U.S. patent application number 17/692721 was filed with the patent office on 2022-06-23 for refrigerant, heat transfer compositions, methods, and systems.
This patent application is currently assigned to HONEYWELL INTERNATIONAL INC.. The applicant listed for this patent is HONEYWELL INTERNATIONAL INC.. Invention is credited to JOSHUA CLOSE, MICHAEL PETERSEN, GUSTAVO POTTKER, ANKIT SETHI, RONALD PETER VOGL, SAMUEL F. YANA MOTTA.
Application Number | 20220195278 17/692721 |
Document ID | / |
Family ID | |
Filed Date | 2022-06-23 |
United States Patent
Application |
20220195278 |
Kind Code |
A1 |
CLOSE; JOSHUA ; et
al. |
June 23, 2022 |
REFRIGERANT, HEAT TRANSFER COMPOSITIONS, METHODS, AND SYSTEMS
Abstract
Disclosed are refrigerants, and heat transfer compositions, heat
transfer systems and heat transfer methods containing such
refrigerants, wherein the refrigerant comprises at least about 97%
by weight of the following three components (a)-(c) and the
following fourth component if present: (a)
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)), (b)
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), (c)
trifluoroiodomethane (CF3I), and. (d)
1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).
Inventors: |
CLOSE; JOSHUA; (CHEEKTOWAGA,
NY) ; SETHI; ANKIT; (BUFFALO, NY) ; YANA
MOTTA; SAMUEL F.; (EAST AMHERST, NY) ; PETERSEN;
MICHAEL; (CLARENCE CENTER, NY) ; POTTKER;
GUSTAVO; (GETZVILLE, NY) ; VOGL; RONALD PETER;
(SPRINGVILLE, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HONEYWELL INTERNATIONAL INC. |
Charlotte |
NC |
US |
|
|
Assignee: |
HONEYWELL INTERNATIONAL
INC.
Charlotte
NC
|
Appl. No.: |
17/692721 |
Filed: |
March 11, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16877829 |
May 19, 2020 |
11274238 |
|
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17692721 |
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15870597 |
Jan 12, 2018 |
10655040 |
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16877829 |
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62522836 |
Jun 21, 2017 |
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62522846 |
Jun 21, 2017 |
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62522851 |
Jun 21, 2017 |
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62522860 |
Jun 21, 2017 |
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62445800 |
Jan 13, 2017 |
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62445816 |
Jan 13, 2017 |
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International
Class: |
C09K 5/04 20060101
C09K005/04 |
Claims
1. A refrigerant comprising at least about 97% by weight of the
following four compounds, with each compound being present in the
following relative percentages: from 1% by weight to 2%+/-0.5% by
weight trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)), from
about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/-0.5% by
weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and from about
6.6% by weight to about 20.6% by weight trifluoroiodomethane
(CF.sub.3I).
2. A heat transfer composition comprising a refrigerant of claim
1.
3. The heat transfer composition of claim 2 further comprising a
lubricant.
4. The heat transfer composition of claim 2 further comprising a
stabilizer.
5. The heat transfer composition of claim 3 further comprising a
stabilizer.
6. A refrigerant comprising at least about 97% by weight of the
following three compounds, with each compound being present in the
following relative percentages of: from 1% by weight to 3% by
weight trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E), from
about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and from about 15%
by weight to about 21% by weight trifluoroiodomethane (CF3I).
7. A heat transfer composition comprising a refrigerant of claim
1.
8. The heat transfer composition of claim 2 further comprising a
lubricant.
9. The heat transfer composition of claim 2 further comprising a
stabilizer.
10. The heat transfer composition of claim 3 further comprising a
stabilizer.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S.
application Ser. No. 16/877,829, filed May 19, 2020, Now pending,
which is a continuation of U.S. application Ser. No. 15/870,597,
filed Jan. 12, 2018, (now U.S. Pat. No. 10,655,040, issued May 19,
2020) which application claims the priority benefit of each of U.S.
Provisional Application Nos. 62/445,800 and 62/445,816, each of
which was filed on Jan. 13, 2017, and each of which is incorporated
herein by reference.
[0002] The present application also claims the priority benefit of
each of US Provisional Application Nos. 62/522,836; 62,522,846;
62/522,851; and 62/522,860, each of which was filed on Jun. 21,
2017 and each of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0003] The present invention relates to compositions, methods and
systems having utility in a heat exchange system, including
refrigeration applications and in particular aspects to
compositions for replacement of the refrigerant R-134a for heating
and cooling applications and to retrofitting heat exchange systems,
including systems which contain R-134a.
BACKGROUND
[0004] Mechanical refrigeration systems, and related heat transfer
devices, such as heat pumps and air conditioners, using refrigerant
liquids are well known in the art for industrial, commercial and
domestic uses. Chlorofluorocarbons (CFCs) were developed in the
1930s as refrigerants for such systems. However, since the 1980s
the effect of CFCs on the stratospheric ozone layer has become the
focus of much attention. In 1987, a number of governments signed
the Montreal Protocol to protect the global environment, setting
forth a timetable for phasing out the CFC products. CFCs were
replaced with more environmentally acceptable materials that
contain hydrogen, namely the hydrochlorofluorocarbons (HCFCs).
[0005] One of the most commonly used hydrochlorofluorocarbon
refrigerants was chlorodifluoromethane (HCFC-22). However,
subsequent amendments to the Montreal protocol accelerated the
phase out of the CFCs and also scheduled the phase-out of HCFCs,
including HCFC-22.
[0006] In response to the requirement for a non-flammable,
non-toxic alternative to the CFCs and HCFCs, industry has developed
a number of hydrofluorocarbons (HFCs) which have zero ozone
depletion potential. R-134a (1,1,1,2-tetrafluoroethane) was adopted
for various heat exchange applications, including refrigeration
applications such as medium temperature refrigeration systems and
vending machines, as well as heat pumps and chillers, as it does
not contribute to ozone depletion.
[0007] However, R-134a has a Global Warming Potential (GWP) of
about 1430 (according to IPCC (2007) Climate Change 2007: The
Physical Science Basis. Contribution of Working Group I to the
Fourth Assessment Report of the Intergovernmental Panel on Climate
Change. S.
[0008] Solomon et al, Cambridge University Press. Cambridge, United
Kingdom p996). There is therefore a need in the art for the
replacement of R-134a with a more environmentally acceptable
alternative.
[0009] It is understood in the art that replacement heat transfer
fluids must possess a mosaic of properties depending on the
particular application. For many of the applications which involve
the cooling or heat of air to which members of public are intended
to be exposed, that mosaic will generally include excellent heat
transfer properties, chemical stability, low or no toxicity,
non-flammability and/or lubricant compatibility amongst others. The
identification of a heat transfer fluid meeting all of these
requirements is not trivial.
[0010] Non-flammability is considered to be an important, and in
some cases, an essential property for many heat transfer
applications Thus, it is frequently beneficial to use compounds in
such compositions, which are non-flammable. As used herein, the
term "non-flammable" refers to compounds or compositions which are
determined to be non-flammable in accordance with ASTM standard
E-681-2001 at conditions described in ASHRAE Standard 34-2013 and
described in Appendix 1 to ASHRAE Standard 34-2013.
[0011] However, non-flammabillity is generally understood to be
inversely correlated to low GWP.
[0012] For example, while R-134a is classed as a non-flammable
(i.e. class 1) refrigerant, it has a high GWP of about 1430. In
contrast, while R152a (1,1-difluoroethane) has a GWP of about 124,
it is classed as a flamamable (i.e. a class 2) refrigerant. Thus,
it is generally difficult to provide a refrigerant which is
non-flammable, and which has a low GWP, that is, a GWP of not
greater than about 150.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1A shows an example of a previously used R-134a
refrigeration system;
[0014] FIG. 1B shows an example of a R-134a refrigeration system
that is the basis for the comparative examples described
herein.
[0015] FIG. 2 shows a cascaded refrigeration system according to
preferred embodiments of the invention;
[0016] FIG. 3 shows an alternative cascaded refrigeration system
according to preferred embodiments of the invention;
[0017] FIG. 4 shows an alternative cascaded refrigeration system
according to embodiments of the invention; and
[0018] FIG. 5 shows an alternative cascaded refrigeration system
according to embodiments of the invention.
SUMMARY OF THE INVENTION
[0019] Applicants have found that the compositions of the present
invention satisfy in an exceptional and unexpected way the need for
alternatives and/or replacements and/or retrofits for refrigerants
in such applications, particularly and preferably HFC-134a (also
referred to herein as "R-134a") that at once have lower GWP values
and provide non-flammable, non-toxic fluids that have a close match
in cooling efficiency and capacity to R-134a in refrigeration
applications in such systems.
[0020] The present invention includes refrigerants comprising at
least about 97% by weight of the following three compounds, with
each compound being present in the following relative
percentages:
[0021] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0022] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and from about
15% by weight to about 21% by weight trifluoroiodomethane
(CF.sub.3I).
[0023] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 1.
[0024] As used herein with respect to percentages based on a list
of compounds or components, the term "relative percentages" means
the percentage of the identified comounds or components based on
the total weight of the listed components.
[0025] As used herein with respect to weight percentages, the term
"about" in relation to the amounts expressed in weight percent
means that the amount of the component can vary by an amount of
+/-2% by weight. The amount of the component is preferably +/-1% by
weight, more preferably +/-0.5% by weight, even more preferably
+/-0.3% by weight, and most preferably +/-0.2% by weight. The
refrigerants and compositions of the invention include in preferred
embodiments amounts of an identified compound or component
specficied as being "about" wherein the amount is the identified
amount +/-1% by weight, and even more preferably +/-0.5% by
weight.
[0026] The present invention includes refrigerants comprising at
least about 98.5% by weight of the following three compounds, with
each compound being present in the following relative
percentages:
[0027] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0028] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and
[0029] from about 15% by weight to about 21% by weight
trifluoroiodomethane (CF.sub.3I).
[0030] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 2.
[0031] The present invention includes refrigerants comprising at
least about 99.5% by weight of the following three compounds, with
each compound being present in the following relative
percentages:
[0032] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0033] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and
[0034] from about 15% by weight to about 21% by weight
trifluoroiodomethane (CF.sub.3I).
[0035] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 3.
[0036] The present invention includes refrigerants consisting
essentially of the following three compounds, with each compound
being present in the following relative percentages:
[0037] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0038] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and
[0039] from about 15% by weight to about 21% by weight
trifluoroiodomethane (CF.sub.3I).
[0040] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 4.
[0041] The present invention includes refrigerants consisting of
the following four compounds, with each compound being present in
the following relative percentages:
[0042] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0043] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and
[0044] from about 15% by weight to about 21% by weight
trifluoroiodomethane (CF.sub.3I).
[0045] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 5.
[0046] The present invention includes refrigerants comprising at
least about 97% by weight of the following three compounds, with
each compound being present in the following relative
percentages:
[0047] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0048] about 78% by weight of trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)), and
[0049] about 20% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 6.
[0050] The present invention includes refrigerants comprising at
least about 98.5% by weight of the following three compounds, with
each compound being present in the following relative
percentages:
[0051] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0052] about 78% by weight of trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)), and
[0053] about 20% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 7.
[0054] The present invention includes refrigerants consisting
essentially of the following three compounds, with each compound
being present in the following relative percentages: 2%+/-0.5% by
weight trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
about 78% by weight of trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)), and about 20% by weight trifluoroiodomethane
(CF3I). Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 8.
[0055] The present invention includes refrigerants consisting of
the following three compounds, with each compound being present in
the following relative percentages: 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)), about 78%
by weight of trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and
about 20% by weight trifluoroiodomethane (CF3I). Refrigerants as
described in this paragraph are sometimes referred to for
convenience as Refrigerant 9.
[0056] The present invention includes refrigerants comprising at
least about 98.5% by weight of the following three compounds, with
each compound being present in the following relative
percentages:
[0057] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0058] 78%+/-0.5% by weight of trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)), and
[0059] 20%+/-0.5% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 10.
[0060] The present invention includes refrigerants consisting
essentially of the following three compounds, with each compound
being present in the following relative percentages:
[0061] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0062] 78%+/-0.5% by weight of trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)), and
[0063] 20%+/-0.5% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 11.
[0064] The present invention includes refrigerants consisting of
the following three compounds, with each compound being present in
the following relative percentages:
[0065] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0066] 78%+/-0.5% by weight of trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)), and
[0067] 20%+/-0.5% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 12.
[0068] The present invention includes refrigerants comprising at
least about 97% by weight of the following four compounds, with
each compound being present in the following relative
percentages:
[0069] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0070] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),
[0071] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0072] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF.sub.3I).
[0073] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 13.
[0074] The present invention includes refrigerants comprising at
least about 98.5% by weight of the following three compounds, with
each compound being present in the following relative
percentages:
[0075] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0076] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/-0.5% by
weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and
[0077] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF3I).
[0078] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 14.
[0079] The present invention includes refrigerants comprising at
least about 99.5% by weight of the following three compounds, with
each compound being present in the following relative
percentages:
[0080] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0081] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/-0.5% by
weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and
[0082] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF.sub.3I).
[0083] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 15.
[0084] The present invention includes refrigerants consisting
essentially of the following four compounds, with each compound
being present in the following relative percentages:
[0085] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0086] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),
[0087] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0088] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF.sub.3I).
[0089] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 16.
[0090] The present invention includes refrigerants consisting of
the following four compounds, with each compound being present in
the following relative percentages:
[0091] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0092] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/-0.5% by
weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and
[0093] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF.sub.3I).
[0094] Refrigerants as described in this paragraph are sometimes
referred to for convenience as Refrigerant 17.
[0095] The present invention includes refrigerants comprising at
least about 98.5% by weight of the following four compounds, with
each compound being present in the following relative
percentages:
[0096] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0097] about 84% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0098] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0099] about 9.6% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 18.
[0100] The present invention includes refrigerants consisting
essentially of the following four compounds, with each compound
being present in the following relative percentages:
[0101] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0102] about 84% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0103] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and about 9.6% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 19.
[0104] The present invention includes refrigerants consisting of
the following four compounds, with each compound being present in
the following relative percentages:
[0105] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0106] about 84% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0107] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0108] about 9.6% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 20.
[0109] The present invention includes refrigerants comprising at
least about 98.5% by weight of the following four compounds, with
each compound being present in the following relative
percentages:
[0110] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0111] 84%+/-0.5% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0112] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0113] 9.6%+/-0.5% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 21.
[0114] The present invention includes refrigerants consisting
essentially of the following four compounds, with each compound
being present in the following relative percentages:
[0115] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0116] 84%+/-0.5% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0117] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0118] 9.6%+/-0.5% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 22.
[0119] The present invention includes refrigerants consisting of
the following four compounds, with each compound being present in
the following relative percentages:
[0120] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0121] 84%+/-0.5% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0122] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0123] 9.6%+/-0.5% by weight trifluoroiodomethane (CF3I).
Refrigerants as described in this paragraph are sometimes referred
to for convenience as Refrigerant 23.
[0124] The present invention also provides refrigerant compositions
in which the refrigerant is non-flammable. As used herein, the term
"non-flammable" refers to compounds or compositions which are
determined to be non-flammable in accordance with ASTM standard
E-681-2016 at conditions described in Appendix 1 to ASHRAE Standard
34-2016. In particular, the present invention provides each of the
refrigerants as identified herein as Refrigerants 1-23 in which the
refrigerant is non-flammable, and for the purposes of convenience,
each such refrigerant is referred to herein as Refrigerant 1NF,
Refrigerant 2NF, Refrigerant 3NF, (and through to) Refrigerant
23NF, respectively.
[0125] The present invention also provides refrigerant compositions
in which the refrigerant has a Global Warming Potential (GWP) of
150 or less. In particular, the present invention provides each of
the refrigerants as identified herein as Refrigerants 1-23 in which
the refrigerant has a GWP of 150 or less, and for the purposes of
convenience, each such refrigerant is referred to herein as
Refrigerant 1GWP150, Refrigerant 2GWP150, Refrigerant 3GWP150, (and
through to) Refrigerant 23GWP150, respectively.
[0126] The phrase "Global Warming Potential" (hereinafter "GWP")
was developed to allow comparisons of the global warming impact of
different gases. Specifically, it is a measure of how much energy
the emission of one ton of a gas will absorb over a given period of
time, relative to the emission of one ton of carbon dioxide. The
larger the GWP, the more that a given gas warms the Earth compared
to CO.sub.2 over that time period. The time period usually used for
GWP is 100 years. GWP provides a common measure, which allows
analysts to add up emission estimates of different gases. See
www.epa.gov.
[0127] The present invention also provides refrigerant compositions
in which the refrigerant has a Global Warming Potential (GWP) of
less than 150 and in which the refrigerant is non-flammable. In
particular, the present invention provides each of the refrigerants
as identified herein as Refrigerants 1-23 in which the refrigerant
is non-flammable and has a GWP of less than 150, and for the
purposes of convenience, each such refrigerant is referred to
herein as Refrigerant 1NFGWP150, Refrigerant 2NFGWP150, Refrigerant
3NFGWP150, (and through to) Refrigerant 23NFGWP150,
respectively.
[0128] The present invention also provides refrigerant compositions
in which the refrigerant has a Global Warming Potential (GWP) of 5
or less. In particular, the present invention provides each of the
refrigerants as identified herein as Refrigerants 1-12 in which the
refrigerant has a GWP of 5 or less, and for the purposes of
convenience, each such refrigerant is referred to herein as
Refrigerant 1GWP5, Refrigerant 2GWP5, Refrigerant 3GWP5, (and
through to) Refrigerant 12GWP5, respectively.
[0129] The present invention also provides refrigerant compositions
in which the refrigerant is non-flammable and has a Global Warming
Potential (GWP) of 5. In particular, the present invention provides
each of the refrigerants as identified herein as Refrigerants 1-12
in which the refrigerant has a GWP of 5 or less and in which the
refrigerant is non-flammable, and for the purposes of convenience,
each such refrigerant is referred to herein as Refrigerant 1NFGWP5,
Refrigerant 2NFGWP5, Refrigerant 3NFGWP5, (and through to)
Refrigerant 12NFGWP5, respectively.
DETAILED DESCRIPTION OF THE INVENTION
[0130] The present invention relates to refrigerants, heat transfer
compositions and heat transfer methods which include or utilize
refrigerant comprising HFCO-1233zd(E), HFO-1234ze(E),
trifluoroiodomethane (CF3I). Trifluoroiodomethane (CF3I) is readily
available from a variety of commercial sources, including Matheson
TriGas, Inc. HFCO-1233zd(E) and HFO-1234ze(E) are commercially
available materials that can be obtained from Honeywell
International, Inc.
[0131] Embodiments of the present invention include also
refrigerants that include HFC-227ea, in addition to HFCO-1233zd(E),
HFO-1234ze(E) and trifluoroiodomethane (CF3I). HFC-227ea is also a
known commercially available material.
[0132] Refrigerants
[0133] Applicants have found that refrigerants of the present
invention are capable of providing exceptionally advantageous
properties including: heat transfer properties, chemical stability,
low or no toxicity, non-flammability, near zero ozone depletion
potential ("ODP"), and lubricant compatibility in combination with
a low GWP. A particular advantage of the refrigerants of the
present invention is that they are non-flammable when tested in
accordance with the non-flammability test defined herein. It will
be appreciated by the skilled person that the flammability of a
refrigerant is an important characteristic for use in certain
important heat transfer applications. Thus, it is a desire in the
art to provide a refrigerant composition which can be used as a
replacement for and/or as a retrofit for R-134a for refrigeration
applications which has excellent heat transfer properties, chemical
stability, low or no toxicity, near zero ODP, and lubricant
compatibility and which maintains non-flammability in use. This
requirement is met by the refrigerants of the present
invention.
[0134] The Applicants have found that the compositions of the
invention are capable of achieving a difficult to achieve
combination of properties including particularly low GWP. Thus, the
compositions of the invention preferably have a GWP of 150 or less,
or 5 or less.
[0135] In addition, the compositions of the invention have a low
ODP. Thus, the compositions of the invention have an ODP of not
greater than 0.05, preferably not greater than 0.02, and more
preferably about zero.
[0136] In addition, the compositions of the invention show
acceptable toxicity and preferably have an Occupational Exposure
Limit ("OEL") of greater than about 400. As used herein, the term
"Occupational Exposure Limit (OEL)" is used in accordance with and
has a value determined in accordance with ASHRAE Standard 34-2016
Designation and Safety Classification of Refrigerants.
[0137] Heat Transfer Compositions
[0138] Preferably, the invention includes heat transfer
compositions comprising any one of the refrigerants of the present
invention, including in particular each of Refrigerants 1-23,
Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, in an amount of greater than 40% by weight of the
heat transfer composition, or greater than about 50% by weight of
the heat transfer composition, or greater than 70% by weight of the
heat transfer composition, or greater than 80% by weight of the
heat transfer composition or greater than 90% by weight of the heat
transfer composition. The heat transfer composition may consist
essentially of or consist of the refrigerant, including in
particular each of Refrigerants 1-23, Refrigerants 1NF-23NF,
Refrigerants 1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150,
Refrigerants 1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5.
[0139] The heat transfer compositions of the invention may include
other components for the purpose of enhancing or providing certain
functionality to the compositions. Such other components may
include one or more of lubricants, dyes, solubilizing agents,
compatibilizers, stabilizers, antioxidants, corrosion inhibitors,
extreme pressure additives and anti wear additives.
[0140] In preferred embodiments the heat transfer compositions
comprise any one of the refrigerants of the present invention,
including in particular any one of Refrigerants 1-23, Refrigerants
1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5 and a stabilizer.
[0141] In preferred embodiments the heat transfer compositions
consist essentially of any one of the refrigerants of the present
invention, including in particular any one of Refrigerants 1-23,
Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5 and a stabilizer.
[0142] In preferred embodiments the heat transfer compositions
comprise any one of the refrigerants of the present invention,
including in particular any one of Refrigerants 1-23, Refrigerants
1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5 and a lubricant.
[0143] In preferred embodiments the heat transfer compositions
consist essentially of any one of the refrigerants of the present
invention, including in particular any one of Refrigerants 1-23,
Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5 and a lubricant.
[0144] In preferred embodiments the heat transfer compositions
comprise any one of the refrigerants of the present invention,
including in particular any one of Refrigerants 1-23, Refrigerants
1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, a stabilizer and a lubricant.
[0145] In preferred embodiments the heat transfer compositions
consist essentially of any one of the refrigerants of the present
invention, including in particular any one of Refrigerants 1-23,
Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, a stabilizer and a lubricant.
[0146] Stabilizers
[0147] Examples of useful stabilizers for use in the heat transfer
compostions hereof include diene-based compounds and/or
phenol-based compounds and/or phosphorus compounds and/or nitrogen
compounds and/or epoxides. Examples of preferred stabilizers
include diene-based compounds and/or phenol-based compounds and/or
phosphorus compounds.
[0148] The stabilizer preferably is provided in the heat transfer
composition in an amount of greater than 0 and preferably from
0.0001% by weight to about 5% by weight, preferably 0.01% by weight
to about 2% by weight, and more preferably from 0.1 to about 1% by
weight. In each case, percentage by weight refers to the weight of
the heat transfer composition.
[0149] The diene-based compounds include C3 to C15 dienes and to
compounds formed by reaction of any two or more C3 to C4 dienes.
Preferably, the diene based compounds are selected from the group
consisting of allyl ethers, propadiene, butadiene, isoprene, and
terpenes. The diene-based compounds are preferably terpenes, which
include but are not limited to terebene, retinal, geraniol,
terpinene, delta-3 carene, terpinolene, phellandrene, fenchene,
myrcene, farnesene, pinene, nerol, citral, camphor, menthol,
limonene, nerolidol, phytol, carnosic acid, and vitamin A.sub.1.
Preferably, the stabilizer is farnesene. Preferred terpene
stabilizers are disclosed in U.S. Provisional Patent Application
No. 60/638,003 filed on Dec. 12, 2004, published as US
2006/0167044A1, which is incorporated herein by reference.
[0150] In addition, the diene based compounds can be provided in
the heat transfer composition in an amount greater than 0 and
preferably from 0.0001% by weight to about 5% by weight, preferably
0.001% by weight to about 2.5% by weight, and more preferably from
0.01% to about 1% by weight. In each case, percentage by weight
refers to the weight of the heat transfer composition.
[0151] The diene based compounds are preferably provided in
combination with a phosphorous compound.
[0152] The phenol can be one or more compounds selected from
4,4'-methylenebis(2,6-di-tert-butylphenol);
4,4'-bis(2,6-di-tert-butylphenol); 2,2- or 4,4-biphenyldiols,
including 4,4'-bis(2-methyl-6-tert-butylphenol); derivatives of
2,2- or 4,4-biphenyldiols;
2,2'-methylenebis(4-ethyl-6-tertbutylphenol);
2,2'-methylenebis(4-methyl-6-tert-butylphenol);
4,4-butylidenebis(3-methyl-6-tert-butylphenol);
4,4-isopropylidenebis(2,6-di-tert-butylphenol);
2,2'-methylenebis(4-methyl-6-nonylphenol);
2,2'-isobutylidenebis(4,6-dimethylphenol);
2,2'-methylenebis(4-methyl-6-cyclohexylphenol);
2,6-di-tert-butyl-4-methylphenol (BHT);
2,6-di-tert-butyl-4-ethylphenol: 2,4-dimethyl-6-tert-butylphenol;
2,6-di-tert-alpha-dimethylamino-p-cresol;
2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol);
4,4'-thiobis(2-methyl-6-tert-butylphenol);
4,4'-thiobis(3-methyl-6-tert-butylphenol);
2,2'-thiobis(4-methyl-6-tert-butylphenol);
bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide; bis
(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, tocopherol,
hydroquinone, 2,2'6,6'-tetra-tert-butyl-4,4'-methylenediphenol and
t-butyl hydroquinone, and preferably BHT.
[0153] The phenol compounds can be provided in the heat transfer
composition in an amount of greater than 0 and preferably from
0.0001% by weight to about 5% by weight, preferably 0.001% by
weight to about 2.5% by weight, and more preferably from 0.01% to
about 1% by weight. In each case, percentage by weight refers to
the weight of the heat transfer composition.
[0154] The phosphorus compound can be a phosphite or a phosphate
compound. For the purposes of this invention, the phosphite
compound can be a diaryl, dialkyl, triaryl and/or trialkyl
phosphite, and/or a mixed aryl/alkyl di- or tri-substituted
phosphite, in particular one or more compounds selected from
hindered phosphites, tris-(di-tert-butylphenyl)phosphite,
di-n-octyl phophite, iso-octyl diphenyl phosphite, iso-decyl
diphenyl phosphite, tri-iso-decyl phosphate, triphenyl phosphite
and diphenyl phosphite, particularly diphenyl phosphite.
[0155] The phosphate compounds can be a triaryl phosphate, trialkyl
phosphate, alkyl mono acid phosphate, aryl diacid phosphate, amine
phosphate, preferably triaryl phosphate and/or a trialkyl
phosphate, particularly tri-n-butyl phosphate.
[0156] The phosphorus compounds can be provided in the heat
transfer composition in an amount of greater than 0 and preferably
from 0.0001% by weight to about 5% by weight, preferably 0.001% by
weight to about 2.5% by weight, and more preferably from 0.01% to
about 1% by weight. In each case, by weight refers to weight of the
heat transfer composition.
[0157] When the stabilizer is a nitrogen compound, the stabilizer
may comprise an amine based compound such as one or more secondary
or tertiary amines selected from diphenylamine, p-phenylenediamine,
triethylamine, tributylamine, diisopropylamine, triisopropylamine
and triisobutylamine. The amine based compound can be an amine
antioxidant such as a substituted piperidine compound, i.e. a
derivative of an alkyl substituted piperidyl, piperidinyl,
piperazinone, or alkyoxypiperidinyl, particularly one or more amine
antioxidants selected from 2,2,6,6-tetramethyl-4-piperidone,
2,2,6,6-tetramethyl-4-piperidinol;
bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate;
di(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
poly(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl
succinate; alkylated paraphenylenediamines such as
N-phenyl-N'-(1,3-dimethyl-butyl)-p-phenylenediamine or
N,N'-di-sec-butyl-p-phenylenediamine and hydroxylamines such as
tallow amines, methyl bis tallow amine and bis tallow amine, or
phenol-alpha-napththylamine or Tinuvin.RTM.765 (Ciba), BLS.RTM.1944
(Mayzo Inc) and BLS.RTM. 1770 (Mayzo Inc). For the purposes of this
invention, the amine based compound also can be an alkyldiphenyl
amine such as bis (nonylphenyl amine), dialkylamine such as
(N-(1-methylethyl)-2-propylamine, or one or more of
phenyl-alpha-naphthyl amine (PANA),
alkyl-phenyl-alpha-naphthyl-amine (APANA), and bis (nonylphenyl)
amine. Preferably the amine based compound is one or more of
phenyl-alpha-naphthyl amine (PANA),
alkyl-phenyl-alpha-naphthyl-amine (APANA) and bis (nonylphenyl)
amine, amd more preferably phenyl-alpha-naphthyl amine (PANA).
[0158] Alternatively, or in addition to the nitrogen compounds
identified above, one or more compounds selected from
dinitrobenzene, nitrobenzene, nitromethane, nitrosobenzene, and
TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] may be used as the
stabilizer.
[0159] The nitrogen compounds can be provided in the heat transfer
composition in an amount of greater than 0 and from 0.0001% by
weight to about 5% by weight, preferably 0.001% by weight to about
2.5% by weight, and more preferably from 0.01% to about 1% by
weight. In each case, percentage by weight refers to the weight of
the heat transfer composition.
[0160] Useful epoxides include aromatic epoxides, alkyl epoxides,
and alkyenyl epoxides.
[0161] The diene based compounds are preferably provided in
combination with a phosphorous compound. Preferably, the heat
transfer composition comprises a refrigerant as set out above and a
stabilizer composition comprising farnesene and a phosphorous
compound selected from a diaryl phosphite, a dialkyl phosphite, a
triaryl phosphate or a trialkyl phosphate, more preferably diphenyl
phosphite and/or tri-n-butyl phosphate. More preferably the heat
transfer composition comprises a refrigerant as described herein
and a stabilizer composition comprising farnesene and one or more
of a diaryl phosphite or a dialkyl phosphite, more preferably
diphenyl phosphite. Preferably the stabilizer comprises farnesene
and diphenyl phosphite.
[0162] The heat transfer composition of the invention can
preferably comprise Refrigerant 1 and a stabilizer composition
comprising BHT, wherein said BHT is present in an amount of from
about 0.0001% by weight to about 5% by weight based on the weight
of heat transfer composition. BHT present in an amount of from
about 0.0001% by weight to about 5% by weight based on the weight
of heat transfer composition is sometimes referred to for
convenience as Stabilizer 1.
[0163] The heat transfer composition of the invention can
preferably comprise Refrigerant 2 and Stabilizer 1.
[0164] The heat transfer composition of the invention can
preferably comprise Refrigerant 3 and Stabilizer 1.
[0165] The heat transfer composition of the invention can
preferably comprise Refrigerant 4 and Stabilizer 1.
[0166] The heat transfer composition of the invention can
preferably comprise Refrigerant 5 and Stabilizer 1.
[0167] The heat transfer composition of the invention can
preferably comprise Refrigerant 6 and Stabilizer 1.
[0168] The heat transfer composition of the invention can
preferably comprise Refrigerant 7 and Stabilizer 1.
[0169] The heat transfer composition of the invention can
preferably comprise Refrigerant 8 and Stabilizer 1.
[0170] The heat transfer composition of the invention can
preferably comprise Refrigerant 9 and Stabilizer 1.
[0171] The heat transfer composition of the invention can
preferably comprise Refrigerant 10 and Stabilizer 1.
[0172] The heat transfer composition of the invention can
preferably comprise Refrigerant 11 and Stabilizer 1.
[0173] The heat transfer composition of the invention can
preferably comprise Refrigerant 12 and Stabilizer 1.
[0174] The heat transfer composition of the invention can
preferably comprise Refrigerant 13 and Stabilizer 1.
[0175] The heat transfer composition of the invention can
preferably comprise Refrigerant 14 and Stabilizer 1.
[0176] The heat transfer composition of the invention can
preferably comprise Refrigerant 15 and Stabilizer 1.
[0177] The heat transfer composition of the invention can
preferably comprise Refrigerant 16 and Stabilizer 1.
[0178] The heat transfer composition of the invention can
preferably comprise Refrigerant 17 and Stabilizer 1.
[0179] The heat transfer composition of the invention can
preferably comprise Refrigerant 18 and Stabilizer 1.
[0180] The heat transfer composition of the invention can
preferably comprise Refrigerant 19 and Stabilizer 1.
[0181] The heat transfer composition of the invention can
preferably comprise Refrigerant 20 and Stabilizer 1.
[0182] The heat transfer composition of the invention can
preferably comprise Refrigerant 21 and Stabilizer 1.
[0183] The heat transfer composition of the invention can
preferably comprise Refrigerant 22 and Stabilizer 1.
[0184] The heat transfer composition of the invention can
preferably comprise Refrigerant 23 and Stabilizer 1.
[0185] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NF-23NF and Stabilizer
1.
[0186] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NFGWP150-23NFGWP150 and
Stabilizer 1.
[0187] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1GWP5-12GWP5 and Stabilizer
1.
[0188] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NFGWP5-12NFGWP5 and
Stabilizer 1.
[0189] The heat transfer composition of the invention can
preferably comprise Refrigerant 1 and a stabilizer composition
comprising farnesene, diphenyl phosphite and BHT, wherein the
farnesene is provided in an amount of from about 0.0001% by weight
to about 5% by weight based on the weight of the heat transfer
composition, the diphenyl phosphite is provided in an amount of
from about 0.0001% by weight to about 5% by weight based on the
weight of the heat transfer composition, and the BHT is provided in
an amount of from about 0.0001% by weight to about 5% by weight
based on the weight of heat transfer composition. A stabilizer
composition comprising farnesene, diphenyl phosphite and BHT,
wherein the farnesene is provided in an amount of from about
0.0001% by weight to about 5% by weight based on the weight of the
heat transfer composition, the diphenyl phosphite is provided in an
amount of from about 0.0001% by weight to about 5% by weight based
on the weight of the heat transfer composition, and the BHT is
provided in an amount of from about 0.0001% by weight to about 5%
by weight based on the weight of heat transfer composition is
sometimes referred to for convenience as Stabilizer 2.
[0190] The heat transfer composition of the invention can
preferably comprise Refrigerant 2 and Stabilizer 2.
[0191] The heat transfer composition of the invention can
preferably comprise Refrigerant 3 and Stabilizer 2.
[0192] The heat transfer composition of the invention can
preferably comprise Refrigerant 4 and Stabilizer 2.
[0193] The heat transfer composition of the invention can
preferably comprise Refrigerant 5 and Stabilizer 2.
[0194] The heat transfer composition of the invention can
preferably comprise Refrigerant 6 and Stabilizer 2.
[0195] The heat transfer composition of the invention can
preferably comprise Refrigerant 7 and Stabilizer 2.
[0196] The heat transfer composition of the invention can
preferably comprise Refrigerant 8 and Stabilizer 2.
[0197] The heat transfer composition of the invention can
preferably comprise Refrigerant 9 and Stabilizer 2.
[0198] The heat transfer composition of the invention can
preferably comprise Refrigerant 10 and Stabilizer 2.
[0199] The heat transfer composition of the invention can
preferably comprise Refrigerant 11 and Stabilizer 2.
[0200] The heat transfer composition of the invention can
preferably comprise Refrigerant 12 and Stabilizer 2.
[0201] The heat transfer composition of the invention can
preferably comprise Refrigerant 13 and Stabilizer 2.
[0202] The heat transfer composition of the invention can
preferably comprise Refrigerant 14 and Stabilizer 2.
[0203] The heat transfer composition of the invention can
preferably comprise Refrigerant 15 and Stabilizer 2.
[0204] The heat transfer composition of the invention can
preferably comprise Refrigerant 16 and Stabilizer 2.
[0205] The heat transfer composition of the invention can
preferably comprise Refrigerant 17 and Stabilizer 2.
[0206] The heat transfer composition of the invention can
preferably comprise Refrigerant 18 and Stabilizer 2.
[0207] The heat transfer composition of the invention can
preferably comprise Refrigerant 19 and Stabilizer 2.
[0208] The heat transfer composition of the invention can
preferably comprise Refrigerant 20 and Stabilizer 2.
[0209] The heat transfer composition of the invention can
preferably comprise Refrigerant 21 and Stabilizer 2.
[0210] The heat transfer composition of the invention can
preferably comprise Refrigerant 22 and Stabilizer 2.
[0211] The heat transfer composition of the invention can
preferably comprise Refrigerant 23 and Stabilizer 2.
[0212] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NF-23NF and Stabilizer
2.
[0213] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NFGWP150-23NFGWP150 and
Stabilizer 2.
[0214] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1GWP5-12GWP5 and Stabilizer
2.
[0215] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NFGWP5-12NFGWP5 and
Stabilizer 2.
[0216] The heat transfer composition of the invention can more
preferably comprise any one of the refrigerants of the invention as
described herein, including in particular any one of Refrigerants
1-23, Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150,
Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and
Refrigerants 1NFGWP5-12NFGWP5, and a stabilizer composition
comprising farnesene, diphenyl phosphite and BHT, wherein the
farnesene is provided in an amount of from about 0.001% by weight
to about 2.5% by weight based on the weight of the heat transfer
composition, the diphenyl phosphite is provided in an amount of
from about 0.001% by weight to about 2.5% by weight based on the
weight of the heat transfer composition, and the BHT is provided in
an amount of from about 0.001% by weight to about 2.5% by weight
based on the weight of heat transfer composition.
[0217] The heat transfer composition of the invention can most
preferably comprise any one of the inventive refrigerants,
including in particular any one of Refrigerants 1-23, Refrigerants
1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1
NFGWP5-12NFGWP5, and a stabilizer composition comprising farnesene,
diphenyl phosphite and BHT, wherein the farnesene is provided in an
amount of from about 0.01% by weight to about 1% by weight based on
the weight of the heat transfer composition, the diphenyl phosphite
is provided in an amount of from about 0.01% by weight to about 1%
by weight based on the weight of the heat transfer composition, and
the BHT is provided in an amount of from about 0.01% by weight to
about 1% by weight based on the weight of heat transfer
composition.
[0218] Lubricants
[0219] Each of the heat transfer compositions of the invention as
defined above may additionally comprise a lubricant. In general,
the heat transfer composition comprises a lubricant, in amounts of
from about 5 to 50% by weight of the heat transfer composition,
preferably about 10 to about 50% by weight of the heat transfer
composition, preferably from about 20 to about 50% by weight of the
heat transfer composition, alternatively about 20 to about 40% by
weight of the heat transfer composition, alternatively about 20 to
about 30% by weight of the heat transfer composition, alternatively
about 30 to about 50% by weight of the heat transfer composition,
alternatively about 30 to about 40% by weight of the heat transfer
composition. The heat transfer composition may comprise a
lubricant, in amounts of from about 5 to about 10% by weight of the
heat transfer composition, preferably around about 8% by weight of
the heat transfer composition.
[0220] Commonly used refrigerant lubricants such as polyol esters
(POEs), polyalkylene glycols (PAGs), silicone oils, mineral oil,
alkylbenzenes (ABs), polyvinyl ethers (PVEs), and
poly(alpha-olefin) (PAO) that are used in refrigerationsystems may
be used with the refrigerant compositions of the present
invention.
[0221] Preferably the lubricants are selected from polyol esters
(POEs), polyalkylene glycols (PAGs), mineral oil, alkylbenzenes
(ABs) and polyvinyl ethers (PVE), more preferably from polyol
esters (POEs), mineral oil, alkylbenzenes (ABs), and polyvinyl
ethers (PVE), particularly from polyol esters (POEs), mineral oil
and alkylbenzenes (ABs), most preferably from polyol esters
(POEs).
[0222] Commercially available mineral oils include Witco LP 250
(registered trademark) from Witco, Suniso 3GS from Witco and
Calumet R015 from Calumet. Commercially available alkylbenzene
lubricants include Zerol 150 (registered trademark) and Zerol 300
(registered trademark) from Shrieve Chemical. Other useful esters
include phosphate esters, di-basic acid esters and fluoro
esters.
[0223] The heat transfer composition of the invention may consist
essentially of or consist of a refrigerant, including in particular
any one of Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants
1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants
1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, a stabilizer
composition and a lubricant as described herein.
[0224] A preferred heat transfer composition comprises Refrigerant
1 and from 10 to 50% by weight of a polyol ester (POE) lubricant,
based on the weight of the heat transfer composition. Polyol ester
(POE) lubricant from 10 to 50% by weight of the heat transfer
composition is sometimes referred to for convenience as Lubricant
1.
[0225] A preferred heat transfer composition comprises Refrigerant
2 and Lubricant 1.
[0226] A preferred heat transfer composition comprises Refrigerant
3 and Lubricant 1.
[0227] A preferred heat transfer composition comprises Refrigerant
4 and Lubricant 1.
[0228] A preferred heat transfer composition comprises Refrigerant
5 and Lubricant 1.
[0229] A preferred heat transfer composition comprises Refrigerant
6 and Lubricant 1
[0230] A preferred heat transfer composition comprises Refrigerant
7 and Lubricant 1.
[0231] A preferred heat transfer composition comprises Refrigerant
8 and Lubricant 1.
[0232] A preferred heat transfer composition comprises Refrigerant
9 and Lubricant 1.
[0233] A preferred heat transfer composition comprises Refrigerant
10 and Lubricant 1.
[0234] A preferred heat transfer composition comprises Refrigerant
11 and Lubricant 1.
[0235] A preferred heat transfer composition comprises Refrigerant
12 and Lubricant 1.
[0236] A preferred heat transfer composition comprises Refrigerant
13 and Lubricant 1.
[0237] A preferred heat transfer composition comprises Refrigerant
14 and Lubricant 1.
[0238] A preferred heat transfer composition comprises Refrigerant
15 and Lubricant 1.
[0239] A preferred heat transfer composition comprises Refrigerant
16 and Lubricant 1.
[0240] A preferred heat transfer composition comprises Refrigerant
17 and Lubricant 1.
[0241] A preferred heat transfer composition comprises Refrigerant
18 and Lubricant 1.
[0242] A preferred heat transfer composition comprises Refrigerant
19 and Lubricant 1.
[0243] A preferred heat transfer composition comprises Refrigerant
20 and Lubricant 1.
[0244] A preferred heat transfer composition comprises Refrigerant
21 and Lubricant 1.
[0245] A preferred heat transfer composition comprises Refrigerant
22 and Lubricant 1.
[0246] A preferred heat transfer composition comprises Refrigerant
23 and Lubricant 1.
[0247] A preferred heat transfer composition comprises any of
Refrigerants 1NF-23NF and Lubricant 1.
[0248] A preferred heat transfer composition comprises any of
Refrigerants 1NFGWP150-23NFGWP150 and Lubricant 1.
[0249] A preferred heat transfer composition comprises any of
Refrigerants 1GWP5-12GWP5 and Lubricant 1.
[0250] A preferred heat transfer composition comprises any of
Refrigerants 1NFGWP5-12NFGWP5 and Lubricant 1.
[0251] The heat transfer composition of the invention can
preferably comprise Refrigerant 1, Stabilizer 1, and Lubricant
1.
[0252] The heat transfer composition of the invention can
preferably comprise Refrigerant 2, Stabilizer 1, and Lubricant
1.
[0253] The heat transfer composition of the invention can
preferably comprise Refrigerant 3, Stabilizer 1, and Lubricant
1.
[0254] The heat transfer composition of the invention can
preferably comprise Refrigerant 4, Stabilizer 1, and Lubricant
1.
[0255] The heat transfer composition of the invention can
preferably comprise Refrigerant 5, Stabilizer 1, and Lubricant
1.
[0256] The heat transfer composition of the invention can
preferably comprise Refrigerant 6, Stabilizer 1, and Lubricant
1.
[0257] The heat transfer composition of the invention can
preferably comprise Refrigerant 7, Stabilizer 1, and Lubricant
1.
[0258] The heat transfer composition of the invention can
preferably comprise Refrigerant 8, Stabilizer 1, and Lubricant
1.
[0259] The heat transfer composition of the invention can
preferably comprise Refrigerant 9, Stabilizer 1, and Lubricant
1.
[0260] The heat transfer composition of the invention can
preferably comprise Refrigerant 10, Stabilizer 1, and Lubricant
1.
[0261] The heat transfer composition of the invention can
preferably comprise Refrigerant 11, Stabilizer 1, and Lubricant
1.
[0262] The heat transfer composition of the invention can
preferably comprise Refrigerant 12, Stabilizer 1, and Lubricant
1.
[0263] The heat transfer composition of the invention can
preferably comprise Refrigerant 13, Stabilizer 1, and Lubricant
1.
[0264] The heat transfer composition of the invention can
preferably comprise Refrigerant 14, Stabilizer 1, and Lubricant
1.
[0265] The heat transfer composition of the invention can
preferably comprise Refrigerant 15, Stabilizer 1, and Lubricant
1.
[0266] The heat transfer composition of the invention can
preferably comprise Refrigerant 16, Stabilizer 1, and Lubricant
1.
[0267] The heat transfer composition of the invention can
preferably comprise Refrigerant 17, Stabilizer 1, and Lubricant
1.
[0268] The heat transfer composition of the invention can
preferably comprise Refrigerant 18, Stabilizer 1, and Lubricant
1.
[0269] The heat transfer composition of the invention can
preferably comprise Refrigerant 19, Stabilizer 1, and Lubricant
1.
[0270] The heat transfer composition of the invention can
preferably comprise Refrigerant 20, Stabilizer 1, and Lubricant
1.
[0271] The heat transfer composition of the invention can
preferably comprise Refrigerant 21, Stabilizer 1, and Lubricant
1.
[0272] The heat transfer composition of the invention can
preferably comprise Refrigerant 22, Stabilizer 1, and Lubricant
1.
[0273] The heat transfer composition of the invention can
preferably comprise Refrigerant 23, Stabilizer 1, and Lubricant
1.
[0274] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NF-23NF, Stabilizer 1, and
Lubricant 1.
[0275] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NFGWP150-23NFGWP150,
Stabilizer 1, and Lubricant 1.
[0276] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1GWP5-12GWP5, Stabilizer 1,
and Lubricant 1.
[0277] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NFGWP5-12NFGWP5,
Stabilizer 1, and Lubricant 1.
[0278] The heat transfer composition of the invention can
preferably comprise Refrigerant 1, Stabilizer 2, and Lubricant
1.
[0279] The heat transfer composition of the invention can
preferably comprise Refrigerant 2, Stabilizer 2, and Lubricant
1.
[0280] The heat transfer composition of the invention can
preferably comprise Refrigerant 3, Stabilizer 2, and Lubricant
1.
[0281] The heat transfer composition of the invention can
preferably comprise Refrigerant 4, Stabilizer 2, and Lubricant
1.
[0282] The heat transfer composition of the invention can
preferably comprise Refrigerant 5, Stabilizer 1, and Lubricant
1.
[0283] The heat transfer composition of the invention can
preferably comprise Refrigerant 6, Stabilizer 2, and Lubricant
1.
[0284] The heat transfer composition of the invention can
preferably comprise Refrigerant 7, Stabilizer 2, and Lubricant
1.
[0285] The heat transfer composition of the invention can
preferably comprise Refrigerant 8, Stabilizer 2, and Lubricant
1.
[0286] The heat transfer composition of the invention can
preferably comprise Refrigerant 9, Stabilizer 2, and Lubricant
1.
[0287] The heat transfer composition of the invention can
preferably comprise Refrigerant 10, Stabilizer 2, and Lubricant
1.
[0288] The heat transfer composition of the invention can
preferably comprise Refrigerant 11, Stabilizer 2, and Lubricant
1.
[0289] The heat transfer composition of the invention can
preferably comprise Refrigerant 12, Stabilizer 2, and Lubricant
1.
[0290] The heat transfer composition of the invention can
preferably comprise Refrigerant 13, Stabilizer 2, and Lubricant
1.
[0291] The heat transfer composition of the invention can
preferably comprise Refrigerant 14, Stabilizer 2, and Lubricant
1.
[0292] The heat transfer composition of the invention can
preferably comprise Refrigerant 15, Stabilizer 2, and Lubricant
1.
[0293] The heat transfer composition of the invention can
preferably comprise Refrigerant 16, Stabilizer 2, and Lubricant
1.
[0294] The heat transfer composition of the invention can
preferably comprise Refrigerant 17, Stabilizer 2, and Lubricant
1.
[0295] The heat transfer composition of the invention can
preferably comprise Refrigerant 18, Stabilizer 2, and Lubricant
1.
[0296] The heat transfer composition of the invention can
preferably comprise Refrigerant 19, Stabilizer 2, and Lubricant
1.
[0297] The heat transfer composition of the invention can
preferably comprise Refrigerant 20, Stabilizer 2, and Lubricant
1.
[0298] The heat transfer composition of the invention can
preferably comprise Refrigerant 21, Stabilizer 2, and Lubricant
1.
[0299] The heat transfer composition of the invention can
preferably comprise Refrigerant 22, Stabilizer 2, and Lubricant
1.
[0300] The heat transfer composition of the invention can
preferably comprise Refrigerant 23, Stabilizer 2, and Lubricant
1.
[0301] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NF-23NF, Stabilizer 2, and
Lubricant 1.
[0302] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NFGWP150-23NFGWP150,
Stabilizer 2, and Lubricant 1.
[0303] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1GWP5-12GWP5, Stabilizer 2,
and Lubricant 1.
[0304] The heat transfer composition of the invention can
preferably comprise any of Refrigerants 1NFGWP5-12NFGWP5,
Stabilizer 2, and Lubricant 1.
[0305] Other additives not mentioned herein can also be included by
those skilled in the art in view of the teaching contained herein
without departing from the novel and basic features of the present
invention.
[0306] Combinations of surfactants and solubilizing agents may also
be added to the present compositions to aid oil solubility as
disclosed in U.S. Pat. No. 6,516,837, the disclosure of which is
incorporated by reference in its entirety.
[0307] In addition the refrigerants according to the present
invention, including in particular any one of Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1 NFGWP5-12NFGWP5, and the heat transfer composition which contain
such refrigerants, show acceptable toxicity and preferably have an
Occupational Exposure Limit (OEL) of greater than about 400.
[0308] Heat Transfer Systems, Uses and Methods
[0309] The refrigerant (and the heat transfer composition
containing the refrigerant) of the invention can be used in heating
and cooling applications.
[0310] The compositions disclosed herein are provided for use in
heat transfer applications, including, low temperature
refrigeration, medium temperature refrigeration, vending machines,
heat pumps (including heat pump water heaters), dehumidifiers,
chillers, and refrigerators and freezers.
[0311] The compositions of the invention may be employed in systems
which are used or are suitable for use with R-134a refrigerant,
such as existing or new heat transfer systems.
[0312] Any reference to the heat transfer composition of the
invention refers to each and any of the heat transfer compositions
as described herein. Thus, for the following discussion of the uses
or applications of the heat transfer compositions of the invention,
the heat transfer composition may comprise or consist essentially
of any of the refrigerants described herein, including in
particular any one of Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150,
Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, in
combination with any of the stabilizers described herein, including
Stabilizer 1 and Stabilizer 2, and any of the lubricants discussed
herein, including Lubricant 1.
[0313] For the purposes of this invention, each and any of the heat
transfer compositions as described herein can be used in a heat
transfer system, such a low temperature refrigeration system, a
medium temperature refrigeration system, a vending machine, a heat
pump (including a heat pump water heater), dehumidifiers, a
chiller, and a refrigerator and/or freezer. The heat transfer
system according to the present invention can comprise a
compressor, an evaporator, a condenser and an expansion device, in
communication with each other.
[0314] Examples of commonly used compressors, for the purposes of
this invention include reciprocating, rotary (including rolling
piston and rotary vane), scroll, screw, and centrifugal
compressors. Thus, the present invention provides each and any of
the refrigerants and/or heat transfer compositions as described
herein for use in a heat transfer system comprising a
reciprocating, rotary (including rolling piston and rotary vane),
scroll, screw, or centrifugal compressor.
[0315] Examples of commonly used expansion devices, for the
purposes of this invention include a capillary tube, a fixed
orifice, a thermal expansion valve, and an electronic expansion
valve. Thus, the present invention provides each and any of the
refrigerants and/or heat transfer compositions as described herein
for use in a heat transfer system comprising a capillary tube, a
fixed orifice, a thermal expansion valve, or an electronic
expansion valve.
[0316] For the purposes of this invention, the evaporator and the
condenser together form a heat exchanger, preferably selected from
a finned tube heat exchanger, a microchannel heat exchanger, a
shell and tube, a plate heat exchanger, and a tube-in-tube heat
exchanger. Thus, the present invention provides each and any of the
refrigerants and/or heat transfer compositions as described herein
for use in a heat transfer system wherein the evaporator and
condenser together form a finned tube heat exchanger, a
microchannel heat exchanger, a shell and tube, a plate heat
exchanger, or a tube-in-tube heat exchanger.
[0317] The present invention also provides heat transfer systems
and methods which utilize sequestration materials to help reduce
the negative impact that refrigerant and/or lubricant deterioration
may have on system operation. With respected to sequestration
materials, the systems of the present invention preferably include
a sequestration material in contact with at least a portion of a
refrigerant according to the present invention wherein the
temperature of the sequestration material and/or the temperature of
the refrigerant when in said contact are at a temperature that is
preferably at least about 10.degree. C.
[0318] For the purposes of the systems and methods of the invention
as described in this application, the term "about" in relation to
temperatures means that the stated temperature can vary by an
amount of +/-5.degree. C. It will be understood that for
temperatures described as being "about" an indicated value, the
present invention included embodiments in which the temperature is
the stated temperature +/-2.degree. C., and more preferably
+/-1.degree. C., most preferably +/-0.5.degree. C.
[0319] Any and all of the refrigerants and any and all of the
sequestration materials as described herein can be used in the
systems of the present invention. In preferred embodiments, the
systems of the present invention include a sequestration material
in contact with at least a portion of a refrigerant according to
the present invention, including in particular any one of
Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants
1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants
1GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5. Preferably the
sequestration material comprises: (a) an anion exchange resin, (b)
activated alumina adsorbants, (c) a moisture-removing molecular
sieve, (d) a molecular sieve (preferably a zeolite) comprising
copper, silver, lead or a combination thereof, and (e) a
combination of above materials.
[0320] Examples of anion exchange resins that are commercially
available and useful according to the present invention include
Amberlyst A21, Amberlyst A22, and Dowex Marathon.
[0321] Examples of activated alumina that are commercially
available and useful according to the present invention include
F200 sold by BASF and CLR-204 sold by Honeywell.
[0322] Examples of moisture-removing molecular sieves that are
commercially available and useful according to the present
invention include sodium aluminosilicate molecular sieves have pore
size types 3 A, 4 A, 5 A, and 13X.
[0323] An example of a zeolite molecular sieve that is commercially
available is IONSIV D7310-C with activated sites used to remove
specific decomposition products.
[0324] As used in connection with the sequestration material, the
term "in contact with at least a portion" is intended in its broad
sense to include each of the sequestration materials and any
combination of sequestration materials being in contact with the
same or separate portions of the refrigerant in the system and is
intended to include but not necessarily limited to embodiments in
which each type or specific sequestration material is: (i) located
physically together with each other type or specific material, if
present; (ii) is located physically separate from each other type
or specific material, if present, and (iii) combinations in which
two or more materials are physically together and at least one
sequestration material is physically separate from at least one
other sequestration material.
[0325] The amount that the anion exchange resin is preferably
present in system in an amount of from about 5% to about 60% by
weight based on the total of amount of lubricant and anion exchange
resin present in the system. Preferably, the anion exchange resin
is present in an amount of of from about 20% to about 50% by weight
and most preferably in an amount of from about 20% to 30% by weight
based on the total of amount of lubricant and anion exchange resin
present in the system.
[0326] The amount of anion exchange resin described herein refers
to the dry weight of the anion exchange resin.
[0327] The amount that the zeolite molecular sieve that is
preferably present the system is from about 1% to about 30% by
weight based on the total of amount of lubricant and zeolite
molecular sieve present in the system. Preferably, the zeolite
molecular sieve is preferably present in an amount of from about
10% to about 30% by weight based on the total of amount of
lubricant and zeolite molecular sieve present in the system.
[0328] The moisture-removing the molecular sieve (e.g., sodium
about 60% by weight relative to the amount of lubricant present and
moisture-removing material in the system. Preferably, the molecular
sieve may be present in an amount of 30% to 45% by weight based on
the total of amount of lubricant and moisture-removing molecular
sieve present in the system.
[0329] The amount that the activated alumina that is preferably
present in system is from about 5% to about 60% by weight based on
the total of amount of lubricant and activated alumina present in
the system.
[0330] Cascaded Refrigeration
[0331] The present invention provides heat transfer systems, uses
and methods that include cascaded refrigeration systems, with such
system containing any of the refrigerants disclosed herein,
including in particular any one of Refrigerants 1-23, Refrigerants
1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, and any heat transfer composition as disclosed
herein. Any of the equipment described herein generally with
respect to use in heat transfer systems is adapatable for use in
any of the cascade systems as described herein.
[0332] A cascade system typically has at least two stages, which
are usually referred to as the "high stage" and the "low stage". A
generalized flow diagram for a cascade heat transfer system is
provided in FIG. 4 hereof. The heat transfer compositions of the
invention are particularly provided for the high stage of the
cascade system. In a cascade system, the high stage cycle generally
has an air-to-refrigerant condenser and a
refrigerant-to-refrigerant evaporator. The high stage typically has
a positive displacement compressor which may be a reciprocating or
rotary compressor, and a thermal or electronic expansion valve. The
refrigerant evaporating temperature of the high stage is preferably
in the range of about -10 to about 20.degree. C. The condensing
temperature of the high stage is preferably in the range of about
40 to about 70.degree. C.
[0333] The low stage of the preferred cascade system generally
(indentified as Inter. HX in FIG. 4) has a
refrigerant-to-refrigerant condenser and a refrigerant-to-air
evaporator to cool the product. The low stage typically has a
positive displacement compressor which may be a reciprocating or
rotary compressor, and a thermal or electronic expansion valve. The
refrigerant evaporating temperature of the low stage is preferably
in the range of about -40 to about -10.degree. C. The condensing
temperature of the low stage is preferably in the range of about 0
to about 30.degree. C. The low stage refrigerant may be, for
example, carbon dioxide.
[0334] The present invention thus includes cascaded systems and
methods in which any of the refrigerants described herein,
including in particular any one of Refrigerants 1-23, Refrigerants
1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, is used as a replacement for or a retrofit for
R-134a in cascade refrigeration system.
[0335] For the purpose of illustration, two cascade systems of know
configuration are illustrated herein in FIG. 1A and FIG. 1B, and
each cascade system of this type, and all know variations of such
systems, are improved by the use of any one of the refrigerants of
the present invention, including in particular any one of
Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants
1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants
1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, and any of the
heat transfer compositions which include any one of such
refrigerants. For the purposes of convenience, such cascade systems
are referred to herein as Cascade System 1A and Cascade System 1B,
respectively, and each is described in detail below,
[0336] Cascade System 1A
[0337] One example of a cascade system of a general type that has
used R-134a is illustrated in FIG. 1A hereof as system 100, which
is a refrigeration system of the type commonly used for commercial
refrigeration in supermarkets. The system 100 is a direct expansion
system which provides both medium and low temperature refrigeration
via medium temperature refrigeration circuit 110 and low
temperature refrigeration circuit 120. Medium temperature
refrigeration is typically provided at an evaporation temperature
level of about -10.degree. C.
[0338] The level and type of cascade refrigeration disclosed herein
in connection with Cascade System 1A is commonly used for products
such as dairy, deli and fresh food. The individual temperature
level for the different products is adjusted based on the product
requirements. Low temperature refrigeration is typically provided
at an evaporation temperature level of about -25.degree. C. This
level of refrigeration is commonly used for products such as ice
cream and frozen goods. Again, the individual temperature level for
the different products is adjusted based on the product
requirements. In preferred embodiments, the low system evaporation
temperatures is -25.degree. C., +/-3.degree. C. or +/-2.degree. C.
In such systems a medium temperature refrigeration circuit 110 has
or would be designed to have, or would be useful with R134a as its
refrigerant, and according to preferred embodiments of the present
invention any of the refrigerants and/or heat transfer compositions
are used in such a system in place of, or a replacement for, or as
a retrofit for R-134a. Such a cascade refrigeration system of the
general type illustrated in FIG. 1A is referred to herein for
convenience as Cascade System 1A.
[0339] In Cascade System 1A the medium temperature refrigeration
circuit 110 preferably provides both the medium temperature cooling
and removes the rejected heat from the lower temperature
refrigeration circuit 120 via a heat exchanger 130. The medium
temperature refrigeration circuit 110 extends between, for example,
a roof 140, a machine room 141 and a sales floor 142. The low
temperature refrigeration circuit 120 on the other hand has an
alternative refrigerant, for example R744, as its refrigerant. The
low temperature refrigeration circuit 120 extends between the
machine room 141 and the sales floor 142. Usefully, as discussed
above, R744 has a low GWP.
[0340] Since prior systems according to Cascade System 1A have been
designed for use with and have been used with R134a as the second
refrigerant (i.e., in the medium temperature circuit), the present
invention includes using any of the refrigerants as disclsclosed
herein, including in particular any one of Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and
Refrigerants 1 NFGWP5-12NFGWP5, as the second refrigerant.
[0341] Cascade System 1B
[0342] FIG. 1B shows an example of a cascade refrigeration system
100 comprising a medium temperature refrigeration circuit 110 and a
low temperature refrigeration circuit 120. To the extent systems of
the type described in Cascade System 1A have elements and features
in common with Cascade System 1B, the description of those elements
or features in connection with Cascade System 1A applies to Cascade
System 1B.
[0343] The low temperature refrigeration circuit 120 as illustrated
in FIG. 1B has a compressor 121, an interface with a heat exchanger
130 for rejecting heat to ambient conditions, an expansion valve
122 and an evaporator 123. The low temperature refrigeration
circuit 120 interfaces with the medium temperature refrigeration
circuit 110 through the inter-circuit heat exchanger 150, which
serves to reject heat to from the low temperature refrigerant to
the medium temperature refrigerant, which may be any refrigerant
according to the present invention, including in particular any one
of Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1
GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1
GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, and thereby
produce a subcooled refrigerant liquid in the low temperature
refrigerant cycle. The evaporator 123 is interfaced with a space to
be chilled, such as the inside of a freezer compartment. The
components of the low temperature refrigeration circuit are
connected in the order: evaporator 123, compressor 121, heat
exchanger 130, inter-circuit heat exchanger 150, and expansion
valve 122. The components are connected together via pipes 124
filled with a low temperature refrigerant.
[0344] Since prior systems according to Cascade System 1B have been
designed for use with and used with R134a as the second refrigerant
(i.e., in the medium temperature circuit), the present invention
includes using any of the refrigerants as disclsclosed herein,
including in particular any one of Refrigerants 1-23, Refrigerants
1 NF-23NF, Refrigerants 1 GWP150-23GWP150, Refrigerants 1
NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants 1
NFGWP5-12NFGWP5, as the second refrigerant.
[0345] The operation of each of Cascade System 1A and 1B will be
described in more detail, especially with respect to features and
elements that apply to each system, and in this connection features
and elements that are similar in each system are labelled in each
figure with the same numeral. The system 100 can in preferred
embodiments span multiple areas, for example, the following three
areas of a building: a roof where the condensers 113 and 130 are
located; a machine room where the compressors 111, 112, heat
exchanger 150, receiving tank 114 and expansion device 118 are
located; and a sales floor 142 where the LT case, the MT case, and
each of their expansion devices are located.
[0346] The low temperature refrigeration circuit 120 and the medium
temperature refrigeration circuit thus each extend between the
sales floor, the machine room and the roof. In use, the medium
temperature circuit 110 provides medium temperature chilling to
spaces to be chilled via the evaporator 119 and the low temperature
circuit 120 provides low temperature chilling to spaces to be
chilled via the evaporator 123. The medium temperature circuit 110
also removes heat from the liquid condensate from the low
temperature condenser 120, thus providing subcooling to the liquid
entering the evaporator 123.
[0347] The individual and overall functionality of the various
components of the medium temperature refrigeration circuit 110 will
now be described. Starting with heat exchanger 150, as described
above the medium temperature refrigerant absorbs heat from the low
temperature refrigerant via the heat exchanger 150. This absorption
of heat causes the refrigerant in the medium temperature circuit
150, which is a low temperature gas and/or a mixture of gas and
liquid on entering the heat exchanger 150, to be change liquid to
the gas phase and/or to increase the temperature of the gas in the
case where superheating will be produced. On leaving the heat
exchanger 150, the gaseous refrigerant is sucked into the
compressor 111 (along with the refrigerant from the evaporator 119)
and is compressed by the compressor 111 to a high temperature and
high pressure gas. This gas is released into the pipes 115 and
travels to the condenser 113 which, in this example, is arranged on
a roof of a building. In the condenser 113, the gaseous medium
temperature refrigerant releases heat to the outside ambient air
and so is cooled and condenses to a liquid. After the condenser
113, the liquid refrigerant collects in a fluid receiver 114. In
this example, the fluid receiver 114 is a tank. On leaving the
fluid receiver 114, the liquid refrigerant is manifolded to
parallel connected medium temperature branch 116 and subcooling
cooling branch 117. In the medium temperature branch 116, the
liquid refrigerant flows to the expansion valve 112 which is used
to lower the pressure and therefore temperature of the liquid
refrigerant. The relatively cold liquid refrigerant then enters the
heat exchanger 119 where it absorbs heat from the space to be
chilled which is interfaced with the evaporator 119f. In the
subcooling branch 117, the liquid refrigerant similarly flows first
to an expansion valve 118 where the pressure and temperature of the
refrigerant is lowered. After the valve 118, the refrigerant flows
to the inter-circuit heat exchanger 150, as described above. From
there, the gaseous refrigerant from the heat exchanger is sucked by
the compressor 111 to the compressor 111 where it re-joins the
refrigerant from the medium temperature cooling branch 116.
[0348] Although not mentioned above, it will be clear that to
function as intended, the temperature of the refrigerant in the
medium temperature circuit 110 as it enters the heat exchanger 150
must be less than the temperature of the refrigerant in the low
temperature circuit 120 as it enters the heat exchanger 150. If
this were not the case, the medium temperature circuit 110 would
not provide the desired subcooling to the low temperature
refrigerant in circuit 120.
[0349] Cascade Systems 2 and 3
[0350] In addition to use of the present refrigerants as
replacements for R-134a in known R-134a systems, applicants have
developed inventive cascade refrigerations systems and and each of
the refrigerants described herein, including in particular any one
of Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1
GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1
GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, can be used in
these inventive systems, and in particular as the refrigerant in
the higher temperature stage circuit. These two embodiments are
illustrated in FIGS. 2 and 3 herein and are explained in detail
below.
[0351] The cascade system according to preferred embodiments
preferably comprises: one or more first refrigeration units, each
refrigeration unit containing a first refrigeration circuit, each
first refrigeration circuit comprising an evaporator and a heat
exchanger; and a second refrigeration circuit; wherein each heat
exchanger is arranged to transfer heat energy between its
respective first refrigeration circuit and the second refrigeration
circuit. The second circuit may be located substantially completely
outside of said plurality of first refrigeration units. As used
herein, the term "substantially completely outside of said
plurality of first refrigeration units" means that the components
of the second refrigeration circuit are not within said first
refrigeration units except that transport piping and the like which
may be considered part of the second refrigeration circuit can pass
into the first refrigeration units in order to provide heat
exchange between the refrigerant of the first and second
refrigeration circuits. As used herein, the term "first
refrigeration unit" means an at least partially closed or closable
structure that is capable of providing cooling within at least a
portion of that structure and which is structurally distinct from
any structure enclosing or containing said second refrigeration
circuit in its entirety. According to and consistent with such
meanings, the first refrigeration circuits of the present invention
are sometimes referred to herein as "self-contained" when contained
within such first refrigeration units, in accordance with the
meanings described herein.
[0352] Each refrigeration unit may be arranged within a first area.
The first area may be a shop floor. This means that each first
refrigeration circuit may also be located within a first area, such
as a shop floor.
[0353] Each refrigeration unit may comprise a space and/or objects
contained within a space to be chilled, and preferably that space
is within the refrigeration unit. Each evaporator may be arranged
to chill its respective space/objects, preferably by cooling air
within the space to be chilled.
[0354] As mentioned above, the second refrigeration circuit may
have components thereof that extend between the first refrigeration
unit and a second area. The second area may be, for example, a
machine room which houses a substantial portion of the components
of the second refrigeration circuit.
[0355] The second refrigeration circuit may extend to a second and
a third area. For The third area may be an area outside of the
building or buildings in which the first refrigeration units and
the second area(s) are located. This allows for ambient cooling to
be exploited.
[0356] Each first refrigeration circuit may comprise at least one
fluid expansion device. The at least one fluid expansion device may
be a capillary tube or an orifice tube. This is enabled by the
conditions imposed on each first refrigeration circuit by its
respective refrigeration unit being relatively constant. This means
that simpler flow control devices, such as capillary and orifice
tubes, can be and preferably are used to advantage in the first
refrigeration circuits.
[0357] The average temperature of each of the first refrigeration
circuits may be lower than the average temperature of the second
refrigeration circuit. This is because the second refrigeration
circuit may be used to provide cooling, that is, remove heat from,
the first refrigeration circuits; and each first refrigeration
circuit may cool a space to be chilled in its respective
refrigeration unit.
[0358] The second refrigeration circuit may cool, that is, remove
heat from, each of the first refrigeration circuits.
[0359] Each heat exchanger may be arranged to transfer heat energy
between its respective first refrigeration circuit and the second
refrigeration circuit at a respective circuit interface
location.
[0360] Each of the circuit interface locations may be coupled in
series-parallel combination with each other of the circuit
interface locations. Usefully, this means that if one of the
circuit interface locations, first refrigeration circuits, or first
refrigeration units has a fault or blockage detected, the location,
circuit or unit at fault can be isolated and/or bypassed by the
second refrigeration circuit so that faults do not propagate
through the system.
[0361] Each of the circuit interface locations may be coupled in
series with at least one other circuit interface location.
[0362] Each of the circuit interface locations may be coupled in
series with each other of the circuit interface locations.
[0363] Each of the circuit interface locations may be coupled in
parallel with at least one other circuit interface location.
[0364] Each of the circuit interface locations may be coupled in
parallel with each other of the circuit interface locations.
[0365] In each preferred embodiment disclosed herein, the second
refrigerant is any refrigerant, including as described herein
and/or any heat transfer composition as described herein, in
particular any one of Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,
Refrigerants 1 GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5.
Since the preferred refrigerants of the present invention are both
low GWP and non-flammable, the use of them is such systems is
highly advantageous since the second refrigerant circuit may span
numerous areas, and so having a non-flammable refrigerant is
important for reducing the severity of potential leaks.
[0366] The second refrigeration circuit may comprise a second
evaporator. The second evaporator may be coupled in parallel with
the circuit interface locations.
[0367] The first refrigerant, which is used in the first
refrigerant circuits, may comprise any of R744, hydrocarbons,
R1234yf, R1234ze(E), R455A and combinations of these. Hydrocarbons
may comprise any of R290, R600a or R1270. These refrigerants are
low GWP.
[0368] The first refrigerant may be one of R744, hydrocarbons,
R1234yf, R1234ze(E), R455A and combinations of these.
[0369] The system as illustrated in each of FIGS. 2 and 3 has a
number of refrigeration units and each of the refrigeration units
has at least one dedicated refrigeration circuit arranged within
it. That is, each refrigeration unit contains at least one
refrigeration circuit.
[0370] The refrigeration circuit contained within a refrigeration
unit may comprise at least a heat exchanger that removes heat to
the refrigerant in the circuit, and an evaporator that adds heat to
the refrigerant.
[0371] The refrigeration circuit contained within a refrigeration
unit may comprise a compressor, at least a heat exchanger that
removes heat from the refrigerant in the circuit (preferably by
removing heat from the refrigerant vapor exiting the compressor),
and an evaporator that adds heat to the refrigerant (preferably by
cooling the area of the refrigeration unit being chilled). Although
it is contemplated that the size of the compressor used in the
first refrigeration circuit, in generally the compressor may be a
small size compressor. As used herein, the term "small size
compressor" means the compressor has a power rating of not greater
than about 1 horsepower. The compressor size may be from 0.1
horsepower to about 1 horsepower. The compressor size may be from
0.1 horsepower to about 0.75 horsepower. The compressor size may be
from 0.1 horsepower to about 0.5 horsepower.
[0372] A refrigeration unit may be an integrated physical entity,
i.e. an entity which is not designed to be dismantled into
component parts. A refrigeration unit might be a fridge or a
freezer, for example.
[0373] The refrigeration circuits provided within each
refrigeration unit may themselves be cooled by a common
refrigeration circuit at least partially external to the
refrigeration units. In contrast to the dedicated refrigeration
circuits contained within each refrigeration unit, common
refrigeration circuits (which are generally referred to herein as
second and third refrigeration circuits) may be extended circuits
which extend between multiple areas of the building housing the
units: such as between a sales floor (where the refrigeration units
are arranged) and a machine room and/or a roof or outside area.
Each refrigeration unit may comprise at least one compartment for
storing goods, such as perishable goods. The compartments may
define a space to be chilled by a refrigeration circuit contained
within the refrigeration unit.
[0374] Any one of the refrigerants described herein, including in
particular Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants
1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants
1 GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, may be used as
the refrigerant in the second refrigeration circuits in any one of
the cascade refrigeration systems described herein, including each
of Cascade Systems 2 and 3, as described herein.
[0375] Cascade System 2
[0376] A cascade refrigeration system useful with the refrigerants
of the present invention is described below in connection with FIG.
2. For the purposes of convenience such cascade refrigeration
systems are referred to herein as Cascade System 2, and of the
refrigerants as disclosed herein, including in particular
Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants
1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150, Refrigerants
1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, may be used in any
Cascade System 2 as the refrigerant in the second refrigeration
circuit (i.e., in the medium temperature refrigeration
circuit).
[0377] FIG. 2 shows a refrigeration system 200 which has, for
example, three first refrigeration circuits 220a, 220b, 220c. Each
of the first refrigeration circuits 220a, 220b, 220c has an
evaporator 223, a compressor 221, a heat exchanger 230 and an
expansion valve 222. In each circuit 220a, 220b, 220c, the
evaporator 223, the compressor 221, the heat exchanger 230 and the
expansion valve 222 are connected in series with one another in the
order listed. Each of the first refrigeration circuits 220a, 220b,
220c is included within a separate respective refrigeration unit
(not shown). In this example, each of the three illustrated
refrigeration units is a freezer unit and the freezer unit houses
its respective first refrigeration circuit. In this way, each
refrigeration unit comprises a self-contained and dedicated
refrigeration circuit.
[0378] The refrigeration units (not shown), and therefore the first
refrigeration circuits 220a, 220b, 220c, are arranged on a sales
floor 242 of a supermarket.
[0379] In this example, the refrigerant in each of the first
refrigeration circuits 220a, 220b, 220c is a low GWP refrigerant
such as R744, hydrocarbons (R290, R600a, R1270), R1234yf,
R1234ze(E) or R455A. As the skilled person will appreciate, the
refrigerants in each of the first refrigeration circuits 220a,
220b, 220c may the same or different to the refrigerants in each
other of the first refrigeration circuits 220a, 220b, 220c.
[0380] The refrigeration system 200 also has a second refrigeration
circuit 210. The second refrigeration circuit 210 has a compressor
211, a condenser 213 and a fluid receiver 214. The compressor 211,
the condenser 213 and the fluid receiver 214 are connected in
series and in the order given. The second refrigeration circuit 210
also has four parallel connected branches: three medium temperature
cooling branches 217a, 217b, 217c; and one low temperature cooling
branch 216. The four parallel connected branches 217a, 217b, 217c
and 216 are connected between the fluid receiver 214 and the
compressor 211. Each of the medium temperature cooling branches
217a, 217b, 217c has an expansion valve 218 and an evaporator 219,
219b and 219c, respectively. The expansion valve 218 and evaporator
219 are connected in series and in the order given between the
fluid receiver 214 and the condenser 211. The low temperature
cooling branch 216 has an expansion valve 212 and an interface, in
the form of inlet and outlet piping, conduits, valves and the like
(represented collectively as 260a, 260b and 260c, respectively)
which bring the second refrigerant to and from each of the heat
exchangers 230a, 230b, 230c of the first refrigeration circuits
220a, 220b, 220c. The low temperature cooling branch 216 interfaces
each of the heat exchangers 230a, 230b, 230c of the first
refrigeration circuits 220a, 220b, 220c at a respective circuit
interface location 231a, 231b, 231c. Each circuit interface
location 231a, 231b, 231c is arranged in series-parallel
combination with each other of the circuit interface locations
231a, 231b, 231c.
[0381] The medium temperature refrigeration circuit 210 has
components which extend between the sales floor 242, a machine room
241 and a roof 140. The low temperature cooling branch 216 and the
medium temperature cooling branches 217a, 217b, 217c of the medium
temperature refrigeration circuit 210 are located on the sales
floor 242.
[0382] The compressor 211 and the fluid receiver 214 are located in
the machine room 241.
[0383] The condenser 213 is located where it can be readily exposed
to ambient conditions, such as on the roof 240.
[0384] In use: [0385] each of the first refrigeration circuits
220a, 220b, 220c absorbs heat via their evaporators 223 to provide
low temperature cooling to a space to be chilled (not shown);
[0386] the second refrigeration circuit 210 absorbs heat from each
of the heat exchangers 230a, 230b, 230c to cool the first
refrigeration circuits 220a, 220b, 220c; [0387] the second
refrigeration circuit 210 absorbs heat at each of the evaporators
219 to provide medium temperature cooling to spaces to be chilled
(not shown); and [0388] the refrigerant in the second refrigeration
circuit 210 is chilled in the chiller 213.
[0389] A number of beneficial results can be achieved using the
arrangement shown in FIG. 2, particularly from each first
refrigeration circuit 230 being self-contained in a respective
refrigeration unit.
[0390] For example, installation and uninstallation of the
refrigeration units and the overall cascaded refrigeration system
200 is simplified. This is because the refrigeration units, with
their built-in, self-contained first refrigeration circuits 220a,
220b, 220c, can be easily connected or disconnected with the second
refrigeration circuit 210, with no modification to the first
refrigeration circuit 220, 220b, 220c required. In other words, the
refrigeration units may simply be `plugged` in to, or out of, the
second refrigeration circuit 210.
[0391] Another advantage is that each refrigeration unit, including
its respective first refrigeration circuit 220a, 220b, 220c, can be
factory tested for defaults before being installed into a live
refrigeration system 200. This mitigates the likelihood of faults,
which can include leaks of potentially harmful refrigerants.
Accordingly, reduced leak rate can be achieved.
[0392] Another advantage is that the lengths of the first
refrigeration circuits 220a, 220b, 220c can be reduced since each
circuit 220a, 220b, 220c is arranged in its respective
refrigeration unit, and does not extend between a series of units.
The reduced circuit length can result in improved efficiency as
there is reduced heat infiltration in shorter lines due to reduced
surface area. Further, reduced circuit length can also result in
reduced pressure drop, which improves the system 200
efficiency.
[0393] The reduced circuit length, and the provision of the
circuits self-contained within respective refrigeration units, also
provides the ability to use more flammable refrigerants, such as
R744, Hydrocarbons (R290, R600a, R1270), R1234yf, R1234ze(E) or
R455A, in the first (low temperature) circuit which applicants have
come to appreciate is a highly beneficial result. This is because
both the likelihood of the refrigerant leaking is reduced (as
discussed above) and because, even if the refrigerant were to leak,
the leak would be contained to the relatively small area and
containable area of the respective refrigeration unit, and because
of the small size of the units, only a relatively small amount of
refrigerant charge is used. In addition, this arrangement would
permit the use of relatively low cost flame mitigation contingency
procedures and/or devices since the area containing potentially
flammable materials is much smaller, confined and uniform. Such
more flammable refrigerants can have lower global warming potential
(GWP). Advantageously therefore, governmental and societal targets
for the use of low GWP refrigerants may be met and potentially even
exceeded without compromising on safety of the system.
[0394] Another advantage is that each first refrigeration circuit
220a, 220b, 220c may only cool their respective refrigeration unit.
This means that the load on each first refrigeration circuit 220a,
220b, 220c may remain relatively constant. That is, constant
conditions are applied to the condensing 231 and evaporating 223
stages of the first refrigeration circuit 220. This allows for the
simplification of the design of the first refrigeration circuit 220
in that passive expansion devices 222, such as capillary tubes or
orifice tubes, can be used. This is in contrast to more complex
circuits where electronic expansion devices and thermostatic
expansion valves need to be used. Since the use of such complex
devices is avoided, costs can be reduced and reliability can be
increased.
[0395] Furthermore, importantly, the provision of a flooded heat
exchanger in the second refrigeration circuit according to such
embodiments results in improved heat transfer between the first and
second circuits. Accordingly, the efficiency of the overall
refrigeration system is improved.
[0396] There are several advantages that may arise from circuit
interface locations being coupled in parallel with other circuit
interface locations. One advantage may be that resilience is
provided in the system since a fault associated with or suffered at
one circuit interface location will not impact other circuit
interface locations. This is because each circuit interface
location is serviced by a respective branch of the second
refrigeration circuit. Another advantage may be that heat transfer
efficiency between first and second refrigeration circuits is
improved because the temperature of the second refrigerant before
each circuit interface location can be kept relatively constant. In
contrast, if two circuit interface locations were coupled in
series, the temperature of the refrigerant in the second
refrigeration circuit may be higher before the downstream circuit
interface location, than before the upstream circuit interface
location.
[0397] Overall, the provision of a plurality of first refrigeration
circuits according to the present invention, with each one arranged
in a respective refrigeration unit, preferably being arranged as a
self-contained refrigeration circuit, has such benefits as:
reducing leak rates; simplifying the overall refrigeration system;
enabling the use of otherwise unsafe low GWP refrigerants;
improving maintenance and installation; and reducing pressure drop,
leading to improved system efficiency.
[0398] As the person skilled in the art will appreciate, there may
be any number of first refrigeration circuits 220. In particular,
there may be as many first refrigeration circuits 220 as there are
refrigeration units to be cooled. Accordingly, the second
refrigeration circuit 210 may be interfaced with any number of
first refrigeration circuits 220.
[0399] As will be clear to the skilled person, there may be any
number and arrangement of medium temperature cooling branches 217
and evaporators 218.
[0400] Cascade System 3
[0401] In alternative arrangements, each first refrigeration
circuit 220 may be arranged fully in parallel with each other first
refrigeration circuit 220. An example of such an arrangement is
shown in FIG. 3 as is referred to herein for convenience as Cascade
System 3. FIG. 3 shows a system 300 where each circuit interface
location 231a, 231b, 231c is arranged fully in parallel with each
other circuit interface location 231a, 231b, 231c. The components
of the system 300 are otherwise the same as in system 200
(described in reference to FIG. 2), and components of the system
300 function in substantially the same way as the system 200,
although it will be appreciated that the performance of the overall
system and other important features of the overall system can be
significantly impacted by this change in the arrangement.
[0402] Usefully, this means that a given portion of refrigerant
from the second refrigeration circuit 210, which can be any
refrigerant as disclosed herein, including in particular
Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1
GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1
GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, only passes
through one heat exchanger 230 before it is returned to the
compressor 211. This arrangement thus ensures that each of the heat
exchangers 230 will receive second refrigerant at about the same
temperature, since the arrangement prevents any of the heat
exchanger from receiving a portion of the refrigerant that is
pre-warmed as a result of passing through an upstream heat
exchanger, as would be the case in a series arrangement;
[0403] As will be clear to the person skilled in the art, many
other arrangements of the circuit interface locations 231a, 231b,
231c with respect to one and the second refrigeration circuit 210
can be achieved and indeed are envisaged.
[0404] An example of a further possible alteration of any of the
systems forming part of this disclosure, including in particular
any of Cascade Systems 1A, 1B, 2 and 3, is that any number of the
self-contained refrigeration circuits may include a suction line
heat exchanger (SLHX).
[0405] Heat Transfer Methods
[0406] The refrigerants, including in particular Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants 1
NFGWP5-12NFGWP5, and any heat transfer composition of the present
invention containing any such refrigerant, can be used in a method
of cooling comprising condensing a heat transfer composition and
subsequently evaporating said composition in the vicinity of an
article or body to be cooled.
[0407] Thus, the invention relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, the process comprising i) condensing a refrigerant or
heat transfer composition as described herein; and ii) evaporating
the refrigerant in the vicinity of body or article to be cooled;
wherein the evaporator temperature of the heat transfer system is
in the range of from about -40.degree. C. to about +10.degree.
C.
[0408] Alternatively, or in addition, the heat transfer composition
can be used in a method of heating comprising condensing the heat
transfer composition in the vicinity of an article or body to be
heated and subsequently evaporating said composition.
[0409] Thus, the invention relates to a method of heating in a heat
transfer system comprising an evaporator, a condenser and a
compressor, the process comprising i) condensing a refrigererant or
heat transfer composition as described herein, in the vicinity of a
body or article to be heated and
[0410] ii) evaporating the refrigerant wherein the evaporator
temperature of the heat transfer system is in the range of about
-30.degree. C. to about 5.degree. C.
[0411] Thus, any of the refrigerant and heat transfer compositions
described herein can be used in any one of: [0412] low temperature
refrigeration systems; [0413] medium temperature refrigeration
systems; [0414] vending machines; [0415] heat pumps, including heat
pump water heater; [0416] dehumidifiers, [0417] chillers,
particularly a positive displacement chillers, more particularly an
air cooled or water cooled direct expansion chiller (preferably
water cooled), which is either modular or conventionally singularly
packaged, [0418] domestic refrigerators, [0419] domestic freezers,
[0420] industrial freezers, [0421] industrial refrigerators, [0422]
water cooler.
[0423] The term "refrigeration system" refers to any system or
apparatus or any part or portion of such a system or apparatus
which employs a refrigerant to provide cooling.
[0424] The heat transfer composition of the invention is provided
for use in mobile air conditioning applications and in commercial
and industrial stationary air conditioning applications,
particularly in chillers that cool water to provide air
conditioning in commercial and industrial applications. Thus, any
of the heat transfer compositions described herein can be used in
any one of: [0425] mobile air conditioning, particularly air
conditioning in trucks, buses and trains, [0426] chiller
applications, particularly a positive displacement chiller or a
centrifugal chiller used to cool water to provide industrial and/or
commercial air conditioning.
[0427] The heat transfer compositions of the invention are Iso
provided for use in heat pump applications. Thus, any of the heat
transfer compositions described herein can be used in any one of:
[0428] a residential heat pump, such as a residential air to water
heat pump/hydronic system, water heater heat pumps, [0429]
dehumidifier, [0430] an industrial heat pump system, or a
commercial heat pump system.
[0431] In particular, R-134a used any of the above-listed systems
and equipment and/or the below-described systems and equipment may
be retrofitted or replaced with the inventive refrigerants and heat
transfer compositions of the present invention.
[0432] Each of the heat transfer compositions described herein is
particularly provided for use in a low temperature refrigeration
system (with an evaporator temperature in the range of about -40 to
about -12.degree. C., particularly about -32.degree. C.).
[0433] Each of the heat transfer compositions described herein is
particularly provided for use in a medium temperature refrigeration
system (with an evaporator temperature in the range of about -12 to
about 0.degree. C., particularly about 70.degree. C.).
[0434] Each of the heat transfer compositions described herein is
particularly provided for use in a cascade refrigeration system
(having a high stage refrigerant and a low stage refrigerant). The
heat transfer compositions of the invitation are used as the high
stage refrigerant in the cascade system (which generally has an
evaporator temperature in the range of about -20 to about
10.degree. C., particularly about -7.degree. C.).
[0435] The heat transfer composition of the invention is provided
for use in a residential heat pump system, wherein the residential
heat pump system is used to supply warm air (said air having a
temperature of for example, about 18.degree. C. to about 24.degree.
C., particularly about 21.degree. C.) to buildings in the winter.
It is usually the same system as the residential air-conditioning
system, while in the heat pump mode the refrigerant flow is
reversed and the indoor coil becomes the condenser and the outdoor
coil becomes the evaporator. Typical system types are split and
mini-split heat pump system. The evaporator and condenser are
usually a round tube plate fin or microchannel heat exchanger. The
compressor is usually a reciprocating or rotary (rolling-piston or
scroll) compressor. The expansion valve is usually a thermal or
electronic expansion valve. The refrigerant evaporating temperature
is preferably in the range of about -20 to about 3.degree. C. The
condensing temperature is preferably in the range of about 35 to
about 50.degree. C.
[0436] The heat transfer composition of the invention is provided
for use in a residential air-to-water heat pump hydronic system,
wherein the residential air-to-water heat pump hydronic system is
used to supply hot water (said water having a temperature of for
example about 50.degree. C.) to buildings for floor heating or
similar applications in the winter. The hydronic system usually has
a round tube plate fin or microchannel evaporator to exchange heat
with ambient air, a reciprocating or rotary compressor, a plate
condenser to heat the water, and a thermal or electronic expansion
valve. The refrigerant evaporating temperature is preferably in the
range of about -20 to about 3.degree. C. The condensing temperature
is preferably in the range of about 50 to about 90.degree. C.
[0437] The heat transfer composition of the invention is provided
for use in a commercial air-conditioning system wherein the
commercial air conditioning system can be a chiller which is used
to supply a chilled heat transfer fluid such as water (said heat
transfer fluid, e.g. water, having a temperature of for example
about 7.degree. C.) to large buildings such as offices and
hospitals, etc. Depending on the application, the chiller system
may be running all year long. The chiller system may be air-cooled
or water-cooled. The air-cooled chiller usually has a plate or
shell-and-tube evaporator to supply chilled water, a centrifugal
compressor or a positive displacement compressor which may be a
reciprocating or scroll compressor, a round tube plate fin or
microchannel condenser to exchange heat with ambient air, and a
thermal or electronic expansion valve. The water-cooled system
usually has a shell-and-tube evaporator to supply chilled water, a
centrifugal compressor or a positive displacement compressor which
may be a reciprocating or scroll compressor, a shell-and-tube
condenser to exchange heat with water from cooling tower or lake,
sea and other natural recourses, and a thermal or electronic
expansion valve. The refrigerant evaporating temperature is
preferably in the range of about 0 to about 10.degree. C. The
condensing temperature is preferably in the range of about 40 to
about 70.degree. C.
[0438] The heat transfer composition of the invention is provided
for use in a medium temperature refrigeration system, wherein the
medium temperature refrigeration system is preferably used to chill
food or beverages such as in a refrigerator or a bottle cooler, or
in a supermarket to chill perishable goods. The system usually has
an air-to-refrigerant evaporator to chill the food or beverage, a
reciprocating or rotary compressor, an air-to-refrigerant condenser
to exchange heat with the ambient air, and a thermal or electronic
expansion valve. The refrigerant evaporating temperature is
preferably in the range of about -12 to about 0.degree. C. The
condensing temperature is preferably in the range of about 40 to
about 70.degree. C. Vending machines are an example of medium
temperature refrigeration systems.
[0439] The heat transfer composition of the invention is provided
for use in a low temperature refrigeration system, wherein said low
temperature refrigeration system is preferably used in a freezer or
an ice cream machine. The system usually has an air-to-refrigerant
evaporator to chill the product, a reciprocating or rotary
compressor, an air-to-refrigerant condenser to exchange heat with
the ambient air, and a thermal or electronic expansion valve. The
refrigerant evaporating temperature is preferably in the range of
about -40 to about -12.degree. C. The condensing temperature is
preferably in the range of about 40 to about 70.degree. C.
[0440] The heat transfer composition of the invention is provided
for use in a cascade refrigeration system, wherein said cascade
refrigeration system is preferably used in applications where there
is a large temperature difference (e.g. about 60-80.degree. C.,
such as about 70-75.degree. C.) between the ambient temperature and
the box temperature (e.g. the difference in temperature between the
air-side of the condenser in the high stage, and the air-side of
the evaporator in the low stage). For example, a cascade system may
be used for freezing products in a supermarket.
[0441] Each of the heat transfer compositions described herein is
particularly provided for use in a vending machine having an
evaporator temperature in the range of about -20 to about
10.degree. C., particularly -7.degree. C.
[0442] Each of the heat transfer compositions described herein is
particularly provided for use in a residential heat pump, such as a
residential air to water heat pump hydronic system, having an
evaporator temperature in the range of about -20 to about 3.degree.
C., particularly about 0.5.degree. C.
[0443] Each of the heat transfer compositions described herein is
particularly provided for use in a medium temperature refrigeration
system (with an evaporator temperature in the range of about -12 to
about 0.degree. C., particularly about -7 C).
[0444] Each of the heat transfer compositions described herein is
particularly provided for use in a water heater heat pump having an
evaporator temperature in the range of from about -20.degree. C. to
about 25.degree. C.
[0445] Each of the heat transfer compositions described herein is
particularly provided for use in a dehumidifier having an
evaporator temperature in the range of from about 0 to about
10.degree. C.
[0446] Each of the heat transfer compositions described herein is
particularly provided for use in a air cooled chiller having an
evaporator temperature in the range of about 0.degree. C. to about
10.degree. C., particularly about 4.5.degree. C. The air cooled
chiller may be an air cooled chiller with a centrifugal compressor
or an air cooled chiller with a positive displacement compressor,
more particularly an air cooled chiller with a reciprocating or
scroll compressor.
[0447] Each of the heat transfer compositions described herein is
particularly provided for use in a water cooled chiller having an
evaporator temperature in the range of about 0.degree. C. to about
10.degree. C., particularly about 4.5.degree. C. The air cooled
chiller may be an air cooled chiller with a centrifugal compressor
or an air cooled chiller with a positive displacement compressor,
more particularly an air cooled chiller with a reciprocating or
scroll compressor.
[0448] Each of the heat transfer compositions described herein is
particularly provided for use in a refrigerator having an
evaporator temperature in the range of about -40.degree. C. to
about 12.degree. C.
[0449] Each of the heat transfer compositions described herein is
particularly provided for use in a freezer having an evaporator
temperature in the range of about -40.degree. C. to about
-12.degree. C.
[0450] Each of the heat transfer compositions described herein is
particularly provided for use in a cascade refrigeration system
(having a high stage refrigerant and a low stage refrigerant). The
heat transfer compositions of the invitation are used as the high
stage refrigerant in the cascade system (which generally has an
evaporator temperature in the range of about -20 to about
10.degree. C., particularly about -7.degree. C.).
[0451] Thus, the invention relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, and any refrigerant of the present invention as
described herein, including particularly Refrigerants 1-23,
Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, or any of the heat transfer compositions as
described herein, the process comprising the steps of i) condensing
the refrigerant, and ii) evaporating the refrigerant in the
vicinity of body or article to be cooled, wherein the evaporator
temperature of the heat transfer system is in the range of from
about -40.degree. C. to about 10.degree. C.
[0452] The invention also relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, and a heat transfer composition comprising any
refrigerant of the present invention as described herein, including
particularly Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,
Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, or
any of the heat transfer compositions as described herein, the
process comprising the steps of i) condensing the refrigerant, and
ii) evaporating the refrigerant in the vicinity of body or article
to be cooled, wherein the evaporator temperature of the heat
transfer system is in the range of from about -40.degree. C. to
about 10.degree. C., wherein said said heat transfer composition
further comprises any stabilizer as described herein, including in
particular Stabilizer 1 or Stabilizer 2.
[0453] The invention also relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, and a heat transfer composition comprising any
refrigerant of the present invention as described herein, including
particularly Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,
Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, or
any of the heat transfer compositions as described herein, the
process comprising the steps of i) condensing the refrigerant, and
ii) evaporating the refrigerant in the vicinity of body or article
to be cooled, wherein the evaporator temperature of the heat
transfer system is in the range of from about -40.degree. C. to
about 10.degree. C., wherein said said heat transfer composition
further comprises any lubricant as described herein, including in
particular Lubricant 1.
[0454] The invention also relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, and a heat transfer composition comprising any
refrigerant of the present invention as described herein, including
particularly Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,
Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, or
any of the heat transfer compositions as described herein, the
process comprising the steps of i) condensing the refrigerant, and
ii) evaporating the refrigerant in the vicinity of body or article
to be cooled, wherein the evaporator temperature of the heat
transfer system is in the range of from about -40.degree. C. to
about 10.degree. C., wherein said heat transfer composition further
comprises any stabilizer as described herein, including in
particular Stabilizer 1 or Stabilizer 2 and any lubricant as
described herein, including in particular Lubricant 1.
[0455] Thus, the invention relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, and any refrigerant of the present invention as
described herein, including particularly Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and
Refrigerants 1 NFGWP5-12NFGWP5, or any of the heat transfer
compositions as described herein, the process comprising the steps
of i) condensing the refrigerant, and ii) evaporating the
refrigerant in the vicinity of body or article to be cooled,
wherein the evaporator temperature of the heat transfer system is
in the range of from about -20.degree. C. to about 3.degree. C.
[0456] The invention also relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, and a heat transfer composition comprising any
refrigerant of the present invention as described herein, including
particularly Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,
Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, or
any of the heat transfer compositions as described herein, the
process comprising the steps of i) condensing the refrigerant, and
ii) evaporating the refrigerant in the vicinity of body or article
to be cooled, wherein the evaporator temperature of the heat
transfer system is in the range of from about -20.degree. C. to
about 3.degree. C., wherein said said heat transfer composition
further comprises any stabilizer as described herein, including in
particular Stabilizer 1 or Stabilizer 2.
[0457] The invention also relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, and a heat transfer composition comprising any
refrigerant of the present invention as described herein, including
particularly Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,
Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, or
any of the heat transfer compositions as described herein, the
process comprising the steps of i) condensing the refrigerant, and
ii) evaporating the refrigerant in the vicinity of body or article
to be cooled, wherein the evaporator temperature of the heat
transfer system is in the range of from about -20.degree. C. to
about 3.degree. C., wherein said said heat transfer composition
further comprises any lubricant as described herein, including in
particular Lubricant 1.
[0458] The invention also relates to a method of cooling in a heat
transfer system comprising an evaporator, a condenser and a
compressor, and a heat transfer composition comprising any
refrigerant of the present invention as described herein, including
particularly Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1GWP150-23GWP150, Refrigerants 1NFGWP150-23NFGWP150,
Refrigerants 1GWP5-12GWP5, and Refrigerants 1NFGWP5-12NFGWP5, or
any of the heat transfer compositions as described herein, the
process comprising the steps of i) condensing the refrigerant, and
ii) evaporating the refrigerant in the vicinity of body or article
to be cooled, wherein the evaporator temperature of the heat
transfer system is in the range of from about -20.degree. C. to
about 3.degree. C., wherein said heat transfer composition further
comprises any stabilizer as described herein, including in
particular Stabilizer 1 or Stabilizer 2 and any lubricant as
described herein, including in particular Lubricant 1.
[0459] The heat transfer composition disclosed herein is provided
as a non-flammable and low Global Warming (GWP) retrofit for the
refrigerant R-134a. Each of the heat transfer compositions of the
present invention, including heat transfer compostions which
includes any one of the refrigerants of the present invention as
described herein, including particularly any one of Refrigerants
1-23, Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and
Refrigerants 1 NFGWP5-12NFGWP5, therefore can be used in a method
of retrofitting an existing heat transfer system designed to
contain or containing R-134a refrigerant. It is preferred that the
method does not require substantial engineering modification of the
existing system, for example, without modification of the
condenser, the evaporator and/or the expansion valve.
[0460] As the term is used herein, "retrofit" with respect to a
particular heat transfer composition of the present invention means
the use of the indicated composition of the present invention in a
heat transfer system that had contained therein a different
refrigerant composition that had been at least partially removed
from the system and in which the indicated composition of the
present invention is introduced.
[0461] The heat transfer composition disclosed herein is provided
as a non-flammable and low Global Warming (GWP) replacement for the
refrigerant R-134a. Each of the heat transfer compositions of the
present invention, including heat transfer compostions which
includes any one of the refrigerants of the present invention as
described herein, including particularly any one of Refrigerants
1-23, Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and
Refrigerants 1 NFGWP5-12NFGWP5, therefore can be used as a
replacement for R-134a refrigerant, and it is preferred that the
method does not require substantial engineering modification of the
system, for example, without modification of the condenser, the
evaporator and/or the expansion valve.
[0462] As the term is used herein, "replacement for" with respect
to a particular heat transfer composition of the present invention
and a particular existing refrigerant means the use of the
indicated composition of the present invention in a heat transfer
system that heretofore had been commonly used with that existing
refrigerant. By way of example, the heat transfer systems that have
heretofore been commonly used with R-134a include the following
systems and the representative operating characteristic of
evaporator temperature:
TABLE-US-00001 R-134a SYSTEMS Evaporator Temp. Range, .degree. C.
(all values understood to be System preceeded by "about" Low
-40.degree. C. to 12.degree. C. ternperature refrigeration Medium
-12.degree. C. to 0.degree. C. ternperature refrigeration Heat
Pumps -12.degree. C. to 10.degree. C.; (including water heater heat
pumps) Heat Pumps -20.degree. C. to 3.degree. C.; (including
residential heat pumps) Dehumidifier -0.degree. C. to 10.degree.
C.; Vending -12.degree. C. to 10.degree. C. machines Chillers
0.degree. C. to 10.degree. C. Refrigerators -40.degree. C. to
2.degree. C. Freezers -40.degree. C. to -12.degree. C.
[0463] Alternatively, the heat transfer composition can be used in
a method of retrofitting an existing heat transfer system designed
to contain or containing R134a refrigerant, wherein the system is
modified for the refrigerant of the invention.
[0464] It will be appreciated that when the heat transfer
composition is used as a non-flammable and low Global Warming
replacement for R-134a or is used in a method of retrofitting an
existing heat transfer system designed to contain or containing
R134a refrigerant or is used in a heat transfer system which is
suitable for use with R134a refrigerant, the heat transfer
composition may consist essentially of any the refrigerant of the
invention as descried herein, including in particular Refrigerants
1-23, Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and
Refrigerants 1 NFGWP5-12NFGWP5. Alternatively, the invention
encompasses the use of the refrigerant of the invention as a
non-flammable and low Global Warming replacement for R-134a or is
used in a method of retrofitting an existing heat transfer system
designed to contain or containing R134a refrigerant or is used in a
heat transfer system which is suitable for use with R134a
refrigerant as described herein.
[0465] As set out above, the method comprises removing at least a
portion of the existing R-134a refrigerant from the system.
Preferably, the method comprises removing at least about 5%, about
10%, about 25%, about 50% or about 75% by weight of the R-134a from
the system and replacing it with the heat transfer compositions of
the invention, including in particular those heat transfer
compositions which include in particular Refrigerants 1-23,
Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1 NFGWP150-23NFGWP150, Refrigerants 1 GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5.
[0466] The compositions of the invention may be employed in systems
which are used or are suitable for use with R-134a refrigerant,
such as existing or new heat transfer systems.
[0467] The refrigerants and heat transfer compositions of the
present invention exhibit many of the desirable characteristics of
R-134a, such as non-flammability, but have a GWP that is
substantially lower than that of R-134a while at the same time
having operating characteristics i.e. efficiency (COP), that are
substantially similar to or substantially match R-134a.
[0468] The refrigerants of the present invention, including in
particular Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants
1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants
1 GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, therefore
preferably exhibit operating characteristics compared with R134a
wherein: [0469] the efficiency (COP) of the refrigerant is from 95
to 105% of the efficiency of R134a.
[0470] in heat transfer systems, in which the refrigerant of the
invention replaces the R134a refrigerant.
[0471] The term "COP" is a measure of energy efficiency and means
the ratio of refrigeration or cooling capacity to the energy
requirement of the refrigeration system, i.e. the energy to run the
compressor, fans, etc. COP is the useful output of the
refrigeration system, in this case the refrigeration capacity or
how much cooling is provided, divided by how power it takes to get
this output. Essentially, it is a measure of the efficiency of the
system.
[0472] The term "capacity" is the amount of cooling provided, in
BTUs/hr, by the refrigerant in the refrigeration system. This is
experimentally determined by multiplying the change in enthalpy in
BTU/lb, of the refrigerant as it passes through the evaporator by
the mass flow rate of the refrigerant. The enthalpy can be
determined from the measurement of the pressure and temperature of
the refrigerant. The capacity of the refrigeration system relates
to the ability to maintain an area to be cooled at a specific
temperature.
[0473] The term "mass flow rate" is the amount "in pounds" of
refrigerant passing through a conduit of a given size in a given
amount of time.
[0474] In order to maintain reliability of the heat transfer
system, it is preferred that the refrigerant of the invention,
including in particular Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,
Refrigerants 1 GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5,
further exhibits the following characteristics compared with
R-134a: [0475] the discharge temperature is not greater than
10.degree. C. higher than that of R-134a; and/or [0476] the
compressor pressure ratio is from 95 to 105% of the compressor
pressure ratio of R-134a
[0477] in heat transfer systems, in which the composition of the
invention is used to replace the R-134a refrigerant.
[0478] It will be appreciated by the skilled person that the
claimed compositions desirably show a low level of glide. Thus, the
refrigerants of present invention, including in particular
Refrigerants 1-23, Refrigerants 1NF-23NF, Refrigerants
1GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants
1 GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, provide an
evaporator glide of less than 2.degree. C., preferably less than
1.5.degree. C.
[0479] The existing heat transfer compositions used with R-134a are
preferably refrigeration systems. Thus, each of the heat transfer
compositions as described herein can be used to replace R134a in in
any one of: [0480] a low temperature refrigeration system, [0481] a
medium temperature refrigeration system, [0482] a commercial
refrigerator, [0483] a commercial freezer, [0484] a cascade
refrigeration system, [0485] an ice machine, [0486] a vending
machine, [0487] a domestic freezer, [0488] a domestic refrigerator,
[0489] an industrial freezer, [0490] an industrial refrigerator
[0491] a water cooler or [0492] a chiller.
[0493] The refrigerants of the invention, including in particular
Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1
GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1
GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, are provided to
replace R134a in heat pump applications. Thus, each of the heat
transfer compositions and refrigerants as described herein,
including an of Refrigerants 1-23, Refrigerants 1 NF-23NF,
Refrigerants 1 GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150,
Refrigerants 1 GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5 can
be used to replace R-134a in any one of: [0494] a residential heat
pump, such as a residential air to water heat pump/hydronic system,
[0495] an industrial heat pump system or [0496] a commercial heat
pump system.
[0497] Each of the heat transfer compositions and refrigerants as
described herein, including in particular any one of Refrigerants
1-23, Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and
Refrigerants 1NFGWP5-12NFGWP5, is particularly provided to replace
R134a in an air cooled chiller (with an evaporator temperature in
the range of about 0 to about 10.degree. C., particularly about
4.5.degree. C.), particularly an air cooled chiller with a
centrifugal or positive displacement compressor, e.g. an air cooled
chiller with a reciprocating or scroll compressor.
[0498] Each of the heat transfer compositions and refrigerants
described herein, including in particular each of Refrigerants
1-23, Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and
Refrigerants 1NFGWP5-12NFGWP5, is particularly provided to replace
R134a in a water cooled chiller (with an evaporator temperature in
the range of about 0 to about 10.degree. C., particularly about
4.5.degree. C.), particularly a water cooled chiller with a
centrifugal or positive displacement compressor, e.g. a water
cooled chiller with a reciprocating or scroll compressor.
[0499] Each of the heat transfer compositions and each of the
refrigerants described herein, in particular any one of
Refrigerants 1-23, Refrigerants 1 NF-23NF, Refrigerants 1
GWP150-23GWP150, Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1
GWP5-12GWP5, and Refrigerants 1 NFGWP5-12NFGWP5, is particularly
provided to replace R134a in a residential heat pump, such as a
residential air to water heat pump hydronic system (with an
evaporator temperature in the range of about -20 to about 3.degree.
C., particularly about 0.5.degree. C.).
[0500] Each of the heat transfer compositions and refrigerants as
described herein, including any one of Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and
Refrigerants 1NFGWP5-12NFGWP5, is particularly provided to replace
R134a in a medium temperature refrigeration system (with an
evaporator temperature in the range of about -12 to about 0.degree.
C., particularly about -7.degree. C.).
[0501] Each of the heat transfer compositions and refrigerants
described herein, including in particular any one of Refrigerants
1-23, Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and
Refrigerants 1NFGWP5-12NFGWP5, is particularly provided to replace
R134a in a low temperature refrigeration system (with an evaporator
temperature in the range of about -40 to about -12.degree. C.,
particularly about -32.degree. C.).
[0502] Each of the heat transfer compositions and refrigerants
described herein, in particular any one of Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1 GWP150-23GWP150,
Refrigerants 1 NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and
Refrigerants 1NFGWP5-12NFGWP5, is particularly provided to replace
R134a in the high stage of a cascade refrigeration system (where
the high stage of the cascade system has an evaporator temperature
in the range of about -20 to about 10.degree. C., particularly
about -7.degree. C.).
[0503] The heat transfer compositions and the refrigerants of the
invention, including in particular any one of Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, is provided for use in a residential heat pump
system, wherein the residential heat pump system is used to supply
warm air (said air having a temperature of for example, about
18.degree. C. to about 24.degree. C., particularly about 21.degree.
C.) to buildings in the winter. It is usually the same system as
the residential air-conditioning system, while in the heat pump
mode the refrigerant flow is reversed and the indoor coil becomes
condenser and the outdoor coil becomes evaporator. Typical system
types are split and mini-split heat pump system. The evaporator and
condenser are usually a round tube plate fin, a finned or
microchannel heat exchanger. The compressor is usually a
reciprocating or rotary (rolling-piston or rotary vane) or scroll
compressor. The expansion valve is usually a thermal or electronic
expansion valve. The refrigerant evaporating temperature is
preferably in the range of about -20 to about 3.degree. C. or about
-30 to about 5.degree. C. The condensing temperature is preferably
in the range of about 35 to about 50.degree. C.
[0504] The heat transfer composition and refrigerants of the
invention, including in particular any one of Refrigerants 1-23,
Refrigerants 1NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, is provided for use in a commercial
air-conditioning system wherein the commercial air conditioning
system can be a chiller which is used to supply chilled water (said
water having a temperature of for example about 7.degree. C.) to
large buildings such as offices and hospitals, etc.
[0505] Depending on the application, the chiller system may be
running all year long. The chiller system may be air-cooled or
water-cooled. The air-cooled chiller usually has a plate,
tube-in-tube or shell-and-tube evaporator to supply chilled water,
a reciprocating or scroll compressor, a round tube plate fin, a
finned tube or microchannel condenser to exchange heat with ambient
air, and a thermal or electronic expansion valve. The water-cooled
system usually has a shell-and-tube evaporator to supply chilled
water, a reciprocating, scroll, screw or centrifugal compressor, a
shell-and-tube condenser to exchange heat with water from cooling
tower or lake, sea and other natural recourses, and a thermal or
electronic expansion valve. The refrigerant evaporating temperature
is preferably in the range of about 0 to about 10.degree. C. The
condensing temperature is preferably in the range of about 40 to
about 70.degree. C.
[0506] The heat transfer composition and the refrigerants of the
invention, including in particular any one of Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, is provided for use in a residential air-to-water
heat pump hydronic system, wherein the residential air-to-water
heat pump hydronic system is used to supply hot water (said water
having a temperature of for example about 50.degree. C. or about
55.degree. C.) to buildings for floor heating or similar
applications in the winter. The hydronic system usually has a round
tube plate fin, a finned tube or microchannel evaporator to
exchange heat with ambient air, a reciprocating, scroll or rotary
compressor, a plate, tube-in-tube or shell-in-tube condenser to
heat the water, and a thermal or electronic expansion valve. The
refrigerant evaporating temperature is preferably in the range of
about -20 to about 3.degree. C., or -30.degree. C. to about
5.degree. C. The condensing temperature is preferably in the range
of about 50.degree. C. to about 90.degree. C.
[0507] Each of the heat transfer compositions and the refrigerants
of the invention, including in particular any one Refrigerants
1-23, Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150,
Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and
Refrigerants 1NFGWP5-12NFGWP5, is particularly provided for use in
a medium temperature refrigeration system. Medium temperature
refrigeration systems utilize one or more compressors and a
condenser temperature of from about 20.degree. C. to about
60.degree. C. and preferably about 25.degree. C. to about
45.degree. C. Medium temperature refrigeration systems have an
evaporator temperature of from about -25.degree. C. to less than
about 0.degree. C., more preferably from about -20.degree. C. to
about -5.degree. C., and most preferably about -10.degree. C. to
about -6.7.degree. C. Moreover, in preferred embodiments of such
medium temperature refrigeration systems, the systems have a degree
of superheat at the evaporator outlet of from about 0.degree. C. to
about 10.degree. C., and preferably with a degree of superheat at
the evaporator outlet of from about 4.degree. C. to about 6.degree.
C. Furthermore, in preferred embodiments of such systems, medium
temperature refrigeration systems have a degree of superheat in the
suction line of from about 5.degree. C. to about 40.degree. C., and
more preferably about 15.degree. C. to about 30.degree. C.
[0508] Each of the heat transfer compositions and the refrigerants
of the invention, including in particular each of Refrigerants
1-23, Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150,
Refrigerants 1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and
Refrigerants 1NFGWP5-12NFGWP5, is particularly provided for use in
a low temperature refrigeration. Low temperature refrigeration
systems utilize one or more compressors and a condenser temperature
of from about 20.degree. C. to about 60.degree. C. and preferably
from about 25.degree. C. to about 45.degree. C. Low temperature
refrigeration systems have an evaporator temperature of from about
-45.degree. C. to less than about 0.degree. C., more preferably
from about -40 to about -12.degree. C., even more preferably from
about -35.degree. C. to about -25.degree. C., and most preferably
about -32.degree. C. Moreover, preferably, the low temperature
refrigeration systems have a degree of superheat at evaporator
outlet of from about 0.degree. C. to about 10.degree. C., and
preferably with a degree of superheat at evaporator outlet of from
about 4.degree. C. to about 6.degree. C. Furthermore, preferably,
low temperature refrigeration systems have a degree of superheat in
the suction line of from about 15.degree. C. to about 50.degree.
C., and preferably with a degree of superheat in the suction line
of from about 25.degree. C. to about 30.degree. C.
[0509] The heat transfer composition and the refrigerants of the
invention, including in particular each of Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, is provided for use in a medium temperature
refrigeration system, wherein the medium temperature refrigeration
system is preferably used to chill food or beverages such as in a
refrigerator or a bottle cooler. The system usually has an
air-to-refrigerant evaporator to chill the food or beverage, a
reciprocating, scroll or screw or rotary compressor, an
air-to-refrigerant condenser to exchange heat with the ambient air,
and a thermal or electronic expansion valve.
[0510] The heat transfer composition and the refrigerants of the
invention, including in particular each of Refrigerants 1-23,
Refrigerants 1 NF-23NF, Refrigerants 1GWP150-23GWP150, Refrigerants
1NFGWP150-23NFGWP150, Refrigerants 1GWP5-12GWP5, and Refrigerants
1NFGWP5-12NFGWP5, is provided for use in a low temperature
refrigeration system, wherein said low temperature refrigeration
system is preferably used in a freezer or an ice making machine.
The system usually has an air-to-refrigerant evaporator to chill
the food or beverage, a reciprocating, scroll or rotary compressor,
an air-to-refrigerant condenser to exchange heat with the ambient
air, and a thermal or electronic expansion valve.
EXAMPLES
[0511] The refrigerant compositions identified in Table 1A and
Table 1B below were analyzed as described herein. Each composition
was subjected to thermodynamic analysis to determine its ability to
match the operating characteristics of R-134a in various
refrigeration systems. The analysis was performed using
experimental data collected for properties of various binary pairs
of components used in the composition. The vapor/liquid equilibrium
behavior of CF.sub.3I was determined and studied in a series of
binary pairs with each of HFCO-1233zd(E), HFO-1234ze(E) and
HFC-227ea. The vapour liquid equilibrium behavior of CF3I was
studied in a series of binary pairs with HFCO-1233zd(E) and
HFC-227ea. The vapour liquid equilibrium behavior of the binary
pairs of HFCO-1233zd(E) and HFC-227ea was also studied. The
composition of each binary pair was varied over a series of
relative percentages in the experimental evaluation and the mixture
parameters for each binary par were regressed to the experimentally
obtained data. Data for individual components is available in the
National Institute of Science and Technology (NIST) Reference Fluid
Thermodynamic and Transport Properties Database software (Refprop
9.1 NIST Standard Database 2013) and was as needed in the Examples.
The parameters selected for conducting the analysis were: same
compressor displacement for all refrigerants, same operating
conditions for all refrigerants, same compressor isentropic and
volumetric efficiency for all refrigerants. In each Example,
simulations were conducted using the measured vapor liquid
equilibrium data. The simulation results are reported for each
Example.
TABLE-US-00002 TABLE 1A Refrigerants of the invention R1234ze(E)
R1233zd(E) CF3I Refrigerant (wt %) (wt %) (wt %) Al 78.0% 1.0%
21.0% A2 77.0% 2.0% 21.0% A3 78.0% 2.0% 20.0% A4 80.0% 2.0% 18.0%
A5 82.0% 2.0% 16.0% A6 83.0% 2.0% 15.0%
TABLE-US-00003 TABLE 1B Refrigerants of the invention R1234ze(E)
R1233zd(E) HFC-227ea CF3I Refrigerant (wt %) (wt %) (wt %) (wt %)
B1 87.0% 2.0% 4.4% 6.6% B2 84.0% 2.0% 4.4% 9.6% B3 81.0% 2.0% 4.4%
12.6% B4 78.0% 2.0% 4.4% 15.6% B5 75.0% 2.0% 4.4% 18.6%
Example 1A: Thermodynamic Glide
[0512] In systems containing direct expansion evaporators, the
evaporator manufacturer generally sets a design limit of a pressure
drop which is equivalent to a loss of 1.degree. C. to 2.degree. C.
in saturation temperature from the inlet to the outlet of the
evaporator (Encyclopedia of Two Phase heat transfer and Flow I,
John T Thome, chapter 6, p144).
[0513] The saturation temperature in the evaporator tends to
increase for refrigerants with glide. This increase in temperature
is equal to the glide of the refrigerant in the evaporator. The
actual temperature variation in the evaporator is the net effect of
both of these processes. Therefore, a refrigerant with a glide of
less than 2.degree. C. in the evaporator will have an almost
constant temperature in the evaporator. This will lead to a very
efficient heat exchanger design, especially for applications such
as reversible heat pumps where the refrigerant flow changes
direction in the heat exchanger, depending on the mode of operation
(i.e. heating or cooling).
[0514] The thermodynamic glide was determined by experimentally
measuring the interaction parameters with the binary pairs of
refrigerants (HFO-1234ze(E)/HFCO-1233zd(E),
HFO-1234ze(E)/CF.sub.3I, HFCO-1233zd(E)/CF.sub.3I) and using NIST
Refprop 9.1 for calculating the difference in bubble (liquid) and
dew (vapor) temperatures.
[0515] The observed glide was unexpectedly lower than predicted by
the NIST Refprop 9.1 database which uses estimated interaction
parameters (without experimental data) between the binary
pairs.
TABLE-US-00004 TABLE 2 Thermodynamic glide of Refrigerant A2 Blend
A2 (R1234ze(E)/R1233zd(E)/CF3I 78%/2%/20%) Thermodynamic glide
Thermodynamic glide with with binary interaction Temperature
modeled binary interaction determined (.degree. C.) (.degree. C.)
experimentally (.degree. C.) 40 1.8 1.3 10 2.4 1.7 0 2.6 1.8 -10
2.9 2.0
[0516] The above data demonstrates that the claimed compositions
have a lower glide than predicted by modelling without taking into
account the unpredictable interaction between the three components
of the blend.
Example 1B: Thermodynamic Glide
[0517] The procedure of Example 1A is repeated except of the
compositon B2. The thermodynamic glide was determined by
experimentally measuring the interaction parameters with the binary
pairs of refrigerants (HFO-1234ze(E)/HFCO-1233zd(E),
HFO-1234ze(E)/CF.sub.3I, HFO-1234ze(E)/HFC-227ea,
HFCO-1233zd(E)/CF.sub.3I, HFC-227ea/CF.sub.3I,
HFCO-1233zd(E)/HFC-227ea) and using NIST Refprop 9.1 for
calculating the difference in bubble (liquid) and dew (vapor)
temperatures.
[0518] The observed glide was unexpectedly lower than predicted by
the NIST Refprop 9.1 database which uses estimated interaction
parameters (without experimental data) between the binary
pairs.
TABLE-US-00005 TABLE 2 Thermodynamic glide of Refrigerant B2 Blend
B2 (R1234ze(E)/R227ea/CF3I/R1233zd(E) 84%/4.4%/9.6%/2%)
Thermodynamic glide Thermodynamic glide with with binary
interaction Temperature modeled binary interaction determined
(.degree. C.) (.degree. C.) experimentally (.degree. C.) 40 1.4 1.1
10 1.9 1.4 0 2.0 1.5 -10 2.2 1.6
[0519] The above data demonstrates that the claimed compositions
have a lower glide than predicted by modelling without taking into
account the unpredictable interaction between the four components
of the blend.
Example 2A: Flammability
[0520] Both CF.sub.3I and HFCO-1233zd(E) are known to be
non-flammable refrigerants, and can act to suppress the
flammability of refrigerant blends which contain flammable
components.
[0521] As set out in Table 3A below, a binary composition
containing HFO-1234ze(E) and CF.sub.3I requires at least 35% of
CF.sub.3I in order to render the composition non-flammable.
Furthermore, a binary composition containing HFCO-1233zd(E) and
HFO-1234ze(E) requires at least 31% of HFCO-1233zd(E) to render the
composition non-flammable. However, the inventors have surprisingly
discovered that when CF.sub.3I and HFCO-1233zd(E) are both used,
the composition requires much less of these components in order to
be non-flammable. For example, a composition containing 20% of a
combination of HFCO-1233zd(E) and CF.sub.3I is non-flammable.
TABLE-US-00006 TABLE 3A Assessment of flammability Refrigerant
Flammability % R1234ze(E) % R1233zd(E) % CF3I Comparative
Non-flammable 69% 31% -- C1 Comparative Non-flammable 65% -- 35% C2
A3 Non-flammable 80% 2% 18%
Example 2B: Flammability
[0522] HFC-227ea, CF.sub.3I and HFCO-1233zd(E) are known to be
non-flammable refrigerants. CF.sub.3I and HFCO-1233zd(E) can act to
suppress the flammability of refrigerant blends which contain
flammable components.
[0523] As set out in Table 3B below, a binary composition
containing HFO-1234ze(E) and CF.sub.3I requires at least 35% of
CF.sub.3I in order to render the composition non-flammable.
Furthermore, a binary composition containing HFCO-1233zd(E) and
HFO-1234ze(E) requires at least 31% of HFCO-1233zd(E) to render the
composition non-flammable.
[0524] While a binary composition of R-227ea and R1234ze(E)
requires 12% of R227ea in order to render the composition
non-flammable, this composition has a GWP of 403, and therefore
does not meet the requirements of the preferred embodiments of the
invention, that is, a non-flammable composition having a GWP of
less than 150.
[0525] However, the inventors have surprisingly discovered that
when R227ea, CF.sub.3I and HFCO-1233zd(E) are all used with
HFO1234ze(E), the composition requires a much smaller amount of
these components in order to be non-flammable, as compared to using
CF.sub.3I or HFCO-1233zd(E) alone. For example, a composition
containing 15% of a combination of HFCO-1233zd(E), CF.sub.3I is
non-flammable, while at the same time having a GWP of less than
150.
TABLE-US-00007 TABLE 3 Assessment of flammability Flamm- % % % %
Refrigerant ability R1234ze(E) R1233zd(E) CF3I R227ea Comp- Non-
69% 31% -- arative flammable Cl Comp- Non- 65% -- 35% arative
flammable C2 Comp- Non- 88% -- -- 12% arative flammable C3 B2 Non-
84% 2% 9.6% 4.4% flammable
Example 3: Performance
Example 3A: Performance in a CO.sub.2 Cascade Refrigeration
System
[0526] Cascade systems are generally used in applications where
there is a large temperature difference (e.g. about 60-80.degree.
C., such as about 70-75.degree. C.) between the ambient temperature
and the box temperature (e.g. the difference in temperature between
the air-side of the condenser in the high stage, and the air-side
of the evaporator in the low stage). For example, a cascade system
may be used for freezing products in a supermarket.
[0527] In the following Example, exemplary compositions of the
invention were tested as the refrigerant in the high stage of a
cascade refrigeration system. The refrigerant used in the low stage
of the system was carbon dioxide. A schematic of an exemplary
cascade system is shown in FIG. 4 and the results are reported in
Table 4A.
[0528] Operating conditions: [0529] 1. Condensing
temperature=45.degree. C. [0530] 2. Condensing Temperature--Ambient
Temperature=10.degree. C. [0531] 3. Condenser
sub-cooling=0.0.degree. C. (system with receiver) [0532] 4.
Evaporating temperature=-30.degree. C., Corresponding box
temperature=-18.degree. C. [0533] 5. Evaporator
Superheat=3.3.degree. C. [0534] 6. Compressor Isentropic
Efficiency=65% [0535] 7. Volumetric Efficiency=100% [0536] 8.
Temperature Rise in Suction Line Low Stage=15.degree. C. [0537] 9.
Temperature Rise in Suction Line High Stage=10.degree. C. [0538]
10. Intermediate Heat Exchanger CO.sub.2 Condensing
Temperature=15.degree. C., 20.degree. C. and 25.degree. C. [0539]
11. Intermediate Heat Exchanger Superheat=3.3.degree. C. [0540] 12.
Difference in Temperature in Intermediate Heat Exchanger=8.degree.
C.
TABLE-US-00008 [0540] TABLE 4 Performance in CO2 Cascade
Refrigeration System Efficiency @ Efficiency @ Efficiency @
Refrigerant Tcond = 15.degree. C. Tcond = 20.degree. C. Tcond =
25.degree. C. R134a 100% 100% 100% Al 100% 101% 101% A2 100% 101%
101% A3 100% 101% 101% A4 100% 101% 101% A5 100% 101% 101% A6 100%
101% 101%
[0541] Table 4A shows the performance of refrigerants A1 to A5 in
the high side of a cascade refrigeration system [0542] Composition
A1 to A5 match the efficiency of R134a for different condensing
temperatures of the low stage cycle
Example 3B: CO.sub.2 Cascade Refrigeration System
[0543] Example 3A is repeated except using compositions E1-B5 and
with the adjustment of the operating conditions as indicated
below:
[0544] Operating conditions: [0545] 1. Condensing
temperature=45.degree. C. [0546] 2. Condensing Temperature--Ambient
Temperature=10.degree. C. [0547] 3. Condenser
sub-cooling=0.0.degree. C. (system with receiver) [0548] 4.
Evaporating temperature=-30.degree. C., Corresponding box
temperature=-18.degree. C. [0549] 5. Evaporator
Superheat=3.3.degree. C. [0550] 6. Compressor Isentropic
Efficiency=65% [0551] 7. Volumetric Efficiency=100% [0552] 8.
Temperature Rise in Suction Line Low Stage=15.degree. C. [0553] 9.
Temperature Rise in Suction Line High Stage=10.degree. C. [0554]
10. Intermediate Heat Exchanger CO.sub.2 Condensing
Temperature=15.degree. C., 20.degree. C. and 25.degree. C. [0555]
11. Intermediate Heat Exchanger Superheat=3.3.degree. C. [0556] 12.
Difference in Temperature in Intermediate Heat Exchanger=8.degree.
C.
[0557] The results are reported in Table 4B below.
TABLE-US-00009 TABLE 4B Performance in CO2 Cascade Refrigeration
System Efficiency @ Efficiency @ Efficiency @ Refrigerant Tcond =
15.degree. C. Tcond = 20.degree. C. Tcond = 25.degree. C. R134a
100% 100% 100% B1 100% 100% 101% B2 100% 100% 101% B3 100% 100%
101% B4 100% 100% 101% B5 100% 100% 101%
[0558] The results are reported in Table 4B below. [0559] Table 4B
shows the performance of exemplary refrigerants of the invention in
a cascade refrigeration system. [0560] Composition 1 to B5 match
the efficiency of R134a at varying condensing temperatures of low
stage cycle.
Example 4A: Performance in Air-Source Heat Pump Water Heaters with
Suction Line/Liquid Line Heat Exchanger
[0561] The compositions of the invention may be used in a
residential air-to-water heat pump hydronic system. A residential
air-to-water heat pump hydronic system is generally used to supply
hot water (said water having a temperature of for example about
50.degree. C.) to buildings for floor heating or similar
applications in the winter. The hydronic system usually has a round
tube plate fin or microchannel evaporator to exchange heat with
ambient air, a reciprocating or rotary compressor, a plate
condenser to heat the water, and a thermal or electronic expansion
valve. The refrigerant evaporating temperature is preferably in the
range of about -20 to about 3.degree. C. The condensing temperature
is preferably in the range of about 50 to about 90.degree. C.
[0562] In the following Example, exemplary compositions of the
invention were tested in a heat pump water heater system, with and
without a Suction Line/Liquid Line Heat Exchanger. A schematic of a
heat pump water heater system, with a Suction Line/Liquid Line Heat
Exchanger is shown in FIG. 2 and reported in Table 5A below.
[0563] Operating conditions: [0564] 1. Condensing
temperature=55.degree. C. [0565] 2. Water Inlet
Temperature=45.degree. C., Water Outlet Temperature=50.degree. C.
[0566] 3. Condenser sub-cooling=5.0.degree. C. [0567] 4.
Evaporating temperature=-5.degree. C., Corresponding ambient
temperature=10.degree. C. [0568] 5. Evaporator
Superheat=3.5.degree. C. [0569] 6. Compressor Isentropic
Efficiency=60% [0570] 7. Volumetric Efficiency=100% [0571] 8.
Temperature Rise in Suction Line=5.degree. C. [0572] 9. Suction
Line/Liquid Line Heat Exchanger Effectiveness: 0%, 35%, 55%,
75%
TABLE-US-00010 [0572] TABLE 5A Performance in Heat Pump Water
Heaters with SL/LL HX SL-LL HX Eff. SL-LL HX Eff. SL-LL HX Eff.
No-SL-LL HX 35% 55% 75% Comp. Comp. Comp. Comp. Discharge Discharge
Discharge Discharge Temp Temp Temp Temp Refrigerant Efficiency
(.degree. C.) Efficiency (.degree. C.) Efficiency (.degree. C.)
Efficiency (.degree. C.) R134a 100% 92.5 100% 117.9 100% 123.7 100%
134.8 A1 100% 84.9 101% 110.3 101% 115.7 102% 126.7 A2 100% 85.4
101% 110.4 101% 116.0 102% 126.9 A3 100% 85.2 101% 110.3 101% 115.8
102% 126.7 A4 100% 85.0 101% 110.1 101% 115.6 102% 126.5 A5 100%
84.8 101% 109.8 101% 115.3 102% 126.2 A6 100% 84.6 101% 109.7 101%
115.2 102% 126.1
[0573] Table 5A shows performance of refrigerants in a heat pump
water heater with and without a suction line/liquid line heat
exchanger (SLLL HX) [0574] Composition A1 to A5 show higher
efficiency than R134a when a SLL Heat Exchanger is employed [0575]
Composition A1 to A5 show lower discharge temperature than R134a,
indicating better reliability for the compressor.
Example 4B: Performance in Air-Source Heat Pump Water Heaters with
Suction Line/Liquid Line Heat Exchanger
[0576] Example 4B is repeated except using compositions B1-B5, and
the results are reported in Table 5B below:
TABLE-US-00011 TABLE 5B Performance in Heat Pump Water Heaters with
SL/LL HX SL-LL HX Eff. SL-LL HX Eff. SL-LL HX Eff. No-SL-LL HX 35%
55% 75% Comp. Comp. Comp. Comp. Discharge Discharge Discharge
Discharge Temp Temp Temp Temp Refrigerant Efficiency (.degree. C.)
Efficiency (.degree. C.) Efficiency (.degree. C.) Efficiency
(.degree. C.) R134a 100% 92.5 100% 117.9 100% 123.7 100% 134.8 B1
100% 82.8 101% 108.0 101% 113.3 102% 124.2 B2 100% 83.1 101% 108.3
101% 113.6 102% 124.5 B3 100% 83.5 101% 108.6 101% 114.0 102% 124.9
B4 100% 83.9 101% 108.9 101% 114.4 102% 125.2 B5 100% 84.2 101%
109.2 101% 114.7 102% 125.6
[0577] Table 5B shows the performance of exemplary refrigerants of
the invention in a heat pump water heater with and without a
suction line/liquid line heat exchanger (SL/LL HX) [0578]
Composition B1 to B5 show the same efficiency (COP) as R134a in the
system without a SL/LL Heat Exchanger, and a better efficiency
(COP) than R134a when a SL/LL Heat Exchanger is employed [0579]
Composition B1 to B5 show lower discharge temperature than R134a,
indicating better reliability for the compressor.
Example 5: Performance in Vending Machines with Suction Line/Liquid
Line Heat Exchanger
[0580] The compositions of the invention may be used in medium
temperature systems. A medium temperature refrigeration system is
preferably used to chill food or beverages such as in a
refrigerator or a bottle cooler, or in a supermarket to chill
perishable goods. The system usually has an air-to-refrigerant
evaporator to chill the food or beverage, a reciprocating or rotary
compressor, an air-to-refrigerant condenser to exchange heat with
the ambient air, and a thermal or electronic expansion valve. The
refrigerant evaporating temperature is preferably in the range of
about -12 to about 0.degree. C. The condensing temperature is
preferably in the range of about 40 to about 70.degree. C. Vending
machines are an example of medium temperature refrigeration
systems.
[0581] In the following Example, exemplary compositions of the
invention were tested in a vending machine system, with and without
a Suction Line/Liquid Line Heat Exchanger, and the results are
reported in Table 6 below.
[0582] Operating conditions: [0583] 1. Condensing
temperature=45.degree. C. [0584] 2. Condensing Temperature--Ambient
Temperature=10.degree. C. [0585] 3. Condenser
sub-cooling=5.5.degree. C. [0586] 4. Evaporating
temperature=-8.degree. C., Corresponding box
temperature=1.7.degree. C. [0587] 5. Evaporator
Superheat=3.5.degree. C. [0588] 6. Compressor Isentropic
Efficiency=60% [0589] 7. Volumetric Efficiency=100% [0590] 8.
Temperature Rise in Suction Line=5.degree. C. [0591] 9. Suction
Line/Liquid Line Heat Exchanger Effectiveness: 0%, 35%, 55%,
75%
TABLE-US-00012 [0591] TABLE 6 Performance in Vending Machine with
SL/LL HX Efficiency Efficiency Efficiency Efficiency Refrigerant @
0% @ 35% @ 55% @ 375% R134a 100% 100% 100% 100% Al 99% 101% 101%
102% A2 99% 101% 101% 102% A3 99% 101% 101% 102% A4 99% 101% 101%
102% A5 99% 101% 101% 102% A6 99% 101% 101% 102%
[0592] Table 6 shows performance of refrigerants in a vending
machine system with and without a suction line/liquid line heat
exchanger (SL/LL HX)
[0593] Composition A1 to A5 show higher efficiency than R134a when
a SL/LL Heat Exchanger is employed.
Example 6: Medium Temperature Refrigeration System with Suction
Line/Liquid Line (SL/LL) Heat Exchanger
[0594] The compositions of the invention may be used in medium
temperature systems. A medium temperature refrigeration system is
preferably used to chill food or beverages such as in a
refrigerator or a bottle cooler, or in a supermarket to chill
perishable goods. The system usually has an air-to-refrigerant
evaporator to chill the food or beverage, a reciprocating or rotary
compressor, an air-to-refrigerant condenser to exchange heat with
the ambient air, and a thermal or electronic expansion valve. The
refrigerant evaporating temperature is preferably in the range of
about -12 to about 0.degree. C. The condensing temperature is
preferably in the range of about 40 to about 70.degree. C.
[0595] In the following Example, exemplary compositions of the
invention were tested in a medium temperature refrigeration system,
with and without a Suction Line/Liquid Line Heat Exchanger. A
schematic of a medium temperature refrigeration system, with a
Suction Line/Liquid Line Heat Exchanger is shown in FIG. 1 and the
results are reported in Table 7 below.
[0596] Operating conditions: [0597] 1. Condensing
temperature=45.degree. C. [0598] 2. Condensing Temperature--Ambient
Temperature=10.degree. C. [0599] 3. Condenser
sub-cooling=0.0.degree. C. (system with receiver) [0600] 4.
Evaporating temperature=-8.degree. C., Corresponding box
temperature=1.7.degree. C. [0601] 5. Evaporator
Superheat=5.5.degree. C. [0602] 6. Compressor Isentropic
Efficiency=65% [0603] 7. Volumetric Efficiency=100% [0604] 8.
Temperature Rise in Suction Line=10.degree. C. [0605] 9. Suction
Line/Liquid Line Heat Exchanger Effectiveness: 0%, 35%, 55%,
75%
TABLE-US-00013 [0605] TABLE 7 Performance in a Medium-Temperature
Refrigeration System with SL/LL HX Efficiency Efficiency Efficiency
Efficiency Refrigerant @ 0% @ 35% @ 55% @ 75% R134a 100% 100% 100%
100% B1 100% 101% 101% 102% B2 100% 101% 101% 102% B3 100% 101%
101% 102% B4 100% 101% 101% 102% B5 100% 101% 101% 102%
[0606] Table 4 shows the performance of exemplary refrigerants of
the invention in a medium temperature refrigeration system as
compared to R134a [0607] Composition B1 to B5 show the same
efficiency (COP) as R134a in the system without a SL/LL Heat
Exchanger, and a better efficiency (COP) than R134a when a SL/LL
Heat Exchanger is employed.
Comparative Example C1: Comparative Cascade System 1B
[0608] Table C1 below shows the results of a cascade refrigeration
system described in reference to FIG. 1B both with and without a
mechanical subcooler in which the refrigerant in the secondary loop
and the primary loop is R404A.
TABLE-US-00014 TABLE C1 Medium Low Relative temper- temper- COP %
of ature ature R404A (second (first (% of refrig- refrig- R404A
eration eration Power Capacity COP w mech Systems circuit) circuit)
[kW] [kW] [-] SC) Compar- R404A 54.8 100 1.823487 100% ative
example Compar- 49.6 100 2.016129 110.6% ative (100%) example with
mechanical subcooler
[0609] Table C1 above includes information on the coefficient of
performance (COP) of each system. The COP is the ratio of useful
cooling output from the system to work input to the system. Higher
COPs equate to lower operating costs. The relative COP is the COP
relative to the comparative example refrigeration system with no
subcooling.
Example 7: Cascade System 2
[0610] Table 8 below shows the results of a cascade refrigeration
system described in reference to FIG. 2 both with and without a
mechanical subcooler in which the refrigerant in the secondary loop
is each of refrigerants A2 and B2 as described above and in which
the refrigerant in the primary loop is R404A. The results are
reported in Table 8 below, with the results from Comparative
Example 1 being repeated in the Table for convenience.
TABLE-US-00015 TABLE 8 Medium Low Relative temper- temper- COP % of
ature ature R404A (second (first (% of refrig- refrig- R404A
eration eration Power Capacity COP w mech circuit) circuit) [kW]
[kW] [-] SC) Comparative R404A 54.8 100 1.82 100% example (FIG. 1B)
Comparative 49.6 100 2.02 110.6% example with (100%) mechanical
subcooler (FIG. 1B) Example 7 A2 R744 46.6 100 2.14 117.6% (FIG. 2)
(106.3%) B2 R744 46.8 100 2.14 117.2% (106.0%)
[0611] It is clear from Table 8 that the cascaded refrigeration
circuit which uses the refrigerants A2 and B2 of the present
invention in the secondary loop in accordance with Cascade System 2
(FIG. 2) achieves the lowest power consumption and the best COP
compared to the comparative systems.
[0612] The results shown in Tables C1 and 8 are based on the below
assumptions, where MT means medium temperature (second
refrigeration circuit) and LT means low temperature (first
refrigeration circuit) and units are as given. [0613] Load
distribution [0614] LT: 1/3 (33,000 W) [0615] MT: 2/3 (67,000 W)
[0616] Volumetric efficiency: 95% for both MT ad LT [0617]
Isentropic efficiency [0618] R404A: MT/LT, 0.72/0.68 [0619]
Condensing temperature: 105 F [0620] MT evaporation temperature: 20
F (22 F for Self-contained units due to lower pressure drop) [0621]
LT evaporation temperature: -25 F [0622] Evaporator superheat: 10 F
[0623] Suction line temperature rise [0624] Comparative example:
MT: 25 F; LT: 50 F [0625] Cascade/self-contained: MT: 10 F; LT: 25
F (Self-contained units have shorter lines and therefore less heat
infiltration) [0626] Cascade/pumped: MT: 10 F; LT: 25 F [0627]
Mechanical sub cooler outlet temperature: 50 F
Example 8: Cascade System 2 with Suction Line Liquid Line Heat
Exchanger
[0628] Table 9 below shows the results of a cascade refrigeration
system described in reference to FIG. 2 both with and without a
mechanical subcooler but which in addition has a SLHX installed in
the second refrigeration loop, with the refrigerant in the
secondary loop being in one case refrigerant A2 and in the other
case refrigerant B2 as described above and in which the refrigerant
in the primary loop is R404A. The results are reported in Table 9
below, with the results from Comparative Example 1 being repeated
in the Table for convenience.
TABLE-US-00016 TABLE 8 Medium Low Relative temper- temper- COP % of
ature ature R404A (second (first (% of refrig- refrig- R404A
eration eration Power Capacity COP w mech circuit) circuit) [kW]
[kW] [-] SC) Comparative R404A 54.8 100 1.82 100% example (FIG. 1B)
Comparative 49.6 100 2.02 110.6% example with (100%) mechanical
subcooler (FIG. 1B) Example 7 A2 R744 43.97 100 2.27 124.7% (FIG.
2) (112.8%) B2 R744 43.98 100 2.27 124.7% (112.8%)
[0629] It is clear from Table 8 that the cascaded refrigeration
circuit which uses the refrigerants A2 and B2 of the present
invention in the secondary loop in accordance with Cascade System 2
(FIG. 2) and an suction line liquid line heat exchanger (SLHX)
achieves the lowest power consumption and the best COP compared to
the comparative systems and to the system of FIG. 2 but without the
SLHX.
[0630] The results shown in Tables C1 and 8 are based on the below
assumptions, where MT means medium temperature (second
refrigeration circuit) and LT means low temperature (first
refrigeration circuit) and units are as given. [0631] Load
distribution [0632] LT: 1/3 (33,000 W) [0633] MT: 2/3 (67,000 W)
[0634] Volumetric efficiency: 95% for both MT ad LT [0635]
Isentropic efficiency [0636] R404A: MT/LT, 0.72/0.68 [0637]
Condensing temperature: 105 F [0638] MT evaporation temperature: 20
F (22 F for Self-contained units due to lower pressure drop) [0639]
LT evaporation temperature: -25 F [0640] Evaporator superheat: 10 F
[0641] Suction line temperature rise [0642] Comparative example:
MT: 25 F; LT: 50 F [0643] Cascade/self-contained: MT: 10 F; LT: 25
F (Self-contained units have shorter lines and therefore less heat
infiltration) [0644] Cascade/pumped: MT: 10 F; LT: 25 F [0645]
Mechanical sub cooler outlet temperature: 50 F
Numbered Embodiment 1
[0646] A refrigerant comprising at least about 97% by weight of the
following three compounds, with each compound being present in the
following relative percentages of:
[0647] from 1% by weight to 3% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),
[0648] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and
[0649] from about 15% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 2
[0650] The refrigerant of numbered embodiment 1 wherein the
refrigerant of three compounds is: from 1% by weight to 3% by
weight trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),
[0651] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and
[0652] from about 18% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 3
[0653] The refrigerant of numbered embodiment 1 or numbered
embodiment 2 wherein the refrigerant of three compounds is
[0654] from 1% by weight to 3% by weight HFCO-1233zd(E),
[0655] from about 77% by weight to about 80% by weight
HFO-1234ze(E), and
[0656] from about 18% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 4
[0657] The refrigerant of any one of numbered embodiments 1 to 3
wherein the HFCO-1233zd(E) is present in an amount of 2%+/-0.5% by
weight of the composition.
Numbered Embodiment 5
[0658] The refrigerant of any one of numbered embodiments 1 to 4
wherein the refrigerant of three compounds is
[0659] 2%+/-0.5% by weight HFCO-1233zd(E),
[0660] about 78% by weight HFO-1234ze(E), and
[0661] about 20% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 6
[0662] The refrigerant of any one of numbered embodiments 1 to 5
wherein the refrigerant of three compounds is
[0663] 2%+/-0.5% by weight HFCO-1233zd(E),
[0664] 78%+/-0.5% by weight HFO-1234ze(E), and
[0665] 20%+/-0.5% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 7
[0666] The refrigerant as claimed in numbered embodiments 1 to 6
wherein the refrigerant comprises at least about 98.5% by weight of
said refrigerant of said three compounds.
Numbered Embodiment 8
[0667] A refrigerant consisting essentially of the following three
compounds, with each compound being present in the following
relative percentages of:
[0668] from 1% by weight to 3% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),
[0669] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and
[0670] from about 15% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 9
[0671] The refrigerant of numbered embodiment 8 wherein the
refrigerant of three compounds is: from 1% by weight to 3% by
weight trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),
[0672] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and
[0673] from about 18% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 10
[0674] The refrigerant of numbered embodiment 8 or numbered
embodiment 9 wherein the refrigerant of three compounds is from 1%
by weight to 3% by weight HFCO-1233zd(E),
[0675] from about 77% by weight to about 80% by weight
HFO-1234ze(E), and
[0676] from about 18% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 11
[0677] The refrigerant of any one of numbered embodiments 8 to 10
wherein the HFCO-1233zd(E) is present in an amount of 2%+/-0.5% by
weight of the composition.
Numbered Embodiment 12
[0678] The refrigerant of any one of numbered embodiments 8 to 11
wherein the refrigerant of three compounds is
[0679] 2%+/-0.5% by weight HFCO-1233zd(E),
[0680] about 78% by weight HFO-1234ze(E), and
[0681] about 20% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 13
[0682] The refrigerant of any one of numbered embodiments 8 to 12
wherein the refrigerant of three compounds is
[0683] 2%+/-0.5% by weight HFCO-1233zd(E),
[0684] 78%+/-0.5% by weight HFO-1234ze(E), and
[0685] 20%+/-0.5% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 14
[0686] A refrigerant consisting of the following three compounds,
with each compound being present in the following relative
percentages of:
[0687] from 1% by weight to 3% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),
[0688] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and
[0689] from about 15% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 15
[0690] The refrigerant of numbered embodiment 14 wherein the
refrigerant of three compounds is: from 1% by weight to 3% by
weight trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E),
[0691] from about 77% by weight to about 83% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), and
[0692] from about 18% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 16
[0693] The refrigerant of numbered embodiment 14 or numbered
embodiment 15 wherein the refrigerant of three compounds is
[0694] from 1% by weight to 3% by weight HFCO-1233zd(E),
[0695] from about 77% by weight to about 80% by weight
HFO-1234ze(E), and
[0696] from about 18% by weight to about 21% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 17
[0697] The refrigerant of any one of numbered embodiments 14 to 16
wherein the HFCO-1233zd(E) is present in an amount of 2%+/-0.5% by
weight of the composition.
Numbered Embodiment 18
[0698] The refrigerant of any one of numbered embodiments 14 to 17
wherein the refrigerant of three compounds is
[0699] 2%+/-0.5% by weight HFCO-1233zd(E),
[0700] about 78% by weight HFO-1234ze(E), and
[0701] about 20% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 19
[0702] The refrigerant of any one of numbered embodiments 14 to 18
wherein the refrigerant of three compounds is
[0703] 2%+/-0.5% by weight HFCO-1233zd(E),
[0704] 78%+/-0.5% by weight HFO-1234ze(E), and
[0705] 20%+/-0.5% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 20
[0706] A heat transfer composition comprising a refrigerant of any
one of numbered embodiments 1 to 19.
Numbered Embodiment 21
[0707] The heat transfer composition as claimed in numbered
embodiment 20, wherein the refrigerant comprises greater than 40%
by weight of the composition.
Numbered Embodiment 22
[0708] The heat transfer composition as claimed in numbered
embodiment 20, wherein the refrigerant comprises greater than 50%
by weight of the composition.
Numbered Embodiment 23
[0709] The heat transfer composition as claimed in numbered
embodiment 20, wherein the refrigerant comprises greater than 60%
by weight of the composition.
Numbered Embodiment 24
[0710] The heat transfer composition as claimed in numbered
embodiment 20 wherein the refrigerant comprises greater than 70% by
weight of the composition.
Numbered Embodiment 25
[0711] The heat transfer composition as claimed in numbered
embodiment 20, wherein the refrigerant comprises greater than 80%
by weight of the composition.
Numbered Embodiment 26
[0712] The heat transfer composition as claimed in numbered
embodiment 20, wherein the refrigerant comprises greater than 90%
by weight of the composition.
Numbered Embodiment 27
[0713] The heat transfer composition of any one of numbered
embodiments 20 to 26 wherein said heat transfer composition further
comprising a stabilizer selected from a diene-based compound and/or
a phenol-based compound and/or a phosphorus compound and/or a
nitrogen compound and/or an epoxide.
Numbered Embodiment 28
[0714] The heat transfer composition of any one of numbered
embodiments 20 to 27 wherein said heat transfer composition further
comprising a stabilizer selected from a diene-based compounds
and/or a phenol-based compound and/or a phosphorus compound.
Numbered Embodiment 29
[0715] The heat transfer composition of numbered embodiments 27 or
28 wherein the diene based compound is a terpene selected from the
group consisting of terebene, retinal, geranoil, terpinene, delta-3
carene, terpinolene, phellandrene, fenchene, myrcene, farnesene,
pinene, nerol, citral, camphor, menthol, limonene, nerolidol,
phytol, carnosic acid and vitamin A.sub.1, preferably,
farnesene.
Numbered Embodiment 30
[0716] The heat transfer composition of numbered embodiment 29
wherein the diene based compound is provided in the heat transfer
composition in an amount of from greater than 0, preferably from
0.0001% by weight to about 5% by weight, more preferably 0.001% by
weight to about 2.5% by weight, most preferably from 0.01% to about
1% by weight.
Numbered Embodiment 31
[0717] The heat transfer composition of numbered embodiments 27 or
28 wherein the phosphorus compound is a phosphite or a phosphate
compound.
Numbered Embodiment 32
[0718] The heat transfer composition of numbered embodiment 31,
wherein the phosphite compound is selected from a diaryl, dialkyl,
triaryl and/or trialkyl phosphite, and/or a mixed aryl/alkyl di- or
tri-substituted phosphite, or one or more compounds selected from
hindered phosphites, tris-(di-tert-butylphenyl)phosphite,
di-n-octyl phophite, iso-octyl diphenyl phosphite, iso-decyl
diphenyl phosphite, tri-iso-decyl phosphate, triphenyl phosphite
and diphenyl phosphite, particularly diphenyl phosphite.
Numbered Embodiment 33
[0719] The heat transfer composition of numbered embodiment 31,
wherein the phosphate compounds is selected from a triaryl
phosphate, trialkyl phosphate, alkyl mono acid phosphate, aryl
diacid phosphate, amine phosphate, preferably triaryl phosphate
and/or a trialkyl phosphate, particularly tri-n-butyl
phosphate.
Numbered Embodiment 34
[0720] The heat transfer composition of numbered embodiments 31 to
33 wherein the phosphorus compound is provided in the heat transfer
composition in an amount of greater than 0, preferably from 0.0001%
by weight to about 5% by weight, more preferably 0.001% by weight
to about 2.5% by weight, most preferably from 0.01% to about 1% by
weight.
Numbered Embodiment 35
[0721] The heat transfer composition of any one of numbered
embodiments 27 or 28 wherein the stabilizer composition comprises a
diene based as claimed in any one of numbered embodiment 29 to 30
and a phosphorous compound as claimed in any one of numbered
embodiments 31 to 34.
Numbered Embodiment 36
[0722] The heat transfer composition of numbered embodiment 35
wherein the phosphorous compound is a phosphite compound selected
from the group consisting of hindered phosphites,
tris-(di-tert-butylphenyl)phosphite, di-n-octyl phophite, iso-decyl
diphenyl phosphite and diphenyl phosphite.
Numbered Embodiment 37
[0723] The heat transfer composition of any one of numbered
embodiments 35 or 36 wherein the phosphorus compounds is provided
in the heat transfer composition in an amount of greater than 0,
preferably from 0.0001% by weight to about 5% by weight, more
preferably 0.001% by weight to about 2.5% by weight, more
preferably from 0.01% to about 1% by weight.
Numbered Embodiment 38
[0724] The heat transfer composition of any one of numbered
embodiments 27 to 37 wherein the stabilizer composition comprises
farnesene and diphenyl phosphite.
Numbered Embodiment 39
[0725] The heat transfer composition of any one of numbered
embodiments 27 to 38, wherein the nitrogen compound is one or more
compounds selected from dinitrobenzene, nitrobenzene, nitromethane,
nitrosobenzene, and TEMPO
[(2,2,6,6-tetramethylpiperidin-1-yl)oxyl], preferably
dinitrobenzene.
Numbered Embodiment 40
[0726] The heat transfer composition of any one of numbered
embodiments 27 to 39 wherein the nitrogen compound is provided in
the heat transfer composition in an amount of greater than 0,
preferably from 0.0001% by weight to about 5% by weight, more
preferably 0.001% by weight to about 2.5% by weight, most
preferably from 0.01% to about 1% by weight.
Numbered Embodiment 41
[0727] The heat transfer composition of any one of numbered
embodiments 27 to 40 wherein the phenol compound is BHT.
Numbered Embodiment 42
[0728] The heat transfer composition of any one of numbered
embodiment 27 to 40 wherein the phenol compound is provided in the
heat transfer composition in an amount of greater than 0,
preferably from 0.0001% by weight to about 5% by weight, more
preferably 0.001% by weight to about 2.5% by weight, most
preferably from 0.01% to about 1% by weight.
Numbered Embodiment 43
[0729] The heat transfer composition of any one of numbered
embodiments 27 to 42 wherein the phenol compound is BHT, wherein
said BHT is present in an amount of from about 0.0001% by weight to
about 5% by weight based on the weight of heat transfer
composition.
Numbered Embodiment 44
[0730] The heat transfer composition any one of numbered
embodiments 27 to 43 comprising a stabilizer composition comprising
farnesene, diphenyl phosphite and BHT, wherein the farnesene is
provided in an amount of from about 0.0001% by weight to about 5%
by weight based on the weight of the heat transfer composition, the
diphenyl phosphite is provided in an amount of from about 0.0001%
by weight to about 5% by weight based on the weight of the heat
transfer composition and the BHT is provided in an amount of from
about 0.0001% by weight to about 5% by weight based on the weight
of heat transfer composition.
Numbered Embodiment 45
[0731] The heat transfer composition of any one of numbered
embodiments 20 to 44 further comprising a lubricant selected from
the group consisting of polyol esters (POEs), polyalkylene glycols
(PAGs), mineral oil, alkylbenzenes (ABs) and polyvinyl ethers
(PVE), more preferably from polyol esters (POEs), mineral oil,
alkylbenzenes (ABs) and polyvinyl ethers (PVE), particularly from
polyol esters (POEs), mineral oil and alkylbenzenes (ABs), most
preferably from polyol esters (POEs).
Numbered Embodiment 46
[0732] The heat transfer composition of numbered embodiment 45
wherein the lubricant is selected from polyol esters (POEs),
polyalkylene glycols (PAGs), mineral oil, alkylbenzenes (ABs) and
polyvinyl ethers (PVE).
Numbered Embodiment 47
[0733] The heat transfer composition of numbered embodiment 45
wherein the lubricant is selected from polyol esters (POEs),
mineral oil, alkylbenzenes (ABs) and polyvinyl ethers (PVE).
Numbered Embodiment 48
[0734] The heat transfer composition of numbered embodiment 45
wherein the lubricant is selected from polyol esters (POEs),
mineral oil and alkylbenzenes (ABs).
Numbered Embodiment 49
[0735] The heat transfer composition of numbered embodiment 45
wherein the lubricant is a polyol ester (POE).
Numbered Embodiment 50
[0736] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from 5 to 60% by weight.
Numbered Embodiment 51
[0737] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from 30 to 50% by weight.
Numbered Embodiment 52
[0738] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from about 10 to 60% by weight
of the system using the heat transfer composition.
Numbered Embodiment 53
[0739] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from about 20 to about 50% by
weight of the system using the heat transfer composition.
Numbered Embodiment 54
[0740] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from about 20 to about 40% by
weight of the system using the heat transfer composition.
Numbered Embodiment 55
[0741] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from about 20 to about 30% by
weight of the system using the heat transfer composition.
Numbered Embodiment 56
[0742] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from about 30 to about 50% by
weight of the system using the heat transfer composition.
Numbered Embodiment 57
[0743] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from about 30 to about 40% by
weight of the system using the heat transfer composition.
Numbered Embodiment 58
[0744] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from about 5 to about 10% by
weight of the system using the heat transfer composition.
Numbered Embodiment 59
[0745] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from around about 8% by weight
of the system using the heat transfer composition.
Numbered Embodiment 60
[0746] The heat transfer composition of any one of numbered
embodiment 45 to 49 wherein the lubricant is present in the heat
transfer composition in an amount of from 10 to 60% by weight and
wherein the lubricant is a polyol ester (POE) lubricant.
Numbered Embodiment 61
[0747] The heat transfer composition of any one of numbered
embodiments 20 to 26 wherein the heat transfer composition consists
essentially of the refrigerant as claimed in any one of numbered
embodiments 1 to 19.
Numbered Embodiment 62
[0748] The heat transfer composition of any one of numbered
embodiments 20 to 26 wherein the heat transfer composition consist
essentially of the refrigerant as claimed in any one of claims 1 to
19 and the stabilizer composition as claimed in any one of numbered
embodiment 27 to 44.
Numbered Embodiment 63
[0749] The heat transfer composition of any one of numbered
embodiments 20 to 26 wherein the heat transfer composition consist
essentially of the refrigerant as claimed in any one of numbered
embodiment 1 to 19, the stabilizer composition as claimed in any
one of numbered embodiments 27 to 44 and the lubricant as claimed
in any one of numbered embodiment 45 to 60.
Numbered Embodiment 64
[0750] The heat transfer composition of any one of numbered
embodiments 20 to 63 having a Global Warming Potential (GWP) of
less than 150.
Numbered Embodiment 65
[0751] The heat transfer composition of any one of numbered
embodiments 20 to 64 having an Ozone Depletion Potential (ODP) of
not greater than 0.05, preferably 0.02, more preferably about
zero.
Numbered Embodiment 66
[0752] A low temperature refrigeration system containing a
refrigerant of any one of numbered embodiments 1-19 or a heat
transfer composition of any one of numbered embodiments to 64.
Numbered Embodiment 67
[0753] A medium temperature refrigeration system containing a
refrigerant of any one of numbered embodiments 1-19 or a heat
transfer composition of any one of numbered embodiments 20 to
64.
Numbered Embodiment 68
[0754] A heat pump containing a refrigerant of any one of numbered
embodiments 1-19 or a heat transfer composition of any one of
numbered embodiments 20 to 64.
Numbered Embodiment 69
[0755] A dehumidifier containing a refrigerant of any one of
numbered embodiments 1-19 or a heat transfer composition of any one
of numbered embodiments 20 to 64.
Numbered Embodiment 70
[0756] A vending machine containing a refrigerant of any one of
numbered embodiments 1-19 or a heat transfer composition of any one
of numbered embodiments 20 to 64.
Numbered Embodiment 71
[0757] A chiller containing a refrigerant of any one of numbered
embodiments 1-19 or a heat transfer composition of any one of
numbered embodiments 20 to 64.
Numbered Embodiment 72
[0758] A refrigerator containing a refrigerant of any one of
numbered embodiments 1-19 or a heat transfer composition of any one
of numbered embodiments 20 to 64.
Numbered Embodiment 73
[0759] A freezer containing a refrigerant of any one of numbered
embodiments 1-19 or a heat transfer composition of any one of
numbered embodiments 20 to 64.
Numbered Embodiment 74
[0760] A cascade refrigeration system containing a refrigerant of
any one of numbered embodiments 1-19 or a heat transfer composition
of any one of numbered embodiments to 64.
Numbered Embodiment 75
[0761] A refrigerant comprising at least about 97% by weight of the
following four compounds, with each compound being present in the
following relative percentages:
[0762] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0763] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/-0.5% by
weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and
[0764] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 76
[0765] A refrigerant comprising at least about 98.5% by weight of
the following three compounds, with each compound being present in
the following relative percentages:
[0766] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0767] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/-0.5% by
weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and
[0768] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 77
[0769] A refrigerant comprising at least about 99.5% by weight of
the following three compounds, with each compound being present in
the following relative percentages:
[0770] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0771] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/-0.5% by
weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and
[0772] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF3I).
Numbered Embodiment 78
[0773] A refrigerant consisting essentially of the following four
compounds, with each compound being present in the following
relative percentages:
[0774] from 1% by weight to 2%+/-0.5% by weight
trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd(E)),
[0775] from about 73% by weight to about 87% by weight
trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 4.4%+/-0.5% by
weight 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and
[0776] from about 6.6% by weight to about 20.6% by weight
trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 79
[0777] A refrigerant comprising at least about 98.5% by weight of
the following four compounds, with each compound being present in
the following relative percentages:
[0778] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0779] about 84% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0780] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0781] about 9.6% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 80
[0782] trifluoropropene (HFCO-1233zd(E)),
[0783] about 84% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0784] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0785] about 9.6% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 81
[0786] A refrigerant consisting of the following four compounds,
with each compound being present in the following relative
percentages:
[0787] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0788] about 84% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0789] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0790] about 9.6% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 82
[0791] A refrigerant comprising at least about 98.5% by weight of
the following four compounds, with each compound being present in
the following relative percentages:
[0792] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0793] 84%+/-0.5% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0794] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0795] 9.6%+/-0.5% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 83
[0796] A refrigerant consisting essentially of the following four
compounds, with each compound being present in the following
relative percentages:
[0797] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0798] 84%+/-0.5% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0799] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0800] 9.6%+/-0.5% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 84
[0801] A refrigerant comprising consisting of the following four
compounds, with each compound being present in the following
relative percentages:
[0802] 2%+/-0.5% by weight trans-1-chloro-3,3,3-trifluoropropene
(HFCO-1233zd(E)),
[0803] 84%+/-0.5% by weight trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze(E)),
[0804] 4.4%+/-0.5% by weight 1,1,1,2,3,3,3-heptafluoropropane
(HFC-227ea), and
[0805] 9.6%+/-0.5% by weight trifluoroiodomethane (CF3I).
Numbered Embodiment 85
[0806] A heat transfer composition comprising a refrigerant of any
one of numbered embodiments 75 to 84.
Numbered Embodiment 86
[0807] The heat transfer composition as claimed in numbered
embodiment 85, wherein the refrigerant comprises greater than 40%
by weight of the composition.
Numbered Embodiment 87
[0808] The heat transfer composition as claimed in numbered
embodiment 85, wherein the refrigerant comprises greater than 50%
by weight of the composition.
Numbered Embodiment 88
[0809] The heat transfer composition as claimed in numbered
embodiment 85, wherein the refrigerant comprises greater than 60%
by weight of the composition.
Numbered Embodiment 89
[0810] The heat transfer composition as claimed in numbered
embodiment 85 wherein the refrigerant comprises greater than 70% by
weight of the composition.
Numbered Embodiment 90
[0811] The heat transfer composition as claimed in numbered
embodiment 85, wherein the refrigerant comprises greater than 80%
by weight of the composition.
Numbered Embodiment 91
[0812] The heat transfer composition as claimed in numbered
embodiment 85, wherein the refrigerant comprises greater than 90%
by weight of the composition.
Numbered Embodiment 92
[0813] The heat transfer composition of any one of numbered
embodiments 85 to 91 wherein said heat transfer composition further
comprises a stabilizer selected from a diene-based compound and/or
a phenol-based compound and/or a phosphorus compound and/or a
nitrogen compound and/or an epoxide.
Numbered Embodiment 93
[0814] The heat transfer composition of any one of numbered
embodiments 85 to 91 wherein said heat transfer composition further
comprises a stabilizer selected from a diene-based compounds and/or
a phenol-based compound and/or a phosphorus compound.
Numbered Embodiment 94
[0815] The heat transfer composition of numbered embodiments 92 or
93 wherein the diene based compound is a terpene selected from the
group consisting of terebene, retinal, geranoil, terpinene, delta-3
carene, terpinolene, phellandrene, fenchene, myrcene, farnesene,
pinene, nerol, citral, camphor, menthol, limonene, nerolidol,
phytol, carnosic acid and vitamin A.sub.1, preferably,
farnesene.
Numbered Embodiment 95
[0816] The heat transfer composition of numbered embodiment 94
wherein the diene based compound is provided in the heat transfer
composition in an amount of from greater than 0, preferably from
0.0001% by weight to about 5% by weight, more preferably 0.001% by
weight to about 2.5% by weight, most preferably from 0.01% to about
1% by weight.
Numbered Embodiment 96
[0817] The heat transfer composition of numbered embodiments 85 to
95 wherein a phosphorous compound is present and wherein the
phosphorus compound is a phosphite or a phosphate compound.
Numbered Embodiment 97
[0818] The heat transfer composition of numbered embodiment 96,
wherein the phosphite compound is selected from a diaryl, dialkyl,
triaryl and/or trialkyl phosphite, and/or a mixed aryl/alkyl di- or
tri-substituted phosphite, or one or more compounds selected from
hindered phosphites, tris-(di-tert-butylphenyl)phosphite,
di-n-octyl phophite, iso-octyl diphenyl phosphite, iso-decyl
diphenyl phosphite, tri-iso-decyl phosphate, triphenyl phosphite
and diphenyl phosphite, particularly diphenyl phosphite.
Numbered Embodiment 98
[0819] The heat transfer composition of numbered embodiment 96,
wherein the phosphate compounds is selected from a triaryl
phosphate, trialkyl phosphate, alkyl mono acid phosphate, aryl
diacid phosphate, amine phosphate, preferably triaryl phosphate
and/or a trialkyl phosphate, particularly tri-n-butyl
phosphate.
Numbered Embodiment 99
[0820] The heat transfer composition of numbered embodiments 97 or
98 wherein the phosphorus compound is provided in the heat transfer
composition in an amount of greater than 0, preferably from 0.0001%
by weight to about 5% by weight, more preferably 0.001% by weight
to about 2.5% by weight, most preferably from 0.01% to about 1% by
weight.
Numbered Embodiment 100
[0821] The heat transfer composition of any one of numbered
embodiments 97 or 98 wherein the stabilizer composition comprises a
diene based as claimed in any one of numbered embodiment 29 to 30
and a phosphorous compound as claimed in any one of numbered
embodiments 31 to 34.
Numbered Embodiment 101
[0822] The heat transfer composition of numbered embodiment 100
wherein the phosphorous compound is a phosphite compound selected
from the group consisting of hindered phosphites,
tris-(di-tert-butylphenyl)phosphite, di-n-octyl phophite, iso-decyl
diphenyl phosphite and diphenyl phosphite.
Numbered Embodiment 102
[0823] The heat transfer composition of any one of numbered
embodiments 100 or 101 wherein the phosphorus compounds is provided
in the heat transfer composition in an amount of greater than 0,
preferably from 0.0001% by weight to about 5% by weight, more
preferably 0.001% by weight to about 2.5% by weight, more
preferably from 0.01% to about 1% by weight.
Numbered Embodiment 103
[0824] The heat transfer composition of any one of numbered
embodiments 92 to 102 wherein the stabilizer composition comprises
farnesene and diphenyl phosphite.
Numbered Embodiment 104
[0825] The heat transfer composition of any one of numbered
embodiments 92 to 103, wherein the nitrogen compound is one or more
compounds selected from dinitrobenzene, nitrobenzene, nitromethane,
nitrosobenzene, and TEMPO
[(2,2,6,6-tetramethylpiperidin-1-yl)oxyl], preferably
dinitrobenzene.
Numbered Embodiment 105
[0826] The heat transfer composition of any one of numbered
embodiments 92 to 104 wherein the nitrogen compound is provided in
the heat transfer composition in an amount of greater than 0,
preferably from 0.0001% by weight to about 5% by weight, more
preferably 0.001% by weight to about 2.5% by weight, most
preferably from 0.01% to about 1% by weight.
Numbered Embodiment 106
[0827] The heat transfer composition of any one of numbered
embodiments 92 to 105 wherein the phenol compound is BHT.
Numbered Embodiment 107
[0828] The heat transfer composition of any one of numbered
embodiment 92 to 105 wherein the phenol compound is provided in the
heat transfer composition in an amount of greater than 0,
preferably from 0.0001% by weight to about 5% by weight, more
preferably 0.001% by weight to about 2.5% by weight, most
preferably from 0.01% to about 1% by weight.
Numbered Embodiment 108
[0829] The heat transfer composition of any one of numbered
embodiments 92 to 105 wherein the phenol compound is BHT, wherein
said BHT is present in an amount of from about 0.0001% by weight to
about 5% by weight based on the weight of heat transfer
composition.
Numbered Embodiment 109
[0830] The heat transfer composition any one of numbered
embodiments 92 to 105 comprising a stabilizer composition
comprising farnesene, diphenyl phosphite and BHT, wherein the
farnesene is provided in an amount of from about 0.0001% by weight
to about 5% by weight based on the weight of the heat transfer
composition, the diphenyl phosphite is provided in an amount of
from about 0.0001% by weight to about 5% by weight based on the
weight of the heat transfer composition and the BHT is provided in
an amount of from about 0.0001% by weight to about 5% by weight
based on the weight of heat transfer composition.
Numbered Embodiment 110
[0831] The heat transfer composition of any one of numbered
embodiments 95 to 109 further comprising a lubricant selected from
the group consisting of polyol esters (POEs), polyalkylene glycols
(PAGs), mineral oil, alkylbenzenes (ABs) and polyvinyl ethers
(PVE), more preferably from polyol esters (POEs), mineral oil,
alkylbenzenes (ABs) and polyvinyl ethers (PVE), particularly from
polyol esters (POEs), mineral oil and alkylbenzenes (ABs), most
preferably from polyol esters (POEs).
Numbered Embodiment 111
[0832] The heat transfer composition of numbered embodiment 110
wherein the lubricant is selected from polyol esters (POEs),
polyalkylene glycols (PAGs), mineral oil, alkylbenzenes (ABs) and
polyvinyl ethers (PVE).
Numbered Embodiment 112
[0833] The heat transfer composition of numbered embodiment 110
wherein the lubricant is selected from polyol esters (POEs),
mineral oil, alkylbenzenes (ABs) and polyvinyl ethers (PVE).
Numbered Embodiment 113
[0834] The heat transfer composition of numbered embodiment 110
wherein the lubricant is selected from polyol esters (POEs),
mineral oil and alkylbenzenes (ABs).
Numbered Embodiment 114
[0835] The heat transfer composition of numbered embodiment 110
wherein the lubricant is a polyol ester (POE).
Numbered Embodiment 115
[0836] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from 5 to 60% by weight.
Numbered Embodiment 116
[0837] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from 30 to 50% by weight.
Numbered Embodiment 117
[0838] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from about 10 to 60% by weight
of the system using the heat transfer composition.
Numbered Embodiment 118
[0839] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from about 20 to about 50% by
weight of the system using the heat transfer composition.
Numbered Embodiment 119
[0840] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from about 20 to about 40% by
weight of the system using the heat transfer composition.
Numbered Embodiment 120
[0841] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from about 20 to about 30% by
weight of the system using the heat transfer composition.
Numbered Embodiment 121
[0842] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from about 30 to about 50% by
weight of the system using the heat transfer composition.
Numbered Embodiment 122
[0843] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from about 30 to about 40% by
weight of the system using the heat transfer composition.
Numbered Embodiment 123
[0844] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from about 5 to about 10% by
weight of the system using the heat transfer composition.
Numbered Embodiment 124
[0845] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from around about 8% by weight
of the system using the heat transfer composition.
Numbered Embodiment 125
[0846] The heat transfer composition of any one of numbered
embodiment 110 to 114 wherein the lubricant is present in the heat
transfer composition in an amount of from 10 to 60% by weight and
wherein the lubricant is a polyol ester (POE) lubricant.
Numbered Embodiment 126
[0847] The heat transfer composition of any one of numbered
embodiments 95 to 101 wherein the heat transfer composition
consists essentially of the refrigerant as claimed in any one of
numbered embodiments 75 to 94.
Numbered Embodiment 127
[0848] The heat transfer composition of any one of numbered
embodiments 75 to 94 wherein the heat transfer composition consist
essentially of the refrigerant as claimed in any one of claims 75
to 84 and the stabilizer composition as claimed in any one of
numbered embodiment 92 to 109.
Numbered Embodiment 128
[0849] The heat transfer composition of any one of numbered
embodiments 92 to 109 wherein the heat transfer composition consist
essentially of the refrigerant as claimed in any one of numbered
embodiment 75 to 84, the stabilizer composition as claimed in any
one of numbered embodiments 92 to 109 and the lubricant as claimed
in any one of numbered embodiment 110 to 125.
Numbered Embodiment 129
[0850] The heat transfer composition of any one of numbered
embodiments 85 to 128 having a Global Warming Potential (GWP) of
less than 150.
Numbered Embodiment 130
[0851] The heat transfer composition of any one of numbered
embodiments 85 to 128 having an Ozone Depletion Potential (ODP) of
not greater than 0.05, preferably 0.02, more preferably about
zero.
Numbered Embodiment 131
[0852] A low temperature refrigeration system containing a
refrigerant of any one of numbered embodiments 75-84 or a heat
transfer composition of any one of numbered embodiments 85 to
128.
Numbered Embodiment 132
[0853] A medium temperature refrigeration system containing a
refrigerant of any one of numbered embodiments 75-84 or a heat
transfer composition of any one of numbered embodiments 85 to
128.
Numbered Embodiment 133
[0854] A heat pump containing a refrigerant of any one of numbered
embodiments 75-84 or a heat transfer composition of any one of
numbered embodiments 85 to 128.
Numbered Embodiment 134
[0855] A dehumidifier containing a refrigerant of any one of
numbered embodiments 75-84 or a heat transfer composition of any
one of numbered embodiments 84 to 128.
Numbered Embodiment 135
[0856] A vending machine containing a refrigerant of any one of
numbered embodiments 75-84 or a heat transfer composition of any
one of numbered embodiments 84 to 128.
Numbered Embodiment 136
[0857] A chiller containing a refrigerant of any one of numbered
embodiments 75-84 or a heat transfer composition of any one of
numbered embodiments 84 to 128.
Numbered Embodiment 137
[0858] A refrigerator containing a refrigerant of any one of
numbered embodiments 75-84 or a heat transfer composition of any
one of numbered embodiments 85 to 128.
Numbered Embodiment 138
[0859] A freezer containing a refrigerant of any one of numbered
embodiments 75-49 or a heat transfer composition of any one of
numbered embodiments 85 to 128.
Numbered Embodiment 139
[0860] A cascade refrigeration system containing a refrigerant of
any one of numbered embodiments 75-84 or a heat transfer
composition of any one of numbered embodiments 85 to 128.
[0861] Although the invention has been described with reference to
preferred embodiments, it will be understood by those skilled in
the art that various changes may be made and equivalents
substituted for elements thereof without departing from the scope
of the invention. In addition, many modifications may be made to
adapt to a particular situation or material to the teachings of the
invention with departing from the essential scope thereof.
Therefore, it 15 is intended that the invention not be limited to
the particular embodiments disclosed, but that the invention will
include all embodiments falling within the scope of the appended
claims or any claims added later.
* * * * *
References