U.S. patent application number 17/556548 was filed with the patent office on 2022-06-09 for 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 Ankit Sethi, Samuel F. Yana Motta, Yang Zou.
Application Number | 20220177760 17/556548 |
Document ID | / |
Family ID | |
Filed Date | 2022-06-09 |
United States Patent
Application |
20220177760 |
Kind Code |
A1 |
Yana Motta; Samuel F. ; et
al. |
June 9, 2022 |
HEAT TRANSFER COMPOSITIONS, METHODS, AND SYSTEMS
Abstract
The present invention relates to a refrigerant composition,
including difluoromethane (HFC-32), pentafluoroethane (HFC-125),
and trifluoroiodomethane (CF.sub.3I) for use in a heat exchange
system, including air conditioning and refrigeration applications
and in particular aspects to the use of such compositions as a
replacement of the refrigerant R-410A for heating and cooling
applications and to retrofitting heat exchange systems, including
systems designed for use with R-410A.
Inventors: |
Yana Motta; Samuel F.;
(Charlotte, NC) ; Sethi; Ankit; (Charlotte,
NC) ; Zou; Yang; (Charlotte, NC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HONEYWELL INTERNATIONAL INC. |
Charlotte |
NC |
US |
|
|
Assignee: |
HONEYWELL INTERNATIONAL
INC.
Charlotte
NC
|
Appl. No.: |
17/556548 |
Filed: |
December 20, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16262570 |
Jan 30, 2019 |
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17556548 |
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62631093 |
Feb 15, 2018 |
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62623887 |
Jan 30, 2018 |
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International
Class: |
C09K 5/04 20060101
C09K005/04; C10M 107/32 20060101 C10M107/32; C10M 107/24 20060101
C10M107/24; C10M 171/00 20060101 C10M171/00 |
Claims
1. A refrigerant comprising at least about 97% by weight of the
following three compounds, with each compound being present in the
following relative percentages: 39 to 45% by weight difluoromethane
(HFC-32), 1 to 4% by weight pentafluoroethane (HFC-125), and 51 to
57% by weight trifluoroiodomethane (CF3I).
2. The refrigerant of claim 1 comprising at least about 99.5% by
weight of the following three compounds, with each compound being
present in the following relative percentages: 39 to 45% by weight
difluoromethane (HFC-32), 1 to 4% by weight pentafluoroethane
(HFC-125), and 51 to 57% by weight trifluoroiodomethane (CF3I).
3. The refrigerant of claim 1 consisting of the following three
compounds, with each compound being present in the following
relative percentages: 39 to 45% by weight difluoromethane (HFC-32),
1 to 4% by weight pentafluoroethane (HFC-125), and 51 to 57% by
weight trifluoroiodomethane (CF3I).
4. The refrigerant of claim 1 comprising at least about 97% by
weight of the following three compounds, with each compound being
present in the following relative percentages: about 41 to about
43% by weight difluoromethane (HFC-32), 1 to 4% by weight
pentafluoroethane (HFC-125), and about 53 to about 56% by weight
trifluoroiodomethane (CF3I).
5. The refrigerant of claim 4 comprising at least about 99.5% by
weight of the following three compounds, with each compound being
present in the following relative percentages: about 41 to about
43% by weight difluoromethane (HFC-32), 1 to 4% by weight
pentafluoroethane (HFC-125), and about 53 to about 56% by weight
trifluoroiodomethane (CF3I).
6. The refrigerant of claim 1 consisting essentially of the
following three compounds, with each compound being present in the
following relative percentages: 41%.+-.1% by weight difluoromethane
(HFC-32), 3.5%.+-.0.5% by weight pentafluoroethane (HFC-125), and
55.5%.+-.0.5% by weight trifluoroiodomethane (CF3I).
7. The refrigerant of claim 6 consisting of the following three
compounds, with each compound being present in the following
relative percentages: 41%.+-.1% by weight difluoromethane (HFC-32),
3.5%.+-.0.5% by weight pentafluoroethane (HFC-125), and
55.5%.+-.0.5% by weight trifluoroiodomethane (CF3I).
8. The refrigerant of claim 6 consisting essentially of the
following three compounds, with each compound being present in the
following relative percentages: 41% by weight difluoromethane
(HFC-32), 3.5% by weight pentafluoroethane (HFC-125), and 55.5% by
weight trifluoroiodomethane (CF3I).
9. A heat transfer composition comprising a refrigerant as claimed
in claim 1.
10. The heat transfer composition of claim 9 further comprising an
alkylated naphthalene.
11. The heat transfer composition of claim 10 further comprising
BHT in an amount of from about 0.0001% by weight to about 5% by
weight of the heat transfer composition.
12. The heat transfer composition of claim 11 further comprising a
lubricant elected from polyol esters (POEs), poly vinyl ethers
(PVEs), mineral oil, and alkylbenzenes (ABs).
13. The heat transfer composition of claim 12 wherein the lubricant
is a polyol ester (POE).
14. The heat transfer composition of claim 12 wherein the lubricant
is a PVE.
15. A method of cooling in a heat transfer system comprising an
evaporator, a condenser and a compressor, the process comprising
the steps of i) condensing a refrigerant of claim 1 and ii)
evaporating the refrigerant in the vicinity of body or article to
be cooled; wherein the temperature of the refrigerant in the
evaporator is in the range of from about -40.degree. C. to about
10.degree. C.
16. The method of claim 15 wherein the temperature of the
refrigerant in the evaporator is in the range of from about
-30.degree. C. to about 5.degree. C.
17. The method of claim 15 wherein the temperature of the
refrigerant in the evaporator is in the range of from about
-40.degree. C. to about -10.degree. C.
18. The method of claim 15 wherein the system is a residential air
conditioning system and wherein the temperature of the refrigerant
in the evaporator is in the range of from about 0.degree. C. to
about 10.degree. C.
19. The method of claim 15 wherein the system is a chiller system
and wherein the temperature of the refrigerant in the evaporator is
in the range of from about 0.degree. C. to about 10.degree. C.
20. The method of claim 15 wherein the system is a low temperature
refrigeration system and wherein the temperature of the refrigerant
in the evaporator is in the range of from about -40.degree. C. to
about -12.degree. C.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the priority benefit of U.S.
Provisional 62/623,887, filed Jan. 30, 2018, which is incorporated
herein by reference in its entirety.
[0002] The present application claims the priority benefit of U.S.
Provisional 62/631,093, filed Feb. 15, 2018, which is incorporated
herein by reference in its entirety.
FIELD OF THE INVENTION
[0003] The present invention relates to compositions, methods and
systems having utility in heat transfer applications, including in
air conditioning and refrigeration applications. In particular
aspects, the invention relates to compositions useful in heat
transfer systems of the type in which the refrigerant R-410A would
have been used. The compositions of the invention are useful in
particular as a replacement of the refrigerant R-410A for heating
and cooling applications and to retrofitting heat exchange systems,
including systems designed for use with R-410A.
BACKGROUND
[0004] Mechanical refrigeration systems, and related heat transfer
devices, such as heat pumps and air conditioners 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 scheduled the phase-out of HCFCs,
including HCFC-22.
[0006] In response to the need 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-410A (a 50:50 w/w blend of difluoromethane (HFC-32)
and pentafluoroethane (HFC-125)) was adopted as the industry
replacement for HCFC-22 in air conditioning and chiller
applications as it does not contribute to ozone depletion. However,
R-410A is not a drop-in replacement for R-22. Thus, the replacement
of R-22 with R-410A required the redesign of major components
within heat exchange systems, including the replacement and
redesign of the compressor to accommodate the substantially higher
operating pressure and volumetric capacity of R-410A, when compared
with R-22.
[0007] While R-410A has a more acceptable Ozone Depleting Potential
(ODP) than R-22, the continued use of R-410A is problematic since
it has a high Global Warming Potential of 2088. There is therefore
a need in the art for the replacement of R-410A with a more
environmentally acceptable alternative.
[0008] The EU implemented the F-gas regulation to limit HFCs which
can be placed on the market in the EU from 2015 onwards, as shown
in Table 1. By 2030, only 21% of the quantity of HFCs that were
sold in 2015 will be available. Therefore, it is desired to limit
GWP below 427 as a long term solution.
TABLE-US-00001 TABLE 1 F-Gas Regulation Year Phasedown Percentage
GWP Level 2015 100% 2034* 2016-2017 93% 1891 2018-2020 63% 1281
2021-2023 45% 915 2024-2026 31% 630 2027-2029 24% 488 After 2030
21% 427 *2015 GWP level is based on UNEP 2012 Use Study with no
growth rate.
[0009] It is understood in the art that it is highly desirable for
a replacement heat transfer fluid to possess a difficult to achieve
mosaic of properties including excellent heat transfer properties
(and in particular heat transfer properties that are well matched
to the needs of the particular application), chemical stability,
low or no toxicity, non-flammability, lubricant miscibility and/or
lubricant compatibility amongst others. In addition, any
replacement for R-410A would ideally be a good match for the
operating conditions of R-410A in order to avoid modification or
redesign of the system. The development of a heat transfer fluid
meeting all of these requirements, many of which are unpredictable,
is a significant challenge.
[0010] With regard to efficiency in use, it is important to note
that a loss of thermodynamic performance or energy efficiency may
result in an increase in fossil fuel usage as a result of the
increased demand for electrical energy. The use of such refrigerant
will therefore have a negative secondary environmental impact.
[0011] Flammability is considered to be an important property for
many heat transfer applications. 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-681-2009 Standard Test Method for Concentration Limits of
Flammability of Chemicals (Vapors and Gases) at conditions
described in ASHRAE Standard 34-2016 Designation and Safety
Classification of Refrigerants and described in Appendix B1 to
ASHRAE Standard 34-2016, which is incorporated herein by reference
and referred to herein for convenience as "Non-Flammability
Test".
[0012] It is very important for maintenance of system efficiency,
and proper and reliable functioning of the compressor, that
lubricant circulating in a vapor compression heat transfer system
is returned to the compressor to perform its intended lubricating
function. Otherwise, lubricant might accumulate and become lodged
in the coils and piping of the system, including in the heat
transfer components. Furthermore, when lubricant accumulates on the
inner surfaces of the evaporator, it lowers the heat exchange
efficiency of the evaporator, and thereby reduces the efficiency of
the system.
[0013] R-410A is currently commonly used with polyol ester (POE)
lubricating oil in air conditioning applications, as R-410A is
miscible with POE at temperatures experienced during use of such
systems. However, R-410A is immiscible with POE at temperatures
typically experienced during operation of low temperature
refrigeration systems, and heat pump systems. Therefore, unless
steps are taken to mitigate against this immiscibility, POE and
R-410A cannot be used in low temperature refrigeration or heat pump
systems.
[0014] Applicants have come to appreciate that it is therefore
desirable to be able to provide compositions which are capable of
being used as a replacement for R-410A in air conditioning
applications, and in particular in residential air conditioning and
commercial air conditioning applications, which include, rooftop
air conditioning, variable refrigerant flow (VRF) air conditioning
and chiller air conditioning applications. Applicants have also
come to appreciate that the compositions, methods and systems of
the invention have advantage in, for example, heat pump and low
temperature refrigeration systems, wherein the drawback of
immiscibility with POE at temperatures experienced during operation
of these systems is eliminated.
SUMMARY
[0015] The present invention includes refrigerant compositions
which can be used as a replacement for R-410A and which exhibit in
preferred embodiments compositions the desired mosaic of properties
of excellent heat transfer properties, chemical stability, low or
no toxicity, non-flammability, lubricant miscibility and lubricant
compatibility in combination with low Global Warming Potential
(GWP) and near zero ODP.
[0016] 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:
39 to 45% by weight difluoromethane (HFC-32), 1 to 4% by weight
pentafluoroethane (HFC-125), and 51 to 57% by weight
trifluoroiodomethane (CF.sub.3I). The refrigerant according to this
paragraph is referred to herein for convenience as Refrigerant
1.
[0017] As used herein with respect to percentages based on a list
of identified compounds the term "relative percentage" means the
percentage of the identified compound based on the total weight of
the listed compounds.
[0018] As used herein with respect to weight percentages, the term
"about" with respect to an amount of an identified component means
the amount of the identified component can vary by an amount of
.+-.1% by weight.
[0019] The present invention also 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:
39 to 45% by weight difluoromethane (HFC-32), 1 to 4% by weight
pentafluoroethane (HFC-125), and 51 to 57% by weight
trifluoroiodomethane (CF.sub.3I). The refrigerant according to this
paragraph is referred to herein for convenience as Refrigerant
2.
[0020] 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:
39 to 45% by weight difluoromethane (HFC-32), 1 to 4% by weight
pentafluoroethane (HFC-125), and 51 to 57% by weight
trifluoroiodomethane (CF.sub.3I). The refrigerant according to this
paragraph is referred to herein for convenience as Refrigerant
3.
[0021] The present invention includes refrigerants consisting
essentially of the following three compounds, with each compound
being present in the following relative percentages:
39 to 45% by weight difluoromethane (HFC-32), 1 to 4% by weight
pentafluoroethane (HFC-125), and 51 to 57% by weight
trifluoroiodomethane (CF.sub.3I). The refrigerant according to this
paragraph is referred to herein for convenience as Refrigerant
4.
[0022] The present invention includes refrigerants consisting of
the following three compounds, with each compound being present in
the following relative percentages:
39 to 45% by weight difluoromethane (HFC-32), 1 to 4% by weight
pentafluoroethane (HFC-125), and 51 to 57% by weight
trifluoroiodomethane (CF.sub.3I), wherein the refrigerant is
non-flammable according to the Non-Flammability Test. The
refrigerant according to this paragraph is referred to herein for
convenience as Refrigerant 5.
[0023] 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:
about 41 to about 43% by weight difluoromethane (HFC-32), 1 to 4%
by weight pentafluoroethane (HFC-125), and about 53 to about 56% by
weight trifluoroiodomethane (CF.sub.3I). The refrigerant according
to this paragraph is referred to herein for convenience as
Refrigerant 6.
[0024] 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:
about 41 to about 43% by weight difluoromethane (HFC-32), 1 to 4%
by weight pentafluoroethane (HFC-125), and about 53 to about 56% by
weight trifluoroiodomethane (CF.sub.3I). The refrigerant according
to this paragraph is referred to herein for convenience as
Refrigerant 7.
[0025] 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:
about 41 to about 43% by weight difluoromethane (HFC-32), 1 to 4%
by weight pentafluoroethane (HFC-125), and about 53 to about 56% by
weight trifluoroiodomethane (CF.sub.3I). The refrigerant according
to this paragraph is referred to herein for convenience as
Refrigerant 8.
[0026] The present invention includes refrigerants consisting
essentially of the following three compounds, with each compound
being present in the following relative percentages:
about 41 to about 43% by weight difluoromethane (HFC-32), 1 to 4%
by weight pentafluoroethane (HFC-125), and about 53 to about 56% by
weight trifluoroiodomethane (CF.sub.3I). The refrigerant according
to this paragraph is referred to herein for convenience as
Refrigerant 9.
[0027] The present invention includes refrigerants consisting of
the following three compounds, with each compound being present in
the following relative percentages:
about 41 to about 43% by weight difluoromethane (HFC-32), 1 to 4%
by weight pentafluoroethane (HFC-125), and about 53 to about 56% by
weight trifluoroiodomethane (CF.sub.3I) wherein the refrigerant is
non-flammable according to the Non-Flammability Test defined below.
The refrigerant ccording to this paragraph is referred to herein
for convenience as Refrigerant 10.
[0028] 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:
41%.+-.1% by weight difluoromethane (HFC-32), 3.5%.+-.0.5% by
weight pentafluoroethane (HFC-125), and 55.5%.+-.0.5% by weight
trifluoroiodomethane (CF.sub.3I). The refrigerant according to this
paragraph is referred to herein for convenience as Refrigerant
11.
[0029] 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:
41%.+-.1% by weight difluoromethane (HFC-32), 3.5%.+-.0.5% by
weight pentafluoroethane (HFC-125), and 55.5%.+-.0.5% by weight
trifluoroiodomethane (CF.sub.3I). The refrigerant according to this
paragraph is referred to herein for convenience as Refrigerant
12.
[0030] 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:
41%.+-.1% by weight by weight difluoromethane (HFC-32),
3.5%.+-.0.5% by weight pentafluoroethane (HFC-125), and
55.5%.+-.0.5% by weight trifluoroiodomethane (CF.sub.3I). The
refrigerant according to this paragraph is referred to herein for
convenience as Refrigerant 13.
[0031] The present invention includes refrigerants consisting
essentially of the following three compounds, with each compound
being present in the following relative percentages:
41%.+-.1% by weight difluoromethane (HFC-32), 3.5%.+-.0.5% by
weight pentafluoroethane (HFC-125), and 55.5%.+-.0.5% by weight
trifluoroiodomethane (CF.sub.3I). The refrigerant according to this
paragraph is referred to herein for convenience as Refrigerant
14.
[0032] The present invention includes refrigerants consisting of
the following three compounds, with each compound being present in
the following relative percentages:
41%.+-.1% by weight difluoromethane (HFC-32), 3.5%.+-.0.5% by
weight pentafluoroethane (HFC-125), and 55.5%.+-.0.5% by weight
trifluoroiodomethane (CF.sub.3I), wherein the refrigerant is
non-flammable according to the Non-Flammability Test. The
refrigerant according to this paragraph is referred to herein for
convenience as Refrigerant 15.
[0033] Refrigerants comprising at least about the percentage by
weight of the three compounds indicated in the following table and
wherein each compound is present in the following relative
percentages in any one of Refrigerants 16 to 18:
TABLE-US-00002 at least % by weight HFC-32 HFC-125 CF.sub.3I of the
following (% by (% by (% by REFRIGERANT three compounds weight)
weight) weight) Refrigerant 16 97 41 .+-. 0.3 3.5 .+-. 0.3 55.5
.+-. 0.5 Refrigerant 17 98.5 41 .+-. 0.3 3.5 .+-. 0.3 55.5 .+-. 0.5
Refrigerant 18 99.5 41 .+-. 0.3 3.5 .+-. 0.3 55.5 .+-. 0.5
[0034] The present invention includes refrigerants consisting
essentially of the following three compounds, with each compound
being present in the following relative percentages:
41%.+-.0.3% by weight difluoromethane (HFC-32), 3.5%.+-.0.3% by
weight pentafluoroethane (HFC-125), and 55.5%.+-.0.3% by weight
trifluoroiodomethane (CF.sub.3I). The refrigerant according to this
paragraph is referred to herein for convenience as Refrigerant
19.
[0035] The present invention includes refrigerants consisting of
the following three compounds, with each compound being present in
the following relative percentages:
41%.+-.0.3% by weight difluoromethane (HFC-32), 3.5%.+-.0.3% by
weight pentafluoroethane (HFC-125), and 55.5%.+-.0.3% by weight
trifluoroiodomethane (CF.sub.3I), wherein the refrigerant is
non-flammable according to the Non-Flammability Test. The
refrigerant according to this paragraph is referred to herein for
convenience as Refrigerant 20.
[0036] Refrigerants comprising at least about the percentage by
weight of the three compounds indicated in the following table and
wherein each compound is present in the following relative
percentages in any one of Refrigerants 21 to 23:
TABLE-US-00003 at least % by weight of HFC-32 HFC-125 CF.sub.3I the
following three (% by (% by (% by REFRIGERANT compounds weight)
weight) weight) Refrigerant 21 97 41 3.5 55.5 Refrigerant 22 98.5
41 3.5 55.5 Refrigerant 23 99.5 41 3.5 55.5
[0037] The present invention includes refrigerants consisting
essentially of the following three compounds, with each compound
being present in the following relative percentages:
[0038] 41% by weight difluoromethane (HFC-32),
[0039] 3.5% by weight pentafluoroethane (HFC-125), and
[0040] 55.5% by weight trifluoroiodomethane (CF3I). The refrigerant
according to this paragraph is referred to herein for convenience
as Refrigerant 24.
[0041] The present invention includes refrigerants consisting of
the following three compounds, with each compound being present in
the following relative percentages:
[0042] 41% by weight difluoromethane (HFC-32),
[0043] 3.5% by weight pentafluoroethane (HFC-125), and
55.5% by weight trifluoroiodomethane (CF.sub.3I), wherein the
refrigerant is non-flammable according to the Non-Flammability
Test. The refrigerant according to this paragraph is referred to
herein for convenience as Refrigerant 25.
BRIEF DESCRIPTION OF THE FIGURE
[0044] FIG. 1 shows the LCCP of one of the refrigerants of the
present invention and certain known refrigerants.
DETAILED DESCRIPTION OF THE INVENTION
[0045] Applicants have found that the refrigerants of the present
invention, including Refrigerants 1-25 as described herein, are
capable of providing exceptionally advantageous properties and in
particular non-flammability, especially with the use of any one of
Refrigerants 1 to 25 of the present invention as a replacement for
R-410A.
[0046] A particular advantage of Refrigerants 1-25 of the present
invention in preferred compositions is that they are non-flammable,
as defined hereinafter. Thus, it is a desire in the art to provide
a refrigerant composition which can be used as a replacement for
R-410A and which has excellent heat transfer properties, low
environmental impact (including particularly low GWP and near zero
ODP) chemical stability, low or no toxicity, and/or lubricant
compatibility and which maintains non-flammability in use. This
desirable advantage can be achieved by the Refrigerants 1-25 of the
present invention.
[0047] The present invention includes heat transfer compositions
that include a refrigerant of the present invention, including
particularly any of Refrigerants 1-25, and preferably, the heat
transfer compositions of the present invention comprise a
refrigerant of the present invention 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 a refrigerant
according to the present invention, including any of Refrigerants
1-25.
[0048] 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 or
additives may include one or more of stabilizers, lubricants, dyes,
solubilizing agents, compatibilizers, antioxidants, corrosion
inhibitors, extreme pressure additives, and anti wear
additives.
Definitions
[0049] For the purposes of this invention, the term "about" in
relation to temperatures in degrees centigrade (.degree. C.) means
that the stated temperature can vary by an amount of +/-5.degree.
C. In preferred embodiments, temperature specified as being about
is preferably +/-2.degree. C., more preferably +/-1.degree. C., and
even more preferably +/-0.5.degree. C. of the identified
temperature
[0050] 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. The capacity of a refrigerant represents the amount of
cooling or heating that it provides and provides some measure of
the capability of a compressor to pump quantities of heat for a
given volumetric flow rate of refrigerant. In other words, given a
specific compressor, a refrigerant with a higher capacity will
deliver more cooling or heating power.
[0051] The phrase "coefficient of performance" (hereinafter "COP")
is a universally accepted measure of refrigerant performance,
especially useful in representing the relative thermodynamic
efficiency of a refrigerant in a specific heating or cooling cycle
involving evaporation or condensation of the refrigerant. In
refrigeration engineering, this term expresses the ratio of useful
refrigeration or cooling capacity to the energy applied by the
compressor in compressing the vapor and therefore expresses the
capability of a given compressor to pump quantities of heat for a
given volumetric flow rate of a heat transfer fluid, such as a
refrigerant. In other words, given a specific compressor, a
refrigerant with a higher COP will deliver more cooling or heating
power. One means for estimating COP of a refrigerant at specific
operating conditions is from the thermodynamic properties of the
refrigerant using standard refrigeration cycle analysis techniques
(see for example, R. C. Downing, FLUOROCARBON REFRIGERANTS
HANDBOOK, Chapter 3, Prentice-Hall, 1988 which is incorporated
herein by reference in its entirety). The phrase "discharge
temperature" refers to the temperature of the refrigerant at the
outlet of the compressor. The advantage of a low discharge
temperature is that it permits the use of existing equipment
without activation of the thermal protection aspects of the system
which are preferably designed to protect compressor components and
avoids the use of costly controls such as liquid injection to
reduce discharge temperature.
[0052] 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 given time period 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. GWP as used herein includes the 100 year given time
period.
[0053] The phrase "Life Cycle Climate Performance" (hereinafter
"LCCP") is a method by which air conditioning and refrigeration
systems can be evaluated for their global warming impact over the
course of their lifetime. LCCP includes the direct impacts of
refrigerant emissions and the indirect impacts of energy
consumption used to operate the system, energy to manufacture the
system, and transport and safely dispose of the system. The direct
impacts of refrigerant emissions are obtained from the
refrigerant's GWP value. For the indirect emissions, the measured
refrigerant properties are used to obtain the system performance
and energy consumption. LCCP is determined by using Equations 1 and
2 as follows. Equation 1 is Direct Emissions=Refrigerant Charge
(kg).times.(Annual Loss Rate.times.Lifetime+End-of-Life
Loss).times.GWP. Equation 2 is Indirect Emissions=Annual Power
Consumption.times.Lifetime.times.CO.sub.2 per kW-hr of electrical
production. The Direct Emissions as determined by Equation 1 and
the Indirect Emissions as determined by Equation 2 are added
together to provide the LCCP. TMY2 and TMY3 data produced by the
National Renewable Laboratory and available in BinMaker.RTM. Pro
Version 4 Software is used for the analysis. The GWP values
reported in the Intergovernmental Panel on Climate Change (IPCC)'s
Assessment Report 4 (AR4) 2007 are used for the calculations. LCCP
is expressed as carbon dioxide mass (kg-CO.sub.2eq) over the
lifetime of the air conditioning or refrigeration systems.
[0054] The term "mass flow rate" is the mass of refrigerant passing
through a conduit per unit of time.
[0055] The term "nonflammable" refers to compounds or compositions
which are determined to be nonflammable as determined in accordance
with ASTM standard E-681-2009 Standard Test Method for
Concentration Limits of Flammability of Chemicals (Vapors and
Gases) at conditions described in ASHRAE Standard 34-2016
Designation and Safety Classification of Refrigerants and described
in Appendix B1 to ASHRAE Standard 34-2016, which is incorporated
herein by reference in its entirety ("Non-Flammability Test").
Flammability is defined as the ability of a composition to ignite
and/or propagate a flame. Under this test, flammability is
determined by measuring flame angles.
[0056] The term "Occupational Exposure Limit (OEL)" is determined
in accordance with ASHRAE Standard 34-2016 Designation and Safety
Classification of Refrigerants.
[0057] As the term is used herein, "replacement for" with respect
to a particular heat transfer composition or refrigerant of the
present invention as a "replacement for" a particular prior
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 prior refrigerant. By way of example,
when a refrigerant or heat transfer composition of the present
invention is used in a heat transfer system that has heretofore
been designed for and/or commonly used with R410A, such as
residential air conditioning and commercial air conditioning
(including roof top systems, variable refrigerant flow (VRF)
systems and chiller systems) then the present refrigerant is a
replacement for R410A is such systems.
[0058] The phrase "thermodynamic glide" applies to zeotropic
refrigerant mixtures that have varying temperatures during phase
change processes in the evaporator or condenser at constant
pressure.
Refrigerants and Heat Transfer Compositions
[0059] Applicants have found that the refrigerants of the present
invention, including each of Refrigerants 1-25 as described herein,
are capable of providing exceptionally advantageous properties and
in particular non-flammability, especially with the use of the
refrigerant of the present invention as a replacement for R-410A
and especially in prior 410A residential air conditioning systems,
and prior R-410A commercial air conditioning systsms (including
prior R-410A roof top systems, prior R-410A variable refrigerant
flow (VRF) systems and prior R-410A chiller systems).
[0060] 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, and as mentioned above there has
been a desire in the art to provide refrigerants and heat transfer
compositions which can be used as a replacement for R-410A in
various systems, and which has excellent heat transfer properties,
low environmental impact (including particularly low GWP and near
zero ODP), excellent chemical stability, low or no toxicity, and/or
lubricant compatibility and which maintains non-flammability in
use. This desirable advantage can be achieved by refrigerants and
heat transfer compositions of the present invention.
[0061] Preferably, the heat transfer compositions comprise any
refrigerant of the present invention, including each of
Refrigerants 1-25, include refrigerant in an amount of greater than
40% by weight of the heat transfer composition.
[0062] Preferably, the heat transfer compositions any refrigerant
of the present invention, including each of Refrigerants 1-25,
include refrigerant in an amount of greater than 50% by weight of
the heat transfer composition.
[0063] Preferably, the heat transfer compositions any refrigerant
of the present invention, including each of Refrigerants 1-25,
include refrigerant in an amount of greater than 70% by weight of
the heat transfer composition.
[0064] Preferably, the heat transfer compositions any refrigerant
of the present invention, including each of Refrigerants 1-25,
include refrigerant in an amount of greater than 80% by weight of
the heat transfer composition.
[0065] Preferably, the heat transfer compositions any refrigerant
of the present invention, including each of Refrigerants 1-25,
include refrigerant in an amount of greater than 90% by weight of
the heat transfer composition.
[0066] Applicants have found that the refrigerants according to the
present invention, including each of Refrigerants 1-25, and the
heat transfer compositions containing any of such refrigrierant of
the invention, are capable of achieving a difficult to achieve
combination of properties including particularly low GWP. Thus, the
refrigerants according to the present invention and the heat
transfer compositions of the invention have a GWP of not greater
than about 427 and preferably the GWP is from about 250 to less
than 427.
[0067] In addition, the refrigerants according to the present
invention, including each of Refrigerants 1-25, and the heat
transfer compositions containing any of such refrigrierant of the
invention, have a low Ozone Depletion Potential (ODP). Thus, the
refrigerants according to the present invention and heat transfer
compositions of the invention have an Ozone Depletion Potential
(ODP) of not greater than 0.05, preferably not greater than 0.02,
more preferably about zero.
[0068] In addition, the refrigerants according to the present
invention, including each of Refrigerants 1-25, and the heat
transfer compositions containing any of such refrigrierant of the
invention, show acceptable toxicity and preferably have an
Occupational Exposure Limit (OEL) of greater than about 400.
[0069] The heat transfer compositions of the invention may include
other components for the purpose of enhancing or providing certain
functionality to the compositions, preferably without negating the
enhanced properties provided in accordance with present invention.
Such other components or additives may include stabilizers,
lubricants,
[0070] Stabilizers:
[0071] The heat transfer composition of the invention particularly
comprises a refrigerant a refrigerant as discussed herein,
including each of Refrigerants 1-25, and a stabilizer.
[0072] The stabilizer component(s) preferably are provided in the
heat transfer composition in an amount of greater than 0 to about
15% by weight of the heat transfer composition, or from about 0.5
to about 10, with the percentages being based on the total weight
of all stabilizers in the heat transfer composition divided by the
total of all components in the heat transfer composition.
[0073] The stabilizer for use in the heat transfer compostions of
the present invention includes a combination of: (i) at least one
alkylated naphthalene compound and (ii) at least one phenol-based
compound. The stabilizer according to this paragraph is sometimes
referred to herein for convenience as Stabilizer 1.
[0074] The stabilizer for use in the heat transfer compostions of
the present invention includes at least one of: (i) alkylated
naphthalene compound(s); (ii) phenol-based compound(s); and (iii)
diene-based compound(s). The stabilizer according to this paragraph
is sometimes referred to herein for convenience as Stabilizer
2.
[0075] The stabilizer for use in the heat transfer compostions of
the present invention includes a combination of: (i) at least one
alkylated naphthalene compound and (ii) at least diene-based
compound. The stabilizer according to this paragraph is sometimes
referred to herein for convenience as Stabilizer 3.
[0076] The stabilizer for use in the heat transfer compostions of
the present invention includes a combination of: (i) at least one
alkylated naphthalene compound and (ii) isobutylene compound. The
stabilizer according to this paragraph is sometimes referred to
herein for convenience as Stabilizer 4.
[0077] The stabilizer for use in the heat transfer compostions of
the present invention includes a combination of: (i) at least one
alkylated naphthalene compound and (ii) at least one phenol-based
compound; and (iii) at least one diene-based compound. The
stabilizer according to this paragraph is sometimes referred to
herein for convenience as Stabilizer 5.
[0078] The stabilizer may include also phosphorus compound(s)
and/or nitrogen compound(s) and/or epoxide(s), wherein if present
the epoxide is preferably selected from the group consisting of
aromatic epoxides, alkyl epoxides, alkyenyl epoxides.
[0079] The stabilizer for use in the heat transfer compostions of
the present invention includes a combination of: (i) at least one
alkylated naphthalene compound and (ii) at least one phenol-based
compound; and (iii) at least one epoxide. The stabilizer according
to this paragraph is sometimes referred to herein for convenience
as Stabilizer 6.
[0080] The stabilizer for use in the heat transfer compostions of
the present invention includes a combination of: (i) at least one
alkylated naphthalene compound and (ii) at least one phenol-based
compound; and (iii) at least one epoxide selected from the group
consisting of aromatic epoxides, alkyl epoxides, alkyenyl epoxides.
The stabilizer according to this paragraph is sometimes referred to
herein for convenience as Stabilizer 7.
[0081] The stabilizer may consist essentially of one or more
alkylated naphthalenes, one or more epoxides and one or more
phenol-based compounds. The stabilizer according to this paragraph
is sometimes referred to herein for convenience as Stabilizer
8.
[0082] Alkylated Naphthalenes
[0083] Applicants have surprisingly and unexpectedly found that
alkylated napthalenes are highly effective as stabilizers for the
heat transfer compositions of the present invention. As used
herein, the term "alkylated naphthalene" refers to compounds having
the following structure:
##STR00001##
[0084] where each R.sub.1-R.sub.8 is independently selected from
linear alkyl group, a branched alkyl group and hydrogen. The
particular length of the alkyl chains and the mixtures or branched
and straight chains and hydrogens can vary within the scope of the
present invention, and it will be appreciated and understood by
those skilled in the art that such variation is reflecteded the
physical properties of the alkylated naphthalene, including in
particular the viscosity of the alkylated compound, and producers
of such materials frequently define the materials by reference to
one or more of such properties as an alternative the specification
of the particular R groups.
[0085] Applicants have found unexpected, surprising and
advantageous results are associated the use of alkylated
naphthalene as a stabilizer according to the present invention
having the following properties, and alkylated naphthalene
compounds having the indicated properties are referred to for
convenience herein as Alkylated Napthalene 1-Alylated Napthalene 4
(AN1-AN4) as indicated respectively in rows 1-5 in the Table AN1
below:
TABLE-US-00004 TABLE AN1 Alkylated Alkylated Alkylated Alkylated
Alkylated Napthalene Napthalene Napthalene Napthalene Napthalene 1
2 3 4 5 Property (AN1) (AN2) (AN3) (AN4) (AN5) Viscosity 20-200
20-100 20-50 30-40 about 36 @ 40.degree. C. (ASTM D445), cSt
Viscosity 3-20 3-10 3-8 5-7 about 5.6 @ 100.degree. C. (ASTM D445),
cSt Pour Point -50 to -20 -45 to -25 -40 to -30 -35 to -30 about
-33 (ASTM D97), .degree. C.
[0086] As used herein in connection with viscosity at 40.degree. C.
measured according to ASTM D445, the term "about" means +/-4
cSt.
[0087] As used herein in connection with viscosity at 100.degree.
C. measured according to ASTM D445, the term "about" means +/-0.4
cSt.
[0088] As used herein in connection with pour point as measured
according to ASTM D97, the term "about" means +/-5.degree. C.
[0089] Applicants have also found that unexpected, surprising and
advantageous results are associated the use of alkylated
naphthalene as a stabilizer according to the present invention
having the following properties, and alkylated naphthalene
compounds having the indicated properties are referred to for
convenience herein as Alkylated Napthalene 6-Alkylated Napthalene
10 (AN6-AN10) as indicated respectively in rows 6-10 in the Table
AN2 below:
TABLE-US-00005 TABLE AN2 Alkylated Alkylated Alkylated Alkylated
Alkylated Napthalene Napthalene Napthalene Napthalene Napthalene 6
7 8 9 10 Property (AN6) (AN7) (AN8) (AN9) (AN10) Viscosity 20-200
20-100 20-50 30-40 about 36 @ 40.degree. C. (ASTM D445), cSt
Viscosity 3-20 3-10 3-8 5-7 about 5.6 @ 100.degree. C. (ASTM D445),
cSt Aniline 40-110 50-90 50-80 60-70 about 36 Point (ASTM D611),
.degree. C. Noack 1-50 5-30 5-15 10-15 about 12 Volatility CEC L40
(ASTM D6375), wt % Pour Point -50 to -20 -45 to -25 -40 to -30 -35
to -30 about -33 (ASTM D97), .degree. C. Flash 200-300 200-270
220-250 230-240 about 236 Point (ASTM D92)), .degree. C.
[0090] Examples of alkylated napthalyenes within the meaning of
Alkylated Naphthalene 1 and Alkylated Naphthalene 6 include those
sold by King Industries under the trade designations NA-LUBE
KR-007A;KR-008, KR-009;KR-015; KR-019; KR-005FG; KR-015FG; and
KR-029FG.
[0091] Examples of alkylated napthalyenes within the meaning of
Alkylated Naphthalene 2 and Alkylated Naphthalene 7 include those
sold by King Industries under the trade designations NA-LUBE
KR-007A;KR-008, KR-009; and KR-005FG.
[0092] An example of an alkylated napthylene that is within the
meaning of Alkylated Naphthalene 5 and Alkylated Naphthalene 10
includes the product sold by King Industries under the trade
designation NA-LUBE KR-008.
[0093] The alkylated naphthalene is preferably in the heat transfer
compositions of the present invention that include a refrigernant
of the present invention, including each of Refrigerants 1-25,
wherein the alkylated naphthalene is present in an amount of from
0.01% to about 10%, or from about 1.5% to about 4.5%, or from about
2.5% to about 3.5%, where amounts are in percent by weight based on
the amount of alkylated naphthalene plus refrigerant in the
system.
[0094] The alkylated naphthalene is preferably in the heat transfer
compositions of the present invention that include a lubricant and
a refrigernant of the present invention, including each of
Refrigerants 1-25, wherein the alkylated naphthalene is present in
an amount of from 0.1% to about 20%, or from about 5% to about a
15%, or from about 8% to about 12%, where amounts are in percent by
weight based on the amount of alkylated naphthalene plus lubricant
in the system.
[0095] The alkylated naphthalene is preferably in the heat transfer
compositions of the present invention that include a POE lubricant
and a refrigernant of the present invention, including each of
Refrigerants 1-25, wherein the alkylated naphthalene is present in
an amount of from 0.1% to about 20%, or from about 5% to about a
15%, or from about 8% to about 12%, where amounts are in percent by
weight based on the amount of alkylated naphthalene plus lubricant
in the system.
[0096] The alkylated naphthalene is preferably in the heat transfer
compositions of the present invention that include a POE lubricant
having a viscosity at 40.degree. C. measured according to ASTM
D445C of from about 30 cSt to about 70 cSt and a refrigernant of
the present invention, including each of Refrigerants 1-25, wherein
the alkylated naphthalene is present in an amount of from 0.1% to
about 20%, or from about 5% to about a 15%, or from about 8% to
about 12%, where amounts are in percent by weight based on the
amount of alkylated naphthalene plus lubricant in the system.
[0097] Diene-Based Compounds
[0098] 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 A1.
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.
[0099] 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.
[0100] Phenol-Based Compounds
[0101] The phenol-based compound 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.
[0102] 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.
[0103] The Phosphorus-Based Compounds
[0104] 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. 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.
[0105] 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.
[0106] The Nitrogen Compound
[0107] 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).
[0108] 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.
[0109] 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.
[0110] Epoxides and Others
[0111] Useful epoxides include aromatic epoxides, alkyl epoxides,
and alkyenyl epoxides.
[0112] Isobutylene may also be used as a stablilizer according to
the present invention.
[0113] Preferably, the heat transfer composition comprises a
refrigerant of the present invention, including each of
Refrigerants 1-25, and a stabilizer composition comprising an
alkylated naphthalene selected from Alkylated Napthalenes 1-5. For
the purposes of the uses, methods and systems described herein, the
stabilizer composition can comprise Alkylated Naphthalene 5 and
BHT. Preferably, the stabilizer composition consists essentially of
Alkylated Naphthalene 5 and BHT. Preferably, the stabilizer
composition consists of Alkylated Naphthalene 5 and BHT.
[0114] Preferably, the heat transfer composition comprises a
refrigerant of the present invention, including each of
Refrigerants 1-25, and a stabilizer composition comprising an
alkylated naphthalene selected from Alkylated Napthalenes 1-5. For
the purposes of the uses, methods and systems described herein, the
stabilizer composition can comprise Alkylated Naphthalene 5, BHT
and epoxide. Preferably, the stabilizer composition consists
essentially of Alkylated Naphthalene 5, BHT and epoxide.
Preferably, the stabilizer composition consists of Alkylated
Naphthalene 5, BHT and epoxide.
[0115] Preferably, the heat transfer composition comprises a
refrigerant of the present invention, including each of
Refrigerants 1-25, and a stabilizer composition comprising
isobutylene and a alkylated naphthalene selected from Alkylated
Napthalenes 1-5. For the purposes of the uses, methods and systems
described herein, the stabilizer composition can comprise
isobutylene, Alkylated Naphthalene 5, and BHT. Preferably, the
stabilizer composition consists essentially of isobutylene,
Alkylated Naphthalene 5, and BHT. Preferably, the stabilizer
composition consists of isobutylene, Alkylated Naphthalene 5 and
BHT.
[0116] The heat transfer composition includes a refrigerant of the
present invention, including each of Refrigerants 1-25, and a
stabilizer composition comprising Alkylated Naphthalene 4.
[0117] The heat transfer composition includes a refrigerant of the
present invention, including each of Refrigerants 1-25, and a
stabilizer composition comprising Alkylated Naphthalene 5.
[0118] The stabilizer can comprise, consist essentially of, or
consist of farnesene and Alkylated Naphthalene 5.
[0119] The stabilizer can comprise, consist essentially of, or
consist of isobutylene and Alkylated Naphthalene 5.
[0120] The heat transfer composition of the invention can
preferably comprise any one and each of Refrigerant 1-25 and any
one and each of Stabilizer 1-Stabilizer 8.
[0121] Heat transfer compositions can comprise the following
combinations of any one of Refrigerants 1 to 25 and Stabilizer 1
and are identified for convenience hearin as the indicated Heat
Transfer Composition:
TABLE-US-00006 HEAT TRANSFER REFRIGERANT STABILIZER COMPOSITION
Refrigerant 1 Stabilizer 1 1 Refrigerant 2 Stabilizer 1 2
Refrigerant 3 Stabilizer 1 3 Refrigerant 4 Stabilizer 1 4
Refrigerant 5 Stabilizer 1 5 Refrigerant 6 Stabilizer 1 6
Refrigerant 7 Stabilizer 1 7 Refrigerant 8 Stabilizer 1 8
Refrigerant 9 Stabilizer 1 9 Refrigerant 10 Stabilizer 1 10
Refrigerant 11 Stabilizer 1 11 Refrigerant 12 Stabilizer 1 12
Refrigerant 13 Stabilizer 1 13 Refrigerant 14 Stabilizer 1 14
Refrigerant 15 Stabilizer 1 15 Refrigerant 16 Stabilizer 1 16
Refrigerant 17 Stabilizer 1 17 Refrigerant 18 Stabilizer 1 18
Refrigerant 19 Stabilizer 1 19 Refrigerant 20 Stabilizer 1 20
Refrigerant 21 Stabilizer 1 21 Refrigerant 22 Stabilizer 1 22
Refrigerant 23 Stabilizer 1 23 Refrigerant 24 Stabilizer 1 24
Refrigerant 25 Stabilizer 1 25
[0122] Heat transfer compositions can comprise the following
combinations of any one of Refrigerants 1 to 25 and Stabilizer 6
and are identified for convenience hearin as the indicated Heat
Transfer Composition:
TABLE-US-00007 HEAT TRANSFER REFRIGERANT STABILIZER COMPOSITION
Refrigerant 1 Stabilizer 6 26 Refrigerant 2 Stabilizer 6 27
Refrigerant 3 Stabilizer 6 28 Refrigerant 4 Stabilizer 6 29
Refrigerant 5 Stabilizer 6 30 Refrigerant 6 Stabilizer 6 31
Refrigerant 7 Stabilizer 6 32 Refrigerant 8 Stabilizer 6 33
Refrigerant 9 Stabilizer 6 34 Refrigerant 10 Stabilizer 6 35
Refrigerant 11 Stabilizer 6 36 Refrigerant 12 Stabilizer 6 37
Refrigerant 13 Stabilizer 6 38 Refrigerant 14 Stabilizer 6 39
Refrigerant 15 Stabilizer 6 40 Refrigerant 16 Stabilizer 6 41
Refrigerant 17 Stabilizer 6 42 Refrigerant 18 Stabilizer 6 43
Refrigerant 19 Stabilizer 6 44 Refrigerant 20 Stabilizer 6 45
Refrigerant 21 Stabilizer 6 46 Refrigerant 22 Stabilizer 6 47
Refrigerant 23 Stabilizer 6 48 Refrigerant 24 Stabilizer 6 49
Refrigerant 25 Stabilizer 6 50
Lubricants:
[0123] Each of the heat transfer compositions of the invention as
described herein, including those heat transfer compositions that
include each of Refrigerants 1-25 and each of Heat Transfer
Compositions 1-50, may additionally comprise a lubricant. In
general, the heat transfer composition comprises a lubricant, in
amounts of from about 5 to 60% by weight of the heat transfer
composition, preferably about 10 to about 60% 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.
[0124] 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) for example, those that are used in refrigeration machinery,
may be used with the refrigerant compositions of the present
invention.
[0125] 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).
[0126] In general, the heat transfer composition of the present
invention, including each of Heat Transfer Compositions 1-50,
preferably comprises a POE lubricant and/or a PVE lubricant wherein
the lubricant is preferably present in amounts preferably of from
about 0.1% by weight to about 5%, or from 0.1% by weight to about
1% by weight, or from 0.1% by weight to about 0.5% by weight, based
on the weigth of the heat transfer composition.
[0127] In general, the heat transfer composition of the present
invention, including each of Heat Transfer Compositions 1-50,
preferably comprises an AB lubricant and/or a mineral oil lubricant
wherein the lubricant is preferably present in amounts preferably
of from about 0.1% by weight to about 5%, or from 0.1% by weight to
about 1% by weight, or from 0.1% by weight to about 0.5% by weight,
based on the weigth of the heat transfer composition.
[0128] The heat transfer composition preferably comprises any one
of Refrigerants 1-25 and a polyol ester (POE) lubricant.
[0129] The heat transfer compositions of the present invention,
including each of Heat Transfer Comp The heat transfer composition
preferably comprises any one of Refrigerants 1-25 and a polyol
ester (POE) lubricant.
[0130] The heat transfer compositions of the present invention,
including each of Heat Transfer Comp The heat transfer composition
preferably comprises any one of Refrigerants 1-25 and a PVE
lubricant.
[0131] The heat transfer compositions of the present invention,
including each of Heat Transfer Compositions 1-50, preferably
comprises a POE lubricant.
[0132] The heat transfer compositions of the present invention,
including each of Heat Transfer Compositions 1-50, preferably
comprises a PVE lubricant.
[0133] 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. Commercially
available esters include neopentyl glycol dipelargonate which is
available as Emery 2917 (registered trademark) and Hatcol 2370
(registered trademark). Other useful esters include phosphate
esters, di-basic acid esters and fluoro esters.
[0134] The heat transfer compositions of the invention, including
each of Heat Transfer Compositions 1-50, may consist essentially of
a refrigerant of the present invention and a lubricant as described
herein.
[0135] The heat transfer composition of the invention may consist
essentially of or consist of a refrigerant, a stabilizer
composition and a lubricant as described herein.
[0136] Polyol ester (POE) lubricant present at from 0.5% to 50% by
weight based on the weight of the heat transfer composition is
referred to for convenience as Lubricant 1.
[0137] Polyol vinyl ether (PVE) lubricant present at from 0.5% to
50% by weight based on the weight of the heat transfer composition
is referred to for convenience as Lubricant 2.
[0138] Heat transfer compositions can comprise the following
combinations of any one of Refrigerants 1 to 25 and Lubricant 1 or
Lubricant 2:
TABLE-US-00008 REFRIGERANT LUBRICANT Refrigerant 1 Lubricant 1 or
Lubricant 2 Refrigerant 2 Lubricant 1 or Lubricant 2 Refrigerant 3
Lubricant 1 or Lubricant 2 Refrigerant 4 Lubricant 1 or Lubricant 2
Refrigerant 5 Lubricant 1 or Lubricant 2 Refrigerant 6 Lubricant 1
or Lubricant 2 Refrigerant 7 Lubricant 1 or Lubricant 2 Refrigerant
8 Lubricant 1 or Lubricant 2 Refrigerant 9 Lubricant 1 or Lubricant
2 Refrigerant 10 Lubricant 1 or Lubricant 2 Refrigerant 11
Lubricant 1 or Lubricant 2 Refrigerant 12 Lubricant 1 or Lubricant
2 Refrigerant 13 Lubricant 1 or Lubricant 2 Refrigerant 14
Lubricant 1 or Lubricant 2 Refrigerant 15 Lubricant 1 or Lubricant
2 Refrigerant 16 Lubricant 1 or Lubricant 2 Refrigerant 17
Lubricant 1 or Lubricant 2 Refrigerant 18 Lubricant 1 or Lubricant
2 Refrigerant 19 Lubricant 1 or Lubricant 2 Refrigerant 20
Lubricant 1 or Lubricant 2 Refrigerant 21 Lubricant 1 or Lubricant
2 Refrigerant 22 Lubricant 1 or Lubricant 2 Refrigerant 23
Lubricant 1 or Lubricant 2 Refrigerant 24 Lubricant 1 or Lubricant
2 Refrigerant 25 Lubricant 1 or Lubricant 2
Heat transfer compositions can comprise the following combinations
of any one of Refrigerants 1 to 25, Stabilizer 1, and Lubricant 1
or Lubricant 2:
TABLE-US-00009 REFRIGERANT STABILIZER LUBRICANT Refrigerant 1
Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant 2 Stabilizer 1
Lubricant 1 or Lubricant 2 Refrigerant 3 Stabilizer 1 Lubricant 1
or Lubricant 2 Refrigerant 4 Stabilizer 1 Lubricant 1 or Lubricant
2 Refrigerant 5 Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant
6 Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant 7 Stabilizer
1 Lubricant 1 or Lubricant 2 Refrigerant 8 Stabilizer 1 Lubricant 1
or Lubricant 2 Refrigerant 9 Stabilizer 1 Lubricant 1 or Lubricant
2 Refrigerant 10 Stabilizer 1 Lubricant 1 or Lubricant 2
Refrigerant 11 Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant
12 Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant 13
Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant 14 Stabilizer 1
Lubricant 1 or Lubricant 2 Refrigerant 15 Stabilizer 1 Lubricant 1
or Lubricant 2 Refrigerant 16 Stabilizer 1 Lubricant 1 or Lubricant
2 Refrigerant 17 Stabilizer 1 Lubricant 1 or Lubricant 2
Refrigerant 18 Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant
19 Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant 20
Stabilizer 1 Lubricant 1 or Lubricant 2 Refrigerant 21 Stabilizer 1
Lubricant 1 or Lubricant 2 Refrigerant 22 Stabilizer 1 Lubricant 1
or Lubricant 2 Refrigerant 23 Stabilizer 1 Lubricant 1 or Lubricant
2 Refrigerant 24 Stabilizer 1 Lubricant 1 or Lubricant 2
Refrigerant 25 Stabilizer 1 Lubricant 1 or Lubricant 2
Heat transfer compositions can comprise the following combinations
of any one of Refrigerants 1 to 25, Stabilizer 6, and Lubricant 1
or Lubricant 2:
TABLE-US-00010 REFRIGERANT STABILIZER LUBRICANT Refrigerant 1
Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant 2 Stabilizer 6
Lubricant 1 or Lubricant 2 Refrigerant 3 Stabilizer 6 Lubricant 1
or Lubricant 2 Refrigerant 4 Stabilizer 6 Lubricant 1 or Lubricant
2 Refrigerant 5 Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant
6 Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant 7 Stabilizer
6 Lubricant 1 or Lubricant 2 Refrigerant 8 Stabilizer 6 Lubricant 1
or Lubricant 2 Refrigerant 9 Stabilizer 6 Lubricant 1 or Lubricant
2 Refrigerant 10 Stabilizer 6 Lubricant 1 or Lubricant 2
Refrigerant 11 Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant
12 Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant 13
Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant 14 Stabilizer 6
Lubricant 1 or Lubricant 2 Refrigerant 15 Stabilizer 6 Lubricant 1
or Lubricant 2 Refrigerant 16 Stabilizer 6 Lubricant 1 or Lubricant
2 Refrigerant 17 Stabilizer 6 Lubricant 1 or Lubricant 2
Refrigerant 18 Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant
19 Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant 20
Stabilizer 6 Lubricant 1 or Lubricant 2 Refrigerant 21 Stabilizer 6
Lubricant 1 or Lubricant 2 Refrigerant 22 Stabilizer 6 Lubricant 1
or Lubricant 2 Refrigerant 23 Stabilizer 6 Lubricant 1 or Lubricant
2 Refrigerant 24 Stabilizer 6 Lubricant 1 or Lubricant 2
Refrigerant 25 Stabilizer 6 Lubricant 1 or Lubricant 2
[0139] 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.
[0140] 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.
[0141] 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 composition of the invention, the heat
transfer composition may comprise or consist essentially of any
refrigerant of the present invention, including any of Refrigerants
1-25 described herein.
Methods, Uses and Systems
[0142] The refrigerants according to the present invention and heat
transfer compositions disclosed herein are provided for use in heat
transfer applications, including air conditioning (including
particularly residential air conditioners), refrigeration, heat
pumps and chillers (including portable water chillers and central
water chillers).
[0143] The heat transfer compositions disclosed herein are provided
for use in heat transfer applications, including air conditioning
applications, with highly preferred air conditioning applications
including residential air conditioning, commercial air conditioning
applications (such as roof top applications, VRF applications and
chillers.
[0144] The present invention also includes methods for providing
heat transfer including methods of air conditioning, with highly
preferred air conditioning methods including providing residential
air conditioning, providing commercial air conditioning (such as
methods of providing roof top air conditioning, methods of
providing VRF air conditioning and methods of providing air
conditioning using chillers.
[0145] The present invention also includes heat transfer systems,
including air conditioning systems, with highly preferred air
conditioning systems including residential air conditioning,
commercial air conditioning systems (such as roof top air
conditioning systems, VRF air conditioning systems and air
conditioning chiller systems).
[0146] The invention also provides uses of the heat transfer
compositions, methods using the heat transfer compositions and
systems containing the heat transfer compostions in connection with
refrigeration, heat pumps and chillers (including portable water
chillers and central water chillers).
[0147] 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, methods, systems or applications of the composition of the
invention, the heat transfer composition may comprise or consist
essentially of any the heat transfer compositions that comprise any
of Refrigerants 1-25 and any of of Heat Transfer Compositions
1-50.
[0148] 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 as an air conditioning system (including
particularly residential air conditioning systems), a refrigeration
system, a heat pump and a chiller system (including a portable
water chiller and a central water chiller). 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.
[0149] 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
Refrigerants 1-25 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.
[0150] 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
Refrigerants 1-25 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.
[0151] 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
Refrigerants 1-25 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.
[0152] For heat transfer systems of the present invention that
include a compressor and lubricant for the compressor in the
system, the system can comprises a loading of refrigerant and
lubricant such that the lubricant loading in the system is from
about 5% to 60% by weight, or from about 10% to about 60% by
weight, or from about 20% to about 50% by weight, or from about 20%
to about 40% by weight, or from about 20% to about 30% by weight,
or from about 30% to about 50% by weight, or from about 30% to
about 40% by weight. As used herein, the term "lubricant loading"
refers to the total weight of lubricant contained in the system as
a percentage of total of lubricant and refrigerant contained in the
system. Such systems may also include a lubricant loading of from
about 5% to about 10% by weight, or about 8% by weight of the heat
transfer composition.
[0153] The heat transfer systems according to the present invention
can comprise a compressor, an evaporator, a condenser and an
expansion device, in fluid communication with each other, a Heat
Transfer Compositions 1-50 and a sequestration material in the
system, wherein said sequestration material preferably comprises:
[0154] i. copper or a copper alloy, or [0155] ii. activated
alumina, or [0156] iii. a zeolite molecular sieve comprising
copper, silver, lead or a combination thereof, or [0157] iv. an
anion exchange resin, or [0158] v. a moisture-removing material,
preferably a moisture-removing molecular sieve, or [0159] vi. a
combination of two or more of the above.
[0160] The present invention also includes methods for transferring
heat of the type comprising evaporating refrigerant liquid to
produce a refrigerant vapor, compressing in a compressor at least a
portion of the refrigerant vapor and condensing refrigerant vapor
in a plurality of repeating cycles, said method comprising:
[0161] (a) providing a heat transfer composition according to the
present invention, including each of Heat Transfer Compositions
1-50;
[0162] (b) optionally but preferably providing lubricant for said
compressor; and
[0163] (b) exposing at least a portion of said refrigerant and/or
at least a portion of said lubricant to a seqestration
material.
Uses, Equipment and Systems
[0164] In preferred embodiments, residential air conditioning
systems and methods have refrigerant evaporating temperatures in
the range of from about 0.degree. C. to about 10.degree. C. and the
condensing temperature is in the range of about 40.degree. C. to
about 70.degree. C.
[0165] In preferred embodiments, residential air conditioning
systems and methods used in a heating mode have refrigerant
evaporating temperatures in the range of from about -20.degree. C.
to about 3.degree. C. and the condensing temperature is in the
range of about 35.degree. C. to about 50.degree. C.
[0166] In preferred embodiments, commercial air conditioning
systems and methods have refrigerant evaporating temperatures in
the range of from about 0.degree. C. to about 10.degree. C. and the
condensing temperature is in the range of about 40.degree. C. to
about 70.degree. C.
[0167] In preferred embodiments, hydronic system systems and
methods have refrigerant evaporating temperatures in the range of
from about -20.degree. C. to about 3.degree. C. and the condensing
temperature is in the range of about 50.degree. C. to about
90.degree. C.
[0168] In preferred embodiments, medium temperature systems and
methods have refrigerant evaporating temperatures in the range of
from about -12.degree. C. to about 0.degree. C. and the condensing
temperature is in the range of about 40.degree. C. to about
70.degree. C.
[0169] In preferred embodiments, low temperature systems and
methods have refrigerant evaporating temperatures in the range of
from about -40.degree. C. to about -12.degree. C. and the
condensing temperature is in the range of about 40.degree. C. to
about 70.degree. C.
[0170] In preferred embodiments, rooftop air conditioning systems
and methods have refrigerant evaporating temperatures in the range
of from about 0.degree. C. to about 10.degree. C. and the
condensing temperature is in the range of about 40.degree. C. to
about 70.degree. C.
[0171] In preferred embodiments, VRF systems and methods have
refrigerant evaporating temperatures in the range of from about
0.degree. C. to about 10.degree. C. and the condensing temperature
is in the range of about 40.degree. C. to about 70.degree. C.
[0172] The present invention includes any of the heat transfer
compositions of the invention, including Heat Transfer Compostions
1-50, in a chiller or in residential air conditioning as indicated
in the following table:
TABLE-US-00011 Heat Transfer Comp SYSTEM Heat Transfer Chiller or
residential Composition 1 air conditioning Heat Transfer Chiller or
residential Composition 2 air conditioning Heat Transfer Chiller or
residential Composition 3 air conditioning Heat Transfer Chiller or
residential Composition 4 air conditioning Heat Transfer Chiller or
residential Composition 5 air conditioning Heat Transfer Chiller or
residential Composition 6 air conditioning Heat Transfer Chiller or
residential Composition 7 air conditioning Heat Transfer Chiller or
residential Composition 8 air conditioning Heat Transfer Chiller or
residential Composition 9 air conditioning Heat Transfer Chiller or
residential Composition 10 air conditioning Heat Transfer Chiller
or residential Composition 11 air conditioning Heat Transfer
Chiller or residential Composition 12 air conditioning Heat
Transfer Chiller or residential Composition 13 air conditioning
Heat Transfer Chiller or residential Composition 14 air
conditioning Heat Transfer Chiller or residential Composition 15
air conditioning Heat Transfer Chiller or residential Composition
16 air conditioning Heat Transfer Chiller or residential
Composition 17 air conditioning Heat Transfer Chiller or
residential Composition 18 air conditioning Heat Transfer Chiller
or residential Composition 19 air conditioning Heat Transfer
Chiller or residential Composition 20 air conditioning Heat
Transfer Chiller or residential Composition 21 air conditioning
Heat Transfer Chiller or residential Composition 22 air
conditioning Heat Transfer Chiller or residential Composition 23
air conditioning Heat Transfer Chiller or residential Composition
24 air conditioning Heat Transfer Chiller or residential
Composition 25 air conditioning Heat Transfer Chiller or
residential Composition 26 air conditioning Heat Transfer Chiller
or residential Composition 27 air conditioning Heat Transfer
Chiller or residential Composition 28 air conditioning Heat
Transfer Chiller or residential Composition 29 air conditioning
Heat Transfer Chiller or residential Composition 30 air
conditioning Heat Transfer Chiller or residential Composition 31
air conditioning Heat Transfer Chiller or residential Composition
32 air conditioning Heat Transfer Chiller or residential
Composition 33 air conditioning Heat Transfer Chiller or
residential Composition 34 air conditioning Heat Transfer Chiller
or residential Composition 35 air conditioning Heat Transfer
Chiller or residential Composition 36 air conditioning Heat
Transfer Chiller or residential Composition 37 air conditioning
Heat Transfer Chiller or residential Composition 38 air
conditioning Heat Transfer Chiller or residential Composition 39
air conditioning Heat Transfer Chiller or residential Composition
40 air conditioning Heat Transfer Chiller or residential
Composition 41 air conditioning Heat Transfer Chiller or
residential Composition 42 air conditioning Heat Transfer Chiller
or residential Composition 43 air conditioning Heat Transfer
Chiller or residential Composition 44 air conditioning Heat
Transfer Chiller or residential Composition 45 air conditioning
Heat Transfer Chiller or residential Composition 46 air
conditioning Heat Transfer Chiller or residential Composition 47
air conditioning Heat Transfer Chiller or residential Composition
48 air conditioning Heat Transfer Chiller or residential
Composition 49 air conditioning Heat Transfer Chiller or
residential Composition 50 air conditioning
[0173] The systems of the present invention thus preferably include
a sequestration material in contact with at least a portion of a
refrigerant and/or at least a portion of a the lubricant according
to the present invention wherein the temperature of said
sequestration material and/or the temperature of said refrigerant
and/or the temperature of said lubricant when in said contact are
at a temperature that is preferably at least about 10C wherein the
sequestration material preferably comprises a combination of:
[0174] an anion exchange resin,
[0175] activated alumina,
[0176] a zeolite molecular sieve comprising silver, and
[0177] a moisture-removing material, preferably a moisture-removing
molecular sieve.
[0178] As used in this application, the term "in contact with at
least a portion" is intended in its broad sense to include each of
said sequestration materials and any combination of sequestration
materials being in contact with the same or separate portions of
the refrigerant and/or the lubricant 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.
[0179] The refrigerants and heat transfer composition of the
invention can be used in heating and cooling applications. In
general, all such systems and methods of cooling and/or heating are
useful with and within the scope of the present invention, however
several exemplary and preferred systems and associated methods,
including such systems and methods which use a sequestration
material in accordance with the present invention, are illustrated
and described in co-pending U.S. application Ser. No. 16/135,962,
which is incorporated herein by reference.
[0180] In a particular feature of the invention, the heat transfer
composition can be used in a method of cooling comprising
condensing the refrigerant of the present invention and
subsequently evaporating the refrigerant in the vicinity of an
article or body to be cooled.
[0181] 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 as
described herein, including in particular any one of Refrigerants
1-25; and ii) evaporating the refrigerant in the vicinity of body
or article to be cooled at a temperature of from about -40.degree.
C. to about +10.degree. C.
[0182] 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.
[0183] 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 refrigerant as
described herein, including in particular any one of Refrigerants
1-25, in the vicinity of a body or article to be heated and ii)
evaporating the refrigerant at a temperature of from about
-30.degree. C. to about 5.degree. C.
[0184] The refrigerants according to the present invention,
including in particular any of Refrigerants 1-25 and heat transfer
composition of the present invention are provided for use in air
conditioning applications including both mobile and stationary air
conditioning applications. As used here, the term mobile air
conditioning systems means mobile, non-passenger car air
conditioning systems, such as air conditioning systems in trucks,
buses, and trains. Thus, any of the refrigerants according to the
present invention, including in particular any of Refrigerants 1-25
and any of the heat transfer compositions described herein can be
used in any one of:
[0185] an air conditioning application including mobile air
conditioning, particularly air conditioning systems in buses and
trains;
[0186] a mobile heat pump, particularly an electric vehicle heat
pump;
[0187] a chiller, particularly a positive displacement chiller,
more particularly an air cooled or water cooled direct expansion
chiller, which is either modular or conventionally singularly
packaged;
[0188] a residential air conditioning system, particularly a ducted
split or a ductless split air conditioning system;
[0189] a residential heat pump;
[0190] a residential air to water heat pump/hydronic system;
[0191] an industrial air conditioning system;
[0192] a commercial air conditioning system, particularly a
packaged rooftop unit and a variable refrigerant flow (VRF)
system;
[0193] a commercial air source, water source or ground source heat
pump system.
[0194] The refrigerants according to the present invention,
including in particular any of Refrigerants 1-25 and the heat
transfer compositions of the invention are provided for use in a
refrigeration system. The term "Refrigeration Systems" refers to
any system or apparatus or any part or portion of such a system or
apparatus which employs a refrigerant to provide cooling. Thus, any
refrigerants according to the present invention, including in
particular any of Refrigerants 1-25 and any of the heat transfer
compositions described herein can be used in any one of the
Refrigeration Systems:
[0195] a low temperature refrigeration system,
[0196] a medium temperature refrigeration system,
[0197] a commercial refrigerator,
[0198] a commercial freezer,
[0199] an ice machine,
[0200] a vending machine,
[0201] a transport refrigeration system,
[0202] a domestic freezer,
[0203] a domestic refrigerator,
[0204] an industrial freezer,
[0205] an industrial refrigerator and
[0206] a chiller.
[0207] Each of the heat transfer compositions described herein,
including heat transfer compositions containing any one of
Refrigerants 1-25, is particularly provided for use in a
residential air-conditioning system (with an evaporator temperature
in the range of about 0 to about 10.degree. C., particularly about
7.degree. C. for cooling and/or in the range of about -20 to about
3.degree. C., particularly about 0.5.degree. C. for heating).
Alternatively, or additionally, each of the heat transfer
compositions described herein, including each heat transfer
composition that includes any on of Refrigerants 1-25 and each of
Heat Transfer Compositions 1-50 is particularly provided for use in
a residential air conditioning system with a reciprocating, rotary
(rolling-piston or rotary vane) or scroll compressor.
[0208] Each of the heat transfer compositions described including
each heat transfer composition that includes any on of Refrigerants
1-25 and each of Heat Transfer Compositions 1-50, is particularly
provided for use 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 positive displacement compressor, more particular an
air cooled chiller with a reciprocating scroll compressor.
[0209] Each of the heat transfer compositions described herein,
including each heat transfer composition that includes any on of
Refrigerants 1-25 and each of Heat Transfer Compositions 1-50, is
particularly provided for use in a residential air to water heat
pump hydronic system (with an evaporator temperature in the range
of about -20.degree. C. to about 3.degree. C., particularly about
0.5.degree. C. or with an evaporator temperature in the range of
about -30.degree. C. to about 5.degree. C., particularly about
0.5.degree. C.).
[0210] Each of the heat transfer compositions including each heat
transfer composition that includes any on of Refrigerants 1-25 and
each of Heat Transfer Compositions 1-50, 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 -8.degree. C.).
[0211] Each of the heat transfer compositions including each heat
transfer composition that includes any on of Refrigerants 1-25 and
each of Heat Transfer Compositions 1-50, is particularly provided
for use in a low temperature refrigeration system (with an
evaporator temperature in the range of about -40.degree. C. to
about -12.degree. C., particularly about from about -40.degree. C.
to about -23.degree. C. or preferably about -32.degree. C.).
[0212] The heat transfer composition of the invention, including
each heat transfer composition that includes any on of Refrigerants
1-25 and each of Heat Transfer Compositions 1-50 is provided for
use in a residential air conditioning system, wherein the
residential air-conditioning system is used to supply cool air
(said air having a temperature of for example, about 10.degree. C.
to about 17.degree. C., particularly about 12.degree. C.) to
buildings for example, in the summer. Typical system types are
split, mini-split, and window, ducted split, ductless split,
window, and portable air-conditioning system. The system usually
has an air-to-refrigerant evaporator (indoor coil), a compressor,
an air-to-refrigerant condenser (outdoor coil), and an expansion
valve. The evaporator and condenser are usually a round tube plate
fin, a finned tube 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
capillary tube, thermal or electronic expansion valve. The
refrigerant evaporating temperature is preferably in the range of
0.degree. C. to 10.degree. C. The condensing temperature is
preferably in the range of 40.degree. C. to 70.degree. C.
[0213] The heat transfer composition of the invention, including
heat transfer compositions containing any one of Refrigerants 1-25,
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 can be 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.degree. C. to about 3.degree. C. or about -30.degree. C.
to about 5.degree. C. The condensing temperature is preferably in
the range of about 35.degree. C. to about 50.degree. C.
[0214] The heat transfer composition of the invention, including
heat transfer compositions containing any one of Refrigerants 1-25,
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. 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.degree. C. to
about 10.degree. C. The condensing temperature is preferably in the
range of about 40.degree. C. to about 70.degree. C.
[0215] The heat transfer composition of the invention, including
heat transfer compositions containing any one of Refrigerants 1-25,
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.degree. C. 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.
[0216] The heat transfer composition of the invention, including
heat transfer compositions containing any one of Refrigerants 1-25,
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. The refrigerant evaporating temperature is
preferably in the range of about -12.degree. C. to about 0.degree.
C. The condensing temperature is preferably in the range of about
40.degree. C. to about 70.degree. C., or about 20.degree. C. to
about 70.degree. C.
[0217] The heat transfer composition of the invention, including
heat transfer compositions containing any one of Refrigerants 1-25,
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 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. The refrigerant evaporating temperature
is preferably in the range of about -40.degree. C. to about
-12.degree. C. The condensing temperature is preferably in the
range of about 40.degree. C. to about 70.degree. C., or about
20.degree. C. to about 70.degree. C.
[0218] Heat transfer compositions comprise any one of Refrigerants
1 to 25 in a chiller or a commercial air conditioning system as
follows:
TABLE-US-00012 REFRIGERANT SYSTEM Refrigerant 1 chiller or
commercial air conditioning Refrigerant 2 chiller or commercial air
conditioning Refrigerant 3 chiller or commercial air conditioning
Refrigerant 4 chiller or commercial air conditioning Refrigerant 5
chiller or commercial air conditioning Refrigerant 6 chiller or
commercial air conditioning Refrigerant 7 chiller or commercial air
conditioning Refrigerant 8 chiller or commercial air conditioning
Refrigerant 9 chiller or commercial air conditioning Refrigerant 10
chiller or commercial air conditioning Refrigerant 11 chiller or
commercial air conditioning Refrigerant 12 chiller or commercial
air conditioning Refrigerant 13 chiller or commercial air
conditioning Refrigerant 14 chiller or commercial air conditioning
Refrigerant 15 chiller or commercial air conditioning Refrigerant
16 chiller or commercial air conditioning Refrigerant 17 chiller or
commercial air conditioning Refrigerant 18 chiller or commercial
air conditioning Refrigerant 19 chiller or commercial air
conditioning Refrigerant 20 chiller or commercial air conditioning
Refrigerant 21 chiller or commercial air conditioning Refrigerant
22 chiller or commercial air conditioning Refrigerant 23 chiller or
commercial air conditioning Refrigerant 24 chiller or commercial
air conditioning Refrigerant 25 chiller or commercial air
conditioning
Heat transfer compositions comprise any one of Refrigerants 1 to 25
and Stabilizer 1 and POE lubricant in a chiller or a commercial air
conditioning system as follows as follows:
TABLE-US-00013 REFRIGERANT STABILIZER Lubricant SYSTEM Refrigerant
1 Stabilizer 1 POE chiller or commercial air conditioning
Refrigerant 2 Stabilizer 1 POE chiller or commercial air
conditioning Refrigerant 3 Stabilizer 1 POE chiller or commercial
air conditioning Refrigerant 4 Stabilizer 1 POE chiller or
commercial air conditioning Refrigerant 5 Stabilizer 1 POE chiller
or commercial air conditioning Refrigerant 6 Stabilizer 1 POE
chiller or commercial air conditioning Refrigerant 7 Stabilizer 1
POE chiller or commercial air conditioning Refrigerant 8 Stabilizer
1 POE chiller or commercial air conditioning Refrigerant 9
Stabilizer 1 POE chiller or commercial air conditioning Refrigerant
10 Stabilizer 1 POE chiller or commercial air conditioning
Refrigerant 11 Stabilizer 1 POE chiller or commercial air
conditioning Refrigerant 12 Stabilizer 1 POE chiller or commercial
air conditioning Refrigerant 13 Stabilizer 1 POE chiller or
commercial air conditioning Refrigerant 14 Stabilizer 1 POE chiller
or commercial air conditioning Refrigerant 15 Stabilizer 1 POE
chiller or commercial air conditioning Refrigerant 16 Stabilizer 1
POE chiller or commercial air conditioning Refrigerant 17
Stabilizer 1 POE chiller or commercial air conditioning Refrigerant
18 Stabilizer 1 POE chiller or commercial air conditioning
Refrigerant 19 Stabilizer 1 POE chiller or commercial air
conditioning Refrigerant 20 Stabilizer 1 POE chiller or commercial
air conditioning Refrigerant 21 Stabilizer 1 POE chiller or
commercial air conditioning Refrigerant 22 Stabilizer 1 POE chiller
or commercial air conditioning Refrigerant 23 Stabilizer 1 POE
chiller or commercial air conditioning Refrigerant 24 Stabilizer 1
POE chiller or commercial air conditioning Refrigerant 25
Stabilizer 1 POE chiller or commercial air conditioning
[0219] For the purposes of this invention, the heat transfer
composition as set out above is provided for use in a chiller with
an evaporating temperature in the range of about 0.degree. C. to
about 10.degree. C. and a condensing temperature in the range of
about 40.degree. C. to about 70.degree. C. The chiller is provided
for use in air conditioning or refrigeration, preferably for
refrigeration. The chiller is preferably a positive displacement
chiller, more particularly an air cooled or water cooled direct
expansion chiller, which is either modular or conventionally
singularly packaged.
[0220] Heat transfer compositions comprise any one of Refrigerants
1 to 25 in an Air Conditioning System where residential air
conditioning is hereinafter abbreviated as Residential AC.
[0221] Heat transfer compositions comprise any one of Refrigerants
1 to 25 in a residential airconditioning system or a heat pump as
indicated in the following table:
TABLE-US-00014 REFRIGERANT SYSTEM Refrigerant 1 Residential AC or
heat pump Refrigerant 2 Residential AC or heat pump Refrigerant 3
Residential AC or heat pump Refrigerant 4 Residential AC or heat
pump Refrigerant 5 Residential AC or heat pump Refrigerant 6
Residential AC or heat pump Refrigerant 7 Residential AC or heat
pump Refrigerant 8 Residential AC or heat pump Refrigerant 9
Residential AC or heat pump Refrigerant 10 Residential AC or heat
pump Refrigerant 11 Residential AC or heat pump Refrigerant 12
Residential AC or heat pump Refrigerant 13 Residential AC or heat
pump Refrigerant 14 Residential AC or heat pump Refrigerant 15
Residential AC or heat pump Refrigerant 16 Residential AC or heat
pump Refrigerant 17 Residential AC or heat pump Refrigerant 18
Residential AC or heat pump Refrigerant 19 Residential AC or heat
pump Refrigerant 20 Residential AC or heat pump Refrigerant 21
Residential AC or heat pump Refrigerant 22 Residential AC or heat
pump Refrigerant 23 Residential AC or heat pump Refrigerant 24
Residential AC or heat pump Refrigerant 25 Residential AC or heat
pump
Heat transfer compositions comprise any one of Refrigerants 1 to 25
and Stabilizer 1 in Residential AC or in a heat pump as
follows:
TABLE-US-00015 REFRIGERANT STABILIZER SYSTEM Refrigerant 1
Stabilizer 1 Residential AC or heat pump Refrigerant 2 Stabilizer 1
Residential AC or heat pump Refrigerant 3 Stabilizer 1 Residential
AC or heat pump Refrigerant 4 Stabilizer 1 Residential AC or heat
pump Refrigerant 5 Stabilizer 1 Residential AC or heat pump
Refrigerant 6 Stabilizer 1 Residential AC or heat pump Refrigerant
7 Stabilizer 1 Residential AC or heat pump Refrigerant 8 Stabilizer
1 Residential AC or heat pump Refrigerant 9 Stabilizer 1
Residential AC or heat pump Refrigerant 10 Stabilizer 1 Residential
AC or heat pump Refrigerant 11 Stabilizer 1 Residential AC or heat
pump Refrigerant 12 Stabilizer 1 Residential AC or heat pump
Refrigerant 13 Stabilizer 1 Residential AC or heat pump Refrigerant
14 Stabilizer 1 Residential AC or heat pump Refrigerant 15
Stabilizer 1 Residential AC or heat pump Refrigerant 16 Stabilizer
1 Residential AC or heat pump Refrigerant 17 Stabilizer 1
Residential AC or heat pump Refrigerant 18 Stabilizer 1 Residential
AC or heat pump Refrigerant 19 Stabilizer 1 Residential AC or heat
pump Refrigerant 20 Stabilizer 1 Residential AC or heat pump
Refrigerant 21 Stabilizer 1 Residential AC or heat pump Refrigerant
22 Stabilizer 1 Residential AC or heat pump Refrigerant 23
Stabilizer 1 Residential AC or heat pump Refrigerant 24 Stabilizer
1 Residential AC or heat pump Refrigerant 25 Stabilizer 1
Residential AC or heat pump
Heat transfer compositions comprise any one of Refrigerants 1 to 25
and Stabilizer 1 and a POE lubricant in Residential AC or a heat
pump as follows:
TABLE-US-00016 AIR CONDITION- REFRIGERANT STABILIZER LUBRICANT ING
SYSTEM Refrigerant 1 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 2 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 3 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 4 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 5 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 6 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 7 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 8 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 9 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 10 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 11 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 12 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 13 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 14 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 15 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 16 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 17 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 18 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 19 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 20 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 21 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 22 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 23 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 24 Stabilizer 2 POE Residential AC or heat pump
Refrigerant 25 Stabilizer 2 POE Residential AC or heat pump
Heat transfer compositions comprise any one of Refrigerants 1 to 25
in a low temperature refrigeration system or a medium temperature
system as follows:
TABLE-US-00017 REFRIGERANT REFRIGERATION SYSTEM Refrigerant 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 2 low temperature refrigeration or medium temperature
refrigeration Refrigerant 3 low temperature refrigeration or medium
temperature refrigeration Refrigerant 4 low temperature
refrigeration or medium temperature refrigeration Refrigerant 5 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 6 low temperature refrigeration or medium temperature
refrigeration Refrigerant 7 low temperature refrigeration or medium
temperature refrigeration Refrigerant 8 low temperature
refrigeration or medium temperature refrigeration Refrigerant 9 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 10 low temperature refrigeration or medium temperature
refrigeration Refrigerant 11 low temperature refrigeration or
medium temperature refrigeration Refrigerant 12 low temperature
refrigeration or medium temperature refrigeration Refrigerant 13
low temperature refrigeration or medium temperature refrigeration
Refrigerant 14 low temperature refrigeration or medium temperature
refrigeration Refrigerant 15 low temperature refrigeration or
medium temperature refrigeration Refrigerant 16 low temperature
refrigeration or medium temperature refrigeration Refrigerant 17
low temperature refrigeration or medium temperature refrigeration
Refrigerant 18 low temperature refrigeration or medium temperature
refrigeration Refrigerant 19 low temperature refrigeration or
medium temperature refrigeration Refrigerant 20 low temperature
refrigeration or medium temperature refrigeration Refrigerant 21
low temperature refrigeration or medium temperature refrigeration
Refrigerant 22 low temperature refrigeration or medium temperature
refrigeration Refrigerant 23 low temperature refrigeration or
medium temperature refrigeration Refrigerant 24 low temperature
refrigeration or medium temperature refrigeration Refrigerant 25
low temperature refrigeration or medium temperature
refrigeration
Heat transfer compositions comprise any one of Refrigerants 1 to 25
and Stabilizer 1 in a low temperature refrigeration system or a
medium temperature refrigeration system as follows:
TABLE-US-00018 REFRIGERANT STABILIZER REFRIGERATION SYSTEM
Refrigerant 1 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 2 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 3 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 4 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 5 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 6 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 7 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 8 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 9 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 10 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 11 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 12 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 13 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 14 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 15 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 16 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 17 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 18 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 19 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 20 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 21 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 22 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 23 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration Refrigerant 24 Stabilizer 1 low
temperature refrigeration or medium temperature refrigeration
Refrigerant 25 Stabilizer 1 low temperature refrigeration or medium
temperature refrigeration
Heat transfer compositions comprise any one of Refrigerants 1 to
25, Stabilizer 1, and POE lubricant in a low temperature
refrigeration or medium temperature refrigeration system as
follows:
TABLE-US-00019 REFRIGERANT STABILIZER LUBRICANT REFRIGERATION
SYSTEM Refrigerant 1 Stabilizer 1 POE low temperature refrigeration
or medium temperature refrigeration Refrigerant 2 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 3 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 4 Stabilizer 1 POE low
temperature refrigeration or medium temperature refrigeration
Refrigerant 5 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 6 Stabilizer 1 POE low
temperature refrigeration or medium temperature refrigeration
Refrigerant 7 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 8 Stabilizer 1 POE low
temperature refrigeration or medium temperature refrigeration
Refrigerant 9 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 10 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 11 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 12 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 13 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 14 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 15 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 16 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 17 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 18 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 19 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 20 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 21 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 22 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 23 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration Refrigerant 24 Stabilizer 1 POE
low temperature refrigeration or medium temperature refrigeration
Refrigerant 25 Stabilizer 1 POE low temperature refrigeration or
medium temperature refrigeration
[0222] The present invention thus includes methods of retrofitting
existing heat transfer system designed for and containing R-410A
refrigerant, without requiring substantial engineering modification
of the existing system, particularly without modification of the
condenser, the evaporator and/or the expansion valve.
[0223] The refrigerants according to the present invention,
including in particular any of Refrigerants 1-25 and the heat
transfer compositions disclosed herein are provided as a low GWP
replacement for the refrigerant R-410A. The heat transfer
compositions and the refrigerants of the present invention
(including each of Refrigerants 1-25 and all heat transfer
compositions containing Refrigerants 1-25) therefore can be used as
a replacement refrigerant/heat transfer composition.
[0224] The present invention thus also includes methods of using a
refrigerant or heat transfer composition of the present invention
as a replacement for R-410A, and in particular as a replacement for
R-410A in residential air conditioning, without requiring
substantial engineering modification of the existing system,
particularly without modification of the condenser, the evaporator
and/or the expansion valve.
[0225] The present invention thus also includes methods of using a
refrigerant or heat transfer composition of the present invention
as a replacement for R-410A, and in particular as a replacement for
R-410A in a chiller system.
[0226] The present invention thus also includes methods of using a
refrigerant or heat transfer composition of the present invention
as a replacement for R-410A, and in particular as a replacement for
R-410A in a residential air conditioning system.
[0227] There is therefore provided a method of retrofitting an
existing heat transfer system that contains R-410A refrigerant,
said method comprising replacing at least a portion of the existing
R-410A refrigerant with a heat transfer composition of the present
invention, including each of Heat Transfer Compositions 1-50. The
step of replacing preferably comprises removing at least a
substantial portion of, and preferably substantially all of, the
existing refrigerant (which can be but is not limited to R-410A)
and introducing a heat transfer composition, including each of Heat
Transfer Compositions 1-50, without any substantial modification of
the system to accommodate the refrigerant of the present invention.
Preferably, the method comprises removing at least about 5%, about
10%, about 25%, about 50%, or about 75% by weight of the R-410A
from the system and replacing it with the heat transfer
compositions of the invention.
[0228] Alternatively, the heat transfer composition can be used in
a method of retrofitting an existing heat transfer system designed
to contain or containing R410A refrigerant, wherein the system is
modified for use with a Heat Transfer Composition of the present
invention.
[0229] Alternatively, the heat transfer composition can be used as
a replacement in a heat transfer system which is designed to
contain or is suitable for use with R-410A refrigerant.
It will be appreciated that the invention encompasses the use of
the heat transfer compositions of the invention as a low Global
Warming replacement for R-410A or is used in a method of
retrofitting an existing heat transfer system or is used in a heat
transfer system which is suitable for use with R-410A refrigerant
as described herein.
[0230] There is therefore provided a method of replacing the R-410A
refrigerant, which would have been used in a particular heat
transfer system, with a refrigerant or a heat transfer composition
of the present invention, including in particular any of
Refrigerants 1-25.
[0231] It will be appreciated that when the heat transfer
composition is used as a low GWP replacement for R-410A, the heat
transfer composition may consist essentially of the refrigerant of
the invention. Alternatively, the invention encompasses the use of
the refrigerant of the invention as a low GWP replacement for
R-410A.
[0232] It will be appreciated by the skilled person that when the
heat transfer composition is provided for use in a method of
retrofitting an existing heat transfer system as described above,
the method preferably comprises removing at least a portion of the
existing R-410A 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-410A from the system and
replacing it with the heat transfer compositions of the
invention.
[0233] The heat transfer compositions of the invention, including
each of the compositions that comprise Refrigerants 1-25 and each
of Heat Transfer Compositions 1-50, may be employed as a
replacement in systems which are used or are suitable for use with
R-410A refrigerant, such as existing or new heat transfer
systems.
[0234] The compositions of the present invention exhibit many of
the desirable characteristics of R-410A but have a GWP that is
substantially lower than that of R-410A while at the same time
having operating characteristics i.e. capacity and/or efficiency
(COP) that are substantially similar to or substantially match, and
preferably are as high as or higher than R-410A. This allows the
claimed compositions to replace R-410A in existing heat transfer
systems without requiring any significant system modification for
example of the condenser, the evaporator and/or the expansion
valve. The composition can therefore be used as a direct
replacement for R-410A in heat transfer systems.
[0235] The heat transfer compositions of the invention, including
each of the compostions that comprise Refrigerants 1-25 and each of
Heat Transfer Compositions 1-50, therefore preferably exhibits
operating characteristics compared with R-410A wherein the
efficiency (COP) of the composition is greater than 90% of the
efficiency of R-410A in the heat transfer system.
[0236] The heat transfer composition of the invention, including
each of the compostions that comprise Refrigerants 1-25 and each of
Heat Transfer Compositions 1-50, therefore preferably exhibits
operating characteristics compared with R-410A wherein the capacity
is from 95 to 105% of the capacity of R-410A in the heat transfer
system.
[0237] It will be appreciated that R-410A is an azeotrope-like
composition. Thus, in order for the claimed compositions to be a
good match for the operating characteristics of R-410A, the any of
the refrigerants included in the heat transfer compositions of the
invention, including each of Heat Transfer Compositions 1-50,
desirably show a low level of glide. Thus, the refrigerants
included in the heat transfer compositions of the invention,
including each of Heat Transfer Compositions 1-50, according to
invention as described herein may provide an evaporator glide of
less than 2.degree. C., preferably less than 1.5.degree. C.
[0238] The heat transfer composition of the invention, including
each of the compostions that comprise Refrigerants 1-25 and each of
Heat Transfer Compositions 1-50, therefore preferably exhibits
operating characteristics compared with R-410A wherein the
efficiency (COP) of the composition is from 100 to 102% of the
efficiency of R-410A in the heat transfer system and wherein the
capacity is from 92 to 102% of the capacity of R-410A in the heat
transfer system.
[0239] Preferably, the heat transfer composition of the invention,
including each of the compostions that comprise Refrigerants 1-25
and each of Heat Transfer Compositions 1-50, preferably exhibit
operating characteristics compared with R-410A wherein: [0240] the
efficiency (COP) of the composition is from 100 to 105% of the
efficiency of R-410A; and/or [0241] the capacity is from 92 to 102%
of the capacity of R-410A. in heat transfer systems, in which the
compositions of the invention are to replace the R-410A
refrigerant.
[0242] In order to enhance the reliability of the heat transfer
system, it is preferred that the heat transfer composition of the
invention, including each of the compostions that comprise
Refrigerants 1-25 and each of Heat Transfer Compositions 1-50,
further exhibit the following characteristics compared with R-410A:
[0243] the discharge temperature is not greater than 10.degree. C.
higher than that of R-410A; and/or [0244] the compressor pressure
ratio is from 98 to 102% of the compressor pressure ratio of R-410A
in heat transfer systems, in which the composition of the invention
is used to replace the R-410A refrigerant.
[0245] The existing heat transfer compositions used to replace
R-410A are preferably used in air conditioning heat transfer
systems including both mobile and stationary air conditioning
systems. As used here, the term mobile air conditioning systems
means mobile, non-passenger car air conditioning systems, such as
air conditioning systems in trucks, buses and trains. Thus, each of
the heat transfer compositions as described herein, including each
of Heat Transfer Compositions 1-50, can be used to replace R-410A
in any one of: [0246] an air conditioning system including a mobile
air conditioning system, particularly air conditioning systems in
trucks, buses and trains, [0247] a mobile heat pump, particularly
an electric vehicle heat pump; [0248] a chiller, particularly a
positive displacement chiller, more particularly an air cooled or
water cooled direct expansion chiller, which is either modular or
conventionally singularly packaged, [0249] a residential air
conditioning system, particularly a ducted split or a ductless
split air conditioning system, [0250] a residential heat pump,
[0251] a residential air to water heat pump/hydronic system, [0252]
an industrial air conditioning system and [0253] a commercial air
conditioning system particularly a packaged rooftop unit and a
variable refrigerant flow (VRF) system; [0254] a commercial air
source, water source or ground source heat pump system
[0255] The heat transfer composition of the invention is
alternatively provided to replace R410A in refrigeration systems.
Thus, each of the heat transfer compositions as described herein,
including the compostions that comprise Refrigerants 1-25 and each
of Heat Transfer Compositions 1-50-can be used to replace R10A in
in any one of: [0256] a low temperature refrigeration system,
[0257] a medium temperature refrigeration system, [0258] a
commercial refrigerator, [0259] a commercial freezer, [0260] an ice
machine, [0261] a vending machine, [0262] a transport refrigeration
system, [0263] a domestic freezer, [0264] a domestic refrigerator,
[0265] an industrial freezer, [0266] an industrial refrigerator and
[0267] a chiller.
[0268] In order to enhance the reliability of the heat transfer
system, it is preferred that the composition of the invention
further exhibits the following characteristic compared with R-410A:
the compressor pressure ratio is from 95 to 105% of the compressor
pressure ratio of R-410A in heat transfer systems, in which the
composition of the invention is used to replace the R-410A
refrigerant.
[0269] Each of the heat transfer compositions described herein
including each of the compostions that comprise Refrigerants 1-25
and each of Heat Transfer Compositions 1-50, is particularly
provided to replace R-410A 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 positive displacement compressor, more particular an
air cooled chiller with a reciprocating scroll compressor.
[0270] Each of the heat transfer compositions described herein
including each of the compostions that comprise Refrigerants 1-25
and each of Heat Transfer Compositions 1-50, is particularly
provided to replace R-410A in a residential air to water heat pump
hydronic system (with an evaporator temperature in the range of
about -20 to about 3.degree. C. or about -30 to about 5.degree. C.,
particularly about 0.5.degree. C.).
[0271] Each of the heat transfer compositions described herein
including each of Refrigerants 1-25, is particularly provided to
replace R-410A in a medium temperature refrigeration system (with
an evaporator temperature in the range of about -12 to about
0.degree. C., particularly about -8.degree. C.)
[0272] Each of the heat transfer compositions described herein
including each of Refrigerants 1-25, is particularly provided to
replace R-410A in a low temperature refrigeration system (with an
evaporator temperature in the range of about -40 to about
-12.degree. C., particularly from about -40.degree. C. to about
-23.degree. C. or preferably about -32.degree. C.).
[0273] There is therefore provided a method of retrofitting an
existing heat transfer system designed to contain or containing
R-410A refrigerant or which is suitable for use with R-410A
refrigerant, said method comprising replacing at least a portion of
the existing R-410A refrigerant with a heat transfer composition of
the present invention, including each of Heat Transfer Compositions
1-50.
[0274] There is therefore provided a method of retrofitting an
existing heat transfer system designed to contain or containing
R-410A refrigerant or which is suitable for use with R-410A
refrigerant, said method comprising replacing at least a portion of
the existing R-410A refrigerant with a heat transfer composition
according to the present invention, including each of Heat Transfer
Compositions 1-50.
[0275] The invention further provides a heat transfer system
comprising a compressor, a condenser and an evaporator in fluid
communication, and a heat transfer composition in said system, said
heat transfer composition comprising any one of Refrigerants
1-25.
[0276] Particularly, the heat transfer system is a residential
air-conditioning system (with an evaporator temperature in the
range of about 0 to about 10.degree. C., particularly about
7.degree. C. for cooling and/or in the range of about -20 to about
3.degree. C. or about -30 to about 5.degree. C., particularly about
0.5.degree. C. for heating) and comprises any one of Refrigerants 1
to 25.
[0277] Particularly, the heat transfer system is 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 positive displacement
compressor, more particular an air cooled chiller with a
reciprocating or scroll compressor and comprises any one of
Refrigerants 1 to 25.
[0278] Particularly, the heat transfer system is a residential air
to water heat pump hydronic system (with an evaporator temperature
in the range of about -20 to about 3.degree. C. or about -30 to
about 5.degree. C., particularly about 0.5.degree. C.) and
comprises any one of Refrigerants 1 to 25.
[0279] The heat transfer system can be a refrigeration system, such
as a low temperature refrigeration system, a medium temperature
refrigeration system, a commercial refrigerator, a commercial
freezer, an ice machine, a vending machine, a transport
refrigeration system, a domestic freezer, a domestic refrigerator,
an industrial freezer, an industrial refrigerator and a chiller and
comprises any one of Refrigerants 1 to 25.
EXAMPLES
[0280] The refrigerant compositions identified in Table 2 below as
Refrigerants A1, A2 and A3 are refrigerants within the scope of the
present invention as described herein. Each of the refrigerants was
subjected to thermodynamic analysis to determine its ability to
match the operating characteristics of R-4104A 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 HFC-32 and R125. 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.
Vapor/liquid equilibrium behavior data for the binary pair HFC-32
and HFC-125 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) were used for 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-00020 TABLE 2 Refrigerants evaluated for Performance
Examples HFC-32 HFC-125 CF.sub.3 I GWP Refrigerant (wt %) (wt %)
(wt %) (100 years) Flammability A1 40% 3.5% 56.5% 393 Non Flammable
A2 41% 3.5% 55.5% 399 Non-Flammable A3 44% 3.5% 52.5% 420
Non-Flammable
Refrigerant A1 comprises 100% by weight of the three compounds
listed in Table 2 in their relative percentages and is
non-flammable. Refrigerant A2 comprises 100% by weight of the three
compounds listed in Table 2 in their relative percentages and is
non-flammable. Refrigerant A3 comprises 100% by weight of the three
compounds listed in Table 2 in their relative percentages and is
non-flammable.
Example 1--Environment/GWP
[0281] LCCP was determined for R410, other known refrigerants, and
a refrigerant of the present invention and reported in Table 3. In
Table 3, the refrigerant having a GWP of 399 is a refrigerant of
the present invention. Known refrigerants were used for the GWPs of
1, 150, 250, 750, and 2088. The known refrigerant having a GWP of
2088 is R410A.
[0282] Table 3 shows LCCP results in four regions: USA, EU, China
and Brazil. As GWP decreases, the direct emissions are lower.
However, system efficiency is lower so it consumes more energy and
increases the indirect emissions. Therefore, the total emissions
(kg-CO.sub.2eq) first decreases and then increases as GWP
decreases. The different energy structures in these regions show
values of the optimum GWP that has the lowest total emissions. The
number of AC units is also different among these regions: USA and
EU have more AC units than China and Brazil. FIG. 1 and the last
column of Table 3 shows the total emissions considering all four
regions and number of AC units. As GWP decreases, the total
emissions decrease until reaching the lowest value for a
refrigerant of the present invention having a GWP of 400. In the
range of GWP between 250 and 750, the total emissions are very
similar. However, total emission significantly increases when GWP
is lower than 150 because the indirect emissions increase
significantly. So the present invention demonstrates a surprising
and unexpected result.
TABLE-US-00021 TABLE 3 LCCP (kg-CO.sub.2eq) GWP (100 years) USA EU
China Brazil Overall 2088 22932 9967 44395 5648 19676 (R410A) 750
21572 8659 42907 4376 18326 400 21523 8453 43112 4121 18238
(refrigerant of present invention) 250 21700 8404 43662 3997 18358
150 22541 8622 45552 4001 19044 1 22552 8534 45727 3880 19030
Example 2--Residential Air-Conditioning System (Cooling)
[0283] Residential air-conditioning system is used to supply cool
air (12.degree. C.) to buildings in the summer. Refrigerants A1,
A2, and A3 were used in a simulation of a residential
air-conditioning system as described above and the performance
results are in Table 4 below. Residential air condition systems
include split air conditioning systems, mini-split air conditioning
systems, and window air-conditioning system, and the testing
described herein is representative of the results from such
systems. The experimental system includes an air-to-refrigerant
evaporator (indoor coil), a compressor, an air-to-refrigerant
condenser (outdoor coil), and an expansion valve. The operating
conditions for the test are: condensing temperature=46.degree. C.;
condenser sub-cooling=5.5.degree. C.; evaporating
temperature=7.degree. C.; evaporator superheat=5.5.degree. C.;
isentropic Efficiency=70%; volumetric efficiency=100%; and
temperature rise in Suction Line=5.5.degree. C.
TABLE-US-00022 TABLE 4 Performance in Residential Air-Conditioning
System (Cooling) Capacity Efficiency Pressure ratio Evaporator (%
of (% of (% of glide Refrigerant R410A) R410A) R410A) (.degree. C.)
R410A 100% 100% 100% 0.1 A1 92% 102% 100% 4.1 A2 93% 102% 100% 3.8
A3 95% 102% 100% 3.0
[0284] Table 4 shows the thermodynamic performance of a residential
air-conditioning system compared to R410A system. Refrigerants A1
to A3 show 92% or higher capacity and higher efficiency than R410A.
It indicates the system performance is similar to R410A.
Refrigerants A1 to A3 show 100% pressure ratio compared to R410A.
It indicates the compressor efficiencies are similar to R410A, and
no changes on R410A compressor are needed.
Example 3--Residential Heat Pump System (Heating)
[0285] Residential heat pump system is used to supply warm air
(21.1.degree. C.) to buildings in the winter. Refrigerants A1, A2,
and A3 were used in a simulation of a residential heat pump system
as described above and the performance results are in Table 5
below. The experimental system includes a residential
air-conditioning system, however, when the system is in in the heat
pump mode the refrigerant flow is reversed and the indoor coil
becomes a condenser and the outdoor coil becomes an evaporator.
Residential heat pump systems include split air conditioning
systems, mini-split air conditioning systems, and window
air-conditioning system, and the testing described herein is
representative of the results from such systems. The operating
conditions are: condensing temperature=41.degree. C.; condenser
sub-cooling=5.5.degree. C.; evaporating temperature=0.5.degree. C.;
evaporator superheat=5.5.degree. C.; isentropic efficiency=70%;
volumetric efficiency=100%; and temperature rise in suction
line=5.5.degree. C.
TABLE-US-00023 TABLE 5 Performance in Residential Heat pump System
(Heating) Capacity Efficiency Pressure ratio Evaporator (% of (% of
(% of glide Refrigerant R410A) R410A) R410A) (.degree. C.) R410A
100% 100% 100% 0.1 A1 89% 101% 100% 4.2 A2 90% 101% 100% 3.9 A3 92%
101% 100% 3.0
[0286] Table 5 shows the thermodynamic performance of a residential
heat pump system compared to R410A system. The capacity of
Refrigerant A1 can be recovered with a larger compressor.
Refrigerants A2 and A3 show 90% or higher capacity and higher
efficiency than R410A. It indicates the system performance is
similar to R410A. Refrigerants A1 to A3 show 100% pressure ratio
compared to R410A. It indicates the compressor efficiencies are
similar to R410A, and no changes on R410A compressor are
needed.
Example 4--Commercial Air-Conditioning System--Chiller
[0287] Commercial air-conditioning system (chiller) is used to
supply chilled water (7.degree. C.) to large buildings such as
office and hospital, etc., and depending on the specific
application, the chiller system may be running all year long. The
testing described herein is representative of the results from such
systems. Refrigerants A1, A2, and A3 were used in a simulation of a
commercial air-conditioning system as described above and the
performance results are in Table 6 below. The operating conditions
are: condensing temperature=46.degree. C.; condenser
sub-cooling=5.5.degree. C.; evaporating temperature=4.5.degree. C.;
evaporator superheat=5.5.degree. C.; isentropic efficiency=70%;
volumetric efficiency=100%; and temperature rise in suction
line=2.degree. C.
TABLE-US-00024 TABLE 6 Performance in Commercial Air-Conditioning
System--Air-Cooled Chiller Capacity Efficiency Pressure ratio
Evaporator (% of (% of (% of glide Refrigerant R410A) R410A) R410A)
(.degree. C.) R410A 100% 100% 100% 0.1 A1 92% 102% 100% 4.1 A2 93%
102% 100% 3.8 A3 95% 102% 100% 3.0
[0288] Table 6 shows the thermodynamic performance of a commercial
air-conditioning system compared to R410A system. Refrigerants A1
to A3 show 92% or higher capacity and higher efficiency than R410A.
It indicates the system performance is similar to R410A.
Refrigerants A1 to A3 show 100% pressure ratio compared to R410A.
It indicates the compressor efficiencies are similar to R410A, and
no changes on R410A compressor are needed.
Example 5--Residential Air-to-Water Heat Pump Hydronic System
[0289] A residential air-to-water heat pump hydronic system is used
to supply hot water (50.degree. C.) to buildings for floor heating
or similar applications in the winter is tested. Refrigerants A1,
A2, and A3 were used in a simulation of a residential heat
pumpsystem as described above and the performance results described
herein are representative of the results from such systems and are
reported in Table 7 below. The operating conditions are: condensing
temperature=60.degree. C. (corresponding indoor leaving water
temperature=about 50.degree. C.); condenser sub-cooling=5.5.degree.
C.; evaporating temperature=0.5.degree. C. (corresponding outdoor
ambient temperature=about 8.3.degree. C.); evaporator
superheat=5.5.degree. C.; isentropic efficiency=70%; volumetric
Efficiency=100%; and temperature rise in suction line=2.degree.
C.
TABLE-US-00025 TABLE 7 Performance in Residential Air-to-Water Heat
Pump Hydronic System Capacity Efficiency Pressure ratio Evaporator
(% of (% of (% of glide Refrigerant R410A) R410A) R410A) (.degree.
C.) R410A 100% 100% 100% 0.1 A1 93% 103% 100% 3.9 A2 94% 103% 100%
3.6 A3 96% 103% 99% 2.8
[0290] Table 7 shows the thermodynamic performance of a residential
heat pump system compared to R410A system. Refrigerants A1 to A3
show 93% or higher capacity and higher efficiency than R410A. It
indicates the system performance is similar to R410A. Refrigerants
A1 to A2 show 100% pressure ratio compared to R410A. It indicates
the compressor efficiencies are similar to R410A, and no changes on
R410A compressor are needed. Further, Refrigerant A2 shows a 100%
pressure ratio compared to R-410A, which indicates that the
compressor efficiencies are sufficiently similar to R-410A that no
changes to the compressor used with R-410A are needed.
Example 6--Medium Temperature Refrigeration System
[0291] A medium temperature refrigeration system is used to chill
the food or beverage such as in refrigerator and bottle cooler is
tested. The experimental system includes an air-to-refrigerant
evaporator to chill the food or beverage, a compressor, an
air-to-refrigerant condenser to exchange heat with the ambient air,
and an expansion valve. Refrigerants A1, A2, and A3 were used in a
simulation of a medium temperature refrigeration system as
described above and the performance results are in Table 8 below.
The operating conditions: condensing temperature=40.6.degree. C.;
condenser sub-cooling=0.degree. C.; (system with receiver);
evaporating temperature=-6.7.degree. C.; evaporator
superheat=5.5.degree. C.; isentropic efficiency=70%; volumetric
efficiency=100%; and degree of superheat in the suction
line=19.5.degree. C.
TABLE-US-00026 TABLE 8 Performance in Medium Temperature
Refrigeration System Evaporator Capacity Efficiency Pressure ratio
glide Refrigerant (% of R410A) (% of R410A) (% of R410A) (.degree.
C.) R410A 100% 100% 100% 0.1 A1 94% 104% 100% 4.1 A2 94% 104% 100%
3.7 A3 97% 104% 99% 2.9
[0292] Table 8 shows the thermodynamic performance of a medium
temperature refrigeration system compared to R410A system.
Refrigerants A1 to A3 show 94% or higher capacity and higher
efficiency than R410A. It indicates the system performance is
similar to R410A. Refrigerants A1 to A2 show 100% pressure ratio
compared to R410A. It indicates the compressor efficiencies are
similar to R410A, and no changes on R410A compressor are needed.
Further, Refrigerant A2 shows a 100% pressure ratio compared to
R-410A, which indicates that the compressor efficiencies are
sufficiently similar to R-410A that no changes to the compressor
used with R-410A are needed.
Example 7--Low Temperature Refrigeration System
[0293] Low temperature refrigeration system is used to freeze the
food such as in ice cream machine and freezer. The experimental
system includes an air-to-refrigerant evaporator to cool or freeze
the food or beverage, a compressor, an air-to-refrigerant condenser
to exchange heat with the ambient air, and a expansion valve. The
testing described herein is representative of the results from such
systems. Refrigerants A1, A2, and A3 were used in a simulation of a
low temperature refrigeration system as described above and the
performance results are in Table 9 below. The operating conditions:
condensing temperature=40.6.degree. C.; condenser
sub-cooling=0.degree. C. (system with receiver); evaporating
temperature=-28.9.degree. C.[; degree of superheat at evaporator
outlet=5.5.degree. C.; isentropic efficiency=65%; volumetric
efficiency=100%; and degree of superheat in the suction
line=44.4.degree. C.
TABLE-US-00027 TABLE 9 Performance in Low Temperature Refrigeration
System Evaporator Capacity Efficiency Pressure ratio glide
Refrigerant (% of R410A) (% of R410A) (% of R410A) (.degree. C.)
R410A 100% 100% 100% 0.1 A1 96% 105% 100% 4.0 A2 97% 105% 99% 3.7
A3 99% 105% 99% 2.7
[0294] Table 9 shows the thermodynamic performance of a low
temperature refrigeration system compared to R410A system.
Refrigerants A1 to A3 show 96% or higher capacity and higher
efficiency than R410A. It indicates the system performance is
similar to R410A. Refrigerants A1 to A3 show 99% or 100% pressure
ratio compared to R410A. It indicates the compressor efficiencies
are similar to R410A, and no changes on R410A compressor are
needed.
Example 8. Commercial Air-Conditioning System--Packaged
Rooftops
[0295] A packaged rooftop commercial air conditioning system
configured to supply cooled or heated air to buildings is tested.
The experimental system includes a packaged rooftop
air-conditioning/heat pump systems and has an air-to-refrigerant
evaporator (indoor coil), a compressor, an air-to-refrigerant
condenser (outdoor coil), and an expansion valve. The testing
described herein is representative of the results from such
systems. The operating conditions for the test are: [0296] 1.
Condensing temperature=about 46.degree. C. (corresponding outdoor
ambient temperature=about 35.degree. C.) [0297] 2. Condenser
sub-cooling=about 5.5.degree. C. [0298] 3. Evaporating
temperature=about 7.degree. C. (corresponding indoor ambient
temperature=26.7.degree. C.) [0299] 4. Evaporator Superheat=about
5.5.degree. C. [0300] 5. Isentropic Efficiency=70% [0301] 6.
Volumetric Efficiency=100% [0302] 7. Temperature Rise in Suction
Line=5.5.degree. C. The performance results from the testing are
reported in Table 8 below:
TABLE-US-00028 [0302] TABLE 8 Performance in Commercial
Air-Conditioning System - Packaged Rooftops Evaporator Pressure
glide Refrigerant Capacity Efficiency ratio (.degree. C.) R-410A
100% 100% 100% 0.1 A1 89% 101% 100% 4.2 A2 90% 101% 100% 3.9 A3 92%
101% 100% 3.0
[0303] Table 8 shows the thermodynamic performance of a rooftop
commercial air conditioning system operating with Refrigerant A1,
A2 and A3 of the present invention compared to R-410A Refrigerants
A2 and A3 show 90% or higher capacity and higher efficiency than
R410A. It indicates the system performance is similar to R410A. The
capacity of Refrigerant A2 and A3 can be recovered with a larger
compressor. Refrigerants A1 to A3 show 100% pressure ratio compared
to R410A. It indicates the compressor efficiencies are similar to
R410A, and no significant changes in R410A compressor design are
needed.
Example 9--Commercial Air-Conditioning System--Variable Refrigerant
Flow Systems
[0304] A commercial air-conditioning system with vaiable
refrigerant flow is configured to supply cooled or heated air to
buildings is tested. The system includes multiple (4 or more)
air-to-refrigerant evaporators (indoor coils), a compressor, an
air-to-refrigerant condenser (outdoor coil), and an expansion
valve. The conditions described herein is representative of the
operating conditions from such systems. The operating conditions
are listed below: [0305] 1. Condensing temperature=about 46.degree.
C., Corresponding outdoor ambient temperature=35.degree. C. [0306]
2. Condenser sub-cooling=about 5.5.degree. C. [0307] 3. Evaporating
temperature=about 7.degree. C. (corresponding indoor ambient
temperature=26.7.degree. C.) [0308] 4. Evaporator Superheat=about
5.5.degree. C. [0309] 5. Isentropic Efficiency=70% [0310] 6.
Volumetric Efficiency=100% [0311] 7. Temperature Rise in Suction
Line=5.5.degree. C.
TABLE-US-00029 [0311] TABLE 9 Performance in Commercial
Air-Conditioning System - Variable Refrigerant Flow Systems
Evaporator Capacity Efficiency Pressure ratio glide Refrigerant (%
of R410A) (% of R410A) (% of R410A) (.degree. C.) R410A 100% 100%
100% 0.1 A1 89% 101% 100% 4.2 A2 90% 101% 100% 3.9 A3 92% 101% 100%
3.0
[0312] Table 9 shows the thermodynamic performance of a rooftop
commercial air conditioning system operating with Refrigerant A1,
A2 and A3 of the present invention compared to R-410A Refrigerants
A2 and A3 show 90% or higher capacity and higher efficiency than
R410A. It indicates the system performance is similar to R410A. The
capacity of Refrigerant A2 and A3 can be recovered with a larger
compressor. Refrigerants A1 to A3 show 100% pressure ratio compared
to R410A. It indicates the compressor efficiencies are similar to
R410A, and no significant changes in R410A compressor design are
needed.
Example 10--Stabilizers for Heat Transfer Compositions Comprising
Refrigerant and Lubricant
[0313] Heat transfer compositions of the present invention are
tested in accordance with ASHRAE Standard 97-"Sealed Glass Tube
Method to Test the Chemical Stability of Materials for Use within
Refrigerant Systems" to simulate long-term stability of the heat
transfer compositions by accelerated aging. After testing, the
level of halides is considered to reflect the stability of the
refrigerant under conditions of use in the heat transfer
composition and total acid number (TAN) is considered to reflect
the stability of the lubricant stability under conditions of use in
the heat transfer composition.
[0314] The following experiment is carried out to show the effect
of the addition of stabilizers according to the present invention
on a refrigerant/lubricant composition. Sealed tubes are prepared
containing 50% by weight of the indicated refrigerant and 50% by
weight of the indicated lubricant, each of which has been degassed.
Each tube contains a coupon of steel, copper, aluminum and bronze.
The stability is tested by placing the sealed tube in an oven
maintained at about 175.degree. C. for 14 days. In each case the
lubricants tested are an ISO 32 POE having a viscosity at
40.degree. C. of about 32 cSt (Lubricant A) an ISO 68 POE having a
viscosity at 40.degree. C. of about 68 cSt (Lubricant B), with each
lubricant having a moisture content of less than 300 ppm. The
following refrigerants described in Table 10A are tested:
TABLE-US-00030 TABLE 10A Refrigerant Moisture, ppm A1 less than 30
A2 less than 30 A3 less than 30
[0315] The test is run for each lubricant and refrigerant pair in
the absence of any stabilizer, and the results are as follows:
[0316] Lubricant Visual--opaque or black [0317] Metals Visual--dull
[0318] Solids Present--Yes [0319] Halides>100 ppm [0320]
TAN>10 mgKOH/g
[0321] The following stabilizers described in Table 10B, with the
weight percent in the table being the weight percent of the
indicated stabilizer in the stabilizer package, are tested in an
amount based on the total weight of the stabilizer plus refrigerant
of from about 1.5% to less than about 10%.
TABLE-US-00031 TABLE 10B Alkylated Napthalene 5 BHT Franasene
Isobutylene Stabilizer (wt %) (wt %) wt %) (wt %) A 100 0 0 0 B 0
100 0 0 C 0 0 100 0 D 0 0 0 100 E 33.3 33.3 33.3 0 F 33.3 33.3 0
33.3
The results of the testing with these stabilizers and lubricant A1,
A2 and A3 are reported below in Table 10C
TABLE-US-00032 TABLE 100 Refrig- TEST RESULTS erant Sta- Halides,
Tan, No. bilizer Visual Metals Solids ppm mbKOH/g A1 A Clear, Shiny
No <300 <3 colorless ppm A1 B Clear, Shiny No <300 <3
colorless ppm A1 C Clear, Shiny No <300 <3 colorless ppm A1 D
Clear, Shiny No <300 <3 colorless ppm A1 E Clear, Shiny No
<300 <3 colorless ppm A1 F Clear, Shiny No <300 <3
colorless ppm A2 A Clear, Shiny No <300 <3 colorless ppm A2 B
Clear, Shiny No <300 <3 colorless ppm A2 C Clear, Shiny No
<300 <3 colorless ppm A2 D Clear, Shiny No <300 <3
colorless ppm A2 E Clear, Shiny No <300 <3 colorless ppm A2 F
Clear, Shiny No <300 <3 colorless ppm A3 A Clear, Shiny No
<300 <3 colorless ppm A3 B Clear, Shiny No <300 <3
colorless ppm A3 C Clear, Shiny No <300 <3 colorless ppm A3 D
Clear, Shiny No <300 <3 colorless ppm A3 E Clear, Shiny No
<300 <3 colorless ppm A3 F Clear, Shiny No <300 <3
colorless ppm
This testing shows that the lubricant in each of these tests was
clear and colorless, the metals were shiny (unchanged), and there
were no solids present, the halide and TAN levels were in
acceptable limits, all of which indicates that the stabilizers were
effective.
Example 11--Miscibility with POE Oil
[0322] Miscibility of ISO POE-32 oil (having a viscosity at about
32 cSt at a temperature of 40.degree. C.) is tested for different
weight ratios of lubricant and refrigerant and different
temperatures for R-410A refrigerant and for Refrigerant A2 as
specified in Table 1 for Example 1 above. The results of this
testing are reported in Table 11 below:
TABLE-US-00033 TABLE 11 Liquid Refrigerant Mass Percentage in
Refrigerant the Refrigerant R-410A Miscibility Temperature A of the
and Lubricant Range present Mixture, % Lower Limit, .degree. C.
Upper Limit, .degree. C. invention 60 about -26 NA Fully miscible
70 about -23 about 55 Fully miscible 80 about -22 about 48 Fully
miscible 90 about -31 about 50 Fully miscible
As can be seen from the table above, R-410A is immiscible with POE
oil below about -22.degree. C., and R-410A cannot therefore be used
in low temperature refrigeration applications without make
provisions to overcome the accumulation of POE oil in the
evaporator. Furthermore, R-410A is immiscible with POE oil above
50.degree. C., which will cause problems in the condenser and
liquid line (e.g. the separated POE oil will be trapped and
accumulated) when R-410A is used in high ambient conditions.
Conversely, applicants have surprisingly and unexpectedly found
that refrigerants of the present invention are fully miscible with
POE oil across a temperature range of -40.degree. C. to 80.degree.
C., thus providing a substantial and unexpected advantage when used
in such systems.
Example 12--Residential Air-Conditioning System (Cooling) with
Sequestration and Heat Transfer Composition with Stabilizer
[0323] Example 2 is repeated, except an oil separator is included
in the system and several sequestration materials consisting
independently of Sequestration Materials 1-4 are included in the
liquid portion of the oil separator. The heat transfer composition
includes Luricant 1 and Stabilizer 1 in amounts as described
herein. The system operated as indicated in Example 2 in each case
and operates to indicate high levels of stability such that
operation with acceptable levels of stability, as per the testing
indicated in Examples 10 and 20-30 hereof, occurs for at least 1
year.
Example 13--Residential Heat Pump System (Heating) with
Sequestration and Heat Transfer Composition with Stabilizer
[0324] Example 3 is repeated, except an oil separator is included
in the system and several sequestration materials consisting
independently of Sequestration Materials 1-4 included in the liquid
portion of the oil separator. The heat transfer composition
includes Luricant 1 and Stabilizer 1 in amounts as described
herein. The system operated as indicated in Example 2 in each case
and operates to indicate high levels of stability such that
operation with acceptable levels of stability, as per the testing
indicated in Examples 10 and 20-30 hereof, occurs for at least 1
year.
Example 14--Commercial Air-Conditioning System (Chiller) with
Sequestration and Heat Transfer Composition with Stabilizer
[0325] Example 4 is repeated, except an oil separator is included
in the system and several sequestration materials consisting
independently of Sequestration Materials 1-4 included in the liquid
portion of the oil separator. The heat transfer composition
includes Luricant 1 and Stabilizer 1 in amounts as described
herein. The system operated as indicated in Example 2 in each case
and operates to indicate high levels of stability such that
operation with acceptable levels of stability, as per the testing
indicated in Examples 10 and 20-30 hereof, occurs for at least 1
year.
Example 15--Residential Air-to-Water Heat Pump Hydronic System with
Sequestration and Heat Transfer Composition with Stabilizer
[0326] Example 5 is repeated, except an oil separator is included
in the system and several sequestration materials consisting
independently of Sequestration Materials 1-4 included in the liquid
portion of the oil separator. The heat transfer composition
includes Luricant 1 and Stabilizer 1 in amounts as described
herein. The system operated as indicated in Example 2 in each case
and operates to indicate high levels of stability such that
operation with acceptable levels of stability, as per the testing
indicated in Examples 10 and 20-30 hereof, occurs for at least 1
year.
Example 16--Medium Temperature Refrigeration System with
Sequestration and Heat Transfer Composition with Stabilizer
[0327] Example 6 is repeated, except an oil separator is included
in the system and several sequestration materials consisting
independently of Sequestration Materials 1-4 included in the liquid
portion of the oil separator. The heat transfer composition
includes Luricant 1 and Stabilizer 1 in amounts as described
herein. The system operated as indicated in Example 2 in each case
and operates to indicate high levels of stability such that
operation with acceptable levels of stability, as per the testing
indicated in Examples 10 and 20-30 hereof, occurs for at least 1
year.
Example 17--Low Temperature Refrigeration System with Sequestration
and Heat Transfer Composition with Stabilizer
[0328] Example 7 is repeated, except an oil separator is included
in the system and several sequestration materials consisting
independently of Sequestration Materials 1-4 included in the liquid
portion of the oil separator. The heat transfer composition
includes Luricant 1 and Stabilizer 1 in amounts as described
herein. The system operated as indicated in Example 2 in each case
and operates to indicate high levels of stability such that
operation with acceptable levels of stability, as per the testing
indicated in Examples 10 and 20-30 hereof, occurs for at least 1
year.
Example 18--Commercial Air-Conditioning System--Packaged Rooftops
with Sequestration and Heat Transfer Composition with
Stabilizer
[0329] Example 8 is repeated, except an oil separator is included
in the system and several sequestration materials consisting
independently of Sequestration Materials 1-4 included in the liquid
portion of the oil separator. The heat transfer composition
includes Luricant 1 and Stabilizer 1 in amounts as described
herein. The system operated as indicated in Example 2 in each case
and operates to indicate high levels of stability such that
operation with acceptable levels of stability, as per the testing
indicated in Examples 10 and 20-30 hereof, occurs for at least 1
year.
Example 19--Commercial Air-Conditioning System--Variable
Refrigerant Flow Systems with Sequestration and Heat Transfer
Composition with Stabilizer
[0330] Example 9 is repeated, except an oil separator is included
in the system and several sequestration materials consisting
independently of Sequestration Materials 1-4 included in the liquid
portion of the oil separator. The heat transfer composition
includes Luricant 1 and Stabilizer 1 in amounts as described
herein. The system operated as indicated in Example 2 in each case
and operates to indicate high levels of stability such that
operation with acceptable levels of stability, as per the testing
indicated in Examples 10 and 20-30 hereof, occurs for at least 1
year.
Example 20--Sequestration Material Comprising Silver Zeolite
[0331] The ability of a zeolite comprising silver to act as a
sequestration material was tested. The zeolite tested was UPO
IONSIV D7310-C, available form Honeywell UOP. The openings have a
size across their largest dimension of from about 15 to about 35
.ANG..
[0332] A blend of 80 wt % POE oil (POE ISO 32, Emkarate RL 32-3MAF)
which comprises a primary anti-oxidant stabilizer BHT in an amount
of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a sealed
tube, and then heated for 2 days at 190.degree. C. These conditions
caused breakdown of the refrigerant and the lubricant. The sealed
tubes were then opened and samples of the oil were taken.
[0333] The oil sample was then placed in Fischer-Porter tubes with
the zeolite. The amount of dry zeolite relative to the sample
(lubricant) was measured. The tubes were then maintained at either
15.degree. C. or 50.degree. C. for 114 hours (4.75 days). The tubes
were shaken every two hours to ensure proper mixing of the zeolite
and the sample.
[0334] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the sample were measured at the start (i.e. after degradation of
the CF.sub.3I and POE oil, and before combination with the
zeolite), and at the end (i.e. after combination with the zeolite,
and at the end of the 114 hours at 15.degree. C. or 50.degree. C.).
TAN, fluoride and iodide concentration were measured according to
the same methods as descried in Example 10.
[0335] The results of the tests are set out in Table 20.
TABLE-US-00034 TABLE 20 Effect of zeolite on TAN, fluoride and
iodide concentration Amount of zeolite relative Fluoride Iodide to
sample TAN (ppm) (ppm) Temp. (pphl) Start End Start End Start End
15.degree. C. 4.8 pphl 30.0 29.4 94.8 61.5 57.4 14.2 20.5 pphl 30.0
24.7 94.8 46.4 57.4 5.5 50.degree. C. 5.4 pphl 30.0 29.7 94.8 45.2
57.4 8.1 22.1 pphl 30.0 23.3 94.8 39.2 57.4 0.1 *pphl means parts
by weight per hundred parts of lubricant
[0336] The above tests demonstrate the ability of the zeolite to
effectively "recover" a composition of POE oil and a CF.sub.3I
refrigerant after it has degraded.
[0337] The results demonstrate that the zeolite was able to reduce
the iodide and the fluoride level of the degraded sample at both
15.degree. C. and 50.degree. C. when using either about 5 pphl
zeolite or about 21 pphl zeolite. However, the zeolite performed
better at 50.degree. C. than at 15.degree. C., and at about 21 pphl
zeolite than at about 5 pphlzeolite. Surprisingly, very little
iodide was detected at about 21 pphl zeolite at 50.degree. C.
[0338] The results also show that, at a concentration of about 21
pphl zeolite, the TAN was reduced at both 15.degree. C. and at
50.degree. C.
Example 21
[0339] The ability of an anion exchange resin to act as a
sequestration material was tested.
[0340] Two different anion exchange resins were tested.
[0341] First Resin
[0342] The first resin was a strongly basic (type 1) anion exchange
resin with chloride exchangeable ions (Dowex.RTM. 1X8 chloride
form).
TABLE-US-00035 Product Name Dowex .RTM. 1x8 chloride form
Composition Moisture content, 43-48% Limit 66.degree. C. max. temp.
Cross-linkage 8% Matrix Styrene-divinylbenzene (gel) Particle size
50-100 mesh Operating pH 0-14 Capacity 1.2 meq/mL total
capacity
[0343] The first resin was used without modification.
[0344] Second Resin
[0345] The second resin was a strongly basic (type 1) anion
exchange resin with chloride exchangeable ions (Dowex.RTM. 1X8
chloride form).
TABLE-US-00036 Product Name Dowex .RTM. 1x8 chloride form
Composition Moisture content, 43-48% Limit 66.degree. C. max. temp.
Cross-linkage 8% Matrix Styrene-divinylbenzene (gel) Particle size
50-100 mesh Operating pH 0-14 Capacity 1.2 meq/mL total
capacity
[0346] The second resin was converted from the chloride form to the
hydroxide form prior to use in the following example by slowly
washing the resin for at least 1 hour with 5 to 10 bed volumes of
4% NaOH, followed by washing with deionized water until the pH of
the effluent is 7, .+-.0.5. The pH was measured using litmus
paper.
[0347] Method and Results
[0348] A blend of 80 wt % POE oil (POE ISO 32, Emkarate RL 32-3MAF)
which comprises a primary anti-oxidant stabilizer BHT in an amount
of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a sealed
tube, and then heated for 2 days at 190.degree. C. These conditions
caused breakdown of the refrigerant and the lubricant. The sealed
tubes were then opened and samples of the oil were taken.
[0349] The sample was then placed in Fischer-Porter tubes with the
anion exchange resin. The amount of dry resin relative to the
sample was measured. The tubes were then maintained at either
15.degree. C. or 50.degree. C. for 114 hours (4.75 days). The tubes
were shaken every two hours to ensure proper mixing of the resin
and the sample.
[0350] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the sample were measured at the start (i.e. after degradation of
the CF.sub.3I and POE oil, and before combination with the resin),
and at the end (i.e. after combination with the resin, and at the
end of the 114 hours at 15.degree. C. or 50.degree. C.). TAN,
fluoride and iodide concentration were measured according to the
same methods as Example 10.
[0351] The results are set out in Table 21 below.
TABLE-US-00037 TABLE 21 Effect of anion exchange resin on TAN,
fluoride and iodide concentration Amount of IE relative to Fluoride
Iodide sample TAN (ppm) (ppm) Material Temp. (lubricant) Start End
Start End Start End First 15.degree. C. 3.9 pphl 30.0 30.7 94.8
65.5 57.4 32.4 resin 16.0 pphl 30.0 30.9 94.8 61.9 57.4 19.9
50.degree. C. 4.5 pphl 30.0 31.1 94.8 55.2 57.4 25.8 16.7 pphl 30.0
39.4 94.8 44.7 57.4 17.5 Second 15.degree. C. 3.8 pphl 30.0 26.0
94.8 54.3 57.4 15.0 resin 15.2 pphl 30.0 14.5 94.8 44.3 57.4 4.5
50.degree. C. 4.8 pphl 30.0 26.8 94.8 46.2 57.4 7.6 16.7 pphl 30.0
13.1 94.8 22.6 57.4 2.5 *pphl means parts by weight per hundred
parts of lubricant
[0352] The above tests demonstrate the ability of anion exchange
resins to effectively "recover" a composition of POE oil and a
CF.sub.3I refrigerant after it has degraded.
[0353] The results demonstrate that both resins were able to reduce
the iodide and the fluoride level of the degraded sample at both
15.degree. C. and 50.degree. C. when using either about 4 pphl
resin or about 16 pphl resin. Both resins performed better at
50.degree. C. than at 15.degree. C., and at about 16 pphl resin
than about 4 pphl zeolite.
[0354] The second resin was able to reduce the TAN of the sample at
both temperatures (i.e. 15.degree. C. and at 50.degree. C.), and at
both concentrations of resin (i.e. at about 4 pphl and about 16
pphl resin).
Example 22
[0355] Example 22 is repeated except that the following two anion
resins were used:
[0356] A--An industrial grade weak base anion exchange resin sold
under the trade designation Amberlyst A21 (Free Base) having the
following characteristics:
TABLE-US-00038 Product Name Amberlyst A21 Composition Moisture
content, 58-62% Limit 100.degree. C. max. temp. Ionic Form Free
Base (FB) Matrix Macroporous Particle size 490-690 .mu.m
Concentration of >4.6 eq/kg active sites >1.3 eq/L
[0357] B--An industrial grade weak basic anion exchange resin sold
under the trade designation Amberlyst A22 having the following
characteristics:
TABLE-US-00039 Product Name Amberlyst A22 Composition Moisture
content, 40-50% Limit 100.degree. C. max. temp. Ionic Form Free
Base (FB) Structure Styrene-divinylbenzene Matrix Macroporous
Particle size 475-600 .mu.m Capacity >1.7 eq/L
[0358] Each of these resins were found to be effect to remove
and/or reduce the above-noted materials.
Example 23
[0359] The ability of combination of anion exchange resin and
zeolite to act as a sequestration material was tested.
[0360] Anion Exchange Resin
[0361] The resin was a strongly basic (type 1) anion exchange resin
with hydroxyl exchangeable ions (Dowex.RTM. Marathon.TM. A,
hydroxide form).
TABLE-US-00040 Product Name Dowex .RTM. Marathon .TM. A, hydroxide
form Moisture 60-72% Matrix Styrene-divinylbenzene (gel) Particle
size 23-27 mesh Capacity 1.0 meq/mL by wetted bed volume
[0362] The resin was used without modification.
[0363] Zeolite
[0364] The zeolite tested was UPO IONSIV D7310-C, available form
Honeywell UOP. The openings have a size across their largest
dimension of from about 15 to about 35 .ANG..
[0365] Method and Results
[0366] A blend of 80 wt % POE oil (POE ISO 32, Emkarate RL 32-3MAF)
which comprises a primary anti-oxidant stabilizer BHT in an amount
of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a sealed
tube, and then heated for 2 days at 175.degree. C. These conditions
caused breakdown of the refrigerant and the lubricant. The sealed
tubes were then opened and samples of the oil (i.e., lubricant)
were taken.
[0367] The lubricant sample was then placed in Fischer-Porter tubes
with the combination of anion exchange resin and zeolite. The
amount of dry resin and zeolite relative to the sample were
measured. The tubes were then maintained at about 50.degree. C. for
192 hours (8 days). The tubes were shaken every two hours to ensure
proper mixing of the resin and the sample.
[0368] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the oil were measured at the start (i.e. after degradation of the
CF.sub.3I and POE oil, and before combination with the resin and
zeolite), and at the end (i.e. after combination with the resin and
zeolite, and at the end of the 192 hours at 50.degree. C.). TAN,
fluoride and iodide concentration were measured according to the
same methods as Example 1.
[0369] The results are set out in Table 23 below.
TABLE-US-00041 TABLE 23 Effect of anion exchange resin and zeolite
on TAN, fluoride and iodide concentration Zeolite: Ion Fluoride
Iodide Exchange TAN (ppm) (ppm) Temp. (IE) Start End Start End
Start End 50.degree. C. 100% IE 8.71 3.20 23.3 5.4 26.9 <0.05
25%: 75% 8.71 <0.05 23.3 0.8 26.9 <0.05 50%: 50% 8.71 0.14
23.3 3.1 26.9 <0.05 75%: 25% 8.71 0.96 23.3 5.4 26.9 <0.05
100% Zeolite 8.71 2.93 23.3 5.3 26.9 <0.05
[0370] The above tests demonstrate the ability of combination of
anion exchange resins and zeolite to effectively "recover" a
composition of POE oil and a CF.sub.3I refrigerant after it has
degraded. The results demonstrate that both resins were able to
reduce the iodide and the fluoride level of the degraded sample at
50.degree. C. when using different ratios of anion exchange resin
and zeolite. The zeolite to ion-exchange weight 25:75 showed
maximum reduction in the TAN of the sample and also showed highest
decrease in iodide and fluoride content (ppm).
Example 24
[0371] The level of removal of fluoride, iodide and TAN reduction
as a function of the amount of zeolite as a percentage of the heat
transfer composition being treated was studied
[0372] The zeolite tested was UPO IONSIV D7310-C, available form
Honeywell UOP. The openings have a size across their largest
dimension of from about 15 to about 35 .ANG..
[0373] A blend of 80 wt % POE oil (POE ISO 32, Emkarate RL 32-3MAF)
which comprises a primary anti-oxidant stabilizer BHT in an amount
of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a sealed
tube, and then heated for 2 days at 175.degree. C. These conditions
caused breakdown of the refrigerant and the lubricant. The sealed
tubes were then opened and samples of the oil were taken.
[0374] A portion of the lubricant sample produced after the
breakdown according to the preceeding paragraph was then filled
into 5 Parr Cells, with each of the cells having a different amount
(by weight) of zeolite based on the weight of the lubricant placed
into the cell. The Parr Cells were then maintained at 50.degree. C.
and the material in each cell was tested every 24 hours for 15
days. The Parr Cells were shaken every day to ensure proper mixing
of the zeolite and the lubricant.
[0375] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the oil were measured at the start (i.e. after degradation of the
CF.sub.3I and POE oil, and before combination with the zeolite),
and after every 24 hours (i.e. after combination with the zeolite,
at 50.degree. C.) for 15 days.
[0376] The results of the tests are set out in Table 5 below:
TABLE-US-00042 TABLE 24 Effect of zeolite on TAN, fluoride and
iodide concentration TAN Fluoride (ppm) Iodide (ppm) Zeolite 5 15 5
15 5 15 Material Temp. (Pphl) Start days days Start days days Start
days days Zeolite 50.degree. C. 1 4.5 4.4 4.6 7.4 1.5 0.96 370 240
33 5 4.5 3.6 3.5 7.4 <0.8 <0.8 370 130 13 10 4.5 2.6 2.6 7.4
<0.8 <0.8 370 49 <4 15 4.5 2.0 2.2 7.4 <0.8 <0.8 370
26 <4 20 4.5 1.8 2 7.4 <0.8 <0.8 370 38 <4
[0377] The above tests demonstrate the ability of the zeolite to
effectively "recover" a composition of lubricant, and in particular
POE oil, and a CF.sub.3I refrigerant after it has degraded.
[0378] The results indicate that amounts of zeolite greater than 10
pphl are more effective in reducing iodide levels to non-detectable
limits, and amount of zeolite material greater than 5 pphl is more
effective in reducing the fluoride levels to non-detectable limits.
The results also show that amount of zeolite greater than 15 pphlis
most effective in reducing the TAN.
Example 25--Preferred Ion Exchange Materials
[0379] The ability of an industrial grade weakly base anion
exchange adsorbent resin Amberlyst A21 (Free Base) to act as a
sequestration material was tested. Weak Base Anion Resin are in the
free base form and they are functionalized with a tertiary amine
(uncharged). Tertiary amine contains a free lone pair of electrons
on the Nitrogen--it gets readily protonated in presence of an acid.
The ion exchange resin is protonated by the acid, then attracts and
binds the anionic counter ion for full acid removal, without
contributing any additional species back into solution.
[0380] Applicants have found that Amberlyst A21 is an excellent
material for use in accordance with the present invention. It has a
macroporous structure makes it physically very stable and resistant
to breakage in the present methods and systems, and ii can
withstand high flow rates of the refrigeration system over a period
of lifetime.
Example 26
[0381] The ability of an industrial grade weakly base anion
exchange adsorbent resin Amberlyst A21 (Free Base) to act as a
sequestration material was tested. Weak Base Anion Resin are in the
free base form and they are functionalized with a tertiary amine
(uncharged). Tertiary amine contains a free lone pair of electrons
on the Nitrogen--it gets readily protonated in presence of an acid.
The ion exchange resin is protonated by the acid, then attracts and
binds the anionic counter ion for full acid removal, without
contributing any additional species back into solution. The matrix
of Amberlyst A21 is macroporous. Its macroporous structure makes it
physically very stable and resistant to breakage. It can withstand
high flow rates of the refrigeration system over a period of
lifetime. An industrial grade weak base anion exchange resin sold
under the trade designation Amberlyst A21 (Free Base) having the
following characteristics:
TABLE-US-00043 Product Name Amberlyst A21 Composition Moisture
content, 58-62% Limit 100.degree. C. max. temp. Ionic Form Free
Base (FB) Matrix Macroporous Particle size 490-690 .mu.m
Concentration of >4.6 eq/kg active sites >1.3 eq/L
[0382] A mixture of 80 wt % POE oil (POE ISO 32, Emkarate RL
32-3MAF) which comprises a primary anti-oxidant stabilizer BHT in
an amount of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a
cylinder, and then heated for 2 days at 175.degree. C. These
conditions caused breakdown of the refrigerant and the lubricant.
The cylinder was then opened and samples of the oil were taken.
[0383] The sample was then placed in parr cells with the Amberlyst
A21. The amount of dry Amberlyst A21 relative to the sample was
measured. The parr cells were then maintained at either 50.degree.
C. for 20 days. The cells were shaken each day to ensure proper
mixing of the Amberlyst A21 and the sample.
[0384] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the sample were measured at the start (i.e. after degradation of
the CF.sub.3I and POE oil, and before combination with the
Amberlyst A21), and at the end (i.e. after combination with the
Amberlyst A21). TAN, fluoride and iodide concentration were
measured according to the methods as described in the
application.
The results of the tests are set out in Table 26.
TABLE-US-00044 TABLE 26 Effect of Amberlyst A21 on TAN, fluoride
and iodide concentration Amount of Amberlyst A21 Fluoride Iodide
relative to oil TAN (ppm) (ppm) Temp. sample (wt %) Start End Start
End Start End 50.degree. C. 20% 7.2 1.4 21 1.6 620 130 30% 7.2 0.6
21 5.2 620 <4 40% 7.2 0.4 21 <4 620 <4
[0385] The above tests demonstrate the ability of the Amberlyst A21
to effectively "recover" a composition of POE oil and a CF.sub.3I
refrigerant after it has degraded.
[0386] The results demonstrate that the Amberlyst A21 was able to
reduce the iodide and the fluoride level below detectable limits of
the degraded sample at 50.degree. C. when using 30 wt % Amberlyst
A21 and above.
Example 27
[0387] The ability of an industrial grade weakly base anion
exchange adsorbent resin Amberlyst A22 (Free Base) to act as a
sequestration material was tested. Weak Base Anion Resin are in the
free base form and they are functionalized with a tertiary amine
(uncharged). Tertiary amine contains a free lone pair of electrons
on the Nitrogen--it gets readily protonated in presence of an acid.
The ion exchange resin is protonated by the acid, then attracts and
binds the anionic counter ion for full acid removal, without
contributing any additional species back into solution. Its
macroporous structure makes it physically very stable and resistant
to breakage. It can withstand high flow rates of the refrigeration
system over a period of lifetime. An industrial grade weak basic
anion exchange resin sold under the trade designation Amberlyst A22
having the following characteristics:
TABLE-US-00045 Product Name Amberlyst A22 Composition Moisture
content, 40-50% Limit 100.degree. C. max. temp. Ionic Form Free
Base (FB) Structure Styrene-divinylbenzene Matrix Macroporous
Particle size 475-600 .mu.m Capacity >1.7 eq/L
[0388] A mixture of 80 wt % POE oil (POE ISO 32, Emkarate RL
32-3MAF) which comprises a primary anti-oxidant stabilizer BHT in
an amount of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a
cylinder, and then heated for 2 days at 175.degree. C. These
conditions caused breakdown of the refrigerant and the lubricant.
The cylinder was then opened and samples of the oil were taken.
[0389] The sample was then placed in parr cells with the Amberlyst
A22. The amount of dry Amberlyst A22 relative to the sample was
measured. The parr cells were then maintained at either 50.degree.
C. for 20 days. The cells were shaken each day to ensure proper
mixing of the Amberlyst A22 and the sample.
[0390] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the sample were measured at the start (i.e. after degradation of
the CF.sub.3I and POE oil, and before combination with the
Amberlyst A22), and at the end (i.e. after combination with the
Amberlyst A22). TAN, fluoride and iodide concentration were
measured according to the methods as described in the
application.
[0391] The results of the tests are set out in Table 27.
TABLE-US-00046 TABLE 27 Effect of Amberlyst A22 on TAN, fluoride
and iodide concentration Amount of Amberlyst A22 Fluoride Iodide
relative to oil TAN (ppm) (ppm) Temp. sample (wt %) Start End Start
End Start End 50.degree. C. 10% 4.3 1.3 6.0 <0.8 170 140 20% 4.3
0.8 6.0 <0.8 170 74
[0392] The above tests demonstrate the ability of the Amberlyst A22
to effectively "recover" a composition of POE oil and a CF.sub.3I
refrigerant after it has degraded.
[0393] The results demonstrate that the Amberlyst A22 was able to
reduce the iodide and the fluoride level of the degraded sample at
50.degree. C. when using 10 wt % and 30 wt % of Amberlyst A22.
Example 28
[0394] The ability of an industrial grade weakly base anion
exchange adsorbent resin Amberlite IRA96 to act as a sequestration
material was tested. Weak Base Anion Resin are in the free base
form and are functionalized with a tertiary amine (uncharged).
Tertiary amine contains a free lone pair of electrons on the
Nitrogen--it gets readily protonated in presence of an acid. The
ion exchange resin is protonated by the acid, then attracts and
binds the anionic counter ion for full acid removal, without
contributing any additional species back into solution. Its
macroporous structure makes it physically very stable and resistant
to breakage. It can withstand high flow rates of the refrigeration
system over a period of lifetime. The high porosity of this resin
allows efficient adsorption of large organic molecules. An
industrial grade weak basic anion exchange resin sold under the
trade designation Amberlite IRA96 having the following
characteristics:
TABLE-US-00047 Product Name Amberlite IRA96 Composition Moisture
content, 59-65% Limit 100.degree. C. max. temp. Ionic Form Free
Base (FB) Structure Macroporous Matrix Styrene divinylbenzene
copolymer Functional Group Tertiary amine Particle size 630-830
.mu.m Concentration of >1.25 eq/L active sites
[0395] A mixture of 80 wt % POE oil (POE ISO 32, Emkarate RL
32-3MAF) which comprises a primary anti-oxidant stabilizer BHT in
an amount of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a
cylinder, and then heated for 2 days at 175.degree. C. These
conditions caused breakdown of the refrigerant and the lubricant.
The cylinder was then opened and samples of the oil were taken.
[0396] The sample was then placed in parr cells with the
AmberliteIRA96. The amount of dry AmberliteIRA96 relative to the
sample was measured. The parr cells were then maintained at either
50.degree. C. for 20 days. The cells were shaken each day to ensure
proper mixing of the AmberliteIRA96 and the sample.
[0397] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the sample were measured at the start (i.e. after degradation of
the CF.sub.3I and POE oil, and before combination with the
AmberliteIRA96), and at the end (i.e. after combination with the
AmberliteIRA96). TAN, fluoride and iodide concentration were
measured according to the methods as described in the
application.
[0398] The results of the tests are set out in Table 28.
TABLE-US-00048 TABLE 28 Effect of Amberlite on TAN, fluoride and
iodide concentration Amount of AmberliteIRA96 Fluoride Iodide
relative to oil TAN (ppm) (ppm) Temp. sample (wt %) Start End Start
End Start End 50.degree. C. 20% 6.3 0.2 30 <0.8 1000 130 30% 6.3
<0.2 30 <0.8 1000 <4 40% 6.3 <0.2 30 <0.8 1000
<4
[0399] The above tests demonstrate the ability of the
AmberliteIRA96 to effectively "recover" a composition of POE oil
and a CF.sub.3I refrigerant after it has degraded.
[0400] The results demonstrate that the AmberliteIRA96 was able to
reduce the iodide and the fluoride level below detectable limits of
the degraded sample at 50.degree. C. when using 30 wt %
AmberliteIRA96 and above.
Example 29
[0401] The ability of an industrial grade activated alumina F200 to
act as a sequestration material was tested.
[0402] A mixture of 80 wt % POE oil (POE ISO 32, Emkarate RL
32-3MAF) which comprises a primary anti-oxidant stabilizer BHT in
an amount of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a
cylinder, and then heated for 2 days at 175.degree. C. These
conditions caused breakdown of the refrigerant and the lubricant.
The cylinder was then opened and samples of the oil were taken.
[0403] The sample was then placed in parr cells with industrial
grade activated alumina F200. The amount of activated alumina
relative to the sample was measured. The parr cells were then
maintained at either 50.degree. C. for 20 days. The cells were
shaken each day to ensure proper mixing of the sample.
[0404] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the sample were measured at the start (i.e. after degradation of
the CF.sub.3I and POE oil, and before exposure to F200), and at the
end (i.e. after exposure to F200). TAN, fluoride and iodide
concentration were measured per the methods described in the
application.
[0405] The results of the tests are set out in Table 29A.
TABLE-US-00049 TABLE 29 Effect of Activated Alumina F200 on TAN,
fluoride and iodide concentration Amount of F200 relative Fluoride
Iodide to oil sample TAN (ppm) (ppm) Temp. (wt %) Start End Start
End Start End 50.degree. C. 20% 7.2 1.6 21 1.4 620 72 30% 7.2 1.0
21 1.0 620 37 40% 7.2 1.3 21 0.9 620 64
Example 30
[0406] The ability of combination of a Amberlyst A21 and Zeolite
IONSIV D7310-C as sequestration material was tested.
[0407] A mixture of 80 wt % POE oil (POE ISO 32, Emkarate RL
32-3MAF) which comprises a primary anti-oxidant stabilizer BHT in
an amount of about 1000 ppm, and 20 wt % CF.sub.3I was placed in a
cylinder, and then heated for 2 days at 175.degree. C. These
conditions caused breakdown of the refrigerant and the lubricant.
The cylinder was then opened and samples of the oil were taken.
[0408] The sample was then placed in parr cells with the
sequestration material. The amount of sequestration material
relative to the sample was 20% by weight. The parr cells were then
maintained at either 50.degree. C. for 20 days. The cells were
shaken each day to ensure proper mixing of the sample.
[0409] The Total Acid Number (TAN), iodide ppm and fluoride ppm of
the sample were measured at the start (i.e. after degradation of
the CF.sub.3I and POE oil, and before exposure to sequestration
material), and at the end (i.e. after exposure to sequestration
material). TAN, fluoride and iodide concentration were measured per
the methods described in the application. The results of the tests
are set out in Table 30.
TABLE-US-00050 TABLE 30 Effect of Amberlyst A21 and Zeolite IONSIV
D7310-C combination on TAN, fluoride and iodide concentration A21:
Fluoride Iodide Zeolite (by TAN (ppm) (ppm) Temp weight) Start End
Start End Start End 50.degree. C. 100% A21 19 3.1 100 2.4 570 9
85:15 19 3.4 100 1.8 570 <4 75:25 19 3.8 100 2.8 570 <4 65:35
19 4.0 100 1.8 570 <4 50:50 19 8.0 100 2.4 570 <4 100%
Zeolite 19 12.0 100 5.6 570 <4
[0410] Although the invention has been described with reference to
preferred compositions, 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 without departing from the essential scope thereof.
Therefore, it is intended that the invention not be limited to the
particular compositions disclosed, but that the invention will
include all compositions falling within the scope of the appended
claims or any claims added later.
Numbered Embodiment 1
[0411] A refrigerant comprising at least about 97% by weight of the
following three compounds, with each compound being present in the
following relative percentages: [0412] 39 to 45% by weight
difluoromethane (HFC-32), [0413] 1 to 4% by weight
pentafluoroethane (HFC-125), and [0414] 51 to 57% by weight
trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 2
[0415] The refrigerant of numbered embodiment 1 wherein the
refrigerant of three compounds is: [0416] about 41 to about 43% by
weight difluoromethane (HFC-32), [0417] 1 to 4% by weight
pentafluoroethane (HFC-125), and [0418] about 53 to about 56% by
weight trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 3
[0419] The refrigerant of numbered embodiment 1 wherein the
refrigerant of three compounds is: [0420] 41%.+-.1% by weight
difluoromethane (HFC-32), [0421] 3.5%.+-.0.5% by weight
pentafluoroethane (HFC-125), and [0422] 55.5%.+-.0.5% by weight
trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 4
[0423] The refrigerant of numbered embodiment 1 wherein the
refrigerant of three compounds is: [0424] 41% by weight
difluoromethane (HFC-32), [0425] 3.5% by weight pentafluoroethane
(HFC-125), and [0426] 55.5% by weight trifluoroiodomethane
(CF.sub.3I).
Numbered Embodiment 5
[0427] The refrigerant as claimed in numbered embodiments 1 to 4
wherein the refrigerant comprises at least about 98.5% by weight of
said three compounds.
Numbered Embodiment 6
[0428] The refrigerant as claimed in numbered embodiments 1 to 4
wherein the refrigerant comprises at least about 99.5% by weight of
said three components.
Numbered Embodiment 7
[0429] A refrigerant consisting essentially of: [0430] 39 to 45% by
weight difluoromethane (HFC-32), [0431] 1 to 4% by weight
pentafluoroethane (HFC-125), and [0432] 51 to 57% by weight
trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 8
[0433] The refrigerant of claim 7, consisting essentially of:
[0434] about 41 to about 43% by weight difluoromethane (HFC-32),
[0435] 1 to 4% by weight pentafluoroethane (HFC-125), and [0436]
about 53 to about 56% by weight trifluoroiodomethane
(CF.sub.3I).
Numbered Embodiment 9
[0437] The refrigerant of numbered embodiment 7 or numbered
embodiment 8 consisting essentially of: [0438] 41%.+-.1% by weight
difluoromethane (HFC-32), [0439] 3.5%.+-.0.5% by weight
pentafluoroethane (HFC-125), and [0440] 55.5%.+-.0.5% by weight
trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 10
[0441] The refrigerant of numbered embodiment 7 or numbered
embodiment 8 consisting essentially of [0442] 41% by weight
difluoromethane (HFC-32), [0443] 3.5% by weight pentafluoroethane
(HFC-125), and [0444] 55.5% by weight trifluoroiodomethane
(CF.sub.3I).
Numbered Embodiment 11
[0445] A refrigerant consisting of: [0446] 39 to 45% by weight
difluoromethane (HFC-32), [0447] 1 to 4% by weight
pentafluoroethane (HFC-125), and [0448] 51 to 57% by weight
trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 12
[0449] The refrigerant of numbered embodiment 11, consisting of:
[0450] about 41 to about 43% by weight difluoromethane (HFC-32),
[0451] 1 to 4% by weight pentafluoroethane (HFC-125), and [0452]
about 53 to about 56% by weight trifluoroiodomethane
(CF.sub.3I).
Numbered Embodiment 13
[0453] The refrigerant of numbered embodiment 11 or numbered
embodiment 12 consisting of: [0454] 41%.+-.1% by weight
difluoromethane (HFC-32), [0455] 3.5%.+-.0.5% by weight
pentafluoroethane (HFC-125), and [0456] 55.5%.+-.0.5% by weight
trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 14
[0457] The refrigerant of numbered embodiment 11 or numbered
embodiment 12 consisting of: [0458] 41% by weight difluoromethane
(HFC-32), [0459] 3.5% by weight pentafluoroethane (HFC-125), and
[0460] 55.5% by weight trifluoroiodomethane (CF.sub.3I).
Numbered Embodiment 15
[0461] A heat transfer composition comprising a refrigerant of any
one of numbered embodiments 1 to 14.
Numbered Embodiment 16
[0462] The heat transfer composition as claimed in numbered
embodiment 15, wherein the refrigerant comprises greater than 40%
by weight of the composition.
Numbered Embodiment 17
[0463] The heat transfer composition as claimed in numbered
embodiment 15 wherein the refrigerant comprises greater than 50% by
weight of the composition.
Numbered Embodiment 18
[0464] The heat transfer composition as claimed in numbered
embodiment 15, wherein the refrigerant comprises greater than 60%
by weight of the composition.
Numbered Embodiment 19
[0465] The heat transfer composition as claimed in numbered
embodiment 15, wherein the refrigerant comprises greater than 70%
by weight of the composition.
Numbered Embodiment 20
[0466] The heat transfer composition as claimed in numbered
embodiment 15, wherein the refrigerant comprises greater than 80%
by weight of the composition.
Numbered Embodiment 21
[0467] The heat transfer composition as claimed in numbered
embodiment 15, wherein the refrigerant comprises greater than 90%
by weight of the composition.
Numbered Embodiment 22
[0468] The heat transfer composition of any one of numbered
embodiments 15 to 21 wherein said heat transfer composition further
comprising an alkylated naphthalene stabilizer.
Numbered Embodiment 23
[0469] The heat transfer composition of any one of numbered
embodiments 15 to 22 wherein said heat transfer composition further
comprising a stabilizer comprising and/or a phenol-based
compound.
Numbered Embodiment 24
[0470] The heat transfer composition of numbered embodiments 22 to
23 wherein heat transfer composition further comprises a stabilizer
comprising an epoxide.
Numbered Embodiment 25
[0471] The heat transfer composition of any one of numbered
embodiments 24 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 26
[0472] The heat transfer composition of numbered embodiment 25
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 27
[0473] The heat transfer composition numbered embodiment 26 further
comprising a lubricant selected from polyol esters (POEs), mineral
oil and alkylbenzenes (ABs).
Numbered Embodiment 28
[0474] The heat transfer composition of numbered embodiment 27
wherein the lubricant is a polyol ester (POE).
Numbered Embodiment 29
[0475] A method of cooling in a heat transfer system comprising an
evaporator, a condenser and a compressor, the process comprising
the steps of i) condensing a heat transfer composition of any one
of numbered embodiments 21 to 29 and ii) evaporating the
composition 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.
Numbered Embodiment 30
[0476] A method of heating in a heat transfer system comprising an
evaporator, a condenser and a compressor, the process comprising
the steps of i) condensing a heat transfer composition of any one
of numbered embodiment 21 to 29, in the vicinity of a body or
article to be heated and ii) evaporating the composition; wherein
the evaporator temperature of the heat transfer system is in the
range of about -20.degree. C. to about 3.degree. C.
Numbered Embodiment 31
[0477] A method of heating in a heat transfer system comprising an
evaporator, a condenser and a compressor, the process comprising
the steps of i) condensing a heat transfer composition in any one
of numbered embodiments 21 to 29, in the vicinity of a body or
article to be heated and ii) evaporating the composition; wherein
the evaporator temperature of the heat transfer system is in the
range of about -30.degree. C. to about 5.degree. C.
Numbered Embodiment 32
[0478] A method of cooling in a heat transfer system comprising an
evaporator, a condenser and a compressor, the process comprising
the steps of i) condensing a heat transfer composition of any one
of numbered embodiments 21 to 29 and ii) evaporating the
composition in the vicinity of body or article to be cooled wherein
the heat transfer system is a refrigeration system.
Numbered Embodiment 33
[0479] The method of numbered embodiment 32, wherein the
refrigeration system is a low temperature refrigeration system or a
medium temperature refrigeration system.
Numbered Embodiment 34
[0480] The method of numbered embodiment 33, wherein the
refrigeration system is a low temperature refrigeration system.
Numbered Embodiment 35
[0481] The method of numbered embodiment 33, wherein the
refrigeration system is a medium temperature refrigeration
system.
Numbered Embodiment 36
[0482] The method of numbered embodiment 35, wherein the
refrigeration system is a medium temperature refrigeration system
(with an evaporator temperature in the range of about -12 to about
0.degree. C., particularly about -8.degree. C.).
Numbered Embodiment 37
[0483] The method of numbered embodiment 34, wherein the
refrigeration system is a low temperature refrigeration system
(with an evaporator temperature in the range of about -40 to about
-12.degree. C., particularly about -23.degree. C. or preferably
about -32.degree. C.).
Numbered Embodiment 38
[0484] A method of replacing an existing refrigerant contained in a
heat transfer system comprising removing at least a portion of said
existing refrigerant from said system, said existing refrigerant
being R-410a and replacing at least a portion of said existing
refrigerant by introducing into said system, a refrigerant as
claimed in any one of numbered embodiments 1 to 14 or a heat
transfer composition as claimed in any one of numbered embodiments
21 to 29.
Numbered Embodiment 39
[0485] The method of numbered embodiment 38, wherein the portion of
the existing R410A refrigerant is at least about 5% by weight of
the R410A from the system.
Numbered Embodiment 40
[0486] The method of numbered embodiment 38, wherein the portion of
the existing R-410A refrigerant is at least about 50% by weight of
the R-410A from the system.
Numbered Embodiment 41
[0487] The method of numbered embodiment 38, wherein the portion of
the existing R-410A refrigerant is about 100% by weight of the
R-410A from the system.
Numbered Embodiment 42
[0488] The use of refrigerant of any one of numbered embodiments 1
to 14 in an air conditioning system.
Numbered Embodiment 43
[0489] The use of numbered embodiment 42 wherein the air
conditioning system is residential air conditioning.
Numbered Embodiment 44
[0490] The use of numbered embodiment 42 wherein the air
conditioning system is a residential heat pump.
Numbered Embodiment 451
[0491] The use of numbered embodiment 58 wherein the air
conditioning system is a chiller.
Numbered Embodiment 46
[0492] A refrigerant of any one of numbered embodiments 1 to 14
wherein said refrigerant [0493] (a) has a COP matching or exceeding
the efficiency of R410A; and [0494] (b) has a capacity of greater
than 90% of the capacity of R410A.
Numbered Embodiment 47
[0495] The refrigerant of numbered embodiment 46, wherein the
refrigerant is provided to replace the R410A refrigerant in a
system.
Numbered Embodiment 48
[0496] The refrigerant of numbered embodiment 47, wherein the
refrigerant has a discharge temperature which is not greater than
10.degree. C. higher than that of R-410A in a heat transfer system
in which the refrigerant is used to replace the R-410A
refrigerant.
Numbered Embodiment 49
[0497] The refrigerant of numbered embodiments 48, wherein the
refrigerant has a compressor pressure ratio of from 95 to 105% of
the compressor pressure ratio of R-410A in a heat transfer system,
in which the refrigerant is used to replace the R-410A
refrigerant.
Numbered Embodiment 50
[0498] The refrigerant of any one of numbered embodiments 1 to 14
or 46-49 having a GWP over a time period of 100 years of not
greater than 427.
Numbered Embodiment 51
[0499] The refrigerant of any one of numbered embodiments 1 to 14
or 46-49 which is non-flammable as determined in accordance with
the Non-Flammability Test.
Numbered Embodiment 52
[0500] The refrigerant of any one of numbered embodiments 1 to 14
or 46-49 which is non-flammable as determined in accordance with
ASTM standard E-681-2009 Standard Test Method for Concentration
Limits of Flammability of Chemicals (Vapors and Gases) at
conditions described in ASHRAE Standard 34-2016 Designation and
Safety Classification of Refrigerants and described in Appendix B1
to ASHRAE Standard 34-2016.
* * * * *
References