Note: Descriptions are shown in the official language in which they were submitted.
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STABILIZED HEAT TRANSFER COMPOSITIONS, METHODS AND SYSTEMS
Field of the Invention
The present invention relates to compositions, methods and systems having
utility in
heat exchange 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
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).
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.
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.
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
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2088. There is therefore a need in the art for the replacement of R-410A with
a more
environmentally acceptable alternative.
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 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.
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.
With regard to efficiency in use, it is important to note that a loss of
refrigerant
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 a
refrigerant will therefore have a negative secondary environmental impact.
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
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ASHRAE Standard 34-2016, which is incorporated herein by reference and
referred to
herein for convenience as "Non-Flammability Test.
It is very important for maintenance of system efficiency and proper and
reliable
functioning of the compressor, that lubricant circulating in a vapour
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.
R-410A is currently commonly used with polyol ester (POE) lubricating oil in
air
conditioning applications, as R-41 OA 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.
Applicants have come to appreciate that it is 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
The present invention provides refrigerant compositions which can be used as a
replacements for R-410A and which exhibit in preferred embodiments 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.
The present invention includes heat transfer compositions comprising
refrigerant,
lubricant and stabilizer, said refrigerant 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),
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Ito 4% by weight pentafluoroethane (HFC-125), and
51 to 57% by weight trifluoroiodomethane (CF31),
said lubricant comprising polyol ester (POE) lubricant and/or polyvinyl ether
(PVE)
lubricant, and said stabilizer comprising alkylated naphthalene, wherein said
alkylated
naphthalene is present in the composition in an amount of from 1% to less than
10% by
weight based on the weight of the alkylated naphthalene and the lubricant. The
heat
transfer composition according to this paragraph is sometimes referred to
herein for
convenience as Heat Transfer Composition 1.
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.
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.
In connection with the use of stabilizers comprising alkylated naphthalene in
heat
transfer compositions comprising CF3I refrigerants and lubricant that
comprises POE and/or
PVE, applicants have found that a critical range exists in which the
stabilizing effect of the
alkylated naphthalene is beneficially and unexpectedly enhanced relative to
the stabilizing
effect outside of the range of from 1% to less than 10% by weight based on the
alkylated
naphthalene and the lubricant, or preferabaly from 1.5% to less than 8%, ore
preferably
from 1.5% to about 6%, or preferably from 1.5 to 5%. The reason for the
enhanced
performance within this critical range derives from the discovery that
stabilizing performance
of the alkylated naphthalene can, in the absence of other solutions described
hereinafter, be
deteriorate to an undesirable extent for some applications when used in
amounts above
about 10%. Furthermore, applicants believe that the stabilizing performance of
alkylated
naphthalene also is less than desirable for some applications when used in
amounts of less
than 1%. The existence of this critical range is unexpected.
Accordingly, the present invention also includes heat transfer compositions
comprising refrigerant, lubricant and stabilizer, said refrigerant consisting
essentially ofthe
following three compounds, with each compound being present in the following
relative
percentages:
39 to 45% by weight difluoromethane (HFC-32),
Ito 4% by weight pentafluoroethane (HFC-125), and
51 to 57% by weight trifluoroiodomethane (CF3I),
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said lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant, and said
stabilizer comprising alkylated naphthalene, wherein said alkylated
naphthalene is present
in an amount of from 1% to 8% by weight based on the weight of the alkylated
naphthalene
and the lubricant. The heat transfer composition according to this paragraph
is sometimes
referred to herein for convenience as Heat Transfer Composition 2.
The present invention includes heat transfer compositions comprising
refrigerant,
lubricant and stabilizer, said refrigerant 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),
Ito 4% by weight pentafluoroethane (HFC-125), and
51 to 57% by weight trifluoroiodomethane (CF31),
said lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant, and said
stabilizer comprising alkylated naphthalene, wherein said alkylated
naphthalene is present
in an amount of from 1.5% to 8% by weight based on the weight of the alkylated
naphthalene and the lubricant. The heat transfer composition according to this
paragraph is
sometimes referred to herein for convenience as Heat Transfer Composition 3.
The present invention includes heat transfer compositions comprising
refrigerant,
lubricant and stabilizer, said refrigerant 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),
Ito 4% by weight pentafluoroethane (HFC-125), and
51 to 57% by weight trifluoroiodomethane (CF31),
said lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant, and said
stabilizer comprising alkylated naphthalene, wherein said alkylated
naphthalene is present
in an amount of from 1.5% to 6% by weight based on the weight of the alkylated
naphthalene and the lubricant. The heat transfer composition according to this
paragraph is
sometimes referred to herein for convenience as Heat Transfer Composition 4.
The present invention includes heat transfer compositions comprising
refrigerant,
lubricant and stabilizer, said refrigerant consisting essentially of 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 (CF31), said lubricant comprising
POE
lubricant and/or polyvinyl ether (PVE) lubricant, and said stabilizer
comprising alkylated
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naphthalene, wherein said alkylated naphthalene is present in an amount of
from 1% to less
than 10% by weight based on the weight of the alkylated naphthalene and the
lubricant. The
heat transfer composition according to this paragraph is sometimes referred to
herein for
convenience as Heat Transfer Composition 5.
The present invention includes heat transfer compositions comprising
refrigerant,
lubricant and stabilizer, said refrigerant consisting essentially of 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), said lubricant comprising
POE
lubricant and/or polyvinyl ether (PVE) lubricant, and said stabilizer
comprising alkylated
naphthalene, wherein said alkylated naphthalene is present in an amount of
from 1% to 8%
by weight based on the weight of the alkylated naphthalene and the lubricant.
The heat
transfer composition according to this paragraph is sometimes referred to
herein for
convenience as Heat Transfer Composition 6.
The present invention includes heat transfer compositions comprising
refrigerant,
lubricant and stabilizer, said refrigerant 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), said lubricant comprising
POE
lubricant and/or polyvinyl ether (PVE) lubricant, and said stabilizer
comprising alkylated
naphthalene, wherein said alkylated naphthalene is present in an amount of
from 1.5 to 8%
by weight based on the weight of the alkylated naphthalene and the lubricant.
The heat
transfer composition according to this paragraph is sometimes referred to
herein for
convenience as Heat Transfer Composition 7.
The present invention includes heat transfer compositions comprising
refrigerant,
lubricant and stabilizer, said refrigerant consisting essentiallyof 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), said lubricant comprising
POE
lubricant and/or polyvinyl ether (PVE) lubricant, and said stabilizer
comprising alkylated
naphthalene, wherein said alkylated naphthalene is present in an amount of
from 1.5 to 6%
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by weight based on the weight of the alkylated naphthalene and the lubricant.
The heat
transfer composition according to this paragraph is sometimes referred to
herein for
convenience as Heat Transfer Composition 8.
The present invention also includes any of Heat Transfer Compositions 1 ¨ 8
wherein said
stabilizer is essentially free of an ADM as defined hereinafter. The heat
transfer composition
according to this paragraph is sometimes referred to herein for convenience as
Heat
Transfer Composition 8A.
The present invention also includes any of Heat Transfer Compositions 1 ¨ 8
wherein said stabilizer is essentially free of an ADM and wherein said
stabilizer further
comprises BHT. The heat transfer composition according to this paragraph is
sometimes
referred to herein for convenience as Heat Transfer Composition 8B.
The present invention also includes heat transfer compositions comprising
refrigerant, lubricant and stabilizer, said refrigerant 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),
Ito 4% by weight pentafluoroethane (HFC-125), and
51 to 57% by weight trifluoroiodomethane (CF31),
said lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant, and said
stabilizer comprising alkylated naphthalene and an acid depleting moiety. The
heat transfer
composition according to this paragraph is sometimes referred to herein for
convenience as
Heat Transfer Composition 9.
As used herein, the term "acid depleting moiety" (which is sometimes referred
to
herein for convenience as "ADM") means a compound or radical which when
present in a
heat transfer composition comprising a refrigerant that contains about 10% by
weigh or
greater of CF3I (said percentage being based in the weight of all the
refrigerants in the heat
transfer composition), has the effect of substantially reducing the acid
moieties that would
otherwise be present in the heat transfer composition. As used herein, the
term
"substantially reducing" as used with respect to the acid moieties in the heat
transfer
composition means that acid moieties are reduced sufficiently to result in a
reduction in TAN
value (as defined hereinafter) of at least about 10 relative percent.
In connection with the use of stabilizers comprising alkylated naphthalene and
an
ADM, applicants have found that certain materials are able to substantially
and
unexpectedly enhance the performance of stabilizers which comprise or consist
essentially
of alkylated naphthalene stabilizer(s). In particular, applicants have found
that certain
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materials are able to aid in the depletion of acidic moieties in heat transfer
compositions
containing CF3I, including any heat transfer compositions of the present
invention.
Applicants have found that formulating heat transfer compositions to have an
ADM provides
an unexpected and synergistic enhancement to the stability function of at
least the alkylated
naphthalene stabilizers according to the present invention. The reason for
this synergistic
effect is not understood with certainty, but without being bound by or to any
theory of
operation, it is believed that the alkylated naphthalene stabilizers of the
present invention
function in large part by stabilizing free radicals formed from the CF3I of
the present
refrigerants, but that this stabilizing effect is at least somewhat diminished
in the presence of
acid moieties. As a result, the presence of the ADM of the present invention
allows the
alkylated naphthalene stabilizers to perform with an unexpected and
synergistically
enhanced effect. Furthermore, applicants have found that the deterioration in
performance
which applicants have observed at relatively high concentrations of alkylated
naphthalene
(i.e., about about 10%) can be counteracted by the incorporation into the heat
transfer
composition (or into a stabilized lubricant) of an ADM.
The present invention therefore includes stabilizer comprising an alkylated
naphthalene and an ADM. The stabilizer according to this paragraph is
sometimes referred
to herein for convenience as Stabilizer 1.
The present invention also includes stabilizer comprising from about 40% by
weight
to about 99.9% of alkylated naphthalenes and from 0.05% to about 50% by weight
of ADM
based on the weight of the stabilizer. The stabilizer according to this
paragraph is
sometimes referred to herein for convenience as Stabilizer 2.
The present invention also includes stabilizer comprising from about 50% by
weight
to about 99.9% of alkylated naphthalenes and an from 0.1% to about 50% by
weight of ADM
based on the weight of the stabilizer. The stabilizer according to this
paragraph is
sometimes referred to herein for convenience as Stabilizer 3.
The present invention also includes stabilizer comprising from about 40% by
weight
to about 95% of alkylated naphthalenes and an from 5% to about 30% by weight
of ADM
based on the weight of the alkylated naphthalenes and ADM in the stabilizer.
The stabilizer
according to this paragraph is sometimes referred to herein for convenience as
Stabilizer 4.
The present invention also includes stabilizer comprising from about 40% by
weight
to about 95% of alkylated naphthalenes and an from 5% to about 20% by weight
of ADM
based on the weight of the alkylated naphthalenes and ADM in the stabilizer.
The stabilizer
according to this paragraph is sometimes referred to herein for convenience as
Stabilizer 5.
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The present invention also includes heat transfer compositions comprising
refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant and
Stabilizer 2, said refrigerant 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),
Ito 4% by weight pentafluoroethane (HFC-125), and
51 to 57% by weight trifluoroiodomethane (CF31). The heat transfer composition
according to this paragraph is sometimes referred to herein for convenience as
Heat
Transfer Composition 10.
The present invention also includes heat transfer compositions comprising
refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant and
Stabilizer 4, said refrigerant 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),
.. Ito 4% by weight pentafluoroethane (HFC-125), and
51 to 57% by weight trifluoroiodomethane (CF31). The heat transfer composition
according
to this paragraph is sometimes referred to herein for convenience as Heat
Transfer
Composition 11.
The present invention also includes heat transfer compositions comprising
.. refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether
(PVE) lubricant and
Stabilizer 5, said refrigerant 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),
Ito 4% by weight pentafluoroethane (HFC-125), and
51 to 57% by weight trifluoroiodomethane (CF31). The heat transfer composition
according
to this paragraph is sometimes referred to herein for convenience as Heat
Transfer
Composition 12.
The present invention also includes heat transfer compositions comprising
refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant and
Stabilizer 1, said refrigerant 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
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55.5% 0.5% by weight trifluoroiodomethane (CF3I). The heat transfer
composition
according to this paragraph is sometimes referred to herein for convenience as
Heat
Transfer Composition 13.
The present invention also includes heat transfer compositions comprising
refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant and
Stabilizer 2, said refrigerant 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). The heat transfer
composition
according to this paragraph is sometimes referred to herein for convenience as
Heat
Transfer Composition 14.
The present invention also includes heat transfer compositions comprising
refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant and
Stabilizer 3, said refrigerant 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). The heat transfer
composition
according to this paragraph is sometimes referred to herein for convenience as
Heat
Transfer Composition 15.
The present invention also includes heat transfer compositions comprising
refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant and
Stabilizer 4, said refrigerant 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). The heat transfer
composition
according to this paragraph is sometimes referred to herein for convenience as
Heat
Transfer Composition 16.
The present invention also includes heat transfer compositions comprising
refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE)
lubricant and
Stabilizer 5, said refrigerant consisting essentially of the following three
compounds, with
each compound being present in the following relative percentages:
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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). The heat transfer
composition
according to this paragraph is sometimes referred to herein for convenience as
Heat
Transfer Composition 17.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant and/or polyvinyl ether (PVE) lubricant; and (b) a stabilizer of the
present invention.
Brief Description of the Fiqure
Figure 1 shows the LCCP of one of the refrigerants of the present invention
and
.. certain known refrigerants.
Description
Definitions:
For the purposes of this invention, the term "about" in relation to
temperatures in
degrees centigrade ( C) means that the stated temperature can vary by an
amount of +/-
5 C. In preferred embodiments, temperature specified as being about is
preferably +/- 2 C,
more preferably +/- 1 C, and even more preferably +/- 0.5 C of the identified
temperature.
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.
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
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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.
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 CO2 over that time period. The time
period usually
used for GWP is 100 years. GWP provides a common measure, which allows
analysts to
add up emission estimates of different gases. See www.epa.gov.
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) x (Annual
Loss Rate x
Lifetime + End-of-Life Loss) x GWP. Equation 2 is Indirect Emissions = Annual
Power
.. Consumption x Lifetime x CO2 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 Bin Maker Pro Version 4 Software is
used for the
analysis. The GWP values reported in the Intergovernmental Panel on Climate
Change
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(IPCC)'s Assessment Report 4 (AR4) 2007 are used for the calculations. LCCP is
expressed as carbon dioxide mass (kg-0O2,q) over the lifetime of the air
conditioning or
refrigeration systems.
The term "mass flow rate" is the mass of refrigerant passing through a conduit
per
unit of time.
The term "Occupational Exposure Limit (OEL)" is determined in accordance with
ASH RAE Standard 34-2016 Designation and Safety Classification of
Refrigerants.
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.
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.
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.
As the term is used herein, "TAN value" refers to the total acid number as
determined 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.
Heat Transfer Compositions
Applicants have found that the heat transfer compositions of the present
invention,
including each of Heat Transfer Compositions 1-17 as described herein, are
capable of
providing exceptionally advantageous properties and in particular stability in
use and non-
flammability, especially with the use of the heat transfer compositions as a
replacement for
R-41 OA 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-41 OA chiller systems).
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As used herein, the reference Heat Transfer Compositions 1 ¨ 17 refers to each
of
Heat Transfer Compositions 1 through 17, including Heat Transfer Compositions
8A and 8B.
A particular advantage of the refrigerants included in the heat transfer
compositions
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-41 OA 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.
Preferably, the heat transfer compositions of the present invention, including
each of
Heat Transfer Compositions 1 ¨ 17, include refrigerant in an amount of greater
than 40% by
weight of the heat transfer composition.
Preferably, the heat transfer compositions of the present invention, including
each of
Heat Transfer 1 ¨ 17, include refrigerant in an amount of greater than 50% by
weight, or
greater than 70% by weight, or greater than 80% by weight, or greater than
90%, of the heat
transfer composition.
Preferably, the heat transfer compositions of the present invention, including
each of
Heat Transfer Compositions 1 ¨ 17, consist essentially of the refrigerant, the
lubricant and
stabilizer.
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 stability provided in accordance with present
invention.
Such other components or additives may include , dyes, solubilizing agents,
compatibilizers,
auxiliary stabilizers, antioxidants, corrosion inhibitors, extreme pressure
additives and anti-
wear additives.
Stabilizers:
Alkylated Naphthalenes
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:
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Rs R1
2
R6 I R3
R5 R4
where each R1¨ R8 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.
Applicants have found unexptected, surprising and advantageous results are
associtated 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 (or
AN1) ¨ Alylated Napthalene 5 (or AN5) as indicated respectively in rows 1 ¨5
in the Table
below:
ALKYLATED NAPHTHALENE TABLE 1
Property AN1 AN2 AN3 AN4 AN5
Viscosity 20 ¨200 20 ¨ 100 20 ¨ 50 30 - 40 about 36
@ 40 C (ASTM D445), cSt
Viscosity 3 ¨ 20 3 ¨ 10 3 ¨ 8 5 - 7 about 5.6
@ 100 C
(ASTM D445), cSt
Pour Point -50 to - -45 to -25 -40 to -30 -45 to -
30 about -33
(ASTM D97), C 20
As used herein in connection with viscosity at 40 C measured according to ASTM
D445, the term "about" means +/- 4 cSt.
As used herein in connection with viscosity at 100 C measured according to
ASTM
D445, the term "about" means +/- 0.4 cSt.
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As used herein in connection with pour point as measured according to ASTM
D97,
the term "about" means +/- 5 C.
Applicants have also found that unexptected, surprising and advantageous
results
are associtated 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 (or
AN6) ¨ Alkylated Napthalene 10 (or AN10) as indicated respectively in rows 6¨
10 in the
Table below:
ALKYLATED NAPHTHALENE TABLE 2
Property AN6 AN7 AN 8 AN 9 AN10
Viscosity 20 ¨200 20 ¨ 100 20 ¨ 50 30 ¨ 40 about 36
@ 40 C (ASTM D445), cSt
Viscosity 3 ¨ 20 3 ¨ 10 3 ¨ 8 5 ¨ 7 about 5.6
@ 100 C
(ASTM D445), cSt
Aniline Point 40 ¨ 110 50 ¨ 90 50 ¨ 80 60 - 70 about 36
(ASTM D611), C
Noack Volatility 1 ¨ 50 5 ¨ 30 5 ¨ 15 10 - 15 about 12
CEC L40
(ASTM D6375), wt%
Pour Point -50 to - -45 to -25 -40 to -30 -45
to - about -33
(ASTM D97), C 20 30
Flash Point 200 ¨ 200 ¨270 220 ¨ 230 - about 236
(ASTM D92) ), C 300 250 240
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.
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.
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
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under the trade designation NA-LUBE KR-008.
The present invention included heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨17 hereof, wherein the alkylated naphthalene is AN1,
AN2, of
AN3, or AN4, or AN5, or AN6, or AN7, or AN8, or AN9 or AN10.
Acid Depleting Moieties (ADM)
Those skilled in the art will be able to determine, without undo
experimentation, a
variety of ADMs that are useful in accordance with the present invention, and
all such AD Ms
are within the scope hereof.
Epoxides
Applicants have found that epoxides, and partculrly alkylated epoxides, are
effective
at producing the enhanced stability discussed herein when used in combination
with
alkylated naphthalene stabilizers, and while applicants are not necessarily
bound by theory
it is believed that this synergistic enhancement stems at least in part due to
its effective
functioning as an ADM in the heat transfer compositions of the present
invention.
In preferred embodiments the epoxide is selected from the group consisting of
epoxides that undergo ring-opening reactions with acids, thereby depleting the
system of
acid while not otherwise deleteriously affecting the system.
Useful epoxides include aromatic epoxides, alkyl epoxides, and alkyenyl
epoxides.
Preferred epoxides include epoxides of the following Formula I:
0
R3
R2 R4
where at least one of said R1¨ R4 is selected from a two to fifteen carbon (C2
¨ C15) acyclic
group, a C2 ¨ C15 aliphatic group and a C2 ¨ C15 ethers. An epoxide according
to Formula
1 is sometimes referred to herein for convenience as ADM1.
In a preferred embodiment, at least one of R1 ¨ R4 of Formula I is an ether
having
the following structure:
R5 -0 R6
where each of R5 and R6 is independently a C1 ¨ C14 straight chain or branched
chain, preferably unsubstituted, alkyl group. An epoxide according to the
paragraph is
sometimes referred to herein for convenience as ADM2.
In a preferred embodiment, one of R1¨ R4 of Formula I is an ether having the
following structure:
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R5 ¨ R6
where each of R5 and R6 is independently a Cl ¨ C14 straight chain or branched
chain,
preferably unsubstituted, alkyl group, and the remaining three of R1¨ R4 are
H. An epoxide
according to the paragraph is sometimes referred to herein for convenience as
ADM3.
In preferred embodiments the epoxide comprises, conists essentially of or
consists
of 2-ethylhexyl glycidyl ether. An epoxide according to this paragraph is
sometimes referred
to herein for convenience as ADM4.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨8 and 9-17 hereof, wherein the alkylated naphthalene
is AN1
and further comprising ADM1.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 - 17, wherein the alkylated naphthalene is
AN1 and
further comprising ADM1.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 - 17, wherein the alkylated naphthalene is
AN1 and
further comprising ADM2.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 - 17, wherein the alkylated naphthalene is
AN1 and
further comprising ADM3.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 - 17, wherein the alkylated naphthalene is
AN1 and
further comprising ADM4.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 - 17, wherein the alkylated naphthalene is
AN5 and
further comprising ADM1.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 - 17, wherein the alkylated naphthalene is
AN5 and
further comprising ADM2.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 - 17, wherein the alkylated naphthalene is
AN5 and
further comprising ADM3.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 - 17, wherein the alkylated naphthalene is
AN5 and
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further comprising ADM4.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 -8 and 9 - 17, wherein the alkylated naphthalene is
AN10 and
further comprising ADM1.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 -8 and 9 - 17, wherein the alkylated naphthalene is
AN10 and
further comprising ADM2.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 -8 and 9 - 17, wherein the alkylated naphthalene is
AN10 and
further comprising ADM3.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 8 and 9 - 17, wherein the alkylated naphthalene is
AN10 and
further comprising ADM4.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 -8 and 9 - 17, wherein the alkylated naphthalene is
AN2, or AN3
or AN4 or AN6, or AN7 or AN8 or AN9 and further comprising ADM1.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 -8 and 9 - 17, wherein the alkylated naphthalene is
AN2, or AN3
or AN4 or AN6, or AN7 or AN8 or AN9 and further comprising ADM2.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 8 and 9 - 17, wherein the alkylated naphthalene is
AN2, or AN3 or
AN4 or AN6, or AN7 or AN8 or AN9 and further comprising ADM3.The present
invention
includes heat transfer compositions, including each of Heat Transfer
Compositions 1 8 and
9 - 17, wherein the alkylated naphthalene is AN2, or AN3 or AN4 or AN6, or AN7
or AN8 or
AN9 and further comprising ADM4.
When the ADM is present in the Heat Transfer Compostions of the present
invention, including each of Heat Transfer Compositions 1 ¨ 8 and 9 - 17, the
alkylated
naphthalene is preferably 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.
When the ADM is present in the Heat Transfer Compostions of the present
invention, including each of Heat Transfer Compositions 1 ¨8 and 9 - 17, the
alkylated
naphthalene is preferably present in an amount of from 0.1% to about 20%, or
from 1,5% to
about 10%, or from 1,5% to about 8%, where amounts are in percent by weight
based on
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the amount of alkylated naphthalene plus lubricant in the system.
Carbodiimides
The ADM can include carbodiimides. In preferred embodiments the carbodiimides
include compounds having the following structure:
RI-N=C=---N-R2
Other Stabilizers
It is contemplated that stabilizers other than the alkylated naphthalenes and
ADM
may be included in the heat transfer compositions of the present invention,
including each of
Heat Transfer Compositions 1 ¨ 17. Examples of such other stabilzers are
described
hereinafter.
Phenol-based Compounds
In preferred embodiments, the stabilizer further includes a phenol based
compound.
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-methy1-6-
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-
buty1-4-
methylphenol (BHT); 2,6-di-tert-butyl-4-ethylphenol: 2,4-dimethy1-6-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-methy1-6-tert-butylphenol); bis(3-methyl-4-hydroxy-5-tert-
butylbenzyl) sulfide; bis
(3,5-di-tert-buty1-4-hydroxybenzyl)sulfide, tocopherol, hydroquinone, 2,2'6,6'-
tetra-tert-buty1-
4,4'-methylenediphenol and t-butyl hydroquinone, and preferably BHT.
The phenol compounds, and in particular BHT, 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.
The phenol compounds, and in particular BHT, can be provided in the heat
transfer
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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
based on the weight of the lubricant in the heat transfer composition.
The present invention also includes stabilizer comprising from about 40% to
about
95% by weight of alkylated naphthalenes, including each of AN1 ¨ AN10, and
from 0.1 to
about 10% by weight of BHT, based on the weight of the all the stabilizer
components in the
composition. The stabilizer according to this paragraph is sometimes referred
to herein for
convenience as Stabilizer 6.
The present invention also includes stabilizer comprising from about 40% to
about
95% by weight of alkylated naphthalenes, including each of AN1 ¨ AN10, from 5%
to about
30% by weight of ADM, including each of ADM1 ¨ADM4, and from 0.1 to about 10%
by
weight of BHT, based on the weight of the all the stabilizer components in the
composition.
The stabilizer according to this paragraph is sometimes referred to herein for
convenience
as Stabilizer 7.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 17 hereof, wherein the heat transfer composition
comprises
Stablizer 6.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9 ¨ 26 hereof, wherein the heat transfer
compositions
comprises Stablizer 7.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨17 hereof, comprising AN1 and BHT.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨17 hereof, comprising AN5 and BHT.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨17 hereof, comprising AN10 and BHT.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨ 8 and 9-17 hereof, comprising of AN5, ADM4 and BHT.
The present invention includes heat transfer compositions, including each of
Heat
Transfer Compositions 1 ¨8 and 9-17 hereof, comprising AN10, ADM4 and BHT.
Diene-based Compounds
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
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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, camosic acid, and vitamin Al. Preferably, the stabilizer is farnesene.
Preferred
terpene stabilizers are disclosed in US Provisional Patent Application No.
60/638,003 filed
on December 12, 2004, published as US 2006/0167044A1, which is incorporated
herein by
reference.
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.
Phosphorus-based Compounds
The phosphorus compound can be a phosphite or a phosphate compound. For the
purposes of this invention, the phosphite compound can be a diary!, 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.
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 /0 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.
Nitrogen Compounds
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
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substituted piperidyl, piperidinyl, piperazinone, or alkyoxypiperidinyl,
particularly one or more
amine antioxidants selected from 2,2,6,6-tetramethy1-4-piperidone, 2,2,6,6-
tetramethy1-4-
piperidinol; bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate; di(2,2,6,6-
tetramethy1-4-
piperidyl)sebacate, poly(N-hydroxyethy1-2,2,6,6-tetramethy1-4-hydroxy-
piperidyl succinate;
alkylated paraphenylenediamines such as N-phenyl-N'-(1,3-dimethyl-buty1)-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@765 (Ciba), BLS@1944 (Mayzo Inc) and BLS 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).
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.
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.
Isobutylene
lsobutylene may also be used as a stablilizer according to the present
invention.
Additional Stabilizer Compositions
The present invention also provides stabilizer comprising alkylated
naphthalene,
including each of AN1 ¨ AN10 and an ADM, including each of ADM1 ¨ADM4 and a
phenol.
A stabilizer according to this paragraph is sometimes referred to herein for
convenience as
Stabilizer 8.
The present invention also provides a stabilizer consisting essentially of
alkylated
naphthalene, including each of AN1 ¨ AN10 and an ADM, including each of ADM1 ¨
ADM4
and a phosphate. A stabilizer according to this paragraph is sometimes
referred to herein
for convenience as Stabilizer 9.
The present invention also provides stabilizer comprising alkylated
naphthalene,
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including each of AN1 ¨ AN10 and an ADM, including each of ADM1 ¨ADM4 and a
combination of a phosphate and a phenol. A stabilizer according to this
paragraph is
sometimes referred to herein for convenience as Stabilizer 10.
The present invention also provides a stabilizer comprising alkylated
naphthalene,
including each of AN1 ¨ AN10, in an amount of from about 40 /0 by weight to
about 95 /0 by
weight, an ADM, including each of ADM1 ¨ADM4, in an amount of from about 0.5%
by
weight to about 25% by weight, and an additional stabilizer selected from a
phosphate, a
phenol and combinations of thesein an amount of from about 0.1% by weight to
about 50%
by weight, wherein said weight percentages are based on the total weight of
the stabilizer.
A stabilizer according to this paragraph is sometimes referred to herein for
convenience as
Stabilizer 11.
The present invention also provides a stabilizer comprising alkylated
naphthalene,
including each of AN1 ¨ AN10, in an amount of from about 70 /0 by weight to
about 95 /0 by
weight, an ADM, including each of ADM1 ¨ADM4, in an amount of from about 0.5%
by
weight to about 15% by weight, and an additional stabilizer selected from a
phosphate, a
phenol and combinations of these in an amount of from about 0.1% by weight to
about 25%
by weight, wherein said weight percentages are based on the total weight of
the stabilizer.
A stabilizer according to this paragraph is sometimes referred to herein for
convenience as
Stabilizer 12.
The present invention also provides a stabilizer consisting essentially of
alkylated
naphthalene, including each of AN1 ¨ AN10 and an ADM, including each of ADM1
¨ADM4
and BHT. A stabilizer according to this paragraph is sometimes referred to
herein for
convenience as Stabilizer 13.
The present invention also provides a stabilizer consisting of alkylated
naphthalene,
including each of AN1 ¨ AN10 and an ADM, including each of ADM1 ¨ADM4 and
BHTI. A
stabilizer according to this paragraph is sometimes referred to herein for
convenience as
Stabilizer 14.
The present invention also provides a stabilizer consisting essentially of
alkylated
naphthalene, including each of AN1 ¨ AN10 and an ADM, including each of ADM1
¨ADM4,
BHT and a phosphate. A stabilizer according to this paragraph is sometimes
referred to
herein for convenience as Stabilizer 15.
The present invention also provides a stabilizer consisting of alkylated
naphthalene,
including each of AN1 ¨ AN10 and an ADM, including each of ADM1 ¨ADM4, BHT and
a
phosphate. A stabilizer according to this paragraph is sometimes referred to
herein for
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convenience as Stabilizer 16.
The present invention also provides a stabilizer comprising alkylated
naphthalene,
including each of AN1 ¨ AN10, in an amount of from about 40 /0 by weight to
about 95 /0 by
weight, an ADM, including each of ADM1 ¨ADM4, in an amount of from about 0.5%
by
weight to about 10% by weight, and BHT, in an amount of from about 0.1% by
weight to
about 50% by weight, wherein said weight percentages are based on the total
weight of the
stabilizer. A stabilizer according to this paragraph is sometimes referred to
herein for
convenience as Stabilizer 17.
The present invention also provides a stabilizer comprising alkylated
naphthalene,
including each of AN1 ¨ AN10, in an amount of from about 70 /0 by weight to
about 95 /0 by
weight, an ADM, including each of ADM1 ¨ADM4, in an amount of from about 0.5%
by
weight to about 10% by weight, and BHT, in an amount of from about 0.1% by
weight to
about 25% by weight, wherein said weight percentages are based on the total
weight of the
stabilizer. A stabilizer according to this paragraph is sometimes referred to
herein for
convenience as Stabilizer 18.
The present invention also provides a stabilizer comprising alkylated
naphthalene,
including each of AN1 ¨ AN10, in an amount of from about 40% by weight to
about 95% by
weight, an ADM, including each of ADM1 ¨ADM4, in an amount of from about 5% by
weight
to about 25% by weight, and a third stabilizer compound selected from BHT, a
phosphate
and combinations of these in an amount of from 1% by weight to about 55% by
weight,
wherein said weight percentages are based on the total weight of the
stabilizer. A stabilizer
according to this paragraph is sometimes referred to herein for convenience as
Stabilizer
19.
The present invention also provides a stabilizer comprising alkylated
naphthalene,
including each of AN1 ¨ AN10, in an amount of from about 40% by weight to
about 95% by
weight, an ADM, including each of ADM1 ¨ADM4, in an amount of from about 5% by
weight
to about 25 /0 by weight, and BHT, in an amount of from about 0.1% by weight
to about 5%
by weight, wherein said weight percentages are based on the total weight of
the stabilizer.
A stabilizer according to this paragraph is sometimes referred to herein for
convenience as
Stabilizer 20.
The stabilizers of the present invention, including each of Stabilizers 1 ¨
20, can be
used in any of the heat transfer compositions of the present invention,
including any of Heat
Transfer compositions 1 ¨ 8 and 9 - 17
The stabilizers of the present invention, including each of Stabilizers 1 ¨ 6,
can also
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be used in any of Heat Transfer compositions 8A and 8B.
LUBRICANTS
In general, the heat transfer composition of the present invention, including
each of
Heat Transfer Compositions 1 ¨45, 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.
POE Lubricants
The POE lubricant of the present invention includes in preferred embodiments a
neopentyl POE lubricant. As used herein, the term neopentyl POE lubricant
refers to polyol
esters (POEs) derived from a reaction between a neopentyl polyol (preferably
pentaerythritol, trimethylolpropane, or neopentyl glycol, and in embodiments
where higher
viscosities are preferred, dipentaerythritol) and a linear or branched
carboxylic acid.
Commercially available POEs include neopentyl glycol dipelargonate which is
available as Emery 2917 (registered trademark) and Hatcol 2370 (registered
trademark) and
pentaerythritol derivatives including those sold under the trade designations
Emkarate
RL32-3MAF and Emkarate RL68H by CPI Fluid Engineering. Emkarate RL32-3MAF and
Emkarate RL68H are preferred neopently POE lubricants having the properties
identified
below:
Property RL32-3MAF RL68H
Viscosity about 31 about 67
@ 40 C (ASTM D445), cSt
Viscosity about 5.6 about 9.4
@ 100 C
(ASTM D445), cSt
Pour Point about -40 about -40
(ASTM D97), C
Other useful esters include phosphate esters, di-basic acid esters and fluoro
esters.
A lubricant consisting essentially of a POE having a viscosity at 40 C
measured in
accordance with ASTM D445 of from about 30 cSt to about 70 cSt and a viscosity
Measured
@ 100 C in accordance with ASTM D445 of from about 5 cSt to about 10 cSt is
referred to
herein as Lubricant 1.
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A lubricant consisting essentially of a neopentyl POE having a viscosity at 40
C
measured in accordance with ASTM D445 of from about 30 cSt to about 70 cSt is
referred
to for convenience as Lubricant 2.
The present invention also provides heat transfer compositons, including each
of
Heat Transfer Compositions 1 ¨ 17, comprising a POE lubricant.
In preferred embodiments, the present Heat Transfer Compositions, including
each
of Heat Transfer Compositions 1 ¨ 17, comprise lubricant consisting
essentially of a POE
lubricant.
In preferred embodiments, the present Heat Transfer Compositions, including
each
of Heat Transfer Compositions 1 ¨ 17, comprise lubricant consisting of a POE
lubricant.
The present invention also provides heat transfer compositons, including each
of
Heat Transfer Compositions 1 ¨ 17, wherein the lubricant is Lubricant 1 and/or
Lubricant 2.
PVE Lubricants
The lubricant of the present invention can include PVE lubricants generally.
In
preferred embodiments the PVE lubricant is as PVE according to Formula II
below:
R ------ Cal¨CH - CH.2.¨CH R4
t
0
1
0
k
. 1
1
R3
õ On
Formula ll
where R2 and R3 are each independently Cl ¨ C10 hydrocarbons, preferably C2 -
C8 hydrocarbons, and R1 and R4 are each independently alkyl, alkylene glycol,
or
polyoxyalkylene glycol units and n and m are selected preferably according to
the needs of
those skilled in the art to obtain a lubricant with the desired properties,
and preferable n and
m are selected to obtain a lubricant with a viscosity at 40 C measured in
accordance with
ASTM D445 of from about 30 to about 70 cSt. A PVE lubricant according to the
description
immediately above is referred to for convenience as Lubricant 3. Commercially
available
polyvinyl ethers include those lubricants sold under the trade designations
FVC32D and
FVC68D, from Idemitsu.
In preferred embodiments, the present Heat Transfer Compositions, including
each
of Heat Transfer Compositions 1 ¨ 17, comprise a PVE lubricant.
In preferred embodiments, the present Heat Transfer Compositions, including
each
of Heat Transfer Compositions 1 ¨ 17, comprise lubricant consist essentially
of a PVE
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lubricant.
In preferred embodiments, the present Heat Transfer Compositions, including
each
of Heat Transfer Compositions 1 ¨ 17, comprise lubricant consisting of a PVE
lubricant.
In preferred embodiments, the PVE in the present Heat Transfer Compositions,
including each of Heat Transfer Compositions 1 ¨17, is a PVE according to
Formula II.
The present invention also provides heat transfer compositons, including each
of
Heat Transfer Compositions 1 ¨ 17, comprising Lubricant 1, or Lubricant 2 or
Lubricant 3.
STABILIZED LUBRICANTS
The present invention also provides stabilized lubricants comprising: (a) POE
lubricant; and (b) a stabilizer of the present invention, including each of
Stabilizers 1 - 20.
The stabilized lubricant according to this paragraph is sometimes referred to
herein for
convenience as Stabilized Lubricant 1.
The present invention also provides stabilized lubricants comprising: (a) neo
pentyl
POE lubricant; and (b) a stabilizer of the present invention, including each
of Stabilizers 1 ¨
20. The stabilized lubricant according to this paragraph is sometimes referred
to herein for
convenience as Stabilized Lubricant 2.
The present invention also provides stabilized lubricants comprising: (a)
Lubricant 1;
and (b) a stabilizer of the present invention, including each of Stabilizers 1
- 20. The
stabilized lubricant according to this paragraph is sometimes referred to
herein for
convenience as Stabilized Lubricant 3.
The present invention also provides stabilized lubricants comprising: (a)
Lubricant 2;
and (b) a stabilizer of the present invention, including each of Stabilizers 1
- 20. The
stabilized lubricant according to this paragraph is sometimes referred to
herein for
convenience as Stabilized Lubricant 4.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 1. The
stabilized lubricant
according to this paragraph is sometimes referred to herein for convenience as
Stabilized
Lubricant 5.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 2. The
stabilized lubricant
according to this paragraph is sometimes referred to herein for convenience as
Stabilized
Lubricant 6.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 3. The
stabilized lubricant
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according to this paragraph is sometimes referred to herein for convenience as
Stabilized
Lubricant 7.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant
and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 4. The stabilized
lubricant
according to this paragraph is sometimes referred to herein for convenience as
Stabilized
Lubricant 8.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant
and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 5. The stabilized
lubricant
according to this paragraph is sometimes referred to herein for convenience as
Stabilized
Lubricant 9.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant; and
(b) from 1% to less than 10% by weight of alkylated naphthalene based on the
weight of the
lubricant and alkylated naphthalene. The stabilized lubricant according to
this paragraph is
sometimes referred to herein for convenience as Stabilized Lubricant 10.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant; and (b) from 1% to 8% by weight of alkylated naphthalene based on
the weight of
the lubricant and alkylated naphthalene. The stabilized lubricant according to
this paragraph
is sometimes referred to herein for convenience as Stabilized Lubricant 11.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant; and (b) from 1.5% to 8% by weight of alkylated naphthalene based on
the weight
of the lubricant and alkylated naphthalene. The stabilized lubricant according
to this
paragraph is sometimes referred to herein for convenience as Stabilized
Lubricant 12.
The present invention also includes stabilized lubricants comprising: (a) POE
lubricant; and (b) from 1.5% to 6% by weight of alkylated naphthalene based on
the weight
of the lubricant and alkylated naphthalene. The stabilized lubricant according
to this
paragraph is sometimes referred to herein for convenience as Stabilized
Lubricant 13.
The present invention includes heat transfer compositions of the invention,
including
each of Heat Transfer Compositions 1 ¨ 17, in which the lubricant and
stabilizer are a
stabilized lubricant of the present invention, including each of Stabilized
Lubricants 1 ¨13.
Methods, Uses and Systems
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.
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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.
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).
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).
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 of Heat
Transfer Compositions 1 ¨17.
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.
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 - 17 and a sequestration
material in the
system, wherein said sequestration material preferably comprises: i. copper or
a copper
alloy, or ii. activated alumina, or iii. a zeolite molecular sieve comprising
copper,
silver, lead or a combination thereof, or iv. an anion exchange resin, or v. a
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moisture-removing material, preferably a moisture-removing molecular sieve, or
vi.a
combination of two or more of the above.
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:
(a) providing a heat transfer composition according to the present invention,
including each of Heat Transfer Compositions 1 - 17;
(b) optionally but preferably providing lubricant for said compressor; and
(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
In preferred embodiments, residential air conditioning systems and methods
have
refrigerant evaporating temperatures in the range of from about 0 C to about
10 C and the
condensing temperature is in the range of about 40 C to about 70 C.
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 C
to about 3 C and the condensing temperature is in the range of about 35 C to
about 50 C.
In preferred embodiments, commercial air conditioning systems and methods have
refrigerant evaporating temperatures in the range of from about 0 C to about
10 C and the
condensing temperature is in the range of about 40 C to about 70 C.
In preferred embodiments, hydronic system systems and methods have refrigerant
evaporating temperatures in the range of from about -20 C to about 3 C and the
condensing temperature is in the range of about 50 C to about 90 C.
In preferred embodiments, medium temperature systems and methods have
refrigerant evaporating temperatures in the range of from about -12 C to about
0 C and the
condensing temperature is in the range of about 40 C to about 70 C.
In preferred embodiments, low temperature systems and methods have refrigerant
evaporating temperatures in the range of from about -40 C to about -12 C and
the
condensing temperature is in the range of about 40 C to about 70 C
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In preferred embodiments, rooftop air conditioning systems and methods have
refrigerant evaporating temperatures in the range of from about 0 C to about
10 C and the
condensing temperature is in the range of about 40 C to about 70 C.
In preferred embodiments, VRF systems and methods have refrigerant evaporating
temperatures in the range of from about 0 C to about 10 C and the condensing
temperature is in the range of about 40 C to about 70 C.
The present invention includes the use of heat transfer compositions of the
present
invention, including each of Heat Transfer Compositions 1 - 17, in a
residential air
conditioning system.
The present invention includes the use of heat transfer compositions of the
present
invention, including each of Heat Transfer Compositions 1 - 17, in a chiller
system.
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
is the refrigerants and/or heat transfer compositions as described herein
for use in a
heat transfer system comprising a reciprocating, rotary (including rolling
piston and
rotary vane), scroll, screw, or centrifugal compressor.
Examples of commonly used expansion devices, for the purposes of this
invention include a capillary tube, a fixed orifice, a thermal expansion valve
and an
electronic expansion valve. Thus, the present invention provides each and any
of
the refrigerants and/or heat transfer compositions as described herein for use
in a
heat transfer system comprising a capillary tube, a fixed orifice, a thermal
expansion
valve or an electronic expansion valve.
For the purposes of this invention, the evaporator and the condenser can each
be in the form a heat exchanger, preferably selected from a finned tube heat
exchanger, a microchannel heat exchanger, a shell and tube, a plate heat
exchanger, and a tube-in-tube heat exchanger. Thus, the present invention
provides each and any of the refrigerants and/or heat transfer compositions as
described herein for use in a heat transfer system wherein the evaporator and
condenser together form a finned tube heat exchanger, a microchannel heat
exchanger, a shell and tube, a plate heat exchanger, or a tube-in-tube heat
exchanger.
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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 100 wherein the sequestration material preferably
comprises a combination of: an anion exchange resin, activated alumina, a
zeolite
molecular sieve comprising silver, and a moisture-removing material,
preferably a
moisture-removing molecular sieve.
io 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
is 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.
20 The heat transfer composition of the invention can be used in heating
and
cooling applications.
In a particular feature of the invention, the heat transfer composition can be
used in a method of cooling comprising condensing a heat transfer composition
and
subsequently evaporating said composition in the vicinity of an article or
body to be
25 cooled.
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 heat transfer composition as described herein; and
ii) evaporating the composition in the vicinity of body or article to be
cooled;
30 wherein the evaporator temperature of the heat transfer system is in the
range of
from about ¨40 C to about +10 C.
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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.
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 heat transfer composition as described herein, 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 C to about 5 C.
The heat transfer composition of the invention is provided for use in air
conditioning applications including both transport and stationary air
conditioning
applications. Thus, any of the heat transfer compositions described herein can
be
used in any one of:
- an air conditioning application including mobile air conditioning,
particularly in
trains and buses conditioning,
- a mobile heat pump, particularly an electric vehicle heat pump;
- 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,
- a residential air conditioning system, particularly a ducted split or a
ductless
split air conditioning system,
- a residential heat pump,
- a residential air to water heat pump/hydronic system,
- an industrial air conditioning system
- a commercial air conditioning system, particularly a packaged rooftop
unit
and a variable refrigerant flow (VRF) system;
- a commercial air source, water source or ground source heat pump system.
The heat transfer composition of the invention is provided for use in a
refrigeration system. The term "refrigeration system" refers to any system or
apparatus or any part or portion of such a system or apparatus which employs a
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refrigerant to provide cooling. Thus, any of the heat transfer compositions
described
herein can be used in any one of:
- 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.
Each of the heat transfer compositions described herein, including Heat
Transfer Compositions 1 ¨ 17, is particularly provided for use in a
residential air-
conditioning system (with an evaporator temperature in the range of about 0 to
about 10 C, particularly about 7 C for cooling and/or in the range of about -
20 to
about 3 C, particularly about 0.5 C for heating). Alternatively, or
additionally, each
of the heat transfer compositions described herein, including each of Heat
Transfer
Compositions 1 ¨ 17, is particularly provided for use in a residential air
conditioning
system with a reciprocating, rotary (rolling-piston or rotary vane) or scroll
compressor.
Each of the heat transfer compositions described, including Heat Transfer
Compositions 1 ¨ 17, is particularly provided for use in an air cooled chiller
(with an
evaporator temperature in the range of about 0 to about 10 C, particularly
about
4.5 C), particularly an air cooled chiller with a positive displacement
compressor,
more particular an air cooled chiller with a reciprocating scroll compressor.
Each of the heat transfer compositions described herein, including Heat
Transfer Compositions 1 ¨ 17, is particularly provided for use in a
residential air to
water heat pump hydronic system (with an evaporator temperature in the range
of
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about -20 to about 3 C, particularly about 0.5 C or with an evaporator
temperature in
the range of about -30 to about 5 C, particularly about 0.5 C).
Each of the heat transfer compositions described herein, including Heat
Transfer Compositions 1 ¨ 17, is particularly provided for use in a medium
temperature refrigeration system (with an evaporator temperature in the range
of
about -12 to about 0 C, particularly about -8 C).
Each of the heat transfer compositions described herein, including Heat
Transfer Compositions 1 ¨ 17, is particularly provided for use in a low
temperature
refrigeration system (with an evaporator temperature in the range of about -40
to
io about -12 C, particularly about from about -400C to about -23 C or
preferably about
-32 C).
The heat transfer composition of the invention, including Heat Transfer
Compositions 1 ¨ 17, is provided for use in a residential air conditioning
system,
wherein the residential air-conditioning system is used to supply cool air
(said air
is having a temperature of for example, about 10 C to about 17 C,
particularly about
12 C) to buildings for example, in the summer.
The heat transfer composition of the invention, including Heat Transfer
Compositions 1 ¨ 17, is thus provided for use in a split residential air
conditioning
system, wherein the residential air-conditioning system is used to supply cool
air
20 (said air having a temperature of for example, about 10 C to about 17 C,
particularly
about 12 C).
The heat transfer composition of the invention, including Heat Transfer
Compositions 1 ¨ 17, is thus provided for use in a ducted split residential
air
conditioning system, wherein the residential air-conditioning system is used
to
25 supply cool air (said air having a temperature of for example, about 10
C to about
17 C, particularly about 12 C).
The heat transfer composition of the invention, including Heat Transfer
Compositions 1 ¨ 17, is thus provided for use in a window residential air
conditioning system, wherein the residential air-conditioning system is used
to
30 supply cool air (said air having a temperature of for example, about 10
C to about
17 C, particularly about 12 C).
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The heat transfer composition of the invention, including Heat Transfer
Compositions 1 ¨ 17 is thus provided for use in a portable 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 C to
about
17 C, particularly about 12 C).
The residential air conditions systems as described herein, including in the
immediately preceeding paragraphs, preferably have an air-to-refrigerant
evaporator (indoor coil), a compressor, an air-to-refrigerant condenser
(outdoor coil),
and an expansion valve. The evaporator and condenser can be round tube plate
fin, a finned tube or microchannel heat exchanger. The compressor can be a
reciprocating or rotary (rolling-piston or rotary vane) or scroll compressor.
The
expansion valve can be a capillary tube, thermal or electronic expansion
valve. The
refrigerant evaporating temperature is preferably in the range of 0 C to 10
C. The
condensing temperature is preferably in the range of 40 C to 70 C.
The heat transfer composition of the invention, including Heat Transfer
Compositions 1 ¨ 17, 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 C to about 24 C, particularly about 21 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 to
about 3 C or about -30 C to about 5 C. The condensing temperature is
preferably
in the range of about 35 C to about 50 C.
The heat transfer composition of the invention, including Heat Transfer
Compositions 1 ¨ 17, is provided for use in a commercial air-conditioning
system
wherein the commercial air conditioning system can be a chiller which is used
to
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supply chilled water (said water having a temperature of for example about 7
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-
s 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
io 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 C to about 10 C. The condensing temperature
is
preferably in the range of about 40 C to about 70 C.
The heat transfer composition of the invention, including Heat Transfer
is .. Compositions 1 ¨ 17, 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 C or about 55 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
20 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 C to about 3 C, or -30 C
to
about 5 C. The condensing temperature is preferably in the range of about 50
C to
25 about 90 C.
The heat transfer composition of the invention, including Heat Transfer
Compositions 1 ¨ 17, is provided for use in a medium temperature refrigeration
system, wherein the refrigerant has and evaporating temperature preferably in
the
range of about -12 C to about 0 C, and in such systems the refrigerant has a
30 condensing temperature preferably in the range of about 40 C to about 70
C, or
about 20 C to about 70 C.
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The present invenition thus provides a medium temperature refrigeration
system used to chill food or beverages, such as in a refrigerator or a bottle
cooler,
wherein the refrigerant has an evaporating temperature preferably in the range
of
about -12 C to about 0 C, and in such systems the refrigerant has a
condensing
temperature preferably in the range of about 40 C to about 70 C, or about
2000 to
about 70 C.
The medium temperature systems of the present invention, including the
systems as described in the immediately preceeding paragraphs, preferably have
an
air-to-refrigerant evaporator to provide chilling, for example to the food or
beverage
io
contained therein, 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 heat transfer composition of the invention,
including
Heat Transfer Compositions 1 ¨ 17, is provided for use in a low temperature
refrigeration system, wherein the refrigerant has an evaporating temperature
that is
is preferably in the range of about 400C to about -12 C and the refrigerant
has a
condensing temperature that is preferably in the range of about 40 C to about
70
C, or about 2000 to about 70 C.
The present invenition thus provides a low temperature refrigeration system
used to provide cooling in a freezer wherein the refrigerant has an
evaporating
20
temperature that is preferably in the range of about -40 C to about -12 C and
the
refrigerant has a condensing temperature that is preferably in the range of
about 40
C to about 70 C, or about 20 to about 70 C.
The present invenition thus also provides a low temperature refrigeration
system used to provide cooling in an cream machine refrigerant has an
evaporating
25
temperature that is preferably in the range of about -40 C to about -12 C and
the
refrigerant has a condensing temperature that is preferably in the range of
about 40
C to about 70 C, or about 20 C to about 70 C.
The low temperature systems of the present invention, including the systems
as described in the immediately preceeding paragraphs, preferably have an air-
to-
30
refrigerant evaporator to chill the food or beverage, a reciprocating, scroll
or rotary
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compressor, an air-to-refrigerant condenser to exchange heat with the ambient
air,
and a thermal or electronic expansion valve.
The present invention therefore provides the use in a chiller of a heat
transfer
compositon of the present invention, including each of Heat Transfer
Compositions 1 -17
wherein said alkylated naphthalene is AN5wherein said heat transfer
composition further
comprises BHT, wherein the AN 5 is provided in an amount of from about 0.001%
by weight
to about 5% by weight based on the weight of the lubricant and the BHT is
provided in an
amount of from about 0.001% by weight to about 5 % by weight based on the
weight of the
lubricant.
The present invention therefore provides the use use in a chiller of a heat
transfer
compositon of the present invention, including each of Heat Transfer
Compositions 1 - 17
wherein said heat transfer composition further comprises BHT, wherein the AN5
is present
in an amount of from about 0.001% by weight to about 5% by weight based on the
weight of
the heat transfer composition and the BHT is present in an amount of from
about 0.001% by
weight to about 5 % by weight based on the weight of heat transfer
composition.
For the purposes of this invention, each heat transfer composition in
accordance
with the present invention, including each of Heat Transfer Compositions 1
¨17, is provided
for use in a chiller with an evaporating temperature in the range of about 0
C to about 10 C
and a condensing temperature in the range of about 40 C to about 70 C. The
chiller is
provided for use in air conditioning or refrigeration, and preferably for
commercial air
conditioning. 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.
The present invention therefore provides the use of each heat transfer
composition
in accordance with the present invention, including each of Heat Transfer
Compositions 1 ¨
26, in stationary air conditioning, particularly residential air conditioning,
industrial air
conditioning or commercial air conditioning.
The present invention therefore provides the use in stationary air
conditioning,
particularly residential air conditioning, industrial air conditioning or
commercial air
conditioning ,of a heat transfer compositon of the present invention,
including each of Heat
Transfer Compositions 1 - 17 wherein said alkylated naphthalene is AN5 and
wherein said
heat transfer composition further comprises BHT, wherein the AN5 is present in
an amount
of from about 0.001% by weight to about 5% by weight based on the weight of
the lubricant
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and the BHT is present in an amount of from about 0.001% by weight to about 5
% by
weight based on the weight of the lubricant.
The present invention therefore provides the use in stationary air
conditioning,
particularly residential air conditioning, industrial air conditioning or
commercial air
conditioning ,of a heat transfer compositon of the present invention,
including each of Heat
Transfer Compositions 1 - 17 wherein said alkylated naphthalene is AN5 and
wherein said
heat transfer composition further comprises BHT, wherein the AN5 is present in
an amount
of from about 0.001% by weight to about 5% by weight based on the weight of
the heat
transfer composition and the BHT is present in an amount of from about 0.001%
by weight
to about 5 % by weight based on the weight of heat transfer composition.
Each heat transfer composition in accordance with the present invention,
including
each of Heat Transfer Compositions 1 ¨ 17, is provided as a low Global Warming
(GWP)
replacement for the refrigerant R-41 OA.
Each heat transfer composition in accordance with the present invention,
including
each of Heat Transfer Compositions 1 ¨ 17, is provided as a low Global Warming
(GWP)
retrofit for the refrigerant R-410A. .
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.
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 refrigerant,
without requiring
substantial engineering modification of the existing system, particularly
without modification
of the condenser, the evaporator and/or the expansion valve.
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.
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.
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
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existing R-410A refrigerant with a heat transfer composition of the present
invention,
including each of Heat Transfer Composiitons 1 ¨ 17.
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-41 OA) and introducing a heat transfer composition , including each of Heat
Transfer
Composiitons 1 ¨ 17, 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.
Alternatively, the heat transfer composition can be used in a method of
retrofitting an
existing heat transfer system designed to contain or containing R41 OA
refrigerant, wherein
the system is modified for use with a Heat Transfer Composition of the present
invention.
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, including each of Heat Transfer Compositions 1
¨ 17, 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.
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 /0, about 50 /0 or about 75 /0 by weight of the R-410A
from the system
and replacing it with the heat transfer compositions of the invention,
including each of Heat
Transfer Compositions 1 ¨17.
The heat transfer compositions of the invention 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.
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
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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.
The heat transfer compositions of the invention 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.
The heat transfer composition of the invention 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.
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 ¨ 17, 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 ¨ 17, according to invention as described
herein may
provide an evaporator glide of less than 2 C, preferably less than 1.5 C.
The heat transfer composition of the invention 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.
Preferably, the heat transfer composition of the invention preferably exhibit
operating
characteristics compared with R-410A wherein:
- the efficiency (COP) of the composition is from 100 to 105% of the
efficiency of R-
410A; and/or
- 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.
In order to enhance the reliability of the heat transfer system, it is
preferred that the heat
transfer composition of the invention further exhibit the following
characteristics compared
with R-410A:
- the discharge temperature is not greater than 10 C higher than that of R-
410A;
and/or
- the compressor pressure ratio is from 98 to 102% of the compressor
pressure ratio
of R-410A
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in heat transfer systems, in which the composition of the invention is used to
replace the R-
410A refrigerant.
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 ¨17, can be used to replace R-410A in any
one of:
- an air conditioning system including a mobile air conditioning system,
particularly air
conditioning systems in trucks, buses and trains,
- a mobile heat pump, particularly an electric vehicle heat pump;
- 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,
- a residential air conditioning system, particularly a ducted split or a
ductless split air
conditioning system,
- a residential heat pump,
- a residential air to water heat pump/hydronic system,
- an industrial air conditioning system and
- a commercial air conditioning system particularly a packaged rooftop unit
and a
variable refrigerant flow (VRF) system;
- a commercial air source, water source or ground source heat pump system
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 each of Heat Transfer Compositions 1 ¨17, can be
used
to replace R10A in in any one of:
- 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,
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- a domestic refrigerator,
- an industrial freezer,
- an industrial refrigerator and
- a chiller.
Each of the heat transfer compositions described herein, including each of
Heat
Transfer Compositions 1 ¨17,, is particularly provided to replace R-410A in a
residential air-
conditioning system (with an evaporator temperature in the range of about 0 C
to about
C, particularly about 7 C for cooling and/or in the range of about -20 C to
about 3 C or
30 to about 5 C, particularly about 0.5 C for heating). Alternatively, or
additionally, each of
10 the heat transfer compositions described herein, including each of Heat
Transfer
Compositions 1 ¨ 17, is particularly provided to replace R-410A in a
residential air
conditioning system with a reciprocating, rotary (rolling-piston or rotary
vane) or scroll
compressor.
Each of the heat transfer compositions described herein, including each of
Heat
Transfer Compositions 1 ¨ 17õ is particularly provided to replace R-410A in an
air cooled
chiller (with an evaporator temperature in the range of about 0 C to about 10
C, particularly
about 4.5 C), particularly an air cooled chiller with a positive displacement
compressor,
more particular an air cooled chiller with a reciprocating scroll compressor.
Each of the heat transfer compositions described herein, including each of
Heat
Transfer Compositions 1 ¨17, 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 C to about 3 C or about -30 C to about 5 C, particularly about 0.5 C).
Each of the heat transfer compositions described herein, including each of
Heat
Transfer Compositions 1 ¨17, is particularly provided to replace R-410A in a
medium
temperature refrigeration system (with an evaporator temperature in the range
of about -12
C to about 0 C, particularly about -8 C).
Each of the heat transfer compositions described herein , including each of
Heat
Transfer Compositions 1 ¨17, is particularly provided to replace R-410A in a
low
temperature refrigeration system (with an evaporator temperature in the range
of about -40
.. C to about -12 C, particularly from about -40 C to about -23 C or
preferably about -32 C).
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
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refrigerant with a heat transfer composition of the present invention,
including each of Heat
Transfer Compositions 1 ¨17.
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 ¨ 17.
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 according to the present
invention, including
each of Heat Transfer Compositions 1 ¨ 17.
Particularly, the heat transfer system is a residential air-conditioning
system (with an
evaporator temperature in the range of about 0 C to about 10 C, particularly
about 7 C for
cooling and/or in the range of about -20 C to about 3 C or about -30 C to
about 5 C,
particularly about 0.5 C for heating).
Particularly, the heat transfer system is an air cooled chiller (with an
evaporator
temperature in the range of about 0 C to about 10 C, particularly about 4.5
C), particularly
an air cooled chiller with a positive displacement compressor, more particular
an air cooled
chiller with a reciprocating or scroll compressor.
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 C to about 3
C or about -
C to about 5 C, particularly about 0.5 C).
The heat transfer system can be a refrigeration system, such as a low
temperature
refrigeration system, a medium temperature refrigeration system, a commercial
refrigerator,
25 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.
EXAMPLES
The refrigerant compositions identified in Table 2 below as Refrigerants Al,
A2 and A3 are
30 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
CF3I was
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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 2: Refrigerants evaluated for Performance Examples
GWP Flammability
HFC-32 HFC-125 CF3 I
Refrigerant (100
(wt%) (wt%) (wt%)
years)
Al 40% 3.5% 56.5% 393 Non Flammable
A2 41% 3.5% 55.5% 400 Non-Flammable
A3 44% 3.5% 52.5% 420 Non-Flammable
Refrigerant Al comprises 100% by weight of the three compounds listed in Table
2 in their
relative percentages and is non-flammable.
Refrigerant Al consists 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 A2 consists of the three
compounds listed in Table 2 in their relative percentages and is non-
flammable.
Refrigerant A3 comprises 100% by weight of the fhree compounds listed in Table
2 in their
relative percentages and is non-flammable.
Refrigerant A3 consists of the three
compounds listed in Table 2 in their relative percentages and is non-
flammable.
Example 1 - Environment/GWP
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
400 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 R41 OA.
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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-0O2,q) 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. Figure 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 3: LCCP (kg-0O2eq)
GWP (100 USA EU China Brazil
Overall
years)
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 2A - Residential Air-Conditionind System (CooDm])
Residential air-conditioning system is used to supply cool air (26.7 C) to
buildings in
the summer. Refrigerants Al, 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.
The operating conditions are: condensing temperature= 46 C; condenser sub-
cooling=
5.5 C; evaporating temperature= 7 C; evaporator superheat= 5.5 C; isentropic
Efficiency=
70%; volumetric efficiency= 100%; and temperature rise in Suction Line=5.5 C.
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Table 4. Performance in Residential Air-Conditioning System (Cooling)
Capacity Efficiency Pressure ratio
Evaporator glide
Refrigerant
(% of R410A) (% of R410A) (% of R410A) ( C)
R410A 100% 100% 100% 0.1
Al 92% 102% 100% 4.1
A2 93% 102% 100% 3.8
A3 95% 102% 100% 3.0
Table 4 shows the thermodynamic performance of a residential air-conditioning
system compared to R410A system. Refrigerants Al to A3 show 92% or higher
capacity
and higher efficiency than R410A. It indicates the system performance is
similar to R410A.
Refrigerants Al 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 2B. - Residential Air-Conditioning System (Cooling)
A residential air-conditioning system configured to supply cool air in
accordance with
Example 2A in which POE lubricant is included in the system and is stabilized
with alkylated
naphthalene according to the present invention (AN4 in an amount of from about
6% to
about 10% based on the weight of the lubricant) and ADM according to the
present
invention (ADM4 in an amount of about 0.05 ¨ 0.5 % by weight based on the
weight of the
lubricant). The system so configured operates continuously for an extended
period of days,
and after such operation the lubricant is tested and is found to have remained
stable during
such actual operation.
Example 3A - Residential Heat pump System (Heating)
Residential heat pump system is used to supply warm air (21.1 C) to buildings
in the
winter. Refrigerants Al, 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
operating conditions are: condensing temperature= 41 C; condenser sub-cooling=
5.5 C;
evaporating temperature= 0.5 C; evaporator superheat= 5.5 C; isentropic
efficiency= 70%;
volumetric efficiency= 100%; and temperature rise in suction line=5.5 C.
Table 5. Performance in Residential Heat pump System (Heating)
Capacity Efficiency Pressure ratio
Evaporator glide
Refrigerant
(% of R410A) (% of R410A) (% of R410A) ( C)
R410A 100% 100% 100% 0.1
Al 89% 101% 100% 4.2
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A2 90% 101% 100% 3.9
A3 92% 101% 100% 3.0
Table 5 shows the thermodynamic performance of a residential heat pump system
compared to R410A system. The capacity of Refrigerant Al 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 Al 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 3B. - Residential Heat Pump System (Heating)
A heat pump system is configured in accordance with Example 3A in which POE
lubricant was included in the system and which iss stabilized with alkylated
naphthalene
according to the present invention (AN4 in an amount of from about 6% to about
10% based
on the weight of the lubricant) and ADM according to the present invention
(ADM4 in an
amount of about 0.05 ¨ 0.5 % by weight based on the weight of the lubricant).
The system
so configured operates continuously for an extended period of days, and after
such
operation the lubricant is tested and was found to have remained stable during
such actual
operation.
Example 4A - Commercial Air-Conditioning System ¨ Chiller
Commercial air-conditioning system (chiller) is used to supply chilled water
(7 C) to
large buildings such as office and hospital, etc. Refrigerants Al, 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 C;
condenser sub-cooling=5.5 C; evaporating temperature=4.5 C;
evaporator
superheat=5.5 C; isentropic efficiency= 70%; volumetric efficiency= 100%; and
temperature
rise in suction line=2 C.
Table 6. Performance in Commercial Air-Conditioning System ¨ Air-Cooled
Chiller
Capacity Efficiency Pressure ratio Evaporator
glide
Refrigerant
(% of R410A) (% of R410A) (% of R410A) ( C)
R410A 100% 100% 100% 0.1
Al 92% 102% 100% 4.1
A2 93% 102% 100% 3.8
A3 95% 102% 100% 3.0
Table 6 shows the thermodynamic performance of a commercial air-conditioning
system compared to R410A system. Refrigerants Al to A3 show 92% or higher
capacity
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and higher efficiency than R410A. It indicates the system performance is
similar to R410A.
Refrigerants Al 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 4B. Commercial Air-Conditionind System ¨ Chiller
A commercial air conditioning is configured in accordance with Example 4A in
which
POE lubricant is included in the system and is stabilized with alkylated
naphthalene
according to the present invention (AN4 in an amount of from about 6% to about
10% based
on the weight of the lubricant) and ADM according to the present invention
(ADM4 in an
amount of about 0.05 ¨ 0.5 % by weight based on the weight of the lubricant).
The system
so configured operates continuously for an extended period of days, and after
such
operation the lubricant is tested and was found to have remained stable during
such actual
operation.
Example 5A - Residential Air-to-Water Heat Pump Hydronic System
Residential air-to-water heat pump hydronic system is used to supply hot water
(50 C) to buildings for floor heating or similar applications in the winter.
Refrigerants Al,
A2, and A3 were used in a simulation of a residential heat pumpsystem as
described above
and the performance results are in Table 7 below. The operating conditions
are:
condensing temperature= 60 C; condenser sub-cooling= 5.5 C; evaporating
temperature=
0.5 C; evaporator superheat= 5.5 C; isentropic efficiency= 70%; volumetric
Efficiency=
100%; and temperature rise in suction line=2 C.
Table 7. Performance in Residential Air-to-Water Heat Pump Hydronic System
Capacity Efficiency Pressure ratio
Evaporator glide
Refrigerant
(% of R410A) (% of R410A) (% of R410A) ( C)
R410A 100% 100% 100% 0.1
Al 93% 103% 100% 3.9
A2 94% 103% 100% 3.6
A3 96% 103% 99% 2.8
Table 7 shows the thermodynamic performance of a residential heat pump system
compared to R410A system. Refrigerants Al to A3 show 93% or higher capacity
and higher
efficiency than R410A. It indicates the system performance is similar to
R410A.
Refrigerants Al 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.
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Example 5B. - Residential Air-to-Water Heat Pump Hydronic System
A residential air-to-water heat pump hydronic system is configured in
accordance
with Example 5A in which POE lubricant is included in the system and is
stabilized with
alkylated naphthalene according to the present invention (AN4 in an amount of
from about
6% to about 10% based on the weight of the lubricant) and ADM according to the
present
invention (ADM4 in an amount of about 0.05 ¨ 0.5 % by weight based on the
weight of the
lubricant). The system so configured operates continuously for an extended
period of days,
and after such operation the lubricant is tested and was found to have
remained stable
during such actual operation.
Example 6A - Medium Temperature Refrigeration System
Medium temperature refrigeration system is used to chill the food or beverage
such
as in refrigerator and bottle cooler. Refrigerants Al, 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 C;
condenser sub-cooling= 0 C (system with receiver); evaporating temperature= -
6.7 C;
evaporator superheat= 5.5 C; isentropic efficiency= 70%; volumetric
efficiency= 100%; and
degree of superheat in the suction line = 19.5 C.
Table 8. Performance in Medium Temperature Refrigeration System
Capacity Efficiency Pressure ratio
Evaporator glide
Refrigerant
(% of R410A) (% of R410A) (% of R410A) ( C)
R410A 100% 100% 100% 0.1
Al 94% 104% 100% 4.1
A2 94% 104% 100% 3.7
A3 97% 104% 99% 2.9
Table 8 shows the thermodynamic performance of a medium temperature
refrigeration system compared to R410A system. Refrigerants Al to A3 show 94%
or
higher capacity and higher efficiency than R410A. It indicates the system
performance is
similar to R410A. Refrigerants Al 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.
Example 6B. Medium Temperature Refrigeration System
A medium temperature refrigeration system is configured to chill food or
beverages
such as in a refrigerator and bottle cooler is configured in accordance with
Example 6A in
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which POE lubricant is included in the system and is stabilized with alkylated
naphthalene
according to the present invention (AN4 in an amount of from about 6% to about
10% based
on the weight of the lubricant) and ADM according to the present invention
(ADM4 in an
amount of about 0.05 ¨ 0.5 % by weight based on the weight of the lubricant).
The system
so configured operates continuously for an extended period of days, and after
such
operation the lubricant is tested and was found to have remained stable during
such actual
operation.
Example 7A - Low Temperature Refrigeration System
Low temperature refrigeration system is used to freeze the food such as in ice
cream
machine and freezer. Refrigerants Al, 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 C;
condenser
sub-cooling= 0 C (system with receiver); evaporating temperature= -28.9 C;
degree of
superheat at evaporator outlet = 5.5 C; isentropic efficiency= 65%; volumetric
efficiency=
100%; and degree of superheat in the suction line = 44.4 C.
Table 9. Performance in Low Temperature Refrigeration System
Capacity Efficiency Pressure ratio
Evaporator glide
Refrigerant
(% of R410A) (% of R410A) (% of R410A) ( C)
R410A 100% 100% 100% 0.1
Al 96% 105% 100% 4.0
A2 97% 105% 99% 3.7
A3 99% 105% 99% 2.7
Table 9 shows the thermodynamic performance of a low temperature refrigeration
system compared to R410A system. Refrigerants Al to A3 show 96% or higher
capacity
and higher efficiency than R410A. It indicates the system performance is
similar to R410A.
Refrigerants Al 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 7B. Low Temperature Refrigeration System
A low temperature refrigeration system is configured to freeze food such as in
an ice
cream machine and a freezer is configured in accordance with Example 7A in
which POE
lubricant is included in the system and is stabilized with alkylated
naphthalene according to
the present invention (AN4 in an amount of from about 6% to about 10% based on
the
weight of the lubricant) and ADM according to the present invention (ADM4 in
an amount of
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about 0.05 ¨ 0.5 % by weight based on the weight of the lubricant). The system
so
configured operates continuously for an extended period of days, and after
such operation
the lubricant is tested and was found to have remained stable during such
actual operation.
Example 8A. Commercial Air-Conditioning System ¨ Packaged Rooftops
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:
1. Condensing temperature = about 46 C (corresponding outdoor ambient
temperature
= about 45 C)
2. Condenser sub-cooling = about 5.5 C
3. Evaporating temperature = about 7 C (corresponding indoor ambient
temperature =
26.7 C)
4. Evaporator Superheat = about 5.5 C
5. Isentropic Efficiency = 70%
6. Volumetric Efficiency= 100%
7. Temperature Rise in Suction Line = 5.5 C
The performance with each of refrigerants Al ¨ A3 is found to be acceptable
Example 8A. Commercial Air-Conditioning System ¨ Packaged Rooftops
A packaged rooftop commercial air conditioning system is configured to supply
cooled or heated air to buildings in accordance with Example 8A in which POE
lubricant is
included in the system and is stabilized with alkylated naphthalene according
to the present
invention (AN4 in an amount of from about 6% to about 10% based on the weight
of the
lubricant) and ADM according to the present invention (ADM4 in an amount of
about 0.05 ¨
0.5 % by weight based on the weight of the lubricant). The system so
configured operates
continuously for an extended period of days, and after such operation the
lubricant is tested
and is found to have remained stable during such actual operation.
Example 9A. Commercial Air-Conditioning System ¨ Variable Refrigerant Flow
Systems
A commercial air-conditioning system with vaiable refrigerant flow is
configured to
supply cooled or heated air to buildings is tested. The experimental system
includes
multiple (4 or more) air-to-refrigerant evaporators (indoor coils), a
compressor, an air-to-
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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:
I. Condensing temperature = about 46 C, Corresponding outdoor ambient
temperature= 45 C
2. Condenser sub-cooling = about 5.5 C
3. Evaporating temperature = about 7 C (corresponding indoor ambient
temperature=
26.7 C)
4. Evaporator Superheat = about 5.5 C
5. Isentropic Efficiency = 70%
6. Volumetric Efficiency = 100%
7. Temperature Rise in Suction Line = 5.5 C.The performance with each of
refrigerants
Al ¨ A3 is found to be acceptable.
Example 9B. Commercial Air-Conditioninq System ¨ Variable Flow Refriqerant
A commercial air-conditioning system with vaiable refrigerant flow is
configured to
supply cooled or heated air to buildings is configured in accordance with
Example 9A in
which POE lubricant is included in the system and is stabilized with alkylated
naphthalene
according to the present invention (AN4 in an amount of from about 6% to about
10% based
on the weight of the lubricant) and ADM according to the present invention
(ADM4 in an
amount of about 0.05 ¨ 0.5 % by weight based on the weight of the lubricant).
The system
so configured operates continuously for an extended period of days, and after
such
operation the lubricant is tested and was found to have remained stable during
such actual
operation.
Comparative Example 1 - Heat Transfer Compositions Comprising Refrigerant and
Lubricant and BHT
A heat transfer compositions of the present invention is 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. The tested refrigerant consists of
41% by
weight R-32, 3.5% by weight of R-125 and 55.5% by weight of CF3I), with 1.7
volume % air
in the refrigerant. The POE lubricant tested was an ISO 32 POE having a
viscosity at 40 C
of about 32 cSt and having a moisture content of 300 ppm or less (Lubricant
A). Included
with the lubricant is the stabilizer BHT, but no alkylated naphthalene and no
ADM were
included. After testing, the fluid is observed for clarity and total acid
number (TAN) is
determined. The TAN value is considered to reflect the stability of the
lubricant in the fluid
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under conditions of use in the heat transfer compostion. The fluid is also
tested for the
presence of trifluormethane (R-23), which is considered to reflect refrigerant
stability since
this compound is believed to be a product of the breakdown of CF3I.
The experiment is carried out by preparing sealed tubes containing 50% by
weight of
the R-466a 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 C for 14
days. The results were as follows:
Lubricant Visual ¨ yellow to brown
TAN - >2 mgKOH/g
R-23 ¨ >1 wt%
Example 10 - Stabilizers for Heat Transfer Compositions Comprising Refrigerant
and
Lubricant
The test of Comparative Example 1 is repeated except that 2% by weight of
alkylated naphthalene (AN4) based on the weight of the lubricant is added. The
results
(designated El 0) are reported in Table 10 below, together with the results
from
Comparative Example 1 (designated CE1).
Table 10
CE1 (no AN) El 0 (2% AN)
Lubricant Visual yellow to brown Clear
TAN mgKOH/g >2 <0.2
R-23 ¨wt% >1 <0.2
As can be seen from the data above, the refrigerant/lubricant fluid without
the
alkylate naphthalene stabilizer according to the present invention exhibits a
less than ideal
visual appearance, and relatively high TAN and R-23 values. This results are
achieved
notwithstanding that BHT stabilizer is included. In contrast, the addition of
2% alkylated
naphthalene according to the present invention produces a dramatic and
unexpected
improvement in all tested stability results, including a dramatic, order of
magnitude
improvement in both TAN and R-23 concentration.
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Example 11 - Stabilizers for Heat Transfer Compositions Comprising Refrigerant
and
Lubricant
The test of Example 10 is repeated except that 4% by weight of alkylated
naphthalene (AN4) based on the weight of the lubricant is added. The results
are similar to
the results of Example 10.
Example 12 - Stabilizers for Heat Transfer Compositions Comprising Refrigerant
and
Lubricant
The test of Example 10 is repeated except that 6% by weight of alkylated
naphthalene (AN4) based on the weight of the lubricant is added. The results
are similar to
Example 10.
Example 13 - Stabilizers for Heat Transfer Compositions Comprising Refrigerant
and
Lubricant
The test of Example 10 is repeated except that 8% by weight of alkylated
naphthalene (AN4) based on the weight of the lubricant is added. The results
are similar to
the results of Example 10.
Example 14 - Stabilizers for Heat Transfer Compositions Comprising Refrigerant
and
Lubricant
The test of Comparative Example 1 is repeated except that 10% by weight of
alkylated naphthalene (AN4) based on the weight of the lubricant is added. The
results
(designated E14) are reported in Table 11 below, together with the results
from
Comparative Example 1 (designated CE1) and Example 10 (designated E10).
Table 11
CE1 (No AN) El 0 (2% AN) E14 (10% AN)
Lubricant Visual yellow to brown Clear Dark Brown to
Black
TAN mgKOH/g >2 <0.2 >5
R-23 ¨wt% >1 <0.2 >1
As can be seen from the data above, the refrigerant/lubricant fluid with 10%
alkylated
naphthalene stabilizer (and no ADM) unexpectedly exhibits a substantial
deterioration in
stabilizing performance for each criteria tested compared to the fluid with
the AN level of
2%.
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Example 15 - Stabilizers for Heat Transfer Compositions Comprising Refrigerant
and
Lubricant
The test of Example 14 is repeated except that in addition to the 10% by
weight of
alkylated naphthalene (AN4) based on the weight of the lubricant being added,
1000 ppm by
weight (0.1 % by weight) of ADM (ADM4) is also added. The results (designated
E15) are
reported in Table 12 below, together with the results from Comparative Example
1
(designated CE1), Example 10 (designated E10) and Example 14 (designated E14).
Table 12
CE1 (No AN) E10 (2% AN)
E14 (10% AN) E15 (10% AN
+ 0.1% ADM)
Lubricant Visual yellow to brown Clear Dark Brown to
Crysal clear
Black
TAN mgKOH/g >2 <0.2 >5 <.1
R-23 ¨wt% >1 <0.2 >1 <0.01
As can be seen from the data above, the refrigerant/lubricant fluid with 10%
alkylated naphthalene stabilizer and 0.1% by weight (1000 ppm) ADM
unexpectedly exhibits
the best performance, with an R-23 value that is even better than the
excellent results from
Example 10.
Example 16 - Stabilizers for Heat Transfer Compositions Comprising Refrigerant
and
Lubricant
The test of Example 15 is repeated except that the lubricant was an ISO 74 POE
having a viscosity at 40 C of about 74 cSt and having a moisture content of
300 ppm or less
(Lubricant B). The results were as follows:
Lubricant Visual ¨ clear to slight yellow
TAN - <0.1 mgKOH/g
R-23 ¨ <0.05 wt%
Example 17 - Stabilizers for Heat Transfer Compositions Comprising Refrigerant
and
Lubricant
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The test of Example 15 is repeated except that the lubricant is an ISO 68 PVE
having a viscosity at 40 C of about 68 cSt and having a moisture content of
300 ppm or less
(Lubricant c). The results were as follows:
Lubricant Visual ¨ crystal clear
TAN - <0.1 mgKOH/g
R-23 ¨ 0.028 wt%
Example 18 - Stabilizers for Heat Transfer Compositions Comprisinq Refriqerant
and
Lubricant
The test of Example 15 is repeated except that the lubricant was an ISO 32 PVE
having a viscosity at 40 C of about 32 cSt and having a moisture content of
300 ppm or less
(Lubricant c). The results were similar to the results from Example 17.
Example 19 ¨ Miscibility with POE oil
Miscibility of ISO POE-32 oil (having a viscosity at about 32 cSt at a
temperature of
40 C) is tested for different weight ratios of lubricant and refrigerant and
different
temperatures for R-410A refrigerant and for each of Refrigerants Al and A3 as
specified in
Table 1 for Example 1 above. The results of this testing are reported in Table
11 below:
TABLE 13
Liquid Refrigerant R-410A Miscibility
Temperature Refrigerant A of the
Mass Percentage in present invention
Range
the Refrigerant
Lower Limit, C Upper Limit, C
and Lubricant
Mixture, %
60 about -26 NA Fully miscible
Fully miscible
70 about -23 about 55
Fully miscible
80 about -22 about 48
Fully miscible
90 about -31 about 50
As can be seen from the table above, R-410A is immiscible with POE oil below
about -22 C, and R-410A cannot therefore be used in low temperature
refrigeration
applications without make provisions to overcomve the accumulation of POE oil
in the
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evaporator. Furthermore, R-410A is immiscible with POE oil above 50 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 C to 80 C, thus
providing a
substantial and unexpected advantage when used in such systems.
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Numbered Embodiments
The invention will now be illustrated by reference to the following numbered
embodiments.
The subject matter of the numbered embodiments may be additionally combined
with
subject matter from the description or from one or more of the claims.
Numbered Embodiment 1. A heat transfer compositions comprising refrigerant,
lubricant
and stabilizer, said refrigerant 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), Ito 4% by weight pentafluoroethane (HFC-125), and 51
to 57%
by weight trifluoroiodomethane (CF3I), said lubricant comprising polyol ester
(POE) lubricant
and/or polyvinyl ether (PVE) lubricant, and said stabilizer comprising
alkylated naphthalene.
Numbered Embodiment 2. A heat transfer composition according to Number
Embodiment
1 wherein said alkylated naphthalene is present in the composition in an
amount of from 1%
to less than 10%.
Numbered Embodiment 3. A heat transfer composition according to Number
Embodiment
1 wherein said alkylated naphthalene is present in the composition in an
amount of from
1.5% to less than 10%.
Numbered Embodiment 4. A heat transfer composition according to Number
Embodiment
1 wherein said alkylated naphthalene is present in the composition in an
amount of from
1.5% to less than 8%.
__ Numbered Embodiment 5. A heat transfer composition according to Number
Embodiment
1 wherein said alkylated naphthalene is present in the composition in an
amount of from
1.5% to less than 6%.
Numbered Embodiment 6. A heat transfer composition according to Number
Embodiment
1 wherein said alkylated naphthalene is present in the composition in an
amount of from
1.5% to less than 5%.
Numbered Embodiment 7. A heat transfer composition according to any of Number
Embodiments 1 ¨6 wherein said refrigerant consists 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).
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Numbered Embodiment 8. A heat transfer composition according to any of Number
Embodiments 1 ¨7 wherein said alkylated naphthalene is selected from AN1, or
AN2, or
AN3, or AN4, or AN5, or AN6, or AN7, or AN8, or AN9 or AN10.
Numbered Embodiment 9. A heat transfer composition according to any of Number
Embodiments 1 ¨ 8 wherein said alkylated naphthalene comprises AN5.
Numbered Embodiment 10. A heat transfer composition according to any of Number
Embodiments 1 ¨ 8 wherein said alkylated naphthalene consists essentially of
AN5.
Numbered Embodiment 11. A heat transfer composition according to any of Number
Embodiments 1 ¨8 wherein said alkylated naphthalene consists of AN5.
.. Numbered Embodiment 12. A heat transfer composition according to any of
Number
Embodiments 1 ¨8 wherein said alkylated naphthalene comprises AN10.
Numbered Embodiment 13 A heat transfer composition according to any of Number
Embodiments 1 ¨8 wherein said alkylated naphthalene consists essentially of
AN10.
Numbered Embodiment 14. A heat transfer composition according to any of Number
Embodiments 1 ¨8 wherein said alkylated naphthalene consists of AN10.
Numbered Embodiment 15. A heat transfer composition according to any of Number
Embodiments 1 ¨14 wherein said stabilizer further comprises an ADM.
Numbered Embodiment 16. A heat transfer composition according to any of Number
Embodiments 1 ¨15 wherein said ADM comprises ADM4.
Numbered Embodiment 17 A heat transfer composition according to any of Number
Embodiments 1 ¨ 15 wherein said ADM consists essentially of ADM4.
Numbered Embodiment 18. A heat transfer composition according to any of Number
Embodiments 1 ¨ 15 wherein said ADM naphthalene consists of ADM4.
Numbered Embodiment 19. A heat transfer composition according to any of Number
Embodiments 1 ¨ 9 wherein said stabilizer is selected from Stablizer 1,
Stablilizer 2,
Stablizer 3, Stablilizer 4, Stablizer 5, Stablilizer 6, Stablizer 7,
Stablilizer 8, Stablizer 9,
Stablilizer 10, Stablizer 11, Stablilizer 12, Stablizer 13, Stablilizer 14,
Stablizer 15, Stablilizer
16, Stablilizer 17, Stablizer 18, Stablilizer 19, Stablizer 20.
Numbered Embodiment 20 A heat transfer composition according to any of Number
Embodiments 1 ¨19 wherein said lubricant comprises POE.
Numbered Embodiment 21. A heat transfer composition according to any of Number
Embodiments 1 ¨19 wherein said lubricant consists essentially of POE.
Numbered Embodiment 22. A heat transfer composition according to any of Number
Embodiments 1 ¨19 wherein said lubricant consists of POE.
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Numbered Embodiment 23. A heat transfer composition according to any of Number
Embodiments 1 ¨22 wherein said lubricant comprises Lubricant 1.
Numbered Embodiment 24. A heat transfer composition according to any of Number
Embodiments 1 ¨22 wherein said lubricant consists essentially of Lubricant 1.
Numbered Embodiment 25. A heat transfer composition according to any of Number
Embodiments 1 ¨22 wherein said lubricant consists of Lubricant 1.
Numbered Embodiment 26. A heat transfer composition according to any of Number
Embodiments 1 ¨19 wherein said lubricant comprises PVE.
Numbered Embodiment 27. A heat transfer composition according to any of Number
Embodiments 1 ¨19 wherein said lubricant consists essentially of PVE.
Numbered Embodiment 28. A heat transfer composition according to any of Number
Embodiments 1 ¨19 wherein said lubricant consists of PVE.
Numbered Embodiment 29. The heat transfer compositions of any one of Numbered
Embodiments 1 to 28, wherein the composition further comprises one or more
component
.. selected from the group consisting of a a dye, a solubilizing agent, a
compatibilizer, a
corrosion inhibitor, an extreme pressure additive and an anti-wear additive.
Numbered Embodiment 30. The heat transfer composition of Numbered Embodiments
1 -
29, wherein the stabilizer further comprises a phenol-based compound.
Numbered Embodiment 31. The heat transfer composition of Numbered Embodiments
1 -
30 wherein the stabilizer further comprises a phosphorus compound and/or a
nitrogen
compound.
Numbered Embodiment 32. The heat transfer composition of any one of Numbered
Embodiments 1 to 8 and 15 to 31, wherein the alkylated naphthalene is one or
more of NA-
LUBE KR-007A;KR- 008, KR-009; KR-0105, KR-019 and KR-005FG.
Numbered Embodiment 33. The heat transfer composition of any one of Numbered
Embodiments 1 to 8 and 15 - 31, wherein the alkylated naphthalene is one or
more of NA-
LUBE KR-007A, KR-008, KR-009 and KR-005FG.
Numbered Embodiment 34. The heat transfer composition of any one of Numbered
Embodiments 1 to 33 wherein the alkylated naphthalene is NA-LUBE KR-008.
Numbered Embodiment 35. The heat transfer composition of any one of Numbered
Embodiments 1 - 34, wherein the stabilizer comprises a phenol based compound
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-
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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-dimethy1-6-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.
Numbered Embodiment 36. The heat transfer composition of any one of Numbered
Embodiments 30 to 34, wherein the stabilizer comprises BHT.
Numbered Embodiment 37. The heat transfer composition of any one of Numbered
Embodiments 30 to 34, wherein the phenol consists essentially of BHT.
Numbered Embodiment 38. The heat transfer composition of any one of Numbered
Embodiments 30 to 34, wherein the phenol consists of BHT.
Numbered Embodiment 39. The heat transfer composition of Numbered Embodiment
30
to 35 wherein said phenol is present 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, where percentage by weight refers to the weight of the heat transfer
composition.
Numbered Embodiment 40. The heat transfer composition of Numbered Embodiment
30
to 35 wherein said phenol is present 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 4% by weight, and more preferably from 1% to 4% by
weight,
where percentage by weight refers to the weight of the lubricant eat transfer
composition.
Numbered Embodiment 41. A heat transfer system comprising a compressor, an
evaporator, a condenser and an expansion device, in fluid communication with
each other,
and a heat transfer composition as defined in any one of Numbered Embodiments
1 to 40.
Numbered Embodiment 42. A heat transfer system according to Number Embodiment
41
and further comprising a sequestration material, wherein said sequestration
material
comprises: i. copper or a copper alloy, or ii. activated alumina, or iii. a
zeolite molecular
sieve comprising copper, silver, lead or a combination thereof, or iv. an
anion exchange
resin, or v. a moisture-removing material, preferably a moisture-removing
molecular sieve,
or vi. a combination of two or more of the above.
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Numbered Embodiment 43. The heat transfer system as defined in any one of
Numbered Embodiments 41 and 42, wherein said system is a residential air
conditioning system, or an industrial air conditioning system, or a commercial
air
conditioning system.
Numbered Embodiment 44. 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 required the heat transfer composition of any of Numbered
Embodiments 1 -
33; and
ii) evaporating the refrigerant in the vicinity of body or article to be
cooled;
wherein the evaporator temperature of the heat transfer system is in the range
of from about
¨40 C to about +10 C.
Numbered Embodiment 45. 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 required the heat transfer composition of any of Numbered
Embodiments 1 -
33; and
ii) evaporating the composition;
wherein the evaporator temperature of the heat transfer system is in the range
of about -
30 C to about 5 C.
Numbered Embodiment 46. The use of a heat transfer composition as defined in
any one
of as required the heat transfer composition of any of Numbered Embodiments 1
¨ 33 for
use in air conditioning.
Numbered Embodiment 47. The use of a heat transfer composition as defined in
Numbered Embodiment 46 wherein said use in air conditioning is selected from
use in a
residential air conditioning system, an industrial air conditioning system, or
a commercial
air conditioning system, or a commercial air conditioning system that is a
roof top system, or
a commercial air conditioning system that is a variable refrigerant flow
system, or a
commercial air conditioning system that is a chiller system, or a transport
air conditioning
system, or a stationary air conditioning.
Numbered Embodiment 48. The use of a heat transfer composition as defined in
any one
of as required the heat transfer composition of any of Numbered Embodiments 1
¨ 33 for
use in a mobile heat pump, or a positive displacement chiller, or in an air
cooled or water
cooled direct expansion chiller, or in a residential heat pump, a residential
air to water heat
pump/hydronic system, or a commercial air source, water source or ground
source heat
pump system, or in a
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a refrigeration system, low temperature refrigeration system, or in a medium
temperature
refrigeration system, or in a commercial refrigerator, or in a commercial
freezer, or in an ice
machine, or in a transport refrigeration system, or a domestic freezer, or in
a domestic
refrigerator, or in an industrial freezer, or in an industrial refrigerator,
or in a chiller.
Numbered Embodiment 49. The use of a heat transfer composition as defined in
Numbered Embodiment 46 wherein said use in air conditioning is selected from
use in a
residential air conditioning system with a reciprocating, rotary (rolling-
piston or rotary vane)
or scroll compressor, or a split residential air conditioning system, or a
ducted residential air
conditioning system, or a window residential air conditioning system, or a
portable
residential air conditioning system, or a medium temperature refrigeration
system.
Numbered Embodiment 50. The use of a heat transfer composition as required by
any
one of Numbered Embodiments 1 to 33, for use as a replacement for R410A.
Numbered Embodiment 51. 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 as defined in Numbered
Embodiments 1 - 33.
Numbered Embodiment 52. The method of Numbered Embodiment 51, wherein the use
of the heat transfer composition as defined in Numbered Embodiments 1 to 33 to
replace
R410A does not require modification of the condenser, the evaporator and/or
the expansion
valve in the heat transfer system.
Numbered Embodiment 53. The method of Numbered Embodiment 51, wherein the use
of the heat transfer composition as defined in Numbered Embodiments 1 to 33 is
provided
as a replacement for R-410A in a chiller system, or a residential air
conditioning system, or
a industrial air conditioning system, or in commercial air conditioning
system, or commercial
air conditioning system is a roof top system, or commercial air conditioning
system that is a
variable refrigerant flow system, or in a commercial air conditioning system
that is a chiller
system.
Numbered Embodiment 54. The method of Numbered Embodiments 51 to 53 comprising
removing at least about 5%, by weight of the R-41 OA from the system and
replacing it with
the heat transfer composition as defined in Numbered Embodiments 1 to 33.
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