained as the first
component.
6. The working fluid for the heat cycle according to claim 1,
wherein propane is contained as the first component.
7. The working fluid for the heat cycle according to claim 1,
wherein a ratio of a total amount of the trifluoroethylene and the
first component with respect to an entire amount of the working
fluid for the heat cycle is over 90 mass % and 100 mass % or less,
and wherein a ratio of an amount of the trifluoroethylene with
respect to the total amount of the trifluoroethylene and the first
component is 20 mass % or more and 95 mass % or less.
8. The working fluid for the heat cycle according to claim 3,
wherein a ratio of a total amount of the trifluoroethylene and the
carbon dioxide with respect to an entire amount of the working
fluid for the heat cycle is over 90 mass % and 100 mass % or less,
and wherein a ratio of an amount of the trifluoroethylene with
respect to the total amount of the trifluoroethylene and the carbon
dioxide is 70 mass % or more and 80 mass % or less.
9. The working fluid for the heat cycle according to claim 4,
wherein a ratio of a total amount of the trifluoroethylene and the
fluoromethane with respect to an entire amount of the working fluid
for the heat cycle is over 90 mass % and 100 mass % or less, and
wherein a ratio of an amount of the trifluoroethylene with respect
to the total amount of the trifluoroethylene and the fluoromethane
is 20 mass % or more and 80 mass % or less.
10. The working fluid for the heat cycle according to claim 5,
wherein a ratio of a total amount of the trifluoroethylene and the
trifluoroiodomethane with respect to an entire amount of the
working fluid for the heat cycle is over 90 mass % and 100 mass %
or less, and wherein a ratio of an amount of the trifluoroethylene
with respect to the total amount of the trifluoroethylene and the
trifluoroiodomethane is 60 mass % or more and 80 mass % or
less.
11. The working fluid for the heat cycle according to claim 6,
wherein a ratio of a total amount of the trifluoroethylene and the
propane with respect to an entire amount of the working fluid for
the heat cycle is over 90 mass % and 100 mass % or less, and
wherein a ratio of an amount of the trifluoroethylene with respect
to the total amount of the trifluoroethylene and the propane is 20
mass % or more and 95 mass % or less.
12. The working fluid for the heat cycle according to claim 1,
further comprising: a second component consisting of at least one
of substance selected from hydrofluorocarbon where fluoromethane is
excluded and hydrofluoroolefin where trifluoroethylene is excluded,
wherein the hydrofluorocarbon and the hydrofluoroolefin have a
global warming potential (100 years) in the Intergovernmental Panel
on Climate Change (IPCC) Fourth Assessment Report of 2000 or
less.
13. The working fluid for the heat cycle according to claim 12,
wherein the second component is consisting of at least one of
substance selected from 2,3,3,3-tetrafluoropropene,
1,3,3,3-tetrafluoropropene and difluoromethane.
14. The working fluid for the heat cycle according to claim 12,
wherein difluoromethane is contained as the second component.
15. The working fluid for the heat cycle according to claim 12,
wherein 2,3,3,3-tetrafluoropropene is contained as the second
component.
16. The working fluid for the heat cycle according to claim 12,
wherein 1,3,3,3-tetrafluoropropene is contained as the second
component.
17. The working fluid for the heat cycle according to claim 12,
wherein a ratio of a total amount of the trifluoroethylene, the
first component and the second component with respect to an entire
amount of the working fluid for the heat cycle is over 90 mass %
and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the first component and the second component is
10 mass % or more and 90 mass % or less, wherein a ratio of an
amount of the first component with respect to the total amount of
the trifluoroethylene, the first component and the second component
is 1 mass % or more and 50 mass % or less, and wherein a ratio of
an amount of the second component with respect to the total amount
of the trifluoroethylene, the first component and the second
component is 1 mass % or more and 70 mass % or less.
18. The working fluid for the heat cycle according to claim 12,
wherein a ratio of a total amount of the trifluoroethylene, the
carbon dioxide and the second component with respect to an entire
amount of the working fluid for the heat cycle is over 90 mass %
and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the second component is
10 mass % or more and 90 mass % or less, wherein a ratio of an
amount of the carbon dioxide with respect to the total amount of
the trifluoroethylene, the carbon dioxide and the second component
is 1 mass % or more and 50 mass % or less, and wherein a ratio of
an amount of the second component with respect to the total amount
of the trifluoroethylene, the carbon dioxide and the second
component is 1 mass % or more and 70 mass % or less.
19. The working fluid for the heat cycle according to claim 14,
wherein a ratio of a total amount of the trifluoroethylene, the
carbon dioxide and the difluoromethane with respect to an entire
amount of the working fluid for the heat cycle is over 90 mass %
and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the difluoromethane is 10
mass % or more and 90 mass % or less, wherein a ratio of an amount
of the carbon dioxide with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the difluoromethane is 1
mass % or more and 50 mass % or less, and wherein a ratio of an
amount of the difluoromethane with respect to the total amount of
the trifluoroethylene, the carbon dioxide and the difluoromethane
is 1 mass % or more and 29 mass % or less.
20. The working fluid for the heat cycle according to claim 15,
wherein a ratio of a total amount of the trifluoroethylene, the
carbon dioxide and the 2,3,3,3-tetrafluoropropene with respect to
an entire amount of the working fluid for the heat cycle is over 90
mass % and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the
2,3,3,3-tetrafluoropropene is 10 mass % or more and 90 mass % or
less, wherein a ratio of an amount of the carbon dioxide with
respect to the total amount of the trifluoroethylene, the carbon
dioxide and the 2,3,3,3-tetrafluoropropene is 1 mass % or more and
50 mass % or less, and wherein a ratio of an amount of the
2,3,3,3-tetrafluoropropene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the
2,3,3,3-tetrafluoropropene is 1 mass % or more and 70 mass % or
less.
21. The working fluid for the heat cycle according to claim 16,
wherein a ratio of a total amount of the trifluoroethylene, the
carbon dioxide and the 1,3,3,3-tetrafluoropropene with respect to
an entire amount of the working fluid for the heat cycle is over 90
mass % and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the
1,3,3,3-tetrafluoropropene is 10 mass % or more and 90 mass % or
less, wherein a ratio of an amount of the carbon dioxide with
respect to the total amount of the trifluoroethylene, the carbon
dioxide and the 1,3,3,3-tetrafluoropropene is 1 mass % or more and
50 mass % or less, and wherein a ratio of an amount of the
1,3,3,3-tetrafluoropropene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the
1,3,3,3-tetrafluoropropene is 1 mass % or more and 70 mass % or
less.
22. The working fluid for the heat cycle according to claim 12,
wherein a ratio of a total amount of the trifluoroethylene, the
propane and the second component with respect to an entire amount
of the working fluid for the heat cycle is over 90 mass % and 100
mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the propane and the second component is 20 mass
% or more and 95 mass % or less, wherein a ratio of an amount of
the propane with respect to the total amount of the
trifluoroethylene, the propane and the second component is 1 mass %
or more and 75 mass % or less, and wherein a ratio of an amount of
the second component with respect to the total amount of the
trifluoroethylene, the propane and the second component is 1 mass %
or more and 75 mass % or less.
23. The working fluid for the heat cycle according to claim 14,
wherein a ratio of a total amount of the trifluoroethylene, the
propane and the difluoromethane with respect to an entire amount of
the working fluid for the heat cycle is over 90 mass % and 100 mass
% or less, wherein a ratio of an amount of the trifluoroethylene
with respect to the total amount of the trifluoroethylene, the
propane and the difluoromethane is 20 mass % or more and 95 mass %
or less, wherein a ratio of an amount of the propane with respect
to the total amount of the trifluoroethylene, the propane and the
difluoromethane is 1 mass % or more and 75 mass % or less, and
wherein a ratio of an amount of the difluoromethane with respect to
the total amount of the trifluoroethylene, the propane and the
difluoromethane is 1 mass % or more and 75 mass % or less.
24. The working fluid for the heat cycle according to claim 15,
wherein a ratio of a total amount of the trifluoroethylene, the
propane and the 2,3,3,3-tetrafluoropropene with respect to an
entire amount of the working fluid for the heat cycle is over 90
mass % and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the propane and the 2,3,3,3-tetrafluoropropene
is 20 mass % or more and 95 mass % or less, wherein a ratio of an
amount of the propane with respect to the total amount of the
trifluoroethylene, the propane and the 2,3,3,3-tetrafluoropropene
is 1 mass % or more and 75 mass % or less, and wherein a ratio of
an amount of the 2,3,3,3-tetrafluoropropene with respect to the
total amount of the trifluoroethylene, the propane and the
2,3,3,3-tetrafluoropropene is 1 mass % or more and 75 mass % or
less.
25. The working fluid for the heat cycle according to claim 16,
wherein a ratio of a total amount of the trifluoroethylene, the
propane and the 1,3,3,3-tetrafluoropropene with respect to an
entire amount of the working fluid for the heat cycle is over 90
mass % and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the propane and the 1,3,3,3-tetrafluoropropene
is 20 mass % or more and 95 mass % or less, wherein a ratio of an
amount of the propane with respect to the total amount of the
trifluoroethylene, the propane and the 1,3,3,3-tetrafluoropropene
is 1 mass % or more and 75 mass % or less, and wherein a ratio of
an amount of the 1,3,3,3-tetrafluoropropene with respect to the
total amount of the trifluoroethylene, the propane and the
1,3,3,3-tetrafluoropropene is 1 mass % or more and 75 mass % or
less.
26. A composition for a heat cycle system, comprising the working
fluid for the heat cycle according to claim 1.
27. A heat cycle system using the composition for the heat cycle
system according to claim 26.
28. The heat cycle system according to claim 27, wherein the heat
cycle system is a refrigerating apparatus, an air-conditioning
apparatus, a power generation system, a heat transport apparatus or
a secondary cooling machine.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of prior International
Application No. PCT/JP2016/065818 filed on May 27, 2016, which is
based upon and claims the benefit of priority from Japanese Patent
Application No. 2015-111614 filed on Jun. 1, 2015; the entire
contents of all of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a working fluid for a heat
cycle, a composition for a heat cycle system and a heat cycle
system using the composition.
BACKGROUND
[0003] In this specification, abbreviated names of halogenated
hydrocarbon compounds are described in parentheses after the
compound names, and the abbreviated names are employed in place of
the compound names as necessary.
[0004] Conventionally, as a working fluid for a heat cycle system
such as a refrigerant for a refrigerator, a refrigerant for an
air-conditioning apparatus, a working fluid for a power generation
system (such as an exhaust heat recovery power generation), a
working fluid for a latent heat transport apparatus (such as a heat
pipe), or a secondary cooling medium, there have been used
chlorofluorocarbon (CFC) such as chlorotrifluoromethane or
dichlorodifluoromethane, and hydrochlorofluorocarbon (HCFC) such as
chlorodifluoromethane. However, effects of CFC and HCFC on the
ozone layer in the stratosphere have been pointed out, and they are
subjected to regulation at present.
[0005] Under such circumstances, as a working fluid for a heat
cycle system, hydrofluorocarbons (HFC) having less effect on the
ozone layer, such as difluoromethane (HFC-32), tetrafluoroethane,
and pentafluoroethane (HFC-125), have been used in place of CFC and
HCFC. For example, R410A (a pseudoazeotropic mixture refrigerant of
HFC-32 and HFC-125 at a mass ratio of 1:1) or the like is a
refrigerant that has been widely used conventionally. However, it
has been pointed out that HFCs may cause global warming.
[0006] R410A has been widely used for normal air-conditioning
apparatuses or the like what is called a packaged air-conditioner
and a room air-conditioner due to its high refrigerating capacity.
However, R410A has a global warming potential (GWP) as high as
2088. It is therefore required to develop a low GWP working fluid.
In this case, it is required to develop a working fluid on the
premise that an apparatus which has been used is continuously used
as it is just by replacing R410A.
[0007] In recent years, expectations are concentrated on
hydrofluoroolefin (HFO), that is, HFC having a carbon-carbon double
bond, which is a working fluid having less effect on the ozone
layer and less effect on global warming because the carbon-carbon
double bond is likely to be decomposed by OH radicals in the air.
In this specification, saturated HFC is called HFC and
discriminated from HFO unless otherwise stated. Further, HFC may be
clearly described as saturated hydrofluorocarbon in some cases.
[0008] As a working fluid using HFO, for example, there is
disclosed a technology relating to a working fluid using
trifluoroethylene (HFO-1123) having the above-stated properties and
capable of obtaining excellent cycle performance in Patent Document
1 (WO 2012/157764 A1). In Patent Document 1, there has further been
attempted to enable a working fluid where various HFCs and HFOs are
used in combination with HFO-1123 in order to increase
incombustibility, cycle performance, and so on of the working
fluid.
[0009] Note that HFO-1123 is known to undergo what is called a
self-decomposition reaction when there is an ignition source at
higher temperature or under high pressure. Accordingly, there is a
problem that it is necessary to improve durability of a working
fluid for a heat cycle using HFO-1123 by suppressing a
self-decomposition property when a composition containing HFO-1123
is practically used as the working fluid for the heat cycle.
SUMMARY
[0010] However, there is no information or suggestion in Patent
Document 1 about combining HFO-1123 and other compounds to make a
working fluid from viewpoints of exerting less effect on global
warming, providing cycle performance such as capacity and
efficiency capable of replacing R410A, suppressing a
self-decomposition property, and so on, as a replacement candidate
of R410A.
[0011] The present invention has been made from the above-described
viewpoints, and an object thereof is to provide: a working fluid
for a heat cycle and a composition for a heat cycle system
containing trifluoroethylene (HFO-1123), sufficiently exerting
excellent cycle performance held by HFO-1123, suppressing a
self-decomposition property and having a low global warming
potential; and a heat cycle system using the composition, exerting
less effect on global warming, and including both high cycle
performance and durability.
[0012] The present invention provides a working fluid for a heat
cycle, a composition for a heat cycle system and a heat cycle
system having the following configurations described in [1] to
[28].
[0013] [1] A working fluid for a heat cycle, comprising:
trifluoroethylene; and a first component consisting of at least one
of substance selected from carbon dioxide, fluoromethane,
trifluoroiodomethane, methane, ethane, propane, helium, neon,
argon, krypton, xenon, nitrogen and ammonia.
[0014] [2] The working fluid for the heat cycle according to [1],
wherein the first component is consisting of at least one of
substance selected from carbon dioxide, fluoromethane,
trifluoroiodomethane and propane.
[0015] [3] The working fluid for the heat cycle according to [1],
wherein carbon dioxide is contained as the first component.
[0016] [4] The working fluid for the heat cycle according to [1],
wherein fluoromethane is contained as the first component.
[0017] [5] The working fluid for the heat cycle according to [1],
wherein trifluoroiodomethane is contained as the first
component.
[0018] [6] The working fluid for the heat cycle according to [1],
wherein propane is contained as the first component.
[0019] [7] The working fluid for the heat cycle according to [1],
wherein a ratio of a total amount of the trifluoroethylene and the
first component with respect to an entire amount of the working
fluid for the heat cycle is over 90 mass % and 100 mass % or less,
and wherein a ratio of an amount of the trifluoroethylene with
respect to the total amount of the trifluoroethylene and the first
component is 20 mass % or more and 95 mass % or less.
[0020] [8] The working fluid for the heat cycle according to [3],
wherein a ratio of a total amount of the trifluoroethylene and the
carbon dioxide with respect to an entire amount of the working
fluid for the heat cycle is over 90 mass % and 100 mass % or less,
and wherein a ratio of an amount of the trifluoroethylene with
respect to the total amount of the trifluoroethylene and the carbon
dioxide is 70 mass % or more and 80 mass % or less.
[0021] [9] The working fluid for the heat cycle according to [4],
wherein a ratio of a total amount of the trifluoroethylene and the
fluoromethane with respect to an entire amount of the working fluid
for the heat cycle is over 90 mass % and 100 mass % or less, and
wherein a ratio of an amount of the trifluoroethylene with respect
to the total amount of the trifluoroethylene and the fluoromethane
is 20 mass % or more and 80 mass % or less.
[0022] [10] The working fluid for the heat cycle according to [5],
wherein a ratio of a total amount of the trifluoroethylene and the
trifluoroiodomethane with respect to an entire amount of the
working fluid for the heat cycle is over 90 mass % and 100 mass %
or less, and wherein a ratio of an amount of the trifluoroethylene
with respect to the total amount of the trifluoroethylene and the
trifluoroiodomethane is 60 mass % or more and 80 mass % or
less.
[0023] [11] The working fluid for the heat cycle according to [6],
wherein a ratio of a total amount of the trifluoroethylene and the
propane with respect to an entire amount of the working fluid for
the heat cycle is over 90 mass % and 100 mass % or less, and
wherein a ratio of an amount of the trifluoroethylene with respect
to the total amount of the trifluoroethylene and the propane is 20
mass % or more and 95 mass % or less.
[0024] [12] The working fluid for the heat cycle according to [1],
further comprising: a second component consisting of at least one
of substance selected from hydrofluorocarbon except fluoromethane
and hydrofluoroolefin except trifluoroethylene, and wherein the
hydrofluorocarbon and the hydrofluoroolefin have a global warming
potential (100 years) in the Intergovernmental Panel on Climate
Change (IPCC) Fourth Assessment Report of 2000 or less.
[0025] [13] The working fluid for the heat cycle according to [12],
wherein the second component is consisting of at least one of
substance selected from 2,3,3,3-tetrafluoropropene,
1,3,3,3-tetrafluoropropene and difluoromethane.
[0026] [14] The working fluid for the heat cycle according to [12],
wherein difluoromethane is contained as the second component.
[0027] [15] The working fluid for the heat cycle according to [12],
wherein 2,3,3,3-tetrafluoropropene is contained as the second
component.
[0028] [16] The working fluid for the heat cycle according to [12],
wherein 1,3,3,3-tetrafluoropropene is contained as the second
component.
[0029] [17] The working fluid for the heat cycle according to [12],
wherein a ratio of a total amount of the trifluoroethylene, the
first component and the second component with respect to an entire
amount of the working fluid for the heat cycle is over 90 mass %
and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the first component and the second component is
10 mass % or more and 90 mass % or less, wherein a ratio of an
amount of the first component with respect to the total amount of
the trifluoroethylene, the first component and the second component
is 1 mass % or more and 50 mass % or less, and wherein a ratio of
an amount of the second component with respect to the total amount
of the trifluoroethylene, the first component and the second
component is 1 mass % or more and 70 mass % or less.
[0030] [18] The working fluid for the heat cycle according to [12],
wherein a ratio of a total amount of the trifluoroethylene, the
carbon dioxide and the second component with respect to an entire
amount of the working fluid for the heat cycle is over 90 mass %
and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the second component is
10 mass % or more and 90 mass % or less, wherein a ratio of an
amount of the carbon dioxide with respect to the total amount of
the trifluoroethylene, the carbon dioxide and the second component
is 1 mass % or more and 50 mass % or less, and wherein a ratio of
an amount of the second component with respect to the total amount
of the trifluoroethylene, the carbon dioxide and the second
component is 1 mass % or more and 70 mass % or less.
[0031] [19] The working fluid for the heat cycle according to [14],
wherein a ratio of a total amount of the trifluoroethylene, the
carbon dioxide and the difluoromethane with respect to an entire
amount of the working fluid for the heat cycle is over 90 mass %
and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the difluoromethane is 10
mass % or more and 90 mass % or less, wherein a ratio of an amount
of the carbon dioxide with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the difluoromethane is 1
mass % or more and 50 mass % or less, and wherein a ratio of an
amount of the difluoromethane with respect to the total amount of
the trifluoroethylene, the carbon dioxide and the difluoromethane
is 1 mass % or more and 29 mass % or less.
[0032] [20] The working fluid for the heat cycle according to [15],
wherein a ratio of a total amount of the trifluoroethylene, the
carbon dioxide and the 2,3,3,3-tetrafluoropropene with respect to
an entire amount of the working fluid for the heat cycle is over 90
mass % and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the
2,3,3,3-tetrafluoropropene is 10 mass % or more and 90 mass % or
less, wherein a ratio of an amount of the carbon dioxide with
respect to the total amount of the trifluoroethylene, the carbon
dioxide and the 2,3,3,3-tetrafluoropropene is 1 mass % or more and
50 mass % or less, and wherein a ratio of an amount of the
2,3,3,3-tetrafluoropropene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the
2,3,3,3-tetrafluoropropene is 1 mass % or more and 70 mass % or
less.
[0033] [21] The working fluid for the heat cycle according to [16],
wherein a ratio of a total amount of the trifluoroethylene, the
carbon dioxide and the 1,3,3,3-tetrafluoropropene with respect to
an entire amount of the working fluid for the heat cycle is over 90
mass % and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the
1,3,3,3-tetrafluoropropene is 10 mass % or more and 90 mass % or
less, wherein a ratio of an amount of the carbon dioxide with
respect to the total amount of the trifluoroethylene, the carbon
dioxide and the 1,3,3,3-tetrafluoropropene is 1 mass % or more and
50 mass % or less, and wherein a ratio of an amount of the
1,3,3,3-tetrafluoropropene with respect to the total amount of the
trifluoroethylene, the carbon dioxide and the
1,3,3,3-tetrafluoropropene is 1 mass % or more and 70 mass % or
less.
[0034] [22] The working fluid for the heat cycle according to [12],
wherein a ratio of a total amount of the trifluoroethylene, the
propane and the second component with respect to an entire amount
of the working fluid for the heat cycle is over 90 mass % and 100
mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the propane and the second component is 20 mass
% or more and 95 mass % or less, wherein a ratio of an amount of
the propane with respect to the total amount of the
trifluoroethylene, the propane and the second component is 1 mass %
or more and 75 mass % or less, and wherein a ratio of an amount of
the second component with respect to the total amount of the
trifluoroethylene, the propane and the second component is 1 mass %
or more and 75 mass % or less.
[0035] [23] The working fluid for the heat cycle according to [14],
wherein a ratio of a total amount of the trifluoroethylene, the
propane and the difluoromethane with respect to an entire amount of
the working fluid for the heat cycle is over 90 mass % and 100 mass
% or less, wherein a ratio of an amount of the trifluoroethylene
with respect to the total amount of the trifluoroethylene, the
propane and the difluoromethane is 20 mass % or more and 95 mass %
or less, wherein a ratio of an amount of the propane with respect
to the total amount of the trifluoroethylene, the propane and the
difluoromethane is 1 mass % or more and 75 mass % or less, and
wherein a ratio of an amount of the difluoromethane with respect to
the total amount of the trifluoroethylene, the propane and the
difluoromethane is 1 mass % or more and 75 mass % or less.
[0036] [24] The working fluid for the heat cycle according to [15],
wherein a ratio of a total amount of the trifluoroethylene, the
propane and the 2,3,3,3-tetrafluoropropene with respect to an
entire amount of the working fluid for the heat cycle is over 90
mass % and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the propane and the 2,3,3,3-tetrafluoropropene
is 20 mass % or more and 95 mass % or less, wherein a ratio of an
amount of the propane with respect to the total amount of the
trifluoroethylene, the propane and the 2,3,3,3-tetrafluoropropene
is 1 mass % or more and 75 mass % or less, and wherein a ratio of
an amount of the 2,3,3,3-tetrafluoropropene with respect to the
total amount of the trifluoroethylene, the propane and the
2,3,3,3-tetrafluoropropene is 1 mass % or more and 75 mass % or
less.
[0037] [25] The working fluid for the heat cycle according to [16],
wherein a ratio of a total amount of the trifluoroethylene, the
propane and the 1,3,3,3-tetrafluoropropene with respect to an
entire amount of the working fluid for the heat cycle is over 90
mass % and 100 mass % or less, wherein a ratio of an amount of the
trifluoroethylene with respect to the total amount of the
trifluoroethylene, the propane and the 1,3,3,3-tetrafluoropropene
is 20 mass % or more and 95 mass % or less, wherein a ratio of an
amount of the propane with respect to the total amount of the
trifluoroethylene, the propane and the 1,3,3,3-tetrafluoropropene
is 1 mass % or more and 75 mass % or less, and wherein a ratio of
an amount of the 1,3,3,3-tetrafluoropropene with respect to the
total amount of the trifluoroethylene, the propane and the
1,3,3,3-tetrafluoropropene is 1 mass % or more and 75 mass % or
less.
[0038] [26] A composition for a heat cycle system, comprising the
working fluid for the heat cycle according to [1].
[0039] [27] A heat cycle system using the composition for the heat
cycle system according to [26].
[0040] [28] The heat cycle system according to [27], wherein the
heat cycle system is a refrigerating apparatus, an air-conditioning
apparatus, a power generation system, a heat transport apparatus or
a secondary cooling machine.
[0041] According to the present invention, it is possible to
provide a working fluid for a heat cycle and a composition for a
heat cycle system containing trifluoroethylene (HFO-1123), exerting
excellent cycle performance held by HFO-1123, suppressing a
self-decomposition property, and further having a low global
warming potential.
[0042] Furthermore, according to the present invention, it is
possible to provide a heat cycle system that has less effect on
global warming and includes both high cycle performance and
durability.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] FIG. 1 is a schematic configuration diagram illustrating a
refrigeration cycle system being one example of a heat cycle system
of the present invention.
[0044] FIG. 2 is a cycle chart illustrating change of state of a
working fluid for a heat cycle in the refrigeration cycle system in
FIG. 1 on a pressure-enthalpy line diagram.
DETAILED DESCRIPTION
[0045] Hereinafter, there will be explained an embodiment of the
present invention.
[0046] <Working Medium for Heat Cycle>
[0047] A working fluid for a heat cycle of this invention contains
HFO-1123 and a first component. The first component is consisting
of at least one of substance selected from carbon dioxide,
fluoromethane (HFC-41), trifluoroiodomethane, methane, ethane,
propane, helium, neon, argon, krypton, xenon, nitrogen and ammonia.
In the first component, one of substance may be independently
contained, or two or more of substances may be contained. The first
component is a component capable of suppressing a
self-decomposition property of HFO-1123 while exerting high cycle
performance of HFO-1123 in the working fluid for the heat cycle
when the first component is used together with HFO-1123 to be made
into the working fluid for the heat cycle.
[0048] The working fluid for the heat cycle of this invention may
further contain a second component. The second component is
consisting of at least one of substance selected from
hydrofluorocarbon other than HFC-41, and hydrofluoroolefin other
than HFO-1123 having a global warming potential (GWP) of 2000 or
less. In the second component, one of substance may be
independently contained, or two or more of substances may be
contained. The global warming potential (GWP) is a value over 100
years described in the Intergovernmental Panel on Climate Change
(IPCC) Fourth Assessment Report (2007), or measured according to a
method described in this report. In this specification, the GWP
means this value unless otherwise stated.
[0049] (Heat Cycle System)
[0050] As a heat cycle system to which the working fluid for the
heat cycle of this invention is applied, a heat cycle system having
a heat exchanger such as a condenser or an evaporator is used
without any particular limitation. The heat cycle system, for
example, a refrigeration cycle system has a mechanism of: a
compressor to compress a gaseous working fluid; a condenser to
obtain a high-pressured liquid by cooling; an expansion valve to
lower the pressure of the high-pressured liquid; and an evapolator
to make evaporation at lower temperature for removing heat by the
heat of vaporization.
[0051] (HFO-1123)
[0052] Relative cycle performance (a relative coefficient of
performance and a relative refrigerating capacity) of HFO-1123
contained as the working fluid for the heat cycle of this invention
are illustrated in Table 1. The relative cycle performance of
HFO-1123 is a relative comparison with R410A (a pseudoazeotropic
mixture refrigerant of HFC-32 and HFC-125 at a mass ratio of
1:1).
TABLE-US-00001 TABLE 1 R410A HFO-1123 Relative coefficient of
performance (RCOP.sub.R410A) 1 0.91 Relative refrigerating capacity
(RQ.sub.R410A) 1 1.11 Temperature gradient [.degree. C.] 0.2 0 GWP
2088 0.3
[0053] Here, the cycle performance is performance which is required
when a working fluid for a heat cycle is applied to a heat cycle
system, and it is evaluated by a coefficient of performance and a
capacity. When the heat cycle system is a refrigeration cycle
system, the capacity means a refrigerating capacity. The
refrigerating capacity (it is also referred to as "Q" in this
specification) is an output in the refrigeration cycle system. The
coefficient of performance (it is also referred to as "COP" in this
specification) is a value where an output (kW) is divided by motive
power (kW) which is consumed to obtain the output (kW), and it
corresponds to energy consumption efficiency. As the value of the
coefficient of performance is higher, it becomes possible to obtain
a large output by a small input. Besides, when the working fluid
for the heat cycle is made up of a mixture, a temperature gradient
becomes an important factor to evaluate the working fluid for the
heat cycle as described later, and a value of the temperature
gradient is preferably smaller.
[0054] Relative cycle performance of the working fluid for the heat
cycle (with respect to R410A) is an index indicating the cycle
performance of the working fluid for the heat cycle by a relative
comparison with the cycle performance of R410A as a replacement
object. The relative cycle performance is represented by a relative
refrigerating capacity (RQ.sub.R410A) and a relative coefficient of
performance (RCOP.sub.R410A) each found according to
later-described methods.
[0055] In this invention, a reference refrigeration cycle system is
used to set the relative cycle performance (with respect to R410A)
as the index. The reference refrigeration cycle system employs the
following temperature condition in the later-described
refrigeration cycle system. The relative refrigerating capacity of
the working fluid for the heat cycle with respect to R410A under
this condition is the relative refrigerating capacity
(RQ.sub.R410A) which is found by the following expression (X).
Similarly, the relative coefficient of performance of the working
fluid for the heat cycle with respect to R410A under this condition
is the relative coefficient of performance (RCOP.sub.R410A) which
is found by the following expression (Y). Note that in each of the
expressions (X), (Y), a sample indicates the working fluid which is
to be relatively evaluated.
[0056] [Temperature Condition]
[0057] Evaporation temperature; 0.degree. C. (note that an average
temperature of an evaporation start temperature and an evaporation
completion temperature in the case of a zeotropic mixture)
Condensation temperature; 40.degree. C. (note that an average
temperature of a condensation start temperature and a condensation
completion temperature in the case of a zeotropic mixture)
[0058] Degree of supercooling (SC); 5.degree. C.
[0059] Degree of superheating (SH); 5.degree. C.
[ Mathematical expression 1 ] Relative refrigerating capacity ( RQ
R 410 A ) = Refrigerating capacity of sample ( Q sample )
Refrigerating capacity of R 410 A ( Q R 410 A ) expression ( X )
Relative coefficient of performance ( RCOP R 410 A ) = Coefficient
of performance of sample ( COP sample ) Coefficient of performance
of R 410 A ( COP R 410 A ) expression ( Y ) ##EQU00001##
[0060] (First Component)
[0061] The first component contained in the working fluid for the
heat cycle of this invention is consisting of at least one of
substance selected from carbon dioxide, HFC-41,
trifluoroiodomethane, methane, ethane, propane, helium, neon,
argon, krypton, xenon, nitrogen and ammonia. This first component
functions as a working fluid and suppresses the self-decomposition
property of HFO-1123.
[0062] As stated above, HFO-1123 has the self-decomposition
property, and therefore, when HFO-1123 is used as the working fluid
for the heat cycle in the heat cycle system, it is exposed to a
state where what is called a self-decomposition reaction is likely
to be induced when, for example, there is an ignition source at
higher temperature or under high pressure.
[0063] In this invention, evaluation of the self-decomposition
property of the working fluid for the heat cycle is performed
specifically using a facility compliant with the A method
recommended as a facility for measuring a combustion range of gas
made by mixing gas containing halogen in an individual notification
in High Pressure Gas Safety Act, according to the following
method.
[0064] A sample (a working fluid for a heat cycle) is enclosed to a
predetermined pressure (at a gauge pressure of 5 MPa) in a
spherical pressure tight case having an internal volume of 280
cm.sup.3 controlled to a predetermined temperature (130.degree. C.)
from the outside, and then energy of about 30 J is applied thereto
by fusing a platinum wire installed therein. The temperature and
pressure changes in the pressure tight case occurring after the
application are measured, and thereby, presence of
self-decomposition reaction of the sample is determined.
[0065] When remarkable pressure rise and temperature rise are
recognized after the energy application compared to before the
energy application, it is determined that the self-decomposition
reaction of the sample occurs, that is, the sample has the
self-decomposition property. On the other hand, when the remarkable
pressure rise and temperature rise are not recognized before and
after the energy application, it is determined that the
self-decomposition reaction of the sample does not occur, that is,
the sample does not have the self-decomposition property.
[0066] When the pressure after the energy application is in a range
of 5 MPaG or more and 6 MPaG or less, it is said that the
remarkable pressure rise is not recognized with respect to an
initial pressure of 5 MPaG regarding the self-decomposition
property of the sample. Besides, when the temperature after the
energy application is in a range of 130.degree. C. or more and
150.degree. C. or less, it is said that the remarkable temperature
rise is not recognized with respect to an initial temperature.
[0067] In the working fluid for the heat cycle of this invention,
the first component is mixed with HFO-1123, and thereby, the
self-decomposition property of HFO-1123 is suppressed. Here, the
self-decomposition property of the working fluid for the heat cycle
becomes higher as a content ratio of HFO-1123 in the working fluid
for the heat cycle becomes larger and as the temperature and the
pressure become higher. The self-decomposition property of the
working fluid for the heat cycle of this invention is suppressed by
adjusting a content of the first component, and it becomes possible
to lower the self-decomposition property to avoid an accelerative
self-decomposition reaction and problems such as heat generation,
even when the working fluid is exposed to a condition causing the
self-decomposition reaction of HFO-1123 such as, for example, being
exposed under higher temperature and higher pressure than the
above-stated condition.
[0068] Besides, all of the global warming potentials of the first
components are 150 or less to be extremely lower than the global
warming potential (2088) of R410A. Accordingly, the working fluid
for the heat cycle of this invention has the low global warming
potential in addition to including excellent durability and cycle
performance by containing the first component.
[0069] Besides, a boiling point of the first component at the
atmospheric pressure (1.013.times.10.sup.5 Pa) is -269.degree. C.
or more and -20.degree. C. or less. The boiling point of the first
component is in the above-stated range, and therefore, the working
fluid for the heat cycle of this invention has a sufficiently small
temperature gradient suitable for a practical use.
[0070] The working fluid for the heat cycle of this invention
preferably contains at least one of substance selected from carbon
dioxide, HFC-41, trifluoroiodomethane and propane, more preferably
contains any one of substance from among carbon dioxide, HFC-41,
trifluoroiodomethane or propane, and further preferably contains
carbon dioxide from among the above-stated substances as the first
component in terms of suppressing the self-decomposition property
while obtaining the low global warming potential and the
sufficiently excellent cycle performance.
[0071] In the working fluid for the heat cycle of this invention, a
ratio of a total amount of HFO-1123 and the first component with
respect to an entire amount of the working fluid for the heat cycle
is preferably over 90 mass % and 100 mass % or less, more
preferably over 92 mass % and 100 mass % or less, and further
preferably over 95 mass % and 100 mass % or less in terms of
obtaining the sufficiently excellent cycle performance and the low
global warming potential.
[0072] In this case, a ratio of an amount of HFO-1123 with respect
to the total amount of HFO-1123 and the first component is
preferably 20 mass % or more and 95 mass % or less, more preferably
60 mass % or more and 80 mass % or less, and further preferably 70
mass % or more and 80 mass % or less. The ratio of HFO-1123 is 20
mass % or more, and thereby, it is possible to obtain the
sufficiently excellent cycle performance, and the ratio of HFO-1123
is 95 mass % or less, and thereby, it is possible to improve
suppression effect of the self-decomposition property of HFO-1123,
and to suppress the self-decomposition property of the working
fluid for the heat cycle under higher temperature and higher
pressure conditions.
[0073] When the working fluid for the heat cycle of this invention
contains carbon dioxide as the first component, a ratio of a total
amount of HFO-1123 and carbon dioxide with respect to the entire
amount of the working fluid for the heat cycle is preferably over
90 mass % and 100 mass % or less, more preferably over 92 mass %
and 100 mass % or less, and further preferably over 95 mass % and
100 mass % or less. The ratio of the total amount of HFO-1123 and
carbon dioxide is in the above-stated range, and thereby, it is
possible to obtain the sufficiently excellent cycle performance and
the low global warming potential.
[0074] In this case, the ratio of the amount of HFO-1123 with
respect to the total amount of HFO-1123 and carbon dioxide is
preferably 70 mass % or more and 95 mass % or less, and more
preferably 70 mass % or more and 80 mass % or less. The ratio of
HFO-1123 is 70 mass % or more, and thereby, it is possible to
obtain the sufficiently excellent cycle performance, and the ratio
of HFO-1123 is 95 mass % or less, and thereby, it is possible to
further suppress the self-decomposition property of the working
fluid for the heat cycle.
[0075] Besides, when the working fluid for the heat cycle of this
invention contains HFC-41 as the first component, a ratio of a
total amount of HFO-1123 and HFC-41 with respect to the entire
amount of the working fluid for the heat cycle is preferably over
90 mass % and 100 mass % or less, more preferably over 92 mass %
and 100 mass % or less, and further preferably over 95 mass % and
100 mass % or less. The ratio of the total amount of HFO-1123 and
HFC-41 is in the above-stated range, and thereby, it is possible to
obtain the sufficiently excellent cycle performance and the low
global warming potential.
[0076] In this case, the ratio of the amount of HFO-1123 with
respect to the total amount of HFO-1123 and HFC-41 is preferably 20
mass % or more and 80 mass % or less, and more preferably 40 mass %
or more and 80 mass % or less. The ratio of HFO-1123 is 20 mass %
or more, and thereby, it is possible to obtain the excellent cycle
performance, and the ratio of HFO-1123 is 80 mass % or less, and
thereby, it is possible to further suppress the self-decomposition
property of the working fluid for the heat cycle.
[0077] When the working fluid for the heat cycle of this invention
contains trifluoroiodomethane as the first component, a ratio of a
total amount of HFO-1123 and trifluoroiodomethane with respect to
the entire amount of the working fluid for the heat cycle is
preferably over 90 mass % and 100 mass % or less, more preferably
over 92 mass % and 100 mass % or less, and further preferably over
95 mass % and 100 mass % or less. The ratio of the total amount of
HFO-1123 and trifluoroiodomethane is in the above-stated range, and
thereby, it is possible to obtain the sufficiently excellent cycle
performance and the low global warming potential.
[0078] In this case, the ratio of the amount of HFO-1123 with
respect to the total amount of HFO-1123 and trifluoroiodomethane is
preferably 60 mass % or more and 80 mass % or less, and more
preferably 70 mass % or more and 80 mass % or less. The ratio of
HFO-1123 is 60 mass % or more, and thereby, it is possible to
obtain the sufficiently excellent cycle performance, and the ratio
of HFO-1123 is 80 mass % or less, and thereby, it is possible to
further suppress the self-decomposition property of the working
fluid for the heat cycle.
[0079] When the working fluid for the heat cycle of this invention
contains propane as the first component, a ratio of a total amount
of HFO-1123 and propane with respect to the entire amount of the
working fluid for the heat cycle is preferably over 90 mass % and
100 mass % or less, more preferably over 92 mass % and 100 mass %
or less, and further preferably over 95 mass % and 100 mass % or
less. The ratio of the total amount of HFO-1123 and propane is in
the above-stated range, and thereby, it is possible to obtain the
sufficiently excellent cycle performance and the low global warming
potential.
[0080] In this case, the ratio of the amount of HFO-1123 with
respect to the total amount of HFO-1123 and propane is preferably
20 mass % or more and 95 mass % or less, and more preferably 20
mass % or more and 80 mass % or less. The ratio of HFO-1123 is 20
mass % or more, and thereby, it is possible to obtain the
sufficiently excellent cycle performance, and the ratio of HFO-1123
is 95 mass % or less, and thereby, it is possible to further
suppress the self-decomposition property of the working fluid for
the heat cycle.
[0081] (Second Component)
[0082] The second component which may be contained in the working
fluid for the heat cycle of this invention is consisting of at
least one of substance selected from hydrofluorocarbon (HFC) other
than HFC-41 and hydrofluoroolefin (HFO) other than HFO-1123 having
the global warming potential (100 years) in the Intergovernmental
Panel on Climate Change (IPCC) Fourth Assessment Report of 2000 or
less. The second component is a component having a function of, for
example, improving the cycle performance of the working fluid for
the heat cycle, a function of lowering the global warming
potential, and a function of reducing the temperature gradient, and
the second component enables to keep a good balance of properties
of the working fluid for the heat cycle.
[0083] Besides, the second component has a function of reducing the
self-decomposition reaction of the working fluid for the heat cycle
by lowering the content ratio of HFO-1123 in the working fluid for
the heat cycle, and the global warming potential thereof is also
lower than that of R410A. The second component is further used in
combination with HFO-1123 and the first component, and thereby, it
is possible to obtain the working fluid for the heat cycle where
the self-decomposition property is suppressed, and the balance
between the cycle performance and the global warming potential is
excellent.
[0084] As the second component, the relative refrigerating capacity
(RQ.sub.R410A) found by the expression (X) is preferably 0.6 or
more, and more preferably 0.8 or more so as to improve the cycle
performance. Besides, the relative coefficient of performance
(RCOP.sub.R410A) found by the expression (Y) is preferably 0.5 or
more, and more preferably 0.65 or more.
[0085] As the second component, there can be concretely cited
2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene
(HFO-1234ze), difluoromethane (HFC-32), 1,1,1,2-tetrafluoroethane
(HFC-134a), HFC-125, 1,2-difluoroethane (HFC-152), and so on.
[0086] The working fluid for the heat cycle of this invention
preferably contains at least one selected from HFO-1234yf,
HFO-1234ze and HFC-32, and more preferably contains HFC-32 from
among the above as the second component so as to improve the cycle
performance, to suppress the self-decomposition property, and to
further lower the global warming potential.
[0087] Besides, the working fluid for the heat cycle of this
invention preferably contains at least one of substance selected
from carbon dioxide, HFC-41, trifluoroiodomethane and propane as
the first component, and contains at least one of substance
selected from HFO-1234yf, HFO-1234ze and HFC-32 as the second
component, and more preferably contains carbon dioxide as the first
component, and contains at least one of substance selected from
HFO-1234yf, HFO-1234ze and HFC-32 as the second component so as to
obtain the lower global warming potential and to improve the cycle
performance.
[0088] When the working fluid for the heat cycle of this invention
contains the second component, a ratio of a total amount of
HFO-1123, the first component and the second component with respect
to the entire amount of the working fluid for the heat cycle is
preferably over 90 mass % and 100 mass % or less, more preferably
over 92 mass % and 100 mass % or less, and further preferably over
95 mass % and 100 mass % or less. The ratio of the total amount of
HFO-1123, the first component and the second component is in the
above-stated range, and thereby, it is possible to suppress the
self-decomposition property of the working fluid for the heat
cycle, to obtain the low global warming potential, and to improve
the cycle performance.
[0089] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 10 mass % or more and 90 mass % or less, a ratio of
an amount of the first component is 1 mass % or more and 50 mass %
or less and a ratio of an amount of the second component is 1 mass
% or more and 70 mass % or less, and it is more preferable that the
ratio of the amount of HFO-1123 is 20 mass % or more and 80 mass %
or less, the ratio of the amount of the first component is 20 mass
% or more and 50 mass % or less and the ratio of the amount of the
second component is 1 mass % or more and 29 mass % or less with
respect to the total amount of HFO-1123, the first component and
the second component, so as to obtain the working fluid for the
heat cycle having the further lower global warming potential.
[0090] When the working fluid for the heat cycle of this invention
contains carbon dioxide as the first component, a ratio of a total
amount of HFO-1123, carbon dioxide and the second component with
respect to the entire amount of the working fluid for the heat
cycle is preferably over 90 mass % and 100 mass % or less, more
preferably over 92 mass % and 100 mass % or less, and further
preferably over 95 mass % and 100 mass % or less.
[0091] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 10 mass % or more and 90 mass % or less, a ratio of
an amount of carbon dioxide is 1 mass % or more and 50 mass % or
less and a ratio of an amount of the second component is 1 mass %
or more and 70 mass % or less, and it is more preferable that the
ratio of the amount of HFO-1123 is 20 mass % or more and 80 mass %
or less, the ratio of the amount of carbon dioxide is 20 mass % or
more and 30 mass % or less and the ratio of the amount of the
second component is 1 mass % or more and 29 mass % or less with
respect to the total amount of HFO-1123, carbon dioxide and the
second component, so as to obtain the working fluid for the heat
cycle where the self-decomposition property is suppressed, and the
balance between the cycle performance and the global warming
potential is excellent.
[0092] Further, when the working fluid for the heat cycle of this
invention contains carbon dioxide as the first component and HFC-32
as the second component, a ratio of a total amount of HFO-1123,
carbon dioxide and HFC-32 with respect to the entire amount of the
working fluid for the heat cycle is preferably over 90 mass % and
100 mass % or less, more preferably over 92 mass % and 100 mass %
or less, and further preferably over 95 mass % and 100 mass % or
less.
[0093] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 10 mass % or more and 90 mass % or less, the ratio
of the amount of carbon dioxide is 1 mass % or more and 50 mass %
or less and a ratio of an amount of HFC-32 is 1 mass % or more and
29 mass % or less, and it is more preferable that the ratio of the
amount of HFO-1123 is 10 mass % or more and 80 mass % or less, the
ratio of the amount of carbon dioxide is 20 mass % or more and 50
mass % or less and the ratio of the amount of HFC-32 is 1 mass % or
more and 29 mass % or less with respect to the total amount of
HFO-1123, carbon dioxide and HFC-32, so as to obtain the working
fluid for the heat cycle having the further lower global warming
potential. Content ratios of HFO-1123, carbon dioxide and HFC-32
are in the above-stated ranges, and thereby, it is possible to
obtain the working fluid for the heat cycle having the global
warming potential of, for example, 200 or less.
[0094] Further, when the working fluid for the heat cycle of this
invention contains carbon dioxide as the first component and
HFO-1234yf as the second component, a ratio of a total amount of
HFO-1123, carbon dioxide and HFO-1234yf with respect to the entire
amount of the working fluid for the heat cycle is preferably over
90 mass % and 100 mass % or less, more preferably over 92 mass %
and 100 mass % or less, and further preferably over 95 mass % and
100 mass % or less.
[0095] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 10 mass % or more and 90 mass % or less, the ratio
of the amount of carbon dioxide is 1 mass % or more and 50 mass %
or less and a ratio of an amount of HFO-1234yf is 1 mass % or more
and 70 mass % or less, and it is more preferable that the ratio of
the amount of HFO-1123 is 10 mass % or more and 80 mass % or less,
the ratio of the amount of carbon dioxide is 20 mass % or more and
50 mass % or less and the ratio of the amount of HFO-1234yf is 1
mass % or more and 70 mass % or less with respect to the total
amount of HFO-1123, carbon dioxide and HFO-1234yf, so as to obtain
the working fluid for the heat cycle having the further excellent
cycle performance.
[0096] Further, when the working fluid for the heat cycle of this
invention contains carbon dioxide as the first component and
HFO-1234ze as the second component, a ratio of a total amount of
HFO-1123, carbon dioxide and HFO-1234ze with respect to the entire
amount of the working fluid for the heat cycle is preferably over
90 mass % and 100 mass % or less, more preferably over 92 mass %
and 100 mass % or less, and further preferably over 95 mass % and
100 mass % or less.
[0097] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 10 mass % or more and 90 mass % or less, the ratio
of the amount of carbon dioxide is 1 mass % or more and 50 mass %
or less and a ratio of an amount of HFO-1234ze is 1 mass % or more
and 70 mass % or less, and it is more preferable that the ratio of
the amount of HFO-1123 is 10 mass % or more and 80 mass % or less,
the ratio of the amount of carbon dioxide is 20 mass % or more and
50 mass % or less and the ratio of the amount of HFO-1234ze is 1
mass % or more and 70 mass % or less with respect to the total
amount of HFO-1123, carbon dioxide and HFO-1234ze, so as to obtain
the working fluid for the heat cycle having the further excellent
cycle performance.
[0098] When the working fluid for the heat cycle of this invention
contains propane as the first component, a ratio of a total amount
of HFO-1123, propane and the second component with respect to the
entire amount of the working fluid for the heat cycle is preferably
over 90 mass % and 100 mass % or less, more preferably over 92 mass
% and 100 mass % or less, and further preferably over 95 mass % and
100 mass % or less.
[0099] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 20 mass % or more and 95 mass % or less, a ratio of
an amount of propane is 1 mass % or more and 75 mass % or less and
the ratio of the amount of the second component is 1 mass % or more
and 75 mass % or less, and it is more preferable that the ratio of
the amount of HFO-1123 is 20 mass % or more and 80 mass % or less,
the ratio of the amount of propane is 5 mass % or more and 50 mass
% or less and the ratio of the amount of the second component is 5
mass % or more and 50 mass % or less with respect to the total
amount of HFO-1123, propane and the second component, so as to
obtain the working fluid for the heat cycle where the
self-decomposition property is suppressed, and the balance between
the cycle performance and the global warming potential is
excellent.
[0100] Further, when the working fluid for the heat cycle of this
invention contains propane as the first component and HFC-32 as the
second component, a ratio of a total amount of HFO-1123, propane
and HFC-32 with respect to the entire amount of the working fluid
for the heat cycle is preferably over 90 mass % and 100 mass % or
less, more preferably over 92 mass % and 100 mass % or less, and
further preferably over 95 mass % and 100 mass % or less.
[0101] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 20 mass % or more and 95 mass % or less, the ratio
of the amount of propane is 1 mass % or more and 75 mass % or less
and a ratio of an amount of HFC-32 is 1 mass % or more and 75 mass
% or less, and it is more preferable that the ratio of the amount
of HFO-1123 is 20 mass % or more and 80 mass % or less, the ratio
of the amount of propane is 5 mass % or more and 50 mass % or less
and the ratio of the amount of HFC-32 is 5 mass % or more and 50
mass % or less with respect to the total amount of HFO-1123,
propane and HFC-32, so as to obtain the working fluid for the heat
cycle having the further lower global warming potential. Content
ratios of HFO-1123, propane and HFC-32 are in the above-stated
ranges, and thereby, it is possible to obtain the working fluid for
the heat cycle having the global warming potential of, for example,
350 or less.
[0102] Further, when the working fluid for the heat cycle of this
invention contains propane as the first component and HFO-1234yf as
the second component, a ratio of a total amount of HFO-1123,
propane and HFO-1234yf with respect to the entire amount of the
working fluid for the heat cycle is preferably over 90 mass % and
100 mass % or less, more preferably over 92 mass % and 100 mass %
or less, and further preferably over 95 mass % and 100 mass % or
less.
[0103] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 20 mass % or more and 95 mass % or less, the ratio
of the amount of propane is 1 mass % or more and 75 mass % or less
and a ratio of an amount of HFO-1234yf is 1 mass % or more and 75
mass % or less, and it is more preferable that the ratio of the
amount of HFO-1123 is 20 mass % or more and 80 mass % or less, the
ratio of the amount of propane is 5 mass % or more and 50 mass % or
less and the ratio of the amount of HFO-1234yf is 5 mass % or more
and 50 mass % or less with respect to the total amount of HFO-1123,
propane and HFO-1234yf, so as to obtain the working fluid for the
heat cycle having the further excellent cycle performance.
[0104] Further, when the working fluid for the heat cycle of this
invention contains propane as the first component and HFO-1234ze as
the second component, a ratio of a total amount of HFO-1123,
propane and HFO-1234ze with respect to the entire amount of the
working fluid for the heat cycle is preferably over 90 mass % and
100 mass % or less, more preferably over 92 mass % and 100 mass %
or less, and further preferably over 95 mass % and 100 mass % or
less.
[0105] In this case, it is preferable that the ratio of the amount
of HFO-1123 is 20 mass % or more and 95 mass % or less, the ratio
of the amount of propane is 1 mass % or more and 75 mass % or less
and a ratio of an amount of HFO-1234ze is 1 mass % or more and 75
mass % or less, and it is more preferable that the ratio of the
amount of HFO-1123 is 20 mass % or more and 80 mass % or less, the
ratio of the amount of propane is 5 mass % or more and 50 mass % or
less and the ratio of the amount of HFO-1234ze is 5 mass % or more
and 50 mass % or less with respect to the total amount of HFO-1123,
propane and HFO-1234ze, so as to obtain the working fluid for the
heat cycle having the further excellent cycle performance.
[0106] (Optional Component)
[0107] The working fluid for the heat cycle of this invention may
optionally contain a compound which is normally used as a working
fluid in addition to HFO-1123, the first component and the second
component in a range not impairing effect of this invention. As
such optional compounds (optional components), there can be cited,
for example, HFC, HFO (fluorohydrocarbon having a carbon-carbon
double bond) other than HFO-1123, the first component and the
second component contained according to need, other components to
be vaporized or liquefied together with HFO-1123 other than the
above, and so on. The optional component is preferred to be HFC,
HFO other than HFO-1123, the first component and the second
component. One of substance may be used independently, or two or
more of substances may be used in combination as the optional
component.
[0108] The optional component is preferred to be a compound capable
of keeping the global warming potential and the temperature
gradient in acceptable ranges while having a function to further
improve the above-described relative coefficient of performance and
relative refrigerating capacity, when used for the heat cycle
system in combination with HFO-1123. When the working fluid for the
heat cycle contains such a compound in combination with HFO-1123,
more favorable cycle performance can be obtained while keeping the
low global warming potential, and effect by the temperature
gradient is also small.
[0109] The optional component is preferred to be selected from the
above-described viewpoints. As HFC as the optional component, there
can be cited 1,1-difluoroethane (HFC-152a), trifluoroethane,
1,1,2,2-tetrafluoroethane (HFC-134), pentafluoropropane,
hexafluoropropane, heptafluoropropane, pentafluorobutane,
heptafluorocyclopentane, and so on. As HFO, there can be cited
1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf),
1,1,2-trifluoropropene (HFO-1243yc), 1,2,3,3,3-pentafluoropropene
(HFO-1225ye), 3,3,3-trifluoropropene (HFO-1243zf), and so on.
[0110] Besides, as the optional component other than the
above-stated HFC and HFO, there can be cited: hydrocarbon such as
propylene, cyclopropane, butane, isobutane, pentane, isopentane;
chlorofluoropropene (CFO) such as
1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya),
1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb),
1,2-dichloro-1,2-difluoroethylene (CFO-1112);
hydrochlorofluoroolefin (HCFO) such as
1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd),
1-chloro-1,2-difluoroethylene (HCFO-1122), and so on. The optional
component is preferred to be a component exerting less effect on
the ozone layer and less effect on global warming.
[0111] When the working fluid for the heat cycle of this invention
contains the above-described optional components, a total content
of the optional components in the working fluid for the heat cycle
is preferably less than 10 mass %, more preferably 8 mass % or
less, and further preferably 5 mass % or less with respect to 100
mass % of the working fluid for the heat cycle.
[0112] (Temperature Gradient)
[0113] When the working fluid for the heat cycle contains an
optional component, the working fluid for the heat cycle has a
considerable temperature gradient except for the case where
HFO-1123 and the optional component form an azeotropic composition.
The temperature gradient of the working fluid for the heat cycle
varies depending on a type of the optional component and a mixing
ratio of HFO-1123 and the optional component.
[0114] When a mixture is used as the working fluid for the heat
cycle, an azeotropic mixture or a pseudoazeotropic mixture such as
R410A is preferably used ordinarily. A non-azeotropic composition
has a problem of undergoing a composition change when put into a
refrigerating and air-conditioning apparatus from a pressure
container. Further, when a refrigerant leaks out of a refrigerating
and air-conditioning apparatus, a refrigerant composition in the
refrigerating and air-conditioning apparatus is highly likely to
change, resulting in difficulty in recovery of the refrigerant
composition to an initial state. On the other hand, the
above-described problems can be avoided as long as the working
fluid for the heat cycle is an azeotropic or pseudoazeotropic
mixture.
[0115] As an index to measure applicability of the mixture to the
working fluid for the heat cycle, the "temperature gradient" is
commonly employed. The temperature gradient is defined as
properties that an initiation temperature and a completion
temperature of a heat exchanger, for example, of evaporation in an
evaporator or of condensation in a condenser differ from each
other. The temperature gradient of the azeotropic mixture is "0"
(zero), and as for the pseudoazeotropic mixture, like the
temperature gradient of R410A being 0.2, for example, the
temperature gradients of the azeotropic mixture and the
pseudoazeotropic mixture are extremely close to "0" (zero).
[0116] When the temperature gradient of the working fluid for the
heat cycle is large, it is a problem because, for example, an inlet
temperature of an evaporator decreases, to make frosting more
likely to occur. Further, in the heat cycle system, in order to
improve heat exchange efficiency, it is common to pass the working
fluid for the heat cycle flowing in a heat exchanger and a heat
source fluid such as water or the air in counterflow. Then, the
temperature difference of the heat source fluid is small in a
stable operation state. Therefore, it is difficult to obtain a heat
cycle system with good energy efficiency when the working fluid for
the heat cycle is a non-azeotropic composition with a large
temperature gradient. Accordingly, when the mixture is used as the
working fluid for the heat cycle, the working fluid for the heat
cycle with an appropriate temperature gradient is desired.
[0117] (Global Warming Potential)
[0118] The working fluid for the heat cycle of this invention
preferably has the global warming potential (GWP) of 250 or less,
and more preferably has that of 200 or less from a viewpoint of
effect on the global warming. Here, the GWP in the mixture is
represented as a weighted average by composition masses of
components.
[0119] (Relative Cycle Performance)
[0120] The relative coefficient of performance of the working fluid
for the heat cycle of this invention is preferably 0.65 or more,
and more preferably 0.8 or more so as to obtain the sufficient
cycle performance. Besides, the relative refrigerating capacity is
preferably 0.5 or more, and more preferably 0.8 or more.
[0121] [Composition for Heat Cycle System]
[0122] The working fluid for the heat cycle of this invention can
be normally mixed with a refrigerant oil, when applied to the heat
cycle system, and used as a composition for the heat cycle system
of this invention. The composition for the heat cycle system of
this invention containing the working fluid for the heat cycle of
this invention and the refrigerant oil may contain publicly-known
additives such as a stabilizer and a leakage detection material in
addition to them.
[0123] (Refrigerant Oil)
[0124] As the refrigerant oil, a publicly-known refrigerant oil
conventionally used in the composition for the heat cycle system
together with the working fluid composed of halogenated hydrocarbon
can be employed without any limitation. As the refrigerant oil,
there can be concretely cited an oxygen-containing synthetic oil
(ester-based refrigerant oil, ether-based refrigerant oil and the
like), a fluorine-based refrigerant oil, a mineral-based
refrigerant oil, a hydrocarbon-based synthetic oil, and the
like.
[0125] As the ester-based refrigerant oil, there can be cited a
dibasic acid ester oil, a polyol ester oil, a complex ester oil, a
polyol carbonate ester oil, and the like.
[0126] As the dibasic acid ester oil, esters of dibasic acids with
5 to 10 carbons (a glutaric acid, an adipic acid, a pimelic acid, a
suberic acid, an azelaic acid, a sebacic acid and the like), with
monohydric alcohols with 1 to 15 carbons having a linear or
branched alkyl group (methanol, ethanol, propanol, butanol,
pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol,
dodecanol, tridecanol, tetradecanol, pentadecanol, and the like)
are preferable. As the dibasic acid ester oil, there can be
concretely cited glutaric acid ditridecyl, di-2-ethylhexy adipate,
di-isodecyl adipate, di-tridecyl adipate, di-3-ethylhexyl sebacate,
and the like.
[0127] As the polyol ester oil, esters of diols (ethylene glycol,
1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol,
1,5-pentanediol, neopentyl glycol, 1,7-heptanediol,
1,12-dodecanediol, and the like) or polyols with 3 to 20 hydroxyl
groups (trimethylol ethane, trimethylolpropane, trimethylolbutane,
pentaerythritol, glycerin, sorbitol, sorbitan, sorbitol-glycerine
condensate, and the like), with fatty acids with 6 to 20 carbons
(linear or branched fatty acids such as a hexanoic acid, a
heptanoic acid, an octanoic acid, a nonanoic acid, a decanoic acid,
an undecanoic acid, a dodecanoic acid, an eicosanoic acid, an oleic
acid, and the like or a what is called a neo acid with a quaternary
c carbon atom, or the like) are preferable. Note that these polyol
ester oils may have a free hydroxyl group.
[0128] As the polyol ester oil, esters (trimethylolpropane
tripelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol
tetrapelargonate, and the like) of hindered alcohols (neopentyl
glycol, trimethylolethane, trimethylolpropane, trimethylolbutane,
pentaerythritol, and the like) are preferable.
[0129] The complex ester oil is an ester of a fatty acid and a
dibasic acid with a monohydric alcohol and a polyol. As the fatty
acid, dibasic acid, monohydric alcohol, and polyol, the same as
those described above can be used.
[0130] The polyol carbonate ester oil is an ester of a carbonic
acid and a polyol. As polyol, there can be cited the diols similar
to the above and the polyols similar to the above. Further, the
polyol carbonate ester oil may be a ring-opening polymer of cyclic
alkylenecarbonate.
[0131] As the ether-based refrigerant oil, there can be cited a
polyvinylether oil and a polyoxyalkylene oil.
[0132] As the polyvinylether oil, there are the one obtained by
polymerizing a vinyl ether monomer such as alkyl vinyl ether, and a
copolymer obtained by copolymerizing a vinyl ether monomer and a
hydrocarbon monomer having an olefinic double bond.
[0133] As for the vinyl ether monomer, one may be used
independently, or two or more may be used in combination.
[0134] As the hydrocarbon monomer having the olefinic double bond,
there can be cited ethylene, propylene, butenes, pentenes, hexenes,
heptenes, octenes, diisobutylene, triisobutylene, styrene,
.alpha.-methylstyrene, alkyl-substituted styrenes and the like. As
for the hydrocarbon monomer having the olefinic double bond, one
may be used independently, or two or more may be used in
combination.
[0135] The polyvinylether copolymer may be either a block or random
copolymer. As for the polyvinylether oil, one may be used
independently, or two or more may be used in combination.
[0136] As the polyoxyalkylene oil, there can be cited
polyoxyalkylene monool, polyoxyalkylene polyol, alkyl etherified
polyoxyalkylene monool and polyoxyalkylene polyol, esterified
polyoxyalkylene monool and polyoxyalkylene polyol, and the
like.
[0137] As polyoxyalkylene monool and polyoxyalkylene polyol, there
can be cited those obtained by a method of subjecting alkylene
oxides with 2 to 4 carbons (ethylene oxide, propylene oxide, and
the like) to ring opening addition polymerization to an initiator
such as water or a hydroxyl group-containing compound in the
presence of a catalyst such as an alkali hydroxide. Further, the
oxyalkylene units in a polyoxyalkylene chain may be the same in one
molecule or two or more of oxyalkylene units may be contained. It
is preferable that at least the oxpropylene unit is contained in
one molecule.
[0138] As the initiator used for reaction, there can be cited
water, monohydric alcohols such as methanol, butanol and the like,
and polyhydric alcohols such as ethylene glycol, propylene glycol,
pentaerythritol, glycerol, and the like.
[0139] As the polyoxyalkylene oil, alkyl etherified or esterified
polyoxyalkylene monool and polyoxyalkylene polyol are preferable.
Further, as the polyoxyalkylene polyol, polyoxyalkylene glycol is
preferable. In particular, alkyl etherified polyoxyalkylene glycol,
called a polyglycol oil, having a hydroxyl group at its terminal
capped with an alkyl group such as a methyl group is
preferable.
[0140] As the fluorine-based refrigerant oil, there can be cited a
compound made by replacing a hydrogen atom of a synthetic oil
(later-described mineral oil, poly-.alpha.-olefin, alkylbenzene,
alkylnaphthalene, or the like) with a fluorine atom, a
perfluoropolyether oil, a fluorinated silicone oil, and the
like.
[0141] As the mineral-based refrigerant oil, there can be cited a
paraffin-based mineral oil, a naphthene-based mineral oil, and the
like made by refining a refrigerant oil distillate obtained by
subjecting a crude oil to atmospheric distillation or vacuum
distillation, the refining is made appropriately in combination of
refining treatments (solvent deasphalting, solvent extraction,
hydrogenolysis, solvent dewaxing, catalytic dewaxing, hydrogenation
refining, clay treatment, and the like).
[0142] As the hydrocarbon-based synthetic oil, there can be cited
poly-.alpha.-olefin, alkylbenzene, alkylnaphthalene, and the
like.
[0143] As for the refrigerant oil, one may be used independently,
or two or more may be used in combination.
[0144] As the refrigerant oil, one or more selected from the
polyolester oil, the polyvinylether oil, and the polyglycol oil are
preferable in terms of compatibility with the working fluid for the
heat cycle.
[0145] A content of the refrigerant oil in the composition for the
heat cycle system only needs to fall in a range not significantly
decreasing the effects of this invention, and is preferably 10
parts by mass or more and 100 parts by mass or less, and more
preferably 20 parts by mass or more and 50 parts by mass or less
with respect to 100 parts by mass of the working fluid for the heat
cycle.
[0146] (Additives)
[0147] The stabilizer which is optionally contained in the
composition for the heat cycle system is a component for improving
stability of the working fluid for the heat cycle against heat and
oxidation. As the stabilizer, a publicly-known stabilizer used for
the heat cycle system, for example, an oxidation resistance
improver, a heat resistance improver, a metal deactivator or the
like can be employed together with the working fluid conventionally
composed of halogenated hydrocarbon without any limitation.
[0148] As the oxidation resistance improver and the heat resistance
improver, there can be cited N,N'-diphenyl-phenylenediamine,
p-octyldiphenylamine, p,p'-dioctyldiphenylamine,
N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine,
N-(p-dodecyl)phenyl-2-naphthylamine, di-1-naphthylamine,
di-2-naphthylamine, N-alkylphenothiazine, 6-(t-butyl)phenol,
2,6-di-(t-butyl)phenol, 4-methyl-2,6-di-(t-butyl)phenol,
4,4'-methylenebis(2,6-di-t-butylphenol), and the like. As for the
oxidation resistance improver and the heat resistance improver, one
may be used independently, or two or more may be used in
combination.
[0149] As the metal deactivator, there can be cited imidazole,
benzimidazole, 2-mercaptobenzothiazole,
2,5-dimethylcaptothiadiazole, salicylidine-propylenediamine,
pyrazole, benzotriazole, tolutriazole, 2-methylbenzamidazole,
3,5-dimethylpyrazole, methylenebis-benzotriazole, organic acids or
their esters, primary, secondary or tertiary aliphatic amine, an
amine salt of an organic acid or an inorganic acid, a heterocyclic
nitrogen containing compound, an amine salt of alkyl acid phosphate
or their derivatives, and the like.
[0150] A content of the stabilizer in the composition for the heat
cycle system only needs to fall in a range not significantly
decreasing the effects of this invention, and is preferably 5 parts
by mass or less, and more preferably 1 part by mass or less with
respect to 100 parts by mass of the working fluid for the heat
cycle.
[0151] As the leakage detection material which is optionally
contained in the composition for the heat cycle system, there can
be cited an ultraviolet fluorescence dye, an odor gas, an odor
masking agent, and the like.
[0152] As the ultraviolet fluorescence dye, there can be cited
publicly-known ultraviolet fluorescence dyes used for the heat
cycle system together with the working fluid conventionally
composed of halogenated hydrocarbon, such as those disclosed in
U.S. Pat. No. 4,249,412, Japanese Translation of PCT International
Application Publication No. H10-502737, Japanese Translation of PCT
International Application Publication No. 2007-511645, Japanese
Translation of PCT International Application Publication No.
2008-500437, and Japanese Translation of PCT International
Application Publication No. 2008-531836.
[0153] As the odor masking agent, there can be cited publicly-known
aroma chemicals used for the heat cycle system together with the
working fluid conventionally composed of halogenated hydrocarbon,
such as those disclosed in Japanese Translation of PCT
International Application Publication No. 2008-500437 and Japanese
Translation of PCT International Application Publication No.
2008-531836.
[0154] In the case of using the leakage detection material, a
solubilizing agent for improving the solubility of the leakage
detection material to the working fluid for the heat cycle may be
used.
[0155] As the solubilizing agent, there can be cited those
disclosed in Japanese Translation of PCT International Application
Publication No. 2007-511645, Japanese Translation of PCT
International Application Publication No. 2008-500437, and Japanese
Translation of PCT International Application Publication No.
2008-531836, and so on.
[0156] A content of the leakage detection material in the
composition for the heat cycle system only needs to fall in a range
not significantly decreasing the effects of this invention, and is
preferably 2 parts by mass or less, and more preferably 0.5 parts
by mass or less with respect to 100 parts by mass of the working
fluid for the heat cycle.
[0157] [Heat Cycle System]
[0158] The heat cycle system of this invention is a system using
the composition for the heat cycle system of this invention. The
heat cycle system of this invention may be a heat pump system
utilizing heat obtained by a condenser or may be a refrigeration
cycle system utilizing coldness obtained by an evaporator.
[0159] As the heat cycle system of this invention, there can be
concretely cited a refrigerating apparatus, an air-conditioning
apparatus, a power generation system, a heat transport apparatus, a
secondary cooling machine, and so on. Among them, the heat cycle
system of this invention is preferably used as an air-conditioning
apparatus to be often disposed outdoors or the like due to being
able to stably and safely exhibit heat cycle performance even in a
high-temperature working environment. Further, the heat cycle
system of this invention is preferably used also as a refrigerating
apparatus.
[0160] As the air-conditioning apparatus, there can be concretely
cited a room air-conditioner, packaged air-conditioners (such as a
store packaged air-conditioner, a building packaged
air-conditioner, and a plant packaged air-conditioner), a gas
engine heat pump, a train air-conditioning system, an automobile
air-conditioning system, and so on.
[0161] As the refrigerating apparatus, there can be concretely
cited showcases (such as a built-in showcase and a separate
showcase), an industrial fridge-freezer, a vending machine, an ice
making machine, and so on.
[0162] As the power generation system, a power generation system by
Rankine cycle system is preferred. As the power generation system,
there can be concretely cited as an example a system in which in an
evaporator, a working fluid is heated by geothermal energy, solar
heat, waste heat in a medium-to-high temperature range at about
50.degree. C. or more and 200.degree. C. or less, or the like, the
vaporized working fluid in a high temperature and high pressure
state is adiabatically expanded by an expansion device, and a power
generator is driven by the work generated by the adiabatic
expansion to thereby perform power generation.
[0163] As the heat transport apparatus, a latent heat transport
apparatus is preferred. As the latent heat transport apparatus,
there can be cited a heat pipe conducting latent heat transport
utilizing a phenomenon such as evaporation, boiling, or
condensation of a working fluid filled in an apparatus and a
two-phase closed thermosiphon apparatus. The heat pipe is applied
to a relatively small-sized cooling apparatus such as a cooling
apparatus of a heat generation part of a semiconductor element and
electronic equipment. The two-phase closed thermosiphon apparatus
is widely utilized for a gas/gas heat exchanger, accelerating snow
melting and preventing freezing of roads, and the like because it
does not require a wick and its structure is simple.
[0164] FIG. 1 is a schematic configuration diagram illustrating a
refrigeration cycle system being one example of the heat cycle
system of this invention. Hereinafter, methods to find the
refrigerating capacity and the coefficient of performance of a
working fluid for a predetermined heat cycle are described by using
the refrigeration cycle system illustrated in FIG. 1.
[0165] As illustrated in FIG. 1, a refrigeration cycle system 10
includes: a compressor 11 that compresses a vapor A of the working
fluid for the heat cycle to make it into a vapor B of the working
fluid for the heat cycle at high temperature and high pressure; a
condenser 12 that cools and liquefies the vapor B of the working
fluid for the heat cycle emitted from the compressor 11 to make it
into a working fluid for a heat cycle C at low temperature and high
pressure; an expansion valve 13 that expands the working fluid for
the heat cycle C emitted from the condenser 12 to make it into a
working fluid for a heat cycle D at low temperature and low
pressure; an evaporator 14 that heats the working fluid for the
heat cycle D emitted from the expansion valve 13 to make it into
the vapor A of the working fluid for the heat cycle at high
temperature and low pressure; a pump 15 that supplies a load fluid
E to the evaporator 14; and a pump 16 that supplies a fluid F to
the condenser 12.
[0166] In the refrigeration cycle system 10, (i) to (iv) cycles
(refrigeration cycle) below are repeated.
[0167] (i) Compressing the vapor A of the working fluid for the
heat cycle emitted from the evaporator 14 in the compressor 11 to
make it into the vapor B of the working fluid for the heat cycle at
high temperature and high pressure. Hereinafter, it is referred to
as an "AB process".
[0168] (ii) Cooling and liquefying the vapor B of the working fluid
for the heat cycle emitted from the compressor 11 by the fluid F in
the condenser 12 to make it into the working fluid for the heat
cycle C at low temperature and high pressure. In this event, the
fluid F is heated to be made into a fluid F' and emitted from the
condenser 12. Hereinafter, it is referred to as a "BC process".
[0169] (iii) Expanding the working fluid for the heat cycle C
emitted from the condenser 12 in the expansion valve 13 to make it
into the working fluid for the heat cycle D at low temperature and
low pressure. Hereinafter, it is referred to as a "CD process".
[0170] (iv) Heating the working fluid for the heat cycle D emitted
from the expansion valve 13 by the load fluid E in the evaporator
14 to make it into the vapor A of the working fluid for the heat
cycle at high temperature and low pressure. In this event, the load
fluid E is cooled to be made into a load fluid E' and emitted from
the evaporator 14. Hereinafter, it is referred to as a "DA
process".
[0171] The refrigeration cycle system 10 is a cycle system achieved
by an adiabatic and isoentropic change, an isenthalpic change, and
an isobaric change. FIG. 2 is a cycle chart illustrating change of
state of the working fluid for the heat cycle in the refrigeration
cycle system 10 in FIG. 1 on a pressure-enthalpy line diagram. The
change of state of the working fluid for the heat cycle can be
expressed as a trapezoid having A, B, C, and D as vertices when the
change is illustrated on the pressure-enthalpy line (curve) diagram
illustrated in FIG. 2.
[0172] The AB process is a process of performing adiabatic
compression in the compressor 11 to make the vapor A of the working
fluid for the heat cycle at high temperature and low pressure into
the vapor B of the working fluid for the heat cycle at high
temperature and high pressure, and is indicated by an AB line in
FIG. 2. As will be described later, the vapor A of the working
fluid for the heat cycle is introduced, in a superheated state,
into the compressor 11, and therefore the vapor B of the working
fluid for the heat cycle to be obtained therein is vapor also in
the superheated state. A compressor discharge gas pressure (a
discharge pressure) is a pressure in the state of B in FIG. 2, and
is the highest pressure in the refrigeration cycle. Note that a
temperature of the state of B in FIG. 2 is a compressor discharge
gas temperature (a discharge temperature), and is the highest
temperature in the refrigeration cycle.
[0173] The BC process is a process of performing isobaric cooling
in the condenser 12 to make the vapor B of the working fluid for
the heat cycle at high temperature and high pressure into the
working fluid for the heat cycle C at low temperature and high
pressure, and is indicated by a BC line in FIG. 2. The pressure in
this event is the condensation pressure. An intersection point
T.sub.1 on a high enthalpy side of intersection points of the
pressure-enthalpy line and the BC line is a condensation
temperature, and an intersection point T.sub.2 on a low enthalpy
side is a condensation boiling temperature.
[0174] The CD process is a process of performing isenthalpic
expansion in the expansion valve 13 to make the working fluid for
the heat cycle C at low temperature and high pressure into the
working fluid for the heat cycle D at low temperature and low
pressure, and is indicated by a CD line in FIG. 2. Incidentally,
when the temperature of the working fluid for the heat cycle C at
low temperature and high pressure is indicated by a temperature
T.sub.3, T.sub.2-T.sub.3 is a degree of supercooling (SC) of the
working fluid for the heat cycle in the cycles of (i) to (iv).
[0175] The DA process is a process of performing isobaric heating
in the evaporator 14 to return the working fluid for the heat cycle
D at low temperature and low pressure to the vapor A of the working
fluid for the heat cycle at high temperature and low pressure, and
is indicated by a DA line in FIG. 2. The pressure in this event is
the evaporation pressure. An intersection point T.sub.6 on a high
enthalpy side of intersection points of the pressure-enthalpy line
and the DA line is an evaporation temperature. When the temperature
of the vapor A of the working fluid for the heat cycle is indicated
by a temperature T.sub.7, T.sub.7-T.sub.6 is a degree of
superheating (SH) of the working fluid for the heat cycle in the
cycles of (i) to (iv). Incidentally, T.sub.4 indicates the
temperature of the working fluid for the heat cycle D.
[0176] Here, Q and COP of the working fluid for the heat cycle are
found by the following expressions (1) and (2) respectively by
using enthalpies h.sub.A, h.sub.B, h.sub.c, and hp in respective
states A (after evaporation, high temperature and low pressure), B
(after compression, high temperature and high pressure), C (after
condensation, low temperature and high pressure), and D (after
expansion, low temperature and low pressure) of the working fluid
for the heat cycle. Note that it is assumed that there is no loss
due to equipment efficiency and no pressure loss in pipes and heat
exchangers.
[0177] The thermodynamic property required for calculation of the
cycle performance of the working fluid for the heat cycle can be
calculated based on a generalized state equation
(Soave-Reclich-Kwong equation) based on a principle of
corresponding states, and on thermodynamic relational expressions.
When the characteristic value cannot be obtained, calculation is
performed using an estimation method based on an atomic group
contribution method.
Q=h.sub.A-h.sub.D expression (1)
COP=Q/compression work=(h.sub.A-h.sub.D)/(h.sub.Bh.sub.A)
expression (2)
[0178] Q expressed by the above (h.sub.A-h.sub.D) corresponds to an
output (kW) of the refrigeration cycle, and the compression work
expressed by the above (h.sub.B-h.sub.A), for example, electric
energy required to operate the compressor corresponds to consumed
motive power (kW). Besides, Q means the capability of refrigerating
the load fluid, and a higher Q means that the same heat cycle
system can perform a larger amount of work. In other words, having
a high Q indicates that a target performance can be obtained by a
small amount of the working fluid for the heat cycle, thus enabling
downsizing of the heat cycle system.
[0179] Note that when operating the heat cycle system, in order to
prevent occurrence of failure due to mixture of moisture and
mixture of noncondensing gas such as oxygen, it is preferable to
provide a means for suppressing the mixture of them.
[0180] Moisture mixed into the heat cycle system may cause problems
when the heat cycle system is used particularly at low temperature.
For example, problems such as freezing in a capillary tube,
hydrolysis of the working fluid for the heat cycle and the
refrigerant oil, deterioration of material due to acid components
generated in the cycle, and generation of contaminants occur. In
particular, when the refrigerant oil is the polyglycol oil, the
polyol ester oil, and the like, the refrigerant oil is extremely
high in hygroscopicity, is likely to cause a hydrolysis reaction,
and decreases in characteristics as the refrigerant oil, resulting
in a major cause to lose long-term reliability of the compressor.
Accordingly, to suppress the hydrolysis of the refrigerant oil, it
is necessary to control the moisture concentration in the heat
cycle system.
[0181] As a method of controlling the moisture concentration in the
heat cycle system, there can be cited a method of using a moisture
removing means such as a drying agent (silica gel, activated
alumina, zeolite, or the like). Bringing the drying agent into
contact with a liquid composition for a heat cycle system is
preferred in terms of dehydration efficiency. For example, the
drying agent is preferably placed at an outlet of the condenser 12
or an inlet of the evaporator 14 to bring the drying agent into
contact with the composition for heat cycle system.
[0182] As the drying agent, a zeolite-based drying agent is
preferable in terms of the chemical reactivity between the drying
agent and the working fluid for the heat cycle and the
hygroscopicity of the drying agent.
[0183] As the zeolite-based drying agent, a zeolite-based drying
agent containing a compound expressed by the following expression
(3) as a main component is preferable in terms of being excellent
in hygroscopicity in the case of using a refrigerant oil higher in
moisture absorption amount than the conventional mineral-based
refrigerant oil.
M.sub.2/nO.Al.sub.2O.sub.3.xSiO.sub.2.yH.sub.2O expression (3)
[0184] M is an element of Group 1 such as Na, K or an element of
Group 2 such as Ca, n is a valence of M, x and y are values decided
by a crystal structure. By changing M, the pore diameter can be
adjusted.
[0185] In selecting the drying agent, a pore diameter and a
breaking strength are important. In the case of using a drying
agent having a pore diameter larger than a molecular diameter of
the working fluid for the heat cycle contained in the composition
for the heat cycle system, the working fluid for the heat cycle is
absorbed into the drying agent. As a result, a chemical reaction
occurs between the working fluid for the heat cycle and the drying
agent, thereby causing unfavorable phenomena such as generation of
noncondensing gas, a decrease in strength of the drying agent, and
a decrease in absorption capacity.
[0186] Accordingly, as the drying agent, it is preferred to use a
zeolite-based drying agent having a small pore diameter. In
particular, a sodium-potassium A type synthetic zeolite having a
pore diameter of 3.5 angstrom or less is preferred. Applying the
sodium-potassium A type synthetic zeolite having the pore diameter
smaller than the molecular diameter of the working fluid for the
heat cycle makes it possible to selectively absorb and remove only
moisture in the heat cycle system without absorbing the working
fluid for the heat cycle. In other words, since the absorption of
the working fluid for the heat cycle to the drying agent is
unlikely occur, thermal decomposition becomes less likely to occur,
thereby making it possible to suppress deterioration of the
material forming the heat cycle system and occurrence of
contaminants.
[0187] The size of the zeolite-based drying agent is preferably
about 0.5 mm or more and 5 mm or less because the zeolite-based
drying agent having a too-small size causes clogging of a valve or
a pipe small portion in the heat cycle system, whereas the
zeolite-based drying agent having a too-large size decreases the
drying ability. The shape of the zeolite-based drying agent is
preferably granular or cylindrical.
[0188] The zeolite-based drying agent can be made into an arbitrary
shape by solidifying powdery zeolite with a binder (bentonite or
the like). As long as the zeolite-based drying agent is used as a
main body, other drying agents (silica gel, activated alumina, or
the like) may be used together. A use ratio of the zeolite-based
drying agent to the composition for the heat cycle system is not
particularly limited.
[0189] Further, the noncondensing gas, when entering the inside of
the heat cycle system, has adverse effects such as failure of
thermal transfer in the condenser and the evaporator and an
increase in working pressure, and therefore the mixture of the
noncondensing gas needs to be suppressed as much as possible. In
particular, oxygen being one noncondensing gas reacts with the
working fluid for the heat cycle and the refrigerant oil to promote
decomposition.
[0190] A concentration of the noncondensing gas is preferably 1.5
volume % or less and particularly preferably 0.5 volume % or less
by volume percent with respect to the working fluid for the heat
cycle in a gas phase part of the working fluid for the heat
cycle.
[0191] According to the above-described heat cycle system of this
invention, use of the working fluid for the heat cycle of this
invention makes it possible to obtain practically sufficient cycle
performance excellent in durability while suppressing effect on
global warming.
EXAMPLES
[0192] Hereinafter, the present invention will be described in
detail using examples, but the present invention is not limited by
the following examples. Note that as values of the global warming
potential (GWP) in compounds used for the following examples, the
values illustrated in the above-described Table 1 and the following
Table 2 were used.
TABLE-US-00002 TABLE 2 Compound GWP CO.sub.2 1.0 HFC-41 150.0
CF.sub.3l 1.0 C.sub.3H.sub.8 3.0 HFC-32 675.0 HFO-1234yf 4.0
HFO-1234ze 6.0
Example 1
[0193] In an example 1, working fluids for a heat cycle
(hereinafter, referred to also as the "working fluids") each made
by mixing HFO-1123 and carbon dioxide (CO.sub.2), fluoromethane
(HFC-41), trifluoroiodomethane (CF.sub.3I) or propane
(C.sub.3H.sub.8) being the first component at percentages listed in
Table 3 were fabricated, and the global warming potential (GWP),
the relative cycle performance (with respect to R410A), and the
self-decomposition property were measured, calculated and
determined by the above-described methods. Results are illustrated
in Table 3 together with compositions of the working fluids. Note
that in Table 3, No. 1, No. 9, No. 10, No. 15, No. 16, No. 21, No.
22, and No. 27 are comparative examples.
TABLE-US-00003 TABLE 3 Evaluation Relative cycle performance (with
respect to R410A) Working medium composition Relative Relative
First component coefficient of refrigerating HFO-1123 CO.sub.2
HFC-41 CF.sub.3I C.sub.3H.sub.8 performance capacity
Self-decomposition No. [mass %] [mass %] [mass %] [mass %] [mass %]
(RCOP.sub.R410A) (RQ.sub.R410A) GWP property 1 100 0 0.91 1.11 0.30
Presence 2 80 20 0.86 1.61 0.44 Absence 3 75 25 0.83 1.68 0.48
Absence 4 70 30 0.80 1.74 0.51 Absence 5 65 35 0.77 1.80 0.55
Absence 6 60 40 0.74 1.84 0.58 Absence 7 40 60 -- -- 0.72 Absence 8
20 80 -- -- 0.86 Absence 9 0 100 -- -- 1.00 Absence 10 100 0 0.91
1.11 0.30 Presence 11 80 20 0.88 1.39 30.24 Absence 12 60 40 0.86
1.57 60.18 Absence 13 40 60 0.84 1.72 90.12 Absence 14 20 80 0.83
1.84 120.06 Absence 15 0 100 0.83 1.94 150.00 Absence 16 100 0 0.91
1.11 0.30 Presence 17 80 20 0.96 0.99 0.44 Absence 18 60 40 1.02
0.88 0.58 Absence 19 40 60 1.09 0.74 0.72 Absence 20 20 80 1.13
0.56 0.86 Absence 21 0 100 1.11 0.33 1.00 Absence 22 100 0 0.91
1.11 0.30 Presence 23 80 20 1.00 0.91 0.84 Absence 24 60 40 1.04
0.78 1.38 Absence 25 40 60 1.05 0.69 1.92 Absence 26 20 80 1.05
0.63 2.46 Absence 27 0 100 1.05 0.58 3.00 Absence
Example 2
[0194] In an example 2, the working fluids each made by mixing
HFO-1123, carbon dioxide (CO.sub.2) as the first component, and
HFC-32, HFO-1234yf or HFO-1234ze as the second component at
percentages listed in Tables 4 to 6 were fabricated, and the global
warming potential (GWP), the relative cycle performance (with
respect to R410A), and the self-decomposition property were
measured, calculated and determined by the above-described methods.
Results are illustrated in Tables 4 to 6 together with compositions
of the working fluids.
TABLE-US-00004 TABLE 4 Evaluation Relative cycle performance
Working medium composition (with respect to R410A) First Second
Relative Relative component component coefficient of refrigerating
Self- HFO-1123 CO.sub.2 HFC-32 performance capacity decomposition
No. [mass %] [mass %] [mass %] (RCOP.sub.R410A) (RQ.sub.R410A) GWP
property 28 90 5 5 0.93 1.29 34.1 Absence 29 85 5 10 0.93 1.30 67.8
Absence 30 80 5 15 0.94 1.30 101.5 Absence 31 75 5 20 0.94 1.31
135.3 Absence 32 70 5 25 0.95 1.31 169.0 Absence 33 85 10 5 0.92
1.42 34.1 Absence 34 80 10 10 0.93 1.43 67.8 Absence 35 75 10 15
0.93 1.43 101.6 Absence 36 70 10 20 0.94 1.43 135.3 Absence 37 65
10 25 0.95 1.43 169.0 Absence 38 60 10 30 0.96 1.42 202.8 Absence
39 40 10 50 0.99 1.40 337.7 Absence 40 20 10 70 1.01 1.36 472.7
Absence 41 80 15 5 0.90 1.53 34.1 Absence 42 75 15 10 0.91 1.53
67.9 Absence 43 70 15 15 0.92 1.53 101.6 Absence 44 65 15 20 0.93
1.53 135.3 Absence 45 60 15 25 0.94 1.53 169.1 Absence 46 75 20 5
0.87 1.62 34.2 Absence 47 70 20 10 0.89 1.62 67.9 Absence 48 65 20
15 0.90 1.62 101.6 Absence 49 60 20 20 0.91 1.62 135.4 Absence 50
55 20 25 0.93 1.62 169.1 Absence 51 50 20 30 0.94 1.62 202.9
Absence 52 30 20 50 0.98 1.59 337.8 Absence 53 10 20 70 1.01 1.54
472.7 Absence 54 60 30 10 0.84 1.77 68.0 Absence 55 40 30 30 0.91
1.78 202.9 Absence 56 20 30 50 0.96 1.74 337.9 Absence 57 50 40 10
0.80 1.90 68.1 Absence 58 30 40 30 0.88 1.92 203.0 Absence 59 10 40
50 0.94 1.88 337.9 Absence 60 40 50 10 0.76 2.01 68.1 Absence 61 20
50 30 0.85 2.05 203.1 Absence 62 30 60 10 0.73 2.11 68.2 Absence 63
10 60 30 0.83 2.17 203.1 Absence 64 20 70 10 -- -- 68.3 Absence 65
10 80 10 -- -- 68.3 Absence
TABLE-US-00005 TABLE 5 Evaluation Relative cycle performance
Working medium composition (with respect to R410A) First Second
Relative Relative component component coefficient of refrigerating
Self- HFO-1123 CO.sub.2 HFO-1234yf performance capacity
decomposition No. [mass %] [mass %] [mass %] (RCOP.sub.R410A)
(RQ.sub.R410A) GWP property 66 80 10 10 0.95 1.36 0.74 Absence 67
60 10 30 1.03 1.24 1.48 Absence 68 40 10 50 1.12 1.12 2.22 Absence
69 20 10 70 1.19 1.00 2.96 Absence 70 70 20 10 0.90 1.55 0.81
Absence 71 50 20 30 0.99 1.45 1.55 Absence 72 30 20 50 1.09 1.35
2.29 Absence 73 10 20 70 1.18 1.24 3.03 Absence 74 60 30 10 0.84
1.69 0.88 Absence 75 40 30 30 0.93 1.60 1.62 Absence 76 20 30 50
1.03 1.51 2.36 Absence 77 50 40 10 0.78 1.80 0.95 Absence 78 30 40
30 0.87 1.72 1.69 Absence 79 10 40 50 0.98 1.64 2.43 Absence 80 40
50 10 0.73 1.90 1.02 Absence 81 20 50 30 0.83 1.83 1.76 Absence 82
30 60 10 0.69 1.98 1.09 Absence 83 10 60 30 0.79 1.94 1.83 Absence
84 20 70 10 -- -- 1.16 Absence 85 10 80 10 -- -- 1.23 Absence
TABLE-US-00006 TABLE 6 Evaluation Relative cycle performance
Working medium composition (with respect to R410A) First Second
Relative Relative component component coefficient of refrigerating
Self- HFO-1123 CO.sub.2 HFO-1234ze performance capacity
decomposition No. [mass %] [mass %] [mass %] (RCOP.sub.R410A)
(RQ.sub.R410A) GWP property 86 80 10 10 0.87 1.23 0.94 Absence 87
60 10 30 0.92 1.05 2.08 Absence 88 40 10 50 0.98 0.89 3.22 Absence
89 20 10 70 1.02 0.73 4.36 Absence 90 70 20 10 0.82 1.39 1.01
Absence 91 50 20 30 0.89 1.23 2.15 Absence 92 30 20 50 0.97 1.07
3.29 Absence 93 10 20 70 1.04 0.92 4.43 Absence 94 60 30 10 0.79
1.56 1.08 Absence 95 40 30 30 0.87 1.39 2.22 Absence 96 20 30 50
0.95 1.24 3.36 Absence 97 50 40 10 0.75 1.69 1.15 Absence 98 30 40
30 0.84 1.53 2.29 Absence 99 10 40 50 0.93 1.38 3.43 Absence 100 40
50 10 0.72 1.80 1.22 Absence 101 20 50 30 0.82 1.66 2.36 Absence
102 30 60 10 0.69 1.91 1.29 Absence 103 10 60 30 0.79 1.78 2.43
Absence 104 20 70 10 0.67 2.01 1.36 Absence 105 10 80 10 -- -- 1.43
Absence
Example 3
[0195] In an example 3, the working fluids each made by mixing
HFO-1123 and propane (C.sub.3H.sub.8) as the first component, and
HFC-32, HFO-1234yf or HFO-1234ze as the second component at
percentages listed in Tables 7 to 9 were fabricated, and the global
warming potential (GWP), the relative cycle performance (with
respect to R410A), and the self-decomposition property were
measured, calculated and determined by the above-described methods.
Results are illustrated in Tables 7 to 9 together with compositions
of the working fluids.
TABLE-US-00007 TABLE 7 Evaluation Relative cycle performance
Working medium composition (with respect to R410A) First Second
Relative Relative component component coefficient of refrigerating
Self- HFO-1123 C.sub.3H.sub.8 HFC-32 performance capacity
decomposition No. [mass %] [mass %] [mass %] (RCOP.sub.R410A)
(RQ.sub.R410A) GWP property 106 90 5 5 0.94 1.07 34.2 Absence 107
85 5 10 0.94 1.09 67.9 Absence 108 80 5 15 0.94 1.11 101.6 Absence
109 75 5 20 0.94 1.12 135.4 Absence 110 70 5 25 0.95 1.13 169.1
Absence 111 85 10 5 0.96 1.03 34.3 Absence 112 80 10 10 0.96 1.05
68.0 Absence 113 75 10 15 0.96 1.05 101.8 Absence 114 70 10 20 0.95
1.08 135.5 Absence 115 65 10 25 0.95 1.10 169.2 Absence 116 60 10
30 0.95 1.12 203.0 Absence 117 40 10 50 0.96 1.15 337.9 Absence 118
20 10 70 0.98 1.17 472.9 Absence 119 80 15 5 0.98 0.98 34.4 Absence
120 75 15 10 0.97 1.01 68.2 Absence 121 70 15 15 0.97 1.03 101.9
Absence 122 65 15 20 0.96 1.05 135.6 Absence 123 60 15 25 0.96 1.07
169.4 Absence 124 75 20 5 1.00 0.95 34.6 Absence 125 70 20 10 0.99
0.98 68.3 Absence 126 65 20 15 0.98 1.00 102.0 Absence 127 60 20 20
0.97 1.02 135.8 Absence 128 55 20 25 0.97 1.04 169.5 Absence 129 50
20 30 0.96 1.06 203.3 Absence 130 30 20 50 0.96 1.13 338.2 Absence
131 10 20 70 0.96 1.17 473.1 Absence 132 60 30 10 1.02 0.93 68.6
Absence 133 40 30 30 0.98 1.02 203.5 Absence 134 20 30 50 0.96 1.10
338.5 Absence 135 50 40 10 1.04 0.89 68.9 Absence 136 30 40 30 0.99
0.99 203.8 Absence 137 10 40 50 0.95 1.07 338.7 Absence 138 40 50
10 1.07 0.86 69.1 Absence 139 20 50 30 1.02 0.97 204.1 Absence 140
30 60 10 1.09 0.83 69.4 Absence 141 20 70 10 1.11 0.81 69.7 Absence
142 10 80 10 1.13 0.80 69.9 Absence
TABLE-US-00008 TABLE 8 Evaluation Relative cycle performance
Working medium composition (with respect to R410A) First Second
Relative Relative component component coefficient of refrigerating
Self- HFO-1123 C.sub.3H.sub.8 HFO-1234yf performance capacity
decomposition No. [mass %] [mass %] [mass %] (RCOP.sub.R410A)
(RQ.sub.R410A) GWP property 143 80 10 10 0.98 0.94 0.9 Absence 144
60 10 30 1.01 0.83 1.7 Absence 145 40 10 50 1.03 0.71 2.4 Absence
146 20 10 70 1.04 0.60 3.2 Absence 147 70 20 10 1.01 0.86 1.2
Absence 148 50 20 30 1.03 0.76 2.0 Absence 149 30 20 50 1.03 0.66
2.7 Absence 150 10 20 70 1.03 0.57 3.4 Absence 151 60 30 10 1.03
0.80 1.5 Absence 152 40 30 30 1.03 0.71 2.2 Absence 153 20 30 50
1.03 0.63 3.0 Absence 154 50 40 10 1.04 0.74 1.8 Absence 155 30 40
30 1.04 0.67 2.5 Absence 156 10 40 50 1.03 0.60 3.2 Absence 157 40
50 10 1.04 0.70 2.0 Absence 158 20 50 30 1.04 0.63 2.8 Absence 159
30 60 10 1.05 0.66 2.3 Absence 160 10 60 30 1.04 0.61 3.0 Absence
161 20 70 10 1.05 0.63 2.6 Absence 162 10 80 10 1.05 0.61 2.8
Absence
TABLE-US-00009 TABLE 9 Evaluation Relative cycle performance
Working medium composition (with respect to R410A) First Second
Relative Relative component component coefficient of refrigerating
Self- HFO-1123 C.sub.3H.sub.8 HFO-1234ze performance capacity
decomposition No. [mass %] [mass %] [mass %] (RCOP.sub.R410A)
(RQ.sub.R410A) GWP property 163 80 10 10 0.99 0.94 1.1 Absence 164
60 10 30 1.02 0.81 2.3 Absence 165 40 10 50 1.05 0.68 3.4 Absence
166 20 10 70 1.08 0.56 4.6 Absence 167 70 20 10 1.01 0.86 1.4
Absence 168 50 20 30 1.03 0.75 2.6 Absence 169 30 20 50 1.04 0.64
3.7 Absence 170 10 20 70 1.05 0.54 4.8 Absence 171 60 30 10 1.03
0.79 1.7 Absence 172 40 30 30 1.04 0.70 2.8 Absence 173 20 30 50
1.04 0.61 4.0 Absence 174 50 40 10 1.04 0.74 2.0 Absence 175 30 40
30 1.04 0.66 3.1 Absence 176 10 40 50 1.04 0.58 4.2 Absence 177 40
50 10 1.04 0.70 2.2 Absence 178 20 50 30 1.04 0.63 3.4 Absence 179
30 60 10 1.05 0.66 2.5 Absence 180 10 60 30 1.04 0.60 3.6 Absence
181 20 70 10 1.05 0.63 2.8 Absence 182 10 80 10 1.05 0.61 3.0
Absence
[0196] It is clear that the working fluids for the heat cycle each
containing HFO-1123 and the first component illustrated in Table 3
do not have the self-decomposition property, have the small global
warming potential, and the sufficiently excellent cycle performance
on practical use. Besides, it is also clear that the working fluids
for the heat cycle each containing HFO-1123, the first component,
and further the second component illustrated in Tables 4 to 9 do
not have the self-decomposition property, have the small global
warming potential, and the sufficiently excellent cycle performance
on practical use.
INDUSTRIAL APPLICABILITY
[0197] The composition for the heat cycle system of this invention
and the heat cycle system using the composition can be utilized for
refrigerating apparatuses (such as a built-in showcase, a separate
showcase, an industrial fridge-freezer, a vending machine, and an
ice making machine), air-conditioning apparatuses (such as a room
air-conditioner, a store packaged air-conditioner, a building
packaged air-conditioner, a plant packaged air-conditioner, a gas
engine heat pump, a train air-conditioning system, and an
automobile air-conditioning system), a power generation system
(such as exhaust heat recovery power generation), a heat transport
apparatus (such as a heat pipe), and a secondary cooling
machine.
* * * * *