U.S. patent application number 15/396855 was filed with the patent office on 2017-05-25 for heat transfer fluid.
This patent application is currently assigned to ARKEMA FRANCE. The applicant listed for this patent is ARKEMA FRANCE. Invention is credited to Wissam RACHED.
Application Number | 20170145276 15/396855 |
Document ID | / |
Family ID | 40627376 |
Filed Date | 2017-05-25 |
United States Patent
Application |
20170145276 |
Kind Code |
A1 |
RACHED; Wissam |
May 25, 2017 |
HEAT TRANSFER FLUID
Abstract
Compositions which are based on tetrafluoropropene and more
particularly relates to compositions inclduing 60% to 90% by weight
of 2,3,3,3-tetrafluoropropene and 10% to 40% by weight of at least
one compound selected from difluoroethane and difluoromethane,
which can be used as a heat transfer fluid. The compositions may
include 60% to 79% by weight of 2,3,3,3-tetrafluoropropene and 21%
to 40% by weight of a compound selected from difluoroethane and
difluoromethane.
Inventors: |
RACHED; Wissam; (Chaponost,
FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ARKEMA FRANCE |
Colombes |
|
FR |
|
|
Assignee: |
ARKEMA FRANCE
Colombes
FR
|
Family ID: |
40627376 |
Appl. No.: |
15/396855 |
Filed: |
January 3, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14873855 |
Oct 2, 2015 |
9599381 |
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15396855 |
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13122606 |
Apr 5, 2011 |
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PCT/FR2009/051814 |
Sep 24, 2009 |
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14873855 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2209/043 20130101;
F25B 45/00 20130101; C08J 9/146 20130101; C09K 2205/22 20130101;
C10M 2203/065 20130101; F25B 31/002 20130101; C10M 171/008
20130101; C10M 2203/003 20130101; C09K 2205/40 20130101; C10N
2020/101 20200501; C09K 5/045 20130101; C09K 2205/126 20130101;
C10N 2040/30 20130101; C10M 2209/1033 20130101; C09K 2205/43
20130101; C09K 2205/122 20130101 |
International
Class: |
C09K 5/04 20060101
C09K005/04; F25B 31/00 20060101 F25B031/00; C10M 171/00 20060101
C10M171/00; F25B 45/00 20060101 F25B045/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 8, 2008 |
FR |
08.56817 |
Oct 9, 2008 |
FR |
08.56836 |
Claims
1-12. (canceled)
13. A heat transfer fluid comprising: 60% to 90% by weight of
2,3,3,3-tetrafluoropropene; and 10% to 40% by weight of a mixture
of difluoromethane and 1,1-difluoroethane.
14. The heat transfer fluid of claim 13 comprising: 60% to 79% by
weight of 2,3,3,3-tetrafluoropropene; and 21% to 40% by weight of a
mixture of difluoromethane and 1,1-difluoroethane.
15. The heat transfer fluid of claim 13 comprising: 60% to 70% by
weight of 2,3,3,3-tetrafluoropropene; and 30% to 40% by weight of a
mixture of difluoromethane and 1,1-difluoroethane.
16. The heat transfer fluid of claim 13 comprising: 60% to 65% by
weight of 2,3,3,3-tetrafluoropropene; and 35% to 40% by weight of a
mixture of difluoromethane and 1,1-difluoroethane.
17. A composition comprising the heat transfer fluid of claim 13
and a stabilizer selected from the group consisting of
nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic
compounds, epoxides, phosphites, phosphates, phosphonates, thiols
and lactones.
18. The composition of claim 17, wherein the stabilizer represents
at most 5% by weight relative to the heat transfer fluid.
19. A composition comprising the heat transfer fluid of claim 13
and a lubricant selected from the group consisting of mineral oil,
alkylbenzene, polyalkylene glycol and polyvinyl ether.
20. A composition comprising the heat transfer fluid of claim 16
and a stabilizer selected from the group consisting of
nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic
compounds, epoxides, phosphites, phosphates, phosphonates, thiols
and lactones.
21. The composition of claim 20, wherein the stabilizer represents
at most 5% by weight relative to the heat transfer fluid.
22. A composition comprising the heat transfer fluid of claim 16
and a lubricant selected from the group consisting of mineral oil,
alkylbenzene, polyalkylene glycol and polyvinyl ether.
23. The heat transfer fluid of claim 16 consisting of: 60% to 65%
by weight of 2,3,3,3-tetrafluoropropene; and 35% to 40% by weight
of a mixture of difluoromethane and 1,1-difluoroethane.
24. A heat transfer fluid comprising: 60% to 80% by weight of
2,3,3,3-tetrafluoropropene; 5% to 35% by weight of difluoromethane;
and 5% to 20% by weight of 1,1-difluoroethane, wherein the total
amount of difluoromethane and 1,1-difluoroethane is 15% to 40% by
weight of the composition.
25. The heat transfer fluid of claim 24 comprising: 60% to 80% by
weight of 2,3,3,3-tetrafluoropropene; 10% to 25% by weight of
difluoromethane; 5% to 20% by weight of 1,1-difluoroethane; and
optionally a stabilizer.
26. A composition comprising the heat transfer fluid of claim 24
and a stabilizer selected from the group consisting of
nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic
compounds, epoxides, phosphites, phosphates, phosphonates, thiols
and lactones.
27. The composition of claim 26, wherein the stabilizer represents
at most 5% by weight relative to the heat transfer fluid.
28. A composition comprising the heat transfer fluid of claim 24
and a lubricant selected from the group consisting of mineral oil,
alkylbenzene, polyalkylene glycol and polyvinyl ether.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S.
application Ser. No. 14/873,855, filed on Oct. 2, 2015, which is a
continuation of U.S. application Ser. No. 13/122,606, filed on Apr.
5, 2011, which is a U.S. national stage of International
Application No. PCT/FR2009/051814, filed on Sep. 24, 2009, which
claims the benefit of French Application No. 08.56836, filed on
Oct. 9, 2008 and French Application No. 08.56817, filed on Oct. 8,
2008. The entire contents of each of U.S. application Ser. No.
14/873,855, U.S. application Ser. No. 13/122,606, International
Application No. PCT/FR2009/051814, French Application No. 08.56836,
and French Application No. 08.56817 are hereby incorporated herein
by reference in their entirety.
FIELD OF INVENTION
[0002] The present invention relates to compositions comprising
hydrofluoroolefins and to their uses as heat transfer fluids,
blowing agents, solvents and aerosols.
BACKGROUND AND SUMMARY
[0003] The problems posed by substances which deplete the
atmospheric ozone layer (ODP: ozone depletion potential) were
tackled at Montreal, where a protocol was signed which imposes a
reduction on the production and use of chlorofluorocarbons (CFCs).
This protocol has been the subject of amendments, which have
imposed the abandonment of CFCs and have extended the regulations
to other products, among them hydrochlorofluorocarbons (HCFCs).
[0004] The refrigeration industry and the air conditioning industry
have invested much in the replacement of these refrigerant fluids,
and a product of this investment has been the commercialization of
hydrofluorocarbons (HFCs).
[0005] (Hydro)chlorofluorocarbons which are used as expandants or
solvents have also been replaced by HFCs.
[0006] In the automotive industry, the air-conditioning systems of
vehicles which are sold in many countries have switched from a
chlorofluorocarbon (CFC-12) refrigerant fluid to that of a
hydrofluorocarbon (1,1,1,2-tetrafluoroethane: HFC-134a), which is
less harmful to the ozone layer. However, in view of the objectives
set by the Kyoto Protocol, HFC-134a (GWP=1300) is considered to
have a high warming potential. The contribution to the greenhouse
effect of a fluid is quantified by a criterion, the GWP (global
warming potential), which indexes the warming potential by taking a
reference value of 1 for carbon dioxide.
[0007] Carbon dioxide, being non-toxic, non-flammable and having a
very low GWP, has been proposed as a refrigerant fluid for
air-conditioning systems, as a replacement for HFC-134a. However,
the use of carbon dioxide presents a number of disadvantages,
associated in particular with the very high pressure of its use as
a refrigerant fluid in existing apparatus and technologies.
[0008] Moreover, the mixture R-404A, composed of 44% by weight of
pentafluoroethane, 52% by weight of trifluoroethane and 4% by
weight of HFC-134a, is widely used as a refrigerant fluid in
superstores (supermarket) and in refrigerated transport. This
mixture, however, has a GWP of 3900. The mixture R-407C, composed
of 52% by weight of HFC-134a, 25% by weight of pentafluoroethane
and 23% by weight of difluoromethane, is used as a heat transfer
fluid in air conditioning and in heat pumps. This mixture, however,
has a GWP of 1800.
[0009] Document JP 4110388 describes the use of hydrofluoropropenes
of formula C.sub.3H.sub.mF.sub.n, where m and n represent an
integer between 1 and 5 inclusive and m+n=6, as heat transfer
fluids, especially tetrafluoropropene and trifluoropropene.
[0010] Document WO 2004/037913 discloses the use of compositions
comprising at least one fluoroalkene having three or four carbon
atoms, more particularly pentafluoropropene and tetrafluoropropene,
preferably having a GWP of not more than 150, as heat transfer
fluids.
[0011] Document WO 2005/105947 teaches the addition to
tetrafluoropropene, preferably 1,3,3,3-tetrafluoropropene, of a
co-blowing agent such as difluoromethane, pentafluoroethane,
tetrafluoroethane, difluoroethane, heptafluoropropane,
hexafluoropropane, pentafluoropropane, pentafluorobutane, water or
carbon dioxide.
[0012] Document WO 2006/094303 discloses an azeotropic composition
containing 7.4% by weight of 2,3,3,3-tetrafluoropropene (1234yf)
and 92.6% by weight of difluoromethane (HFC-32). This document
likewise discloses an azeotropic composition containing 91% by
weight of 2,3,3,3-tetrafluoropropene and 9% by weight of
difluoroethane (HFC-152a).
DETAILED DESCRIPTION
[0013] The applicant has now developed compositions which contain
hydrofluoropropenes, which can be used as a heat transfer fluid,
which do not have the aforementioned drawbacks and which combine a
zero ODP with a GWP lower than that of existing heat transfer
fluids such as R-404A or R-407C or R22 (chlorodifluoromethane).
[0014] The compositions according to the present invention are
characterized in that they comprise 60% to 90% by weight of
2,3,3,3-tetrafluoropropene and 10% to 40% by weight of at least one
compound selected from difluoroethane and difluoromethane.
[0015] According to a first embodiment of the invention the
compositions comprise 60% to 79% by weight of
2,3,3,3-tetrafluoropropene and 21% to 40% by weight of a compound
selected from difluoroethane and difluoromethane.
[0016] The compositions according to this first embodiment
preferably comprise 60% to 70% by weight of
2,3,3,3-tetrafluoropropene and 30% to 40% by weight of a compound
selected from difluoroethane and difluoromethane.
[0017] Advantageously the compositions according to this first
embodiment comprise 60% to 65% by weight of
2,3,3,3-tetrafluoropropene and 35% to 40% by weight of a compound
selected from difluoroethane and difluoromethane.
[0018] The compositions which are particularly preferred according
to this first embodiment comprise 2,3,3,3-tetrafluoropropene and
difluoromethane.
[0019] Advantageously these compositions contain essentially
2,3,3,3-tetrafluoropreopene and difluoromethane.
[0020] According to a second embodiment of the invention the
compositions comprise 60% to 90% by weight of
2,3,3,3-tetrafluoropropene and 10% to 40% by weight of a mixture
composed of dichloromethane and difluoroethane.
[0021] The compositions which are preferred according to this
second embodiment comprise 60% to 80% by weight of
2,3,3,3-tetrafluoropropene and 20% to 40% by weight of a mixture
composed of difluoromethane and difluoroethane.
[0022] The compositions which are advantageously preferred
according to this second embodiment comprise 60% to 75% by weight
of 2,3,3,3-tetrafluoropropene and 25% to 40% by weight of a mixture
composed of difluoromethane and difluoroethane.
[0023] Particularly preferred compositions comprise 60% to 80% by
weight of 2,3,3,3-tetrafluoropropene and 5% to 35% by weight of
difluoromethane and 5% to 35% by weight of difluoroethane.
[0024] The compositions which are of interest are those comprising
or containing essentially 60% to 80% by weight of
2,3,3,3-tetrafluoropropene and 10% to 30% by weight of
difluoromethane and 10% to 30% by weight of difluoroethane.
[0025] The compositions according to the invention may comprise a
stabilizer for 2,3,3,3-tetrafluoropropene. The stabilizer
represents not more than 5% by weight, relative to the total
composition.
[0026] Stabilizers include more particularly nitromethane, ascorbic
acid, terephthalic acid, azoles such as tolutriazole or
benzotriazole, phenolic compounds such as tocopherol, hydroquinone,
tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides
(alkyl, optionally fluorinated or perfluorinated, or alkenyl or
aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl
ether, allyl glycidyl ether and butylphenyl glycidyl ether,
phosphites, phosphates, phosphonates, thiols and lactones.
[0027] The compositions according to the present invention may
comprise lubricants such as mineral oil, alkylbenzene, polyalkylene
glycol and polyvinyl ether.
[0028] The compositions according to the present invention are
suitable for replacing R-404A in refrigeration and/or R-407C in air
conditioning and heat pumps in existing systems. They may also be
suitable for replacing R-404A in refrigeration systems with a
cascaded compression regime in which at least one stage is operated
with the compositions according to the present invention. Examples
of compositions which are of particular interest for the
replacement of R-404A in existing systems include those comprising
or containing essentially 60% by weight of
2,3,3,3-tetrafluoropropene and 40% by weight of difluoromethane;
70% by weight of 2,3,3,3-tetrafluoropropene and 30% by weight of
difluoromethane; and 60% by weight of 2,3,3,3-tetrafluoropropene,
30% by weight of difluoromethane and 10% by weight of
difluoroethane.
[0029] Examples of compositions which are of particular interest
for the replacement of R-404A in systems operating with a cascaded
compression regime include those comprising or containing
essentially 60% by weight of 2,3,3,3-tetrafluoropropene and 40% by
weight of difluoroethane; 70% by weight of
2,3,3,3-tetrafluoropropene and 30% by weight of difluoroethane; and
75% by weight of 2,3,3,3-tetrafluoropropene, 20% by weight of
difluoromethane and 5% by weight of difluoroethane.
[0030] The compositions according to the present invention may also
be used as a replacement for R-407C, for example in heat pumps.
[0031] Examples of compositions which are of particular interest
for the replacement of R-407C in existing systems include those
comprising or containing essentially 60% by weight of
2,3,3,3-tetrafluoropropene and 40% by weight of difluoromethane;
70% by weight of 2,3,3,3-tetrafluoropropene and 30% by weight of
difluoromethane; 60% by weight of 2,3,3,3-tetrafluoropropene, 30%
by weight of difluoromethane and 10% by weight of difluoroethane;
and 70% by weigh of 2,3,3,3-tetrafluoropropene, 25% by weight of
difluoromethane and 5% by weight of difluoroethane.
[0032] The compositions according to the present invention can be
used, furthermore, as blowing agents, aerosols and solvents.
EXPERIMENTAL SECTION
[0033] The performance data of the compositions according to the
invention under the operating conditions of refrigeration are given
in Table 1. The values of the constituents (1234yf, 32 and 152a)
for each composition are given as percentages by weight.
[0034] For R404A, the nominal operating pressure is 18 bar, the
volumetric capacity is 1500 kJ/m .sup.3 and the COP is 1.8 under
the following operating conditions.:
[0035] Evaporation temperature: -20.degree. C.
[0036] Condensation temperature: 40.degree. C.
[0037] Compressor inlet temperature: -5.degree. C.
[0038] Super cooled liquid temperature: 33.degree. C.
[0039] Isentropic yield of the compressor: 70%
[0040] BP: pressure at the evaporator
[0041] HP: pressure at the condenser
[0042] Ratio: compression ratio
[0043] T comp outlet: temperature at the compressor outlet
[0044] COP: coefficient of performance--defined, for the purposes
of refrigeration, as being the useful cooling power supplied by the
system, as a proportion of the power provided or consumed by the
system.
[0045] CAP: volumetric capacity (kJ/m.sup.3)
[0046] % CAP or COP is the ratio of the value of the CAP or COP of
the mixture in relation to the same value for R404A.
TABLE-US-00001 TABLE 1 T BP HP Ratio comp. Compositions (bar) (bar)
(p/p) outlet % COP % CAP R404A 3 18 6.10 77 100 100 1234yf 32 152a
60 40 0 2.7 21 7.57 111 96 102 70 30 0 2.4 19 8.02 104 94 89 75 25
0 2.2 18 8.19 101 94 83 60 20 20 2.0 16 8.01 100 98 76 60 30 10 2.3
18 7.94 106 96 88 70 25 5 2.2 18 8.10 101 95 83 70 20 10 2.0 16
8.07 98 96 77 75 20 5 2.0 16 8.16 97 95 77 75 15 10 1.9 15 8.01 93
97 72 85 10 5 1.8 14 7.92 86 99 67 60 0 40 1.5 10 6.60 79 114 59 70
0 30 1.5 10 6.53 76 113 59
[0047] The performance data of the compositions according to the
present invention under the operating conditions of a heat pump and
air conditioning are given in Table 2. The values of the
constituents (1234yf, 32 and 152a) for each composition are given
as percentages by weight.
[0048] For R407C, the nominal operating pressure is 34 bar, the
volumetric capacity is 1461 kJ/m .sup.3 and the COP is 2.1 under
the following operating conditions:
[0049] Evaporation temperature: -5.degree. C.
[0050] Condensation temperature: 70.degree. C.
[0051] Compressor inlet temperature: 5.degree. C.
[0052] Supercooled liquid temperature: 65.degree. C.
[0053] Isentropic yield of the compressor: 70%
[0054] BP: pressure at the evaporator
[0055] HP: pressure at the condenser
[0056] Ratio: compression ratio
[0057] T comp outlet: temperature at the compressor outlet
[0058] COP: coefficient of performance--defined, for the purposes
of a heat pump, as being the useful heating power supplied by the
system, as a proportion of the power provided or consumed by the
system.
[0059] CAP: volumetric capacity (kJ/m.sup.3)
[0060] % CAP or COP is the ratio of the value of the CAP or COP of
the mixture in relation to the same value for the R-407C.
TABLE-US-00002 TABLE 2 T BP HP Ratio comp. Compositions (bar) (bar)
(p/p) outlet % COP % CAP R407C 3.9 34.4 127 100 100 1234yf 32 152a
60 40 0 4.8 39.7 8.30 133 91.9 112 70 30 0 4.2 36.5 8.69 126 92.4
99 75 25 0 3.9 34.6 8.85 122 93.2 93 60 20 20 3.5 30.1 8.64 121
101.5 89 60 30 10 4.1 35.0 8.60 128 97.1 101 70 25 5 3.9 33.9 8.74
123 95.5 94 70 20 10 3.6 31.2 8.70 119 98.3 88 75 20 5 3.6 31.8
8.79 118 96.4 88 75 15 10 3.3 28.9 8.64 113 99.3 82 85 10 5 3.1
26.7 8.58 107 99.3 75 60 0 40 2.6 18.9 7.27 98 113.7 67 70 0 30 2.7
19.1 7.19 95 111.3 66
* * * * *