Language selection

Search

Patent 2834894 Summary

Third-party information liability

Some of the information on this Web page has been provided by external sources. The Government of Canada is not responsible for the accuracy, reliability or currency of the information supplied by external sources. Users wishing to rely upon this information should consult directly with the source of the information. Content provided by external sources is not subject to official languages, privacy and accessibility requirements.

Claims and Abstract availability

Any discrepancies in the text and image of the Claims and Abstract are due to differing posting times. Text of the Claims and Abstract are posted:

  • At the time the application is open to public inspection;
  • At the time of issue of the patent (grant).
(12) Patent Application: (11) CA 2834894
(54) English Title: HEAT TRANSFER COMPOSITIONS AND METHODS
(54) French Title: PROCEDES ET COMPOSITIONS DE TRANSFERT DE CHALEUR
Status: Dead
Bibliographic Data
(51) International Patent Classification (IPC):
  • C09K 5/04 (2006.01)
(72) Inventors :
  • MOTTA, SAMUEL F. YANA (United States of America)
  • SPATZ, MARK W. (United States of America)
  • VOGL, RONALD P. (United States of America)
  • BECERRA, ELIZABET DEL CARMEN VERA (United States of America)
(73) Owners :
  • HONEYWELL INTERNATIONAL INC. (United States of America)
(71) Applicants :
  • HONEYWELL INTERNATIONAL INC. (United States of America)
(74) Agent: GOWLING WLG (CANADA) LLP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2012-05-02
(87) Open to Public Inspection: 2012-11-08
Examination requested: 2017-04-25
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2012/036056
(87) International Publication Number: WO2012/151238
(85) National Entry: 2013-10-31

(30) Application Priority Data:
Application No. Country/Territory Date
13/099,218 United States of America 2011-05-02
61/598,056 United States of America 2012-02-13

Abstracts

English Abstract

Compositions, methods and systems which comprise or utilize a multi-component mixture comprising: (a) from about 10% to about 35% by weight of HFC-32; (b) from about 10% to about 35% by weight of HFC-125; (c) from about 20% to about 50% by weight of HFO-1234ze, HFO-1234yf and combinations of these; (d) from about 15% to about 35% by weight of HFC-134a; and optionally (e) up to about 10% by weight of CF3I and up to about 5% by weight of HFCO-1233ze, with the weight percent being based on the total of the components (a) - (e) in the composition


French Abstract

Compositions, procédés et systèmes renfermant ou faisant appel à un mélange à plusieurs constituants, qui contient : (a) d'environ 10 % à environ 35 % en poids de HFC-32; (b) d'environ 10 % à environ 35 % en poids de HFC-125; (c) d'environ 20 % à environ 50 % en poids de HFO-1234ze, de HFO-1234yf et de combinaisons de ceux-ci; (d) d'environ 15 % à environ 35 % en poids de HFC-134a; et éventuellement (e) jusqu'à environ 10 % en poids de CF3I et jusqu'à environ 5 % en poids de HFCO-1233ze, le pourcentage en poids étant rapporté au poids total des constituants (a) - (e) de la composition.

Claims

Note: Claims are shown in the official language in which they were submitted.


WHAT IS CLAIMED IS:
1. A heat transfer composition comprising: (a) from about 20% to about 30%
by
weight of HFC-32; (b) from about 20% to about 30% by weight of HFC-125; (c)
from about 0% to about 15% by weight of HFO-1234yf and from about 10% to
about 30% by weight of HFO-1234ze; (d) from about 15% to about 30% by
weight of HFC-134a, with the weight percent being based on the total of the
components (a) ¨ (d) in the composition.
2. The heat transfer composition of claim 1 wherein said HFO-1234ze
comprises
trans-HFO-1234ze.
3. The heat transfer composition of claim 1 having a weight ratio of HFC-
32:HFC-
125 of from about 0.9:1.2 to about 1.2:0.9.
4. The heat transfer composition of claim 1 comprising from greater than 0%
to
about 15% by weight of HF0-1234yf and from about 10% to about 30% by
weight of HFO-1234ze.
5. The heat transfer composition of claim 1 having a weight ratio of 134a
to a
combination of HFO-1234ze and HFO-1234yf between about 5:7 to about 1:1.
6. The heat transfer composition of claim 1 wherein HFO-1234ze is provided
in an
amount of about 20% and HFO-1234yf is provided in an amount of about 9%.
7. The heat transfer composition of claim 1 wherein HFO-1234ze is provided
in an
amount of about 26%.
8. The heat transfer composition of claim 1 wherein HFO-1234ze is provided
in an
amount of about 17 % and HFO-1234yf is provided in an amount of about 9%.
9. A method of replacing an existing heat transfer fluid contained in heat
transfer
system comprising removing at least a portion of said existing heat transfer
fluid
from said system, said existing heat transfer fluid being HFC-404A and
replacing
16

at least a portion of said existing heat transfer fluid by introducing into
said
system a heat transfer composition comprising: (a) from about 20% to about 30%

by weight of HFC-32; (b) from about 20% to about 30% by weight of HFC-125;
(c) from about 0% to about 15% by weight of HFO-1234yf and from about 15% to
about 30% by weight of HFO-1234ze; (d) from about 15% to about 30% by
weight of HFC-134a, with the weight percent being based on the total of the
components (a) ¨ (d) in the composition.
10.
A heat transfer system comprising a compressor, a condenser and an evaporator
in fluid communication, and a heat transfer composition in said system, said
heat
transfer composition comprising: (a) from about 20% to about 30% by weight of
HFC-32; (b) from about 20% to about 30% by weight of HFC-125; (c) from about
0% to about 15% by weight of HFO-1234yf and from about 15% to about 30% by
weight of HFO-1234ze; (d) from about 15% to about 30% by weight of HFC-
134a, with the weight percent being based on the total of the components (a) ¨
(d) in the composition, said condenser having an operating temperature of from

about 35°C to about 45°C.
17

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
HEAT TRANSFER COMPOSITIONS AND METHODS
RELATED APPLICATIONS
The present application is related to and claims the priority benefit of each
of U.S.
Application No. 13/099,218, filed May 2, 2011 and U.S. Application No.
61/598,056,
filed February 13, 2012. Each of the above-identified applications is
incorporated in its
entirety herein by reference.
FIELD OF THE INVENTION
This invention relates to compositions, methods and systems having utility in
refrigeration applications, with particular benefit in medium and low
temperature
refrigeration applications, and in particular aspects to refrigerant
compositions for
replacement of refrigerant HFC-404A for heating and cooling applications and
to
retrofitting medium and low temperature refrigerant systems, including systems

designed for use with HFC-404A.
BACKGROUND
Mechanical refrigeration systems, and related heat transfer devices such as
heat
pumps and air conditioners, using refrigerant liquids are well known in the
art for
industrial, commercial and domestic uses. Fluorocarbon based fluids have found

widespread use in many residential, commercial and industrial applications,
including as
the working fluid in systems such as air conditioning, heat pump and
refrigeration
systems. Because of certain suspected environmental problems, including the
relatively
high global warming potentials associated with the use of some of the
compositions that
have heretofore been used in these applications, it has become increasingly
desirable
to use fluids having low or even zero ozone depletion and global warming
potentials,
such as hydrofluorocarbons ("HFCs"). For example, a number of governments have

signed the Kyoto Protocol to protect the global environment and setting forth
a reduction
of CO2 emissions (global warming). Thus, there is a need for a low- or non-
flammable,
non-toxic alternative to replace certain of high global warming HFCs.
1

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
One important type of refrigeration system is known as a "low temperature
refrigeration system." Such systems are particularly important to the food
manufacture,
distribution and retail industries in that they play a vital role in ensuring
that food which
reaches the consumer is both fresh and fit to eat. In such low temperature
refrigeration
systems, a commonly used refrigerant liquid has been HFC-404A (the combination
of
HFC-125:HFC-143a:HFC134a in an approximate 44:52:4 weight ratio is referred to
in
the art as HFC-404A or R-404A). R-404A has an estimated high Global Warming
Potential (GWP) of 3922.
There has thus been an increasing need for new fluorocarbon and
hydrofluorocarbon compounds and compositions that are attractive alternatives
to the
compositions heretofore used in these and other applications. For example, it
has
become desirable to retrofit chlorine-containing refrigeration systems by
replacing
chlorine-containing refrigerants with non-chlorine-containing refrigerant
compounds that
will not deplete the ozone layer, such as hydrofluorocarbons (HFC's). Industry
in
general and the heat transfer industry in particular are continually seeking
new
fluorocarbon based mixtures that offer alternatives to, and are considered
environmentally safer substitutes for, CFCs and HCFCs. It is generally
considered
important, however, at least with respect to heat transfer fluids, that any
potential
substitute must also possess those properties present in many of the most
widely used
fluids, such as excellent heat transfer properties, chemical stability, low-
or no- toxicity,
non-flammability and/or lubricant compatibility, among others.
With regard to efficiency in use, it is important to note that a loss in
refrigerant
thermodynamic performance or energy efficiency may have secondary
environmental
impacts through increased fossil fuel usage arising from an increased demand
for
electrical energy.
Furthermore, it is generally considered desirable for CFC refrigerant
substitutes
to be effective without major engineering changes to conventional vapor
compression
technology currently used with CFC refrigerants.
Flammability is another important property for many applications. That is, it
is
considered either important or essential in many applications, including
particularly in
heat transfer applications, to use compositions which are non-flammable. Thus,
it is
2

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
frequently beneficial to use in such compositions compounds which are
nonflammable.
As used herein, the term "nonflammable" refers to compounds or compositions
which
are determined to be nonflammable as determined in accordance with ASTM
standard
E-681, dated 2002, which is incorporated herein by reference. Unfortunately,
many
HFC's which might otherwise be desirable for used in refrigerant compositions
are not
nonflammable as that term is used herein. For example, the fluoroalkane
difluoroethane (HFC-152a) and the fluoroalkene 1,1,1¨trifluorpropene (HF0-
1243zf) are
each flammable and therefore not viable for use in many applications.
Applicants have thus come to appreciate a need for compositions, and
particularly heat transfer compositions, that are highly advantageous in
heating and
cooling systems and methods, particularly vapor compression heating and
cooling
systems, and even more particularly low temperature refrigerant systems,
including
systems which are used with and/or have been designed for use with HFC-404A.
SUMMARY
Applicants have found that the above-noted needs, and other needs, can be
satisfied by compositions, methods and systems which comprise or utilize a
multi-
component mixture comprising: (a) from about 10% to about 35% by weight of
difluoromethane (HFC-32); (b) from about 10% to about 35% by weight of
pentafluoroethane (HFC-125); (c) from about 20% to about 50% by weight of HFO-
1234ze, HF0-1234yf and combinations of these; (d) from about 15% to about 35%
by
weight of 1,1,1,2-tetrafluoroethane (HFC-134a); and optionally (e) up to about
10% by
weight of CF3I and up to about 5% by weight of HFC0-1233ze, with the weight
percent
being based on the total of the components (a) ¨ (e) in the composition.
In certain preferred embodiments, the compositions comprise a multi-component
mixture comprising: (a) from about 15% to about 30% by weight of HFC-32; (b)
from
about 10% to about 30% by weight of HFC-125; (c) from about 20% to about 50%
by
weight of HF0-1234ze, HF0-1234yf, and combinations of these; (d) from about
15% to
about 35% by weight of HFC-134a; and optionally (e) up to about 5% by weight
of CF3I
and up to about 5% by weight of HFC0-1233ze, with the weight percent being
based on
the total of the components (a) ¨ (e) in the composition.
3

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
In further embodiments, the compositions comprise a multi-component mixture
comprising: (a) from about 20% to about 30% by weight of HFC-32; (b) from
about 20%
to about 30% by weight of HFC-125; (c) from about 0% (and/or greater than 0%)
to
about 15% by weight of HF0-1234yf and from about 10% to about 30% by weight of

HF0-1234ze; (d) from about 15% to about 30% by weight of HFC-134a; and
optionally
(e) up to about 5% by weight of CF3I and up to about 5% by weight of HFC0-
1233ze,
with the weight percent being based on the total of the components (a) ¨ (e)
in the
composition.
The present invention provides also methods and systems which utilize the
compositions of the present invention, including methods and systems for heat
transfer
and for retrofitting existing heat transfer systems. Certain preferred method
aspects of
the present invention relate to methods of providing relatively low
temperature cooling,
such as in low temperature refrigeration systems. Other preferred method
aspects of
the present invention provide methods of retrofitting an existing
refrigeration system,
preferably low temperature refrigeration systems, designed to contain and/or
containing
R-404A refrigerant comprising introducing a composition of the present
invention into
the system without substantial engineering modification of said existing
refrigeration
system.
The term HF0-1234ze is used herein generically to refer to 1,1,1,3-
tetrafluoropropene, independent of whether it is the cis- or trans- form. The
terms
"cisHF0-1234ze" and "transHF0-1234ze" are used herein to describe the cis- and

trans- forms of 1,1,1,3-tetrafluoropropene respectively. The term "HF0-1234ze"

therefore includes within its scope cisHF0-1234ze, transHF0-1234ze, and all
combinations and mixtures of these.
The term "HFO-1233" is used herein to refer to all
trifluoro,monochloropropenes.
Among the trifluoro,monochloropropenes are included 1,1,1,trifluoro-2,chloro-
propene
(HFC0-1233xf), both cis- and trans-1,1,1-trifluo-3,chlororopropene (HFC0-
1233zd).
The term HFC0-1233zd is used herein generically to refer to 1,1,1-trifluo-
3,chloro-
propene, independent of whether it is the cis- or trans- form. The terms
"cisHFC0-
1233zd" and "transHFC0-1233zd" are used herein to describe the cis- and trans-
forms
of 1, 1, 1-trifluo,3-chlororopropene, respectively. The term "HFC0-1233zd"
therefore
4

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
includes within its scope cisHFC0-1233zd, transHFC0-1233zd, and all
combinations
and mixtures of these.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Low temperature refrigeration systems are important in many applications, such

as to the food manufacture, distribution and retail industries. Such systems
play a vital
role in ensuring that food which reaches the consumer is both fresh and fit to
eat. In
such low temperature refrigeration systems, one of the refrigerant liquids
which has
been commonly used has been HFC-404A, which has an estimated high Global
Warming Potential (GWP) of 3922. Applicants have found that the compositions
of the
present invention satisfy in an exceptional and unexpected way the need for
alternatives
and/or replacements for refrigerants in such applications, particularly and
preferably
HFC-404A, that at once have lower GWP values and provide substantially non-
flammable, non-toxic fluids that have a close match in cooling capacity and/or
efficiency
to HFC-404A in such systems.
The present invention may also encompass medium temperature refrigeration
composition, systems and methods. According to certain preferred embodiments,
the
present methods and systems involve evaporator temperatures of from above
about
-15 C to about 5 C. An example of such a medium temperature system and method
involves providing cooling in the fresh food compartment of a residential
refrigerator.
HEAT TRANSFER COMPOSITIONS
The compositions of the present invention are generally adaptable for use in
heat
transfer applications, that is, as a heating and/or cooling medium, but are
particularly
well adapted for use, as mentioned above, in medium and low temperature
refrigeration
systems, and preferably in low temperature systems, that have heretofor used
HFC-
404A and/or systems that have heretofor used R-22.
Applicants have found that use of the components of the present invention
within
the broad and narrowedranges described herein is important to achieve the

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
advantageous but difficult to achieve combinations of properties exhibited by
the
present compositions, particularly in the preferred systems and methods, and
that use
of these same components but substantially outside of the identified ranges
can have a
deleterious effect on one or more of the important properties of the
compositions,
systems or methods of the invention. Highly preferred combinations of
properties are
achieved for compositions having a weight ratio of HFC-32:HFC-125 of from
about
0.9:1.2 to about 1.2:0.9, with a ratio of about 1:1 being preferred in certain

embodiments. Applicants have found that highly preferred combinations of
properties
are also achieved for compositions having a weight ratio of HF0-1234ze:HF0-
1234yf of
from about 5:1 to about 0,7:1, more preferably from about 1:1 about 3:1. In
certain
preferred embodiments, a ratio of about 4:1 is preferred.
For the purposes of convenience, the combination HF0-1234ze and HF0-1234yf
is referred to herein as the "tetrafluoropropene component" or "TFC," and in
certain
embodiments highly preferred combinations of properties can be achieved for
composition which comprise a weight ratio of HFC-134a:TFC of from about 5:7 to
about
1:1, with a ratio of about 4:6 being preferred in certain embodiments.
Although it is contemplated that either isomer of HF0-1234ze may be used,
applicants have found that it is preferred, in certain embodiments, that the
HF0-1234ze
comprise transHF0-1234ze, and preferably comprise transHF0-1234ze in major
proportion, and in certain embodiments consist essentially of transHF0-1234ze.
As mentioned above, applicants have found that the compositions of the present

invention are capable of achieving a difficult to achieve combination of
properties,
including particularly low GWP. By way of non-limiting example, the following
Table A
illustrates the substantial improvement in GWP exhibited by certain
compositions of the
present invention in comparison to the GWP of HFC-404A, which has a GWP of
3922.
TABLE A
GWP as a
Composition of the Invention (weight fraction, based on
Name GWP Percentageof
identified components)
R404A GWP
6

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
R125/R134a/R143a(0.44/0.04/0.52) R404A 3922
R32/R125/R134a/1234ze/1234yf (0.25/0.25/0.21/0.20/0.09) Al 1344 34%
R32/R125/R134a/1234yf(0.25/0.25/0.2/0.3) A2 1330 34%
R32/R125/R134a/1234ze/1234yf (0.26/0.26/0.21/0.17/0.1) A3 1386 35%
R32/R125/R134a/1234ze (0.26/0.26/0.21/0.27) A4 1386 35%
The compositions of the present invention may include other components for the

purpose of enhancing or providing certain functionality to the composition, or
in some
cases to reduce the cost of the composition. For example, refrigerant
compositions
according to the present invention, especially those used in vapor compression

systems, include a lubricant, generally in amounts of from about 30 to about
50 percent
by weight of the composition, and in some case potentially in amount greater
than about
50 percent and other cases in amounts as low as about 5 percent. Furthermore,
the
present compositions may also include a compatibilizer, such as propane, for
the
purpose of aiding compatibility and/or solubility of the lubricant. Such
compatibilizers,
including propane, butanes and pentanes, are preferably present in amounts of
from
about 0.5 to about 5 percent by weight of the composition. Combinations of
surfactants
and solubilizing agents may also be added to the present compositions to aid
oil
solubility, as disclosed by U.S. Patent No. 6,516,837, the disclosure of which
is
incorporated by reference. Commonly used refrigeration lubricants such as
Polyol
Esters (POEs) and Poly Alkylene Glycols (PAGs), PAG oils, silicone oil,
mineral oil,
alkyl benzenes (ABs) and poly(alpha-olefin) (PAO) that are used in
refrigeration
machinery with hydrofluorocarbon (HFC) refrigerants may be used with the
refrigerant
7

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
compositions of the present invention. Commercially available mineral oils
include
Witco LP 250 (registered trademark) from Witco, Zero! 300 (registered
trademark) from
Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet.
Commercially available alkyl benzene lubricants include Zero! 150 (registered
trademark). Commercially available esters include neopentyl glycol
dipelargonate,
which is available as Emery 2917 (registered trademark) and Hatcol 2370
(registered
trademark). Other useful esters include phosphate esters, dibasic acid esters,
and
fluoroesters. In some cases, hydrocarbon based oils are have sufficient
solubility with
the refrigerant that is comprised of an iodocarbon, the combination of the
iodocarbon
and the hydrocarbon oil might more stable than other types of lubricant. Such
combination may therefore be advantageous. Preferred lubricants include
polyalkylene
glycols and esters. Polyalkylene glycols are highly preferred in certain
embodiments
because they are currently in use in particular applications such as mobile
air-
conditioning. Of course, different mixtures of different types of lubricants
may be used.
Other additives not mentioned herein can also be included by those skilled in
the
art in view of the teachings contained herein without departing from the novel
and basic
features of the present invention.
HEAT TRANSFER METHODS AND SYSTEMS
The present methods, systems and compositions are thus adaptable for use in
connection with a wide variety of heat transfer systems in general and
refrigeration
systems in particular, such as air-conditioning (including both stationary and
mobile air
conditioning systems), refrigeration, heat-pump systems, and the like. In
certain
preferred embodiments, the compositions of the present invention are used in
refrigeration systems originally designed for use with an HFC refrigerant,
such as, for
example, R-404. The preferred compositions of the present invention tend to
exhibit
many of the desirable characteristics of R-404A but have a GWP that is
substantially
lower than that of R-404A while at the same time having a capacity and/or
efficiency
that is substantially similar to or substantially matches, and preferably is
as high as or
higher than R-404A. In particular, applicants have recognized that certain
preferred
embodiments of the present compositions tend to exhibit relatively low global
warming
8

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
potentials ("GWPs"), preferably less than about 2500, more preferably less
than about
2400, and even more preferably not greater than about 2300. In certain
embodiments,
the present compositions have a GWP of about 1500 or less, and even more
preferable
of less than about 1000.
In certain other preferred embodiments, the present compositions are used in
refrigeration systems which had contained and/or had originally been designed
for use
with R-404A. Preferred refrigeration compositions of the present invention may
be
used in refrigeration systems containing a lubricant used conventionally with
R-404A,
such as mineral oils, polyalkylbenzene, polyalkylene glycol oils, and the
like, or may be
used with other lubricants traditionally used with HFC refrigerants. As used
herein the
term "refrigeration system" refers generally to any system or apparatus, or
any part or
portion of such a system or apparatus, which employs a refrigerant to provide
cooling.
Such refrigeration systems include, for example, air conditioners, electric
refrigerators,
chillers (including chillers using centrifugal compressors), and the like.
As mentioned above, the present invention achieves exceptional advantage in
connection with systems known as low temperature refrigeration systems. As
used
herein the term "low temperature refrigeration system" refers to vapor
compression
refrigeration systems which utilize one or more compressors and a condenser
temperature of from about 35 C to about 45 C. In preferred embodiments of such

systems, the systems have an evaporator temperature of from about ¨ 40 C and
less
than about -15 C, more preferably from about ¨ 35 C to about ¨ 25 C, with an
evaporator temperature preferably of about ¨ 32 C. Moreover, in preferred
embodiments of such systems, the systems have a degree of superheat at
evaporator
outlet of from about 0 C to about 10 C, with a degree of superheat at
evaporator outlet
preferably of from about 4 C to about 6 C. Furthermore, in preferred
embodiments of
such systems, the systems have a degree of superheat in the suction line of
from about
15 C to about 25 C, with a degree of superheat in the suction line preferably
of from
about 20 C to about 25 C.
In one non-limiting embodiment, the heat transfer compositions of the present
invention may be used to retrofit an existing refrigeration system with or
without having
to substantially modify the system and with or without having to drain
completely the
9

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
existing refrigerant. In one aspect, part of the refrigerant charge is drained
from the
system, which may include more than 5%, 10%, 25%, 50%, 75% or the like. The
removed refrigerant charge is then replaced with one or a combination of the
non-
flammable, low GWP refrigerants discussed herein.
In alternative embodiments, rather than partially draining the existing
system, the
refrigerants of the present invention may be used to "top off existing systems
after a
partial refrigerant leak. Many commercial systems, for example, have
relatively high
refrigerant leak rates which require routine addition of refrigerant over the
life of the
system. In one method of the present invention, a refrigerant system is
provided with
less than the full or designed charge of refrigerant in the system, which, in
preferred
embodiments, occurs as a result of leakage of refrigerant from the system, and
a
refrigerant composition of the present invention is used to recharge the
system,
preferably during normal recharge maintenance. If the system leaked R404A, for

example, it would be recharged with one or a combination of the blends
identified
herein. The present methods permit such to occur while substantially
maintaining
capacity of the system, maintaining or improving energy efficiency (lower
electricity
consumption which equates to lower operating cost for the users), and lowering
the
GWP of the refrigerant contained in the system (lowering environmental
impact). In
preferred embodiments, such a method can be performed regardless of how much
refrigerant has leaked, preferably without a blend calculation, and provides a
simple
(and low cost) way to reduce environmental impact associated with recharging
of an
existent system without deviating from the routine maintenance schedule of the
system.
In accordance with the foregoing, applicants' have recognized that even
relatively
large amounts of R404A when used in combination with the blends of the present

invention, whether in the form of an unintentional contaminant, as an
intentionally added
ingredient or as the remaining refrigerant after a system replacement or
recharge, do
not have a substantially deleterious effect on the performance of the
refrigerants and/or
refrigeration systems of the present invention. Conversely, applicants have
also come
to recognize that relatively large amounts of the blends of the present
invention in
R404A, whether in the form of an unintentional contaminant or as an
intentionally added
ingredient, do not have a substantially deleterious effect on the performance
of the

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
refrigerant. Accordingly, whereas in other cases the presence of such a
contaminant
might otherwise disqualify the use of the refrigerant with the contaminant,
applicants
have come to recognize that the use of such mixtures of refrigerants will
generally be
acceptable for the intended purpose. Accordingly, one advantage of the methods
and
compositions of the present invention is that, from a workability standpoint,
there is
generally not a great incentive to ensure that R404A is entirely absent from
the low
GWP refrigerants, and vice versa, and under such circumstances there is an
increased
possibility that, in the absence of the methods provided by the present
invention,
substantial and severe problems would arise with the operation of many
existing
automatic purge systems. However, the present methods overcome these problems
and add reliability, safety and efficiency to the systems.
EXAMPLES
The following examples are provided for the purpose of illustrating the
present
invention but without limiting the scope thereof.
EXAMPLE 1: Performance Parameters
The coefficient of performance (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 to the energy applied by the compressor in
compressing the
vapor. The capacity of a refrigerant represents the amount of cooling or
heating 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. 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).
A low temperature refrigeration system is provided. In the case of such a
system
11

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
illustrated in this Example, the condenser temperature is set to 40.55 C,
which generally
corresponds to an outdoor temperature of about 35 C. The degree of subcooling
at the
expansion device inlet is set to 5.55 C. The evaporating temperature is set to
-31.6 C,
which corresponds to a box temperature of about -26 C. The degree of superheat
at
evaporator outlet is set to 5.55 C. The degree of superheat in the suction
line is set to
13.88 C, and the compressor efficiency is set to 65%. The pressure drop and
heat
transfer in the connecting lines (suction and liquid lines) are considered
negligible, and
heat leakage through the compressor shell is ignored. Several operating
parameters
are determined for the compositions Al ¨ A4 identified in Table A above in
accordance
with the present invention, and these operating parameters are reported in
Table 1
below, based upon HFC-404A having a COP value of 100%, a capacity value of
100%
and a discharge temperature of 97.6 C
TABLE 1
Evaporator Capacity COP
Name GWP
Glide ( C) (0/0) (0/0)
R404A 3922 0.5 100% 100%
Al 1344 4.9 96% 110%
A2 1330 3.5 103% 108%
A3 1386 4.7 99% 109%
A4 1386 5.4 95% 110%
As can be seen from the Table 1 above, applicants have found that the
compositions of
the present invention are capable of at once achieving many of the important
refrigeration system performance parameters close to the parameters for R-
404A, and
in particular sufficiently close to permit such compositions to be used as a
drop-in
replacement for R-404A in low temperature refrigeration systems and/or for use
in such
existing systems with only minor system modification. For example,
compositions Al ¨
A4 exhibit capacities in this low temperature refrigeration system that are
within about
8%, and even more preferably within about 5% of that of R404A. . All these
blends
have efficiencies (COPs) higher than that of R404A by as much as 10% which is
very
desirable. Especially in view of the improved GWP of compositions Al ¨ A4,
these
12

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
compositions of the present invention are excellent candidates for use as drop-
in
replacements for low temperature refrigeration systems originally containing
and/or
designed to contain R-404A
Since many existing low temperature refrigeration systems have been designed
for R-404A, or for other refrigerants with properties similar to R-404A, those
skilled in
the art will appreciate the substantial advantage of a refrigerant with low
GWP and
superior efficiency which can be used as replacement for R-404A or like
refrigerants
with relatively minimal modifications to the system. Furthermore, those
skilled in the art
will appreciate that the present compositions are capable of providing
substantial
advantage for use in new or newly designed refrigeration systems, including
preferably,
low temperature refrigeration systems.
EXAMPLE 2: Retrofit Parameters
It is contemplated that in certain embodiments the present invention provides
retrofitting methods which comprise removing at least a portion of the
existing
refrigerant from the system and replacing at least a portion of the removed
refrigerant
with a composition of the present invention, preferably without substantial
modification
of the system and even more preferably without any change in major system
components, such as compressors, condensers, evaporators, and expansion
valves.
Due to certain characteristics of low temperature refrigeration systems,
including
particularly low temperature refrigeration systems containing or designed to
contain
R404A refrigerant, it is important in certain embodiments that such systems
are capable
of exhibiting reliable system operating parameters with drop-in refrigerants.
Such
operating parameters include:
= High-Side Pressure that is within about 105%, and even more preferably
within
about 103% of the high side pressure of the system using R404A. This
parameter is important in such embodiments because it allows the use of
existing
pressure components.
= Discharge Temperature that is preferably lower than about 130 C, and even

more preferably lower than about 125 C. The advantage of such a characteristic

is that it permits the use of existing equipment without activation of the
thermal
13

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
protection aspects of the system, which are preferably designed to protect
compressor components. This parameter is advantageous in that it avoids the
use of costly controls such as liquid injection to reduce discharge
temperature.
= Lower suction pressures are acceptable if they do not cause the system to
go
into sub-atmospheric pressure at low evaporation temperatures. This positive
pressure is required to ensure that the system has always positive pressure,
avoiding any contamination with humid air in case of leak. To evaluate this
requirement, one would employ a property called "Normal Boiling Temperature"
(NBT: boiling temperature at atmospheric pressure) of the fluid in question.
This
NBT should be as close as possible to the one of the fluid replaced (R404A)
and
at least lower than the lowest evaporation temperature found in typical
commercial systems (example: -40 C).
The above-noted and other operating parameters are determined for the
compositions A1 ¨ A4 identified in Table A above in accordance with the
present
invention, and these operating parameters is reported in Table 2 below:
TABLE 2
Normal
Discharge Di.scharge Suction
Boiling
Name Pressure Pressure
Temp. Cc) Temp.
(0/0) (0/0)
( c)
R404A 100% 91.9 100% -46.2
Al 96% 117.7 78% -44.9
A2 103% 113.4 87% -46.1
A3 99% 118.3 80% -45.3
A4 95% 120.4 76% -44.8
In certain preferred embodiments the replacement step is a drop-in replacement
in the
sense that no substantial redesign or modification of the system is required
and no
major item of equipment needs to be replaced in order to accommodate the
refrigerant
of the present invention. That is the case with the compositions A1 ¨ A4,
which in
14

CA 02834894 2013-10-31
WO 2012/151238 PCT/US2012/036056
general can be used in most retrofit procedures without any change of major
components. In all compositions A1 ¨ A4, the discharge pressure and
temperature is
below the limit and the Normal Boiling Temperature is similar to R404A
therefore they
can be used in most existent refrigeration systems.
Although the invention has been described with reference to preferred
embodiments, it will be understood by those skilled in the art that various
changes may
be made and equivalents may be substituted for elements thereof without
departing
from the scope of the invention. In addition, many modifications may be made
to adapt
to a particular situation or material to the teachings of the invention
without departing
from the essential scope thereof. Therefore, it is intended that the invention
not be
limited to the particular embodiments disclosed, but that the invention will
include all
embodiments falling within the scope of the appended claims or any claims
later added.

Representative Drawing

Sorry, the representative drawing for patent document number 2834894 was not found.

Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date Unavailable
(86) PCT Filing Date 2012-05-02
(87) PCT Publication Date 2012-11-08
(85) National Entry 2013-10-31
Examination Requested 2017-04-25
Dead Application 2019-08-23

Abandonment History

Abandonment Date Reason Reinstatement Date
2018-08-23 R30(2) - Failure to Respond
2019-05-02 FAILURE TO PAY APPLICATION MAINTENANCE FEE

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $400.00 2013-10-31
Maintenance Fee - Application - New Act 2 2014-05-02 $100.00 2014-04-23
Maintenance Fee - Application - New Act 3 2015-05-04 $100.00 2015-04-22
Maintenance Fee - Application - New Act 4 2016-05-02 $100.00 2016-04-28
Maintenance Fee - Application - New Act 5 2017-05-02 $200.00 2017-04-12
Request for Examination $800.00 2017-04-25
Maintenance Fee - Application - New Act 6 2018-05-02 $200.00 2018-04-20
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
HONEYWELL INTERNATIONAL INC.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
Documents

To view selected files, please enter reCAPTCHA code :



To view images, click a link in the Document Description column. To download the documents, select one or more checkboxes in the first column and then click the "Download Selected in PDF format (Zip Archive)" or the "Download Selected as Single PDF" button.

List of published and non-published patent-specific documents on the CPD .

If you have any difficulty accessing content, you can call the Client Service Centre at 1-866-997-1936 or send them an e-mail at CIPO Client Service Centre.


Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 2013-10-31 1 66
Claims 2013-10-31 2 66
Description 2013-10-31 15 728
Cover Page 2013-12-16 1 33
Examiner Requisition 2018-02-23 3 182
PCT 2013-10-31 9 342
Assignment 2013-10-31 4 94
Request for Examination 2017-04-25 2 44