U.S. patent application number 16/942121 was filed with the patent office on 2020-11-12 for tetrafluoropropene compositions and uses thereof.
This patent application is currently assigned to THE CHEMOURS COMPANY FC, LLC. The applicant listed for this patent is THE CHEMOURS COMPANY FC, LLC. Invention is credited to DONALD BERNARD BIVENS, THOMAS JOSEPH LECK, BARBARA HAVILAND MINOR.
Application Number | 20200354618 16/942121 |
Document ID | / |
Family ID | 1000004986567 |
Filed Date | 2020-11-12 |
United States Patent
Application |
20200354618 |
Kind Code |
A1 |
MINOR; BARBARA HAVILAND ; et
al. |
November 12, 2020 |
TETRAFLUOROPROPENE COMPOSITIONS AND USES THEREOF
Abstract
The present invention relates to compositions for use in
refrigeration, air-conditioning, and heat pump systems wherein the
composition comprises a tetrafluoropropene and at least one other
component. The compositions of the present invention are useful in
processes for producing cooling or heat, as heat transfer fluids,
foam blowing agents, aerosol propellants, and fire suppression and
fire extinguishing agents.
Inventors: |
MINOR; BARBARA HAVILAND;
(ELKTON, MD) ; LECK; THOMAS JOSEPH; (HOCKESSIN,
DE) ; BIVENS; DONALD BERNARD; (KENNETT SQUARE,
PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THE CHEMOURS COMPANY FC, LLC |
Wilmington |
DE |
US |
|
|
Assignee: |
THE CHEMOURS COMPANY FC,
LLC
WILMINGTON
DE
|
Family ID: |
1000004986567 |
Appl. No.: |
16/942121 |
Filed: |
July 29, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16239466 |
Jan 3, 2019 |
10767092 |
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16942121 |
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15362354 |
Nov 28, 2016 |
10208236 |
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16239466 |
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14499454 |
Sep 29, 2014 |
9540556 |
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15362354 |
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13858182 |
Apr 8, 2013 |
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14499454 |
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12618890 |
Nov 16, 2009 |
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13858182 |
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61180281 |
May 21, 2009 |
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61116029 |
Nov 19, 2008 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2207/2835 20130101;
C10M 105/32 20130101; C10M 2201/1023 20130101; C09K 2205/43
20130101; C10M 2203/065 20130101; F28C 3/08 20130101; C10M 105/50
20130101; C09K 2205/47 20130101; C10M 171/008 20130101; C09K
2205/22 20130101; C10M 2203/024 20130101; C10M 105/76 20130101;
C10M 2211/003 20130101; C10M 107/24 20130101; C10N 2040/30
20130101; C10M 105/06 20130101; F25B 2400/121 20130101; C09K 5/045
20130101; F25B 1/00 20130101; F25B 31/002 20130101; C09K 2205/126
20130101; C09K 2205/122 20130101; C10M 2209/043 20130101; C10M
2223/003 20130101; C08J 9/146 20130101; C09K 3/30 20130101; C10M
101/02 20130101; C09K 2205/40 20130101; C10M 2229/02 20130101; C10M
107/34 20130101; F25B 45/00 20130101; C10M 2209/1033 20130101; C09K
2205/42 20130101 |
International
Class: |
C09K 5/04 20060101
C09K005/04; C08J 9/14 20060101 C08J009/14; C09K 3/30 20060101
C09K003/30; F28C 3/08 20060101 F28C003/08; C10M 101/02 20060101
C10M101/02; C10M 105/06 20060101 C10M105/06; C10M 105/32 20060101
C10M105/32; C10M 105/50 20060101 C10M105/50; C10M 105/76 20060101
C10M105/76; C10M 107/24 20060101 C10M107/24; C10M 107/34 20060101
C10M107/34; C10M 171/00 20060101 C10M171/00; F25B 1/00 20060101
F25B001/00; F25B 31/00 20060101 F25B031/00; F25B 45/00 20060101
F25B045/00 |
Claims
1-14. (canceled)
15. A composition comprising a non-flammable refrigerant consisting
essentially of HFO-1234yf and HFC-134a, wherein said refrigerant
contains no more than about 60 weight percent HFO-1234yf and at
least about 40 weight percent HFC-134a.
16. The composition of claim 15, wherein said refrigerant consists
essentially of from about 52.5 to 60 weight percent HFO-1234yf and
from about 47.5 to 40 weight percent HFC-134a.
17. The composition of claim 15, wherein said refrigerant consists
essentially of from about 55 to 60 weight percent HFO-1234yf and
from about 45 to 40 weight percent HFC-134a.
18. The composition of claim 15, wherein said refrigerant consists
essentially of from about 55 to 57.5 weight percent HFO-1234yf and
from about 45 to 42.5 weight percent HFC-134a.
19. The composition of claim 15 further comprising at least one
lubricant selected from the group consisting of mineral oils,
alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly
alpha olefins, polyalkylene glycols, dibasic acid esters,
polyesters, neopentyl esters, polyvinyl ethers, silicones, silicate
esters, fluorinated compounds, phosphate esters and mixtures
thereof.
20. A process to produce cooling comprising condensing a
composition of claim 15 and thereafter evaporating said composition
in the vicinity of a body to be cooled.
21. A process to produce heat comprising condensing the composition
of claim 15 in the vicinity of a body to be heated and thereafter
evaporating said composition.
22. A method for replacing R12, R134a, R22, R404A, R407A, R407C,
R408A, R410A, R413A, R417A, R419A, R422A, R422B, R422C, R422D,
R423A, R424A, R426A, R428A, R430A, R434A, R437A, R438A, R502,
R507A, R507B, and R508, in a system that uses, used or was designed
to use R12, R134a, R22, R404A, R407A, R407C, R408A, R410A, R413A,
R417A, R419A, R422A, R422B, R422C, R422D, R423A, R424A, R426A,
R428A, R430A, R434A, R437A, R438A, R502, R507A, R507B, and R508,
wherein said method comprises providing the composition of claim 15
to said system.
23. A refrigeration, air-conditioning or heat pump apparatus
containing the composition of claim 15.
24. The refrigeration, air-conditioning or heat pump apparatus of
claim 23 comprising a stationary air-conditioning system.
25. The refrigeration, air-conditioning or heat pump apparatus of
claim 23 comprising a stationary refrigeration system.
26. The refrigeration, air-conditioning or heat pump apparatus of
claim 23 comprising a chiller.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the priority benefit of U.S.
Provisional Patent Application No. 61/116,029, filed Nov. 19, 2008,
and U.S. Provisional Patent Application No. 61/180,281, filed May
21, 2009.
BACKGROUND
1. Field of the Disclosure
[0002] The present disclosure relates to compositions for use in
refrigeration, air-conditioning, and heat pump systems wherein the
composition comprises a tetrafluoropropene and at least one other
compound. The compositions of the present invention are useful in
processes for producing cooling or heat, as heat transfer fluids,
foam blowing agents, aerosol propellants, and fire suppression and
fire extinguishing agents.
2. Description of Related Art
[0003] The refrigeration industry has been working for the past few
decades to find replacement refrigerants for the ozone depleting
chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs)
being phased out as a result of the Montreal Protocol. The solution
for most refrigerant producers has been the commercialization of
hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants,
HFC-134a being the most widely used at this time, have zero ozone
depletion potential and thus are not affected by the current
regulatory phase out as a result of the Montreal Protocol.
[0004] Further environmental regulations may ultimately cause
global phase out of certain HFC refrigerants. Currently, the
automobile industry is facing regulations relating to global
warming potential for refrigerants used in mobile air-conditioning.
Therefore, there is a great current need to identify new
refrigerants with reduced global warming potential for the mobile
air-conditioning market. Should the regulations be more broadly
applied in the future, for instance for stationary air conditioning
and refrigeration systems, an even greater need will be felt for
refrigerants that can be used in all areas of the refrigeration and
air-conditioning industry.
[0005] Currently proposed replacement refrigerants for HFC-134a
include HFC-152a, pure hydrocarbons such as butane or propane, or
"natural" refrigerants such as CO.sub.2. Many of these suggested
replacements are toxic, flammable, and/or have low energy
efficiency. New replacements are also being proposed for HCFC-22,
R404A, R407C, and R410A among others. Therefore, new alternative
refrigerants are being sought.
BRIEF SUMMARY
[0006] The object of the present disclosure is to provide novel
refrigerant compositions and heat transfer fluid compositions that
provide unique characteristics to meet the demands of low or zero
ozone depletion potential and lower global warming potential as
compared to current refrigerants.
[0007] Disclosed are compositions selected from the group
consisting of compositions comprising: [0008] HFO-1234yf, HFC-152a,
and HFC-134a; [0009] HFO-1234yf, HFC-125, and HFC-152a; [0010]
HFO-1234yf, HFC-125, and HFC-134a; [0011] HFO-1234yf, HFC-32, and
HFC-134a; [0012] HFO-1234yf, HFC-32, HFC-125, and HFC-134a; [0013]
HFO-1234ze and HFC-32; [0014] HFO-1234ze and HFC-125; [0015]
HFO-1234ze, HFC-125, and HFC-152a; [0016] HFO-1234ze, HFC-125, and
HFC-134a; [0017] HFO-1234ze, HFC-32, and HFC-134a; [0018] and
[0019] HFO-1234ze, HFC-32, HFC-125, and HFC-134a.
[0020] Also disclosed are non-flammable compositions comprising no
more than about 60 weight percent HFO-1234yf and at least about 40
weight percent HFC-134a.
[0021] Also disclosed are compositions comprising at least about 85
weight percent HFO-1234yf and up to about 15 weight percent
HFC-32.
DETAILED DESCRIPTION
[0022] Before addressing details of embodiments described below,
some terms are defined or clarified.
Definitions
[0023] As used herein, the term heat transfer composition means a
composition used to carry heat from a heat source to a heat
sink.
[0024] A heat source is defined as any space, location, object or
body from which it is desirable to add, transfer, move or remove
heat. Examples of heat sources is spaces (open or enclosed)
requiring refrigeration or cooling, such as refrigerator or freezer
cases in a supermarket, building spaces requiring air-conditioning,
industrial water chillers or the passenger compartment of an
automobile requiring air-conditioning. In some embodiments, the
heat transfer composition may remain in a constant state throughout
the transfer process (i.e., not evaporate or condense). In other
embodiments, evaporative cooling processes may utilize heat
transfer compositions as well.
[0025] A heat sink is defined as any space, location, object or
body capable of absorbing heat. A vapor compression refrigeration
system is one example of such a heat sink.
[0026] A heat transfer system is the system (or apparatus) used to
produce a heating or cooling effect in a particular space. A heat
transfer system may be a mobile system or a stationary system.
[0027] Examples of heat transfer systems included but are not
limited to air conditioners, freezers, refrigerators, heat pumps,
water chillers, flooded evaporator chillers, direct expansion
chillers, walk-in coolers, mobile refrigerators, mobile air
conditioning units, dehumidifiers, and combinations thereof.
[0028] As used herein, mobile heat transfer system refers to any
refrigeration, air conditioner, or heating apparatus incorporated
into a transportation unit for the road, rail, sea or air. In
addition, mobile refrigeration or air conditioner units, include
those apparatus that are independent of any moving carrier and are
known as "intermodal" systems. Such intermodal systems include
"container" (combined sea/land transport) as well as "swap bodies"
(combined road/rail transport).
[0029] As used herein, stationary heat transfer systems are systems
that are fixed in place during operation. A stationary heat
transfer system may be associated within or attached to buildings
of any variety or may be stand alone devices located out of doors,
such as a soft drink vending machine. These stationary applications
may be stationary air conditioning and heat pumps (including but
not limited to chillers, high temperature heat pumps, residential,
commercial or industrial air conditioning systems, and including
window, ductless, ducted, packaged terminal, chillers, and those
exterior but connected to the building such as rooftop systems). In
stationary refrigeration applications, the disclosed compositions
may be useful in equipment including commercial, industrial or
residential refrigerators and freezers, ice machines,
self-contained coolers and freezers, flooded evaporator chillers,
direct expansion chillers, walk-in and reach-in coolers and
freezers, and combination systems. In some embodiments, the
disclosed compositions may be used in supermarket refrigeration
systems. Additionally, stationary applications may utilize a
secondary loop system that uses a primary refrigerant to produce
cooling in one location that is transferred to a remote location
via a secondary heat transfer fluid.
[0030] Refrigeration capacity (sometimes referred to as cooling
capacity) is a term to define the change in enthalpy of a
refrigerant in an evaporator per pound of refrigerant circulated,
i.e., the heat removed by the refrigerant in the evaporator per a
given time. The refrigeration capacity is a measure of the ability
of a refrigerant or heat transfer composition to produce cooling.
Therefore, the higher the capacity the greater the cooling that is
produced.
[0031] Coefficient of performance (COP) is the amount of heat
removed divided by the required energy input to operate the cycle.
The higher the COP, the higher is the energy efficiency. COP is
directly related to the energy efficiency ratio (EER) that is the
efficiency rating for refrigeration or air conditioning equipment
at a specific set of internal and external temperatures.
[0032] The term "subcooling" is meant the reduction of the
temperature of a liquid below that liquid's saturation point for a
given pressure. The saturation point is the temperature at which
the vapor is completely condensed to a liquid, but subcooling
(continues to cool the liquid to a lower temperature liquid at the
given pressure. By cooling a liquid below the saturation
temperature (or bubble point temperature), the net refrigeration
capacity can be increased. Subcooling thereby improves
refrigeration capacity and energy efficiency of a system. Subcool
amount is the amount of cooling below the saturation temperature
(in degrees).
[0033] Superheat is a term that defines how far above its
saturation vapor temperature (the temperature at which, if the
composition is cooled, the first drop of liquid is formed, also
referred to as the "dew point") a vapor composition is heated.
[0034] Temperature glide (sometimes referred to simply as "glide")
is the absolute value of the difference between the starting and
ending temperatures of a phase-change process by a refrigerant
within a component of a refrigerant system, exclusive of any
subcooling or superheating. This term may be used to describe
condensation or evaporation of a near azeotropic or non-azeotropic
composition.
[0035] By azeotropic composition is meant a constant-boiling
mixture of two or more substances that behave as a single
substance. One way to characterize an azeotropic composition is
that the vapor produced by partial evaporation or distillation of
the liquid has the same composition as the liquid from which it is
evaporated or distilled, i.e., the mixture distills/refluxes
without compositional change. Constant-boiling compositions are
characterized as azeotropic because they exhibit either a maximum
or minimum boiling point, as compared with that of the
non-azeotropic mixture of the same compounds. An azeotropic
composition will not fractionate within a refrigeration or air
conditioning system during operation. Additionally, an azeotropic
composition will not fractionate upon leakage from a refrigeration
or air conditioning system.
[0036] A near-azeotropic composition (also commonly referred to as
an "azeotrope-like composition") is a substantially constant
boiling liquid admixture of two or more substances that behaves
essentially as a single substance. One way to characterize a
near-azeotropic composition is that the vapor produced by partial
evaporation or distillation of the liquid has substantially the
same composition as the liquid from which it was evaporated or
distilled, that is, the admixture distills/refluxes without
substantial composition change. Another way to characterize a
near-azeotropic composition is that the bubble point vapor pressure
and the dew point vapor pressure of the composition at a particular
temperature are substantially the same. Herein, a composition is
near-azeotropic if, after 50 weight percent of the composition is
removed, such as by evaporation or boiling off, the difference in
vapor pressure between the original composition and the composition
remaining after 50 weight percent of the original composition has
been removed is less than about 10 percent.
[0037] A non-azeotropic composition is a mixture of two or more
substances that behaves as a simple mixture rather than a single
substance. One way to characterize a non-azeotropic composition is
that the vapor produced by partial evaporation or distillation of
the liquid has a substantially different composition as the liquid
from which it was evaporated or distilled, that is, the admixture
distills/refluxes with substantial composition change. Another way
to characterize a non-azeotropic composition is that the bubble
point vapor pressure and the dew point vapor pressure of the
composition at a particular temperature are substantially
different. Herein, a composition is non-azeotropic if, after 50
weight percent of the composition is removed, such as by
evaporation or boiling off, the difference in vapor pressure
between the original composition and the composition remaining
after 50 weight percent of the original composition has been
removed is greater than about 10 percent.
[0038] As used herein, the term "lubricant" means any material
added to a composition or a compressor (and in contact with any
heat transfer composition in use within any heat transfer system)
that provides lubrication to the compressor to aid in preventing
parts from seizing.
[0039] As used herein, compatibilizers are compounds which improve
solubility of the hydrofluorocarbon of the disclosed compositions
in heat transfer system lubricants. In some embodiments, the
compatibilizers improve oil return to the compressor. In some
embodiments, the composition is used with a system lubricant to
reduce oil-rich phase viscosity.
[0040] As used herein, oil-return refers to the ability of a heat
transfer composition to carry lubricant through a heat transfer
system and return it to the compressor. That is, in use, it is not
uncommon for some portion of the compressor lubricant to be carried
away by the heat transfer composition from the compressor into the
other portions of the system. In such systems, if the lubricant is
not efficiently returned to the compressor, the compressor will
eventually fail due to lack of lubrication.
[0041] As used herein, "ultra-violet" dye is defined as a UV
fluorescent or phosphorescent composition that absorbs light in the
ultra-violet or "near" ultra-violet region of the electromagnetic
spectrum. The fluorescence produced by the UV fluorescent dye under
illumination by a UV light that emits at least some radiation with
a wavelength in the range of from 10 nanometers to about 775
nanometers may be detected.
[0042] Flammability is a term used to mean the ability of a
composition to ignite and/or propagate a flame. For refrigerants
and other heat transfer compositions, the lower flammability limit
("LFL") is the minimum concentration of the heat transfer
composition in air that is capable of propagating a flame through a
homogeneous mixture of the composition and air under test
conditions specified in ASTM (American Society of Testing and
Materials) E681. The upper flammability limit ("UFL") is the
maximum concentration of the heat transfer composition in air that
is capable of propagating a flame through a homogeneous mixture of
the composition and air under the same test conditions. The
flammability test, ASTM E681, is run on the liquid phase and the
vapor phase present in a closed container above the liquid at
specified temperatures as designated by ASHRAE (American Society of
Heating, Refrigerating and Air-Conditioning Engineers) in the
ASHRAE Standard 34. In order to be classified by ASHRAE as
non-flammable, a refrigerant must be non-flammable under the
conditions of ASTM E681 as formulated in both the liquid and vapor
phase as well as during leakage scenarios.
[0043] Global warming potential (GWP) is an index for estimating
relative global warming contribution due to atmospheric emission of
a kilogram of a particular greenhouse gas compared to emission of a
kilogram of carbon dioxide. GWP can be calculated for different
time horizons showing the effect of atmospheric lifetime for a
given gas. The GWP for the 100 year time horizon is commonly the
value referenced. For mixtures, a weighted average can be
calculated based on the individual GWPs for each component.
[0044] Ozone depletion potential (ODP) is a number that refers to
the amount of ozone depletion caused by a substance. The ODP is the
ratio of the impact on ozone of a chemical compared to the impact
of a similar mass of CFC-11 (fluorotrichloromethane). Thus, the ODP
of CFC-11 is defined to be 1.0. Other CFCs and HCFCs have ODPs that
range from 0.01 to 1.0. HFCs have zero ODP because they do not
contain chlorine.
[0045] As used herein, the terms "comprises," "comprising,"
"includes," "including," "has," "having" or any other variation
thereof, are intended to cover a non-exclusive inclusion. For
example, a composition, process, method, article, or apparatus that
comprises a list of elements is not necessarily limited to only
those elements but may include other elements not expressly listed
or inherent to such composition, process, method, article, or
apparatus. Further, unless expressly stated to the contrary, "or"
refers to an inclusive or and not to an exclusive or. For example,
a condition A or B is satisfied by any one of the following: A is
true (or present) and B is false (or not present), A is false (or
not present) and B is true (or present), and both A and B are true
(or present).
[0046] The transitional phrase "consisting of" excludes any
element, step, or ingredient not specified. If in the claim such
would close the claim to the inclusion of materials other than
those recited except for impurities ordinarily associated
therewith. When the phrase "consists of" appears in a clause of the
body of a claim, rather than immediately following the preamble, it
limits only the element set forth in that clause; other elements
are not excluded from the claim as a whole.
[0047] The transitional phrase "consisting essentially of" is used
to define a composition, method or apparatus that includes
materials, steps, features, components, or elements, in addition to
those literally disclosed provided that these additional included
materials, steps, features, components, or elements do materially
affect the basic and novel characteristic(s) of the claimed
invention. The term `consisting essentially of` occupies a middle
ground between "comprising" and `consisting of`.
[0048] Where applicants have defined an invention or a portion
thereof with an open-ended term such as "comprising," it should be
readily understood that (unless otherwise stated) the description
should be interpreted to also describe such an invention using the
terms "consisting essentially of" or "consisting of."
[0049] Also, use of "a" or "an" are employed to describe elements
and components described herein. This is done merely for
convenience and to give a general sense of the scope of the
invention. This description should be read to include one or at
least one and the singular also includes the plural unless it is
obvious that it is meant otherwise.
[0050] Unless otherwise defined, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this invention belongs. Although
methods and materials similar or equivalent to those described
herein can be used in the practice or testing of embodiments of the
disclosed compositions, suitable methods and materials are
described below. All publications, patent applications, patents,
and other references mentioned herein are incorporated by reference
in their entirety, unless a particular passage is cited. In case of
conflict, the present specification, including definitions, will
control. In addition, the materials, methods, and examples are
illustrative only and not intended to be limiting.
Compositions
[0051] Disclosed are compositions comprising tetrafluoropropene and
at least one other compound. Tetrafluoropropene may be either
1,3,3,3-tetrafluoropropene (HFO-1234ze) or
2,3,3,3-tetrafluoropropene (HFO-1234yf). HFO-1234ze may exist as
different configurational isomers, E-(trans-) or Z-(cis-), or
stereoisomers. The present invention is intended to include all
single configurational isomers, single stereoisomers or any
combination or mixture thereof.
[0052] Both HFO-1234ze and HFO-1234yf may be made by methods known
in the art.
[0053] The disclosed compositions also contain other fluorinated
compounds selected from the group consisting of difluoromethane
(HFC-32), tetrafluoroethane, pentafluoroethane (HFC-125), and
difluoroethane (1,1-difluoroethane or HFC-152a). Tetrafluoroethane
may be 1,1,1,2-tetrafluoroethane (HFC-134a) or
1,1,2,2-tetrafluoroethane (HFC-134). These fluorinated compounds
are commercially available or may be made by methods known in the
art.
[0054] In one embodiment, compositions are disclosed comprising:
[0055] HFO-1234yf and HFC-32; [0056] HFO-1234yf and HFC-134a;
[0057] HFO-1234yf, HFC-152a, and HFC-134a; [0058] HFO-1234yf,
HFC-125, and HFC-152a; [0059] HFO-1234yf, HFC-125, and HFC-134a;
[0060] HFO-1234yf, HFC-32, and HFC-134a; [0061] HFO-1234yf, HFC-32,
and HFC-125; [0062] HFO-1234yf, HFC-32, HFC-125, and HFC-134a;
[0063] HFO-1234ze and HFC-32; [0064] HFO-1234ze and HFC-125; [0065]
HFO-1234ze, HFC-125, and HFC-152a; [0066] HFO-1234ze, HFC-125, and
HFC-134a; [0067] HFO-1234ze, HFC-32, and HFC-134a; [0068]
HFO-1234ze, HFC-32, and HFC-125; and [0069] HFO-1234ze, HFC-32,
HFC-125, and HFC-134a.
[0070] In another embodiment, compositions are disclosed consisting
essentially of: [0071] HFO-1234yf and HFC-32; [0072] HFO-1234yf and
HFC-134a; [0073] HFO-1234yf, HFC-152a, and HFC-134a; [0074]
HFO-1234yf, HFC-125, and HFC-152a; [0075] HFO-1234yf, HFC-125, and
HFC-134a; [0076] HFO-1234yf, HFC-32, and HFC-134a; [0077]
HFO-1234yf, HFC-32, and HFC-125; [0078] HFO-1234yf, HFC-32,
HFC-125, and HFC-134a; [0079] HFO-1234ze and HFC-32; [0080]
HFO-1234ze and HFC-125; [0081] HFO-1234ze, HFC-125, and HFC-152a;
[0082] HFO-1234ze, HFC-125, and HFC-134a; [0083] HFO-1234ze,
HFC-32, and HFC-134a; [0084] HFO-1234ze, HFC-32, and HFC-125; and
[0085] HFO-1234ze, HFC-32, HFC-125, and HFC-134a.
[0086] In one embodiment, any of the disclosed compositions may be
generally useful when the tetrafluoropropene is present at about 1
weight percent to about 99 weight percent of the overall
composition. In another embodiment, the useful compositions
comprise about 20 weight percent to about 99 weight percent
tetrafluoropropene. In another embodiment, the useful compositions
comprise about 40 weight percent to about 99 weight percent
tetrafluoropropene. And in yet another embodiment, the useful
compositions comprise about 50 weight percent to about 99 weight
percent tetrafluoropropene.
[0087] For ternary compositions as described herein, in one
embodiment, the compositions may comprise from about 1 weight
percent to about 98 weight percent tetrafluoropropene. In another
embodiment, the compositions comprise from about 20 weight percent
to about 98 weight percent tetrafluoropropene. In another
embodiment, the compositions comprise from about 40 weight percent
to about 98 weight percent tetrafluoropropene. And in yet another
embodiment, the compositions comprise from about 50 weight percent
to about 98 weight percent tetrafluoropropene. In certain
embodiments, the disclosed compositions comprising trans-HFO-1234ze
and HFC-125 contain from about 80 weight percent to about 99 weight
percent trans-HFO-1234ze and from about 20 weight percent to about
1 weight percent HFC-125. In other embodiments, the compositions
comprise from about 85 weight percent to about 95 weight percent
HFO-1234ze and from about 15 weight percent to about 5 weight
percent HFC-125.
[0088] In some embodiment, the disclosed compositions comprising
trans-HFO-1234ze and HFC-32 contain from about 20 weight percent to
about 90 weight percent trans-HFO-1234ze and from about 80 weight
percent to about 10 weight percent HFC-32.
[0089] In one embodiment, the disclosed compositions are generally
expected to maintain the desired properties and functionality when
the components are present in the concentrations as listed +/-2
weight percent.
[0090] In some embodiments, the disclosed compositions are found to
be near-azeotropic. Near-azeotropic compositions comprising
tetrafluoropropene have been identified at the specified
temperature as listed in Table 1.
TABLE-US-00001 TABLE 1 Near-azeotrope range Temp Components (weight
percent) (.degree. C.) HFO-1234yf/HFC-152a/HFC-134a 1-98/1-98/1-98
23 HFO-1234yf/152a/125 1-98/1-98/1-98 23
HFO-1234yf/HFC-125/HFC-134a 1-98/1-98/1-98 23
HFO-1234yf/HFC-32/HFC-134a 1-98/1-4/1-98 and 23 1-55/45-98/1-55
HFO-1234yf/HFC-134a/HFC-125/ 1-97/1-97/1-97/1-5, 23 HFC-32
1-35/1-40/30-78/6-39, and 1-50/1-40/1-50/40-97
[0091] Certain of the compositions of the present invention are
non-azeotropic compositions. A non-azeotropic composition may have
certain advantages over azeotropic or near azeotropic mixtures. The
temperature glide of a non-azeotropic composition provides an
advantage in counter current flow heat exchanger arrangements.
[0092] In some embodiments, the disclosed compositions are
non-flammable as determined using ASTM (American Society of Testing
and Materials) E681-2004, the standard test for measuring
flammability of refrigerants.
[0093] In one embodiment, the composition is a non-flammable
composition comprising no more than about 60 weight percent
HFO-1234yf and at least about 40 weight percent HFC-134a at about
60.degree. C.
[0094] In another embodiment, the composition is a non-flammable
composition comprising no more than about 53 weight percent
HFO-1234yf and at least about 47 weight percent HFC-134a at about
100.degree. C.
[0095] In one embodiment, a refrigerant mixture with some
temperature glide may be acceptable in the industry or even have
advantages as mentioned previously herein. R407C is an example of a
commercial refrigerant product with glide. It has been demonstrated
that certain compositions as disclosed herein provide a refrigerant
composition with temperature glide that approaches the temperature
glide of R407C.
[0096] In one embodiment, the compositions comprise at least about
85 weight percent HFO-1234yf and up to about 15 weight percent
HFC-32. Such compositions have been demonstrated to have minimal
temperature glide and maintain cooling capacity and energy
efficiency at a similar level to R407C. In another embodiment, the
compositions comprise at least about 90 weight percent HFO-1234yf
and up to about 10 weight percent HFC-32. In another embodiment,
the compositions comprise at least about 95 weight percent
HFO-1234yf and up to about 5 weight percent HFC-32.
[0097] In some embodiments, in addition to the tetrafluoropropene
and fluorinated compounds, the disclosed compositions may comprise
optional other components.
[0098] In some embodiments, the optional other components (also
referred to herein as additives) in the compositions disclosed
herein may comprise one or more components selected from the group
consisting of lubricants, dyes, solubilizing agents,
compatibilizers, stabilizers, tracers, perfluoropolyethers, anti
wear agents, extreme pressure agents, corrosion and oxidation
inhibitors, metal surface energy reducers, metal surface
deactivators, free radical scavengers, foam control agents,
viscosity index improvers, pour point depressants, detergents,
viscosity adjusters, and mixtures thereof. Indeed, many of these
optional other components fit into one or more of these categories
and may have qualities that lend themselves to achieve one or more
performance characteristic.
[0099] In some embodiments, one or more additive is present in the
compositions disclosed in small amounts relative to the overall
composition. In some embodiments, the amount of additive(s)
concentration in the disclosed compositions is from less than about
0.1 weight percent to as much as about 5 weight percent of total
additive. In some the additives are present in the disclosed
compositions in an amount between about 0.1 weight percent to about
3.5 weight percent. The additive component(s) selected for the
disclosed composition is selected on the basis of the utility
and/or individual equipment components or the system
requirements.
[0100] In some embodiments, the disclosed compositions include at
least one lubricant selected from the group consisting of mineral
oils (oils of mineral origin), synthetic lubricants, and mixtures
thereof.
[0101] In some embodiment, the disclosed compositions further
comprise at least one lubricant selected from the group consisting
of mineral oils, alkylbenzenes, synthetic paraffins, synthetic
naphthenes, poly alpha olefins, polyalkylene glycols, dibasic acid
esters, polyesters, neopentyl esters, polyvinyl ethers, silicones,
silicate esters, fluorinated compounds, phosphate esters and
mixtures thereof.
[0102] In some embodiments, the disclosed compositions include at
least one lubricant selected from those suitable for use with
refrigeration or air-conditioning equipment. In some embodiments,
the disclosed compositions include at least one synthetic oil
selected from those readily known in the field of compression
refrigeration lubrication.
[0103] In some embodiments, at least one optional component is a
mineral oil lubricant. In some embodiments, the mineral oil
lubricant is selected from the group consisting of paraffins
(including straight carbon chain saturated hydrocarbons, branched
carbon chain saturated hydrocarbons, and mixtures thereof),
naphthenes (including saturated cyclic and ring structures),
aromatics (those with unsaturated hydrocarbons containing one or
more ring, wherein one or more ring is characterized by alternating
carbon-carbon double bonds) and non-hydrocarbons (those molecules
containing atoms such as sulfur, nitrogen, oxygen and mixtures
thereof), and mixtures and combinations of thereof.
[0104] Some embodiments may contain one or more synthetic
lubricant. In some embodiments, the synthetic lubricant is selected
from the group consisting of alkyl substituted aromatics (such as
benzene or naphthalene substituted with linear, branched, or
mixtures of linear and branched alkyl groups, often generically
referred to as alkylbenzenes), synthetic paraffins and naphthenes,
poly (alpha olefins), polyglycols (including polyalkylene glycols),
dibasic acid esters, polyesters, neopentyl esters, polyvinyl ethers
(PVEs), silicones, silicate esters, fluorinated compounds,
phosphate esters and mixtures and combinations thereof.
[0105] In some embodiments, the compositions disclosed herein
contain at least one commercially available lubricant. In some
embodiments the compositions disclosed herein contain at least one
lubricant selected from the group consisting of BVM 100 N
(paraffinic mineral oil sold by BVA Oils), Suniso.RTM. 1GS,
Suniso.RTM. 3GS and Suniso.RTM. 5GS (naphthenic mineral oils sold
by Crompton Co.), Sontex.RTM. 372LT (naphthenic mineral oil sold by
Pennzoil), Calumet.RTM. RO-30 (naphthenic mineral oil sold by
Calumet Lubricants), Zerol.RTM. 75, Zerol.RTM. 150 and Zerol.RTM.
500 (linear alkylbenzenes sold by Shrieve Chemicals) and HAB 22
(branched alkylbenzene sold by Nippon Oil), polyol esters (POEs)
such as Castrol.RTM. 100 (Castrol, United Kingdom), polyalkylene
glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland,
Mich.), and mixtures thereof.
[0106] In other embodiments, at least one of the lubricants further
include those lubricants that have been designed for use with
hydrofluorocarbon refrigerants and are miscible with compositions
as disclosed herein under compression refrigeration and
air-conditioning apparatus' operating conditions. In some
embodiments, the lubricants are selected by considering a given
compressor's requirements and the environment to which the
lubricant will be exposed.
[0107] In some embodiments, the lubricant is present in an amount
of less than 5.0 weight percent to the total composition. In other
embodiments, the amount of lubricant is between about 0.1 and 3.5
weight percent of the total composition.
[0108] Notwithstanding the above weight ratios for compositions
disclosed herein, it is understood that in some heat transfer
systems, while the composition is being used, it may acquire
additional lubricant from one or more equipment component of such
heat transfer system. For example, in some refrigeration, air
conditioning and heat pump systems, lubricants may be charged in
the compressor and/or the compressor lubricant sump. Such lubricant
would be in addition to any lubricant additive present in the
refrigerant in such a system. In use, the refrigerant composition
when in the compressor may pick up an amount of the equipment
lubricant to change the refrigerant-lubricant composition from the
starting ratio.
[0109] In such heat transfer systems, even when the majority of the
lubricant resides within the compressor portion of the system, the
entire system may contain a total composition with as much as about
75 weight percent to as little as about 1.0 weight percent of the
composition being lubricant. In one embodiment, in some systems,
for example supermarket refrigerated display cases, the system may
contain about 3 weight percent lubricant (over and above any
lubricant present in the refrigerant composition prior to charging
the system) and 97 weight percent refrigerant. In another
embodiment, in some systems, for example mobile air conditioning
systems, the system may contain about 20 weight percent lubricant
(over and above any lubricant present in the refrigerant
composition prior to charging the system) and about 80 weight
percent refrigerant.
[0110] In some embodiments, the disclosed compositions include at
least one dye. In some embodiments, the disclosed compositions
include at least one ultra-violet (UV) dye.
[0111] In some embodiments, the disclosed compositions include at
least one UV dye that is a fluorescent dye. In some embodiments,
the described compositions include at least one UV dye that is a
fluorescent dye selected from the group consisting of naphthalim
ides, perylenes, coumarins, anthracenes, phenanthracenes,
xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and
derivatives of said dye and combinations thereof.
[0112] In some embodiments, the disclosed compositions contain from
about 0.001 weight percent to about 1.0 weight percent UV dye. In
other embodiments, the UV dye is present in an amount of from about
0.005 weight percent to about 0.5 weight percent; and in other
embodiments, the UV dye is present in an amount of from 0.01 weight
percent to about 0.25 weight percent of the total composition.
[0113] In some embodiments, the UV dye is a useful component for
detecting leaks of the composition by permitting one to observe the
fluorescence of the dye at or in the vicinity of a leak point in an
apparatus (e.g., refrigeration unit, air-conditioner or heat pump).
One may observe the UV emission, e.g., fluorescence from the dye
under an ultra-violet light. Therefore, if a composition containing
such a UV dye is leaking from a given point in an apparatus, the
fluorescence can be detected at the leak point, or in the vicinity
of the leak point.
[0114] In some embodiments, the described compositions further
contain at least one solubilizing agent selected to improve the
solubility of one or more dye in the disclosed compositions. In
some embodiments, the weight ratio of dye to solubilizing agent
ranges from about 99:1 to about 1:1.
[0115] In some embodiments, solubilizing agents in the disclosed
compositions include at least one compound selected from the group
consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene
glycol ethers (such as dipropylene glycol dimethyl ether), amides,
nitriles, ketones, chlorocarbons (such as methylene chloride,
trichloroethylene, chloroform, or mixtures thereof), esters,
lactones, aromatic ethers, fluoroethers and 1,1,1-trifluoroalkanes
and mixtures thereof.
[0116] In some embodiments, at least one compatibilizer is selected
to improve the compatibility of one or more lubricant with the
disclosed compositions. In some embodiments, the compatibilizer is
selected from the group consisting of hydrocarbons, hydrocarbon
ethers, polyoxyalkylene glycol ethers (such as dipropylene glycol
dimethyl ether), amides, nitriles, ketones, chlorocarbons (such as
methylene chloride, trichloroethylene, chloroform, or mixtures
thereof), esters, lactones, aromatic ethers, fluoroethers,
1,1,1-trifluoroalkanes, and mixtures thereof.
[0117] In some embodiments, one or more solubilizing agent and/or
compatibilizer is selected from the group consisting of hydrocarbon
ethers consisting of the ethers containing only carbon, hydrogen
and oxygen, such as dimethyl ether (DME) and mixtures thereof.
[0118] In some embodiments, the disclosed composition includes at
least one linear or cyclic aliphatic or aromatic hydrocarbon
compatibilizer containing from 5 to 15 carbon atoms. In some
embodiments, the compatibilizer is selected from the group
consisting of at least one hydrocarbon; in other embodiments, the
compatibilizer is a hydrocarbon selected from the group consisting
of at least pentane, hexane, octane, nonane, decane, commercially
available from Exxon Chemical (USA) under the trademarks
Isopar.RTM. H (a high purity C.sub.11 to C.sub.12 iso-paraffinic),
Aromatic 150 (a C.sub.9 to C.sub.11 aromatic), Aromatic 200 (a
C.sub.9 to C.sub.15 aromatic) and Naptha 140 and mixtures
thereof.
[0119] In some embodiments, the disclosed compositions include at
least one polymeric compatibilizer. In some embodiments, the
disclosed compositions include at least one a polymeric
compatibilizer selected from those that are random copolymers of
fluorinated and non-fluorinated acrylates, wherein the polymer
comprises repeating units of at least one monomer represented by
the formulae CH.sub.2.dbd.C(R.sup.1)CO.sub.2R.sup.2,
CH.sub.2.dbd.C(R.sup.3)C.sub.6H.sub.4R.sup.4, and
CH.sub.2.dbd.C(R.sup.5)C.sub.6H.sub.4XR.sup.6, wherein X is oxygen
or sulfur; R.sup.1, R.sup.3, and R.sup.5 are independently selected
from the group consisting of H and C.sub.1-C.sub.4 alkyl radicals;
and R.sup.2, R.sup.4, and R.sup.6 are independently selected from
the group consisting of carbon-chain-based radicals containing C,
and F, and may further contain H, Cl, ether oxygen, or sulfur in
the form of thioether, sulfoxide, or sulfone groups and mixtures
thereof. Examples of such polymeric compatibilizers include those
commercially available from E. I. du Pont de Nemours & Co.
(Wilmington, Del., 19898, USA) under the trademark Zonyl.RTM. PHS.
Zonyl.RTM. PHS is a random copolymer made by polymerizing 40 weight
percent
CH.sub.2.dbd.C(CH.sub.3)CO.sub.2CH.sub.2CH.sub.2(CF.sub.2CF.sub.2).sub.mF
(also referred to as Zonyl.RTM. fluoromethacrylate or ZFM) wherein
m is from 1 to 12, primarily 2 to 8, and 60 weight percent lauryl
methacrylate
(CH.sub.2.dbd.C(CH.sub.3)CO.sub.2(CH.sub.2).sub.11CH.sub.3, also
referred to as LMA).
[0120] In some embodiments, the compatibilizer component contains
from about 0.01 to 30 weight percent (based on total amount of
compatibilizer) of an additive which reduces the surface energy of
metallic copper, aluminum, steel, or other metals and metal alloys
thereof found in heat exchangers in a way that reduces the adhesion
of lubricants to the metal. Examples of metal surface energy
reducing additives include those commercially available from DuPont
under the trademarks Zonyl.RTM. FSA, Zonyl.RTM. FSP, and Zonyl.RTM.
FSJ.
[0121] In some embodiments, the disclosed compositions further
include metal surface deactivators. In some embodiments, at least
one metal surface deactivator is selected from the group consisting
of areoxalyl bis (benzylidene) hydrazide (CAS reg no. 6629-10-3),
N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS
reg no. 32687-78-8),
2,2,'-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate
(CAS reg no. 70331-94-1), N,N'-(disalicyclidene)-1,2-diaminopropane
(CAS reg no. 94-91-7) and ethylenediaminetetra-acetic acid (CAS reg
no. 60-00-4) and its salts, and mixtures thereof.
[0122] In some embodiments, the compositions disclosed herein
further include at least one stabilizer selected from the group
consisting of hindered phenols, thiophosphates, butylated
triphenylphosphorothionates, organo phosphates, or phosphites, aryl
alkyl ethers, terpenes, terpenoids, epoxides, fluorinated epoxides,
oxetanes, ascorbic acid, thiols, lactones, thioethers, amines,
nitromethane, alkylsilanes, benzophenone derivatives, aryl
sulfides, divinyl terephthalic acid, diphenyl terephthalic acid,
ionic liquids, and mixtures thereof.
[0123] In some embodiments, said at least one stabilizer is
selected from the group consisting of tocopherol; hydroquinone;
t-butyl hydroquinone; monothiophosphates; and dithiophosphates,
commercially available from Ciba Specialty Chemicals, Basel,
Switzerland, hereinafter "Ciba", under the trademark Irgalube 63;
dialkylthiophosphate esters, commercially available from Ciba under
the trademarks Irgalube.RTM. 353 and Irgalube 350, respectively;
butylated triphenylphosphorothionates, commercially available from
Ciba under the trademark Irgalube.RTM. 232; amine phosphates,
commercially available from Ciba under the trademark Irgalube.RTM.
349 (Ciba); hindered phosphites, commercially available from
[0124] Ciba as Irgafos.RTM. 168 and
Tris-(di-tert-butylphenyl)phosphite, commercially available from
Ciba under the trademark Irgafos.RTM. OPH; (Di-n-octyl phosphite);
and iso-decyl diphenyl phosphite, commercially available from Ciba
under the trademark Irgafos.RTM. DDPP; trialkyl phosphates, such as
trimethyl phosphate, triethylphosphate, tributyl phosphate,
trioctyl phosphate, and tri(2-ethylhexyl)phosphate; triaryl
phosphates including triphenyl phosphate, tricresyl phosphate, and
trixylenyl phosphate; and mixed alkyl-aryl phosphates including
isopropylphenyl phosphate (IPPP), and bis(t-butylphenyl)phenyl
phosphate (TBPP); butylated triphenyl phosphates, such as those
commercially available under the trademark Syn-O-Ad.RTM. including
Syn-O-Ad.RTM. 8784; tert-butylated triphenyl phosphates such as
those commercially available under the trademark Durad.RTM.620;
isopropylated triphenyl phosphates such as those commercially
available under the trademarks Durad.RTM. 220 and Durad.RTM.110;
anisole; 1,4-dimethoxybenzene; 1,4-diethoxybenzene;
1,3,5-trimethoxybenzene; myrcene, alloocimene, limonene (in
particular, d-limonene); retinal; pinene; menthol; geraniol;
farnesol; phytol; Vitamin A; terpinene; delta-3-carene;
terpinolene; phellandrene; fenchene; dipentene; caratenoids, such
as lycopene, beta carotene, and xanthophylls, such as zeaxanthin;
retinoids, such as hepaxanthin and isotretinoin; bornane;
1,2-propylene oxide; 1,2-butylene oxide; n-butyl glycidyl ether;
trifluoromethyloxirane; 1,1-bis(trifluoromethyl)oxirane;
3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co.,
Ltd); 3-ethyl-3-((phenoxy)methyl)-oxetane, such as OXT-211
(Toagosei Co., Ltd); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane,
such as OXT-212 (Toagosei Co., Ltd); ascorbic acid; methanethiol
(methyl mercaptan); ethanethiol (ethyl mercaptan); Coenzyme A;
dimercaptosuccinic acid (DMSA); grapefruit mercaptan
((R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol)); cysteine
((R)-2-amino-3-sulfanyl-propanoic acid); lipoamide
(1,2-dithiolane-3-pentanamide);
5,7-bis(1,1-dimethylethyl)-3-[2,3(or
3,4)-dimethylphenyl]-2(3H)-benzofuranone, commercially available
from Ciba under the trademark Irganox.RTM. HP-136; benzyl phenyl
sulfide; diphenyl sulfide; diisopropylamine; dioctadecyl
3,3'-thiodipropionate, commercially available from Ciba under the
trademark Irganox.RTM. PS 802 (Ciba); didodecyl
3,3'-thiopropionate, commercially available from Ciba under the
trademark Irganox.RTM. PS 800;
di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, commercially
available from Ciba under the trademark Tinuvin.RTM. 770;
poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl
succinate, commercially available from Ciba under the trademark
Tinuvin.RTM. 622LD (Ciba); methyl bis tallow amine; bis tallow
amine; phenol-alpha-naphthylamine; bis(dimethylamino)methylsilane
(DMAMS); tris(trimethylsilyl)silane (TTMSS); vinyltriethoxysilane;
vinyltrimethoxysilane; 2,5-difluorobenzophenone;
2',5'-dihydroxyacetophenone; 2-aminobenzophenone;
2-chlorobenzophenone; benzyl phenyl sulfide; diphenyl sulfide;
dibenzyl sulfide; ionic liquids; and mixtures and combinations
thereof.
[0125] In some embodiments, the disclosed composition includes at
least one ionic liquid stabilizer selected from the group
consisting of organic salts that are liquid at room temperature
(approximately 25.degree. C.), those salts containing cations
selected from the group consisting of pyridinium, pyridazinium,
pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium,
oxazolium and triazolium and mixtures thereof; and anions selected
from the group consisting of [BF.sub.4]--, [PF.sub.6]--,
[SbF.sub.6]--, [CF.sub.3SO.sub.3]--, [HCF.sub.2CF.sub.2SO.sub.3]--,
[CF.sub.3HFCCF.sub.2SO.sub.3]--, [HCCIFCF.sub.2SO.sub.3]--,
[(CF.sub.3SO.sub.2).sub.2N]--,
[(CF.sub.3CF.sub.2SO.sub.2).sub.2N]--,
[(CF.sub.3SO.sub.2).sub.3C]--, [CF.sub.3CO.sub.2]--, and F-- and
mixtures thereof. In some embodiments, ionic liquid stabilizers are
selected from the group consisting of emim BF.sub.4
(1-ethyl-3-methylimidazolium tetrafluoroborate); bmim BF.sub.4
(1-butyl-3-methylimidazolium tetraborate); emim PF.sub.6
(1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim
PF.sub.6 (1-butyl-3-methylimidazolium hexafluorophosphate), all of
which are available from Fluka (Sigma-Aldrich).
[0126] In some embodiments, at least one stabilizer is a hindered
phenol, which are any substituted phenol compound including phenols
comprising one or more substituted or cyclic, straight chain, or
branched aliphatic substituent group, such as, alkylated
monophenols including 2,6-di-tert-butyl-4-methylphenol;
2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tertbutylphenol;
tocopherol; and the like, hydroquinone and alkylated hydroquinones
including t-butyl hydroquinone, other derivatives of hydroquinone;
and the like, hydroxylated thiodiphenyl ethers, including
4,4'-thio-bis(2-methyl-6-tert-butylphenol);
4,4'-thiobis(3-methyl-6-tertbutylphenol);
2,2'-thiobis(4methyl-6-tert-butylphenol); and the like,
alkylidene-bisphenols including,:
4,4'-methylenebis(2,6-di-tert-butylphenol);
4,4'-bis(2,6-di-tert-butylphenol); derivatives of 2,2'- or
4,4-biphenoldiols; 2,2'-methylenebis(4-ethyl-6-tertbutylphenol);
2,2'-methylenebis(4-methyl-6-tertbutylphenol);
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, 2,2- or
4,4-biphenyldiols including
2,2'-methylenebis(4-ethyl-6-tert-butylphenol); butylated
hydroxytoluene (BHT, or 2,6-di-tert-butyl-4-methylphenol),
bisphenols comprising heteroatoms including
2,6-di-tert-alpha-dimethylamino-p-cresol,
4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols;
2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol); sulfides
including; bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;
bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide and mixtures and
combinations thereof.
[0127] In some embodiments, the disclosed compositions contain at
least one tracer. In some embodiments, the tracer additive in the
disclosed compositions consists of two or more tracer compounds
from the same class of compounds or from different classes of
compounds.
[0128] In some embodiments, the tracer component or tracer blend is
present in the compositions at a total concentration of about 50
parts per million by weight (ppm) to about 1000 ppm. In other
embodiments, the tracer compound or tracer blend is present at a
total concentration of about 50 ppm to about 500 ppm. In other
embodiment, the tracer compound or tracer blend is present at a
total concentration of about 100 ppm to about 300 ppm.
[0129] In some embodiments, the disclosed compositions include at
least one tracer selected from the group consisting of
hydrofluorocarbons
[0130] (HFCs), deuterated hydrofluorocarbons, perfluorocarbons,
fluoroethers, brominated compounds, iodated compounds, alcohols,
aldehydes and ketones, nitrous oxide and combinations thereof. Some
embodiments of the disclosed compositions include at least one
tracer selected from the group consisting of fluoroethane,
1,1,-difluoroethane, 1,1,1-trifluoroethane,
1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3,3-heptafluoropropane,
1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane,
1,1,1,2,3,4,4,5,5,5-decafluoropentane,
1,1,1,2,2,3,4,5,5,6,6,7,7,7-tridecafluoroheptane,
iodotrifluoromethane, deuterated hydrocarbons, deuterated
hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated
compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous
oxide (N.sub.2O) and mixtures thereof. In some embodiments, the
tracer additive is a tracer blend containing two or more
hydrofluorocarbons, or one hydrofluorocarbon in combination with
one or more perfluorocarbons.
[0131] In some embodiments, at least one tracer composition is
added to the disclosed compositions in previously determined
quantities to allow detection of any dilution, contamination or
other alteration of the composition.
[0132] In other embodiments, the compositions disclosed herein may
further include a perfluoropolyether. A common characteristic of
perfluoropolyethers is the presence of perfluoroalkyl ether
moieties.
[0133] Perfluoropolyether is synonymous to perfluoropolyalkylether.
Other synonymous terms frequently used include "PFPE", "PFAE",
"PFPE oil", "PFPE fluid", and "PFPAE". In some embodiments, the
perfluoropolyether has the formula of
CF.sub.3--(CF.sub.2).sub.2--O--[CF(CF.sub.3)--CF.sub.2--O]j'--R'f,
and is commercially available from DuPont under the trademark
Krytox.RTM.. In the immediately preceding formula, j' is 2-100,
inclusive and R'f is CF.sub.2CF.sub.3, a C3 to C6 perfluoroalkyl
group, or combinations thereof.
[0134] Other PFPEs, commercially available from Ausimont of Milan,
Italy, and Montedison S.p.A., of Milan, Italy, under the trademarks
Fomblin.RTM. and Golden.RTM., respectively, and produced by
perfluoroolefin photooxidation, can also be used.
[0135] PFPE commercially available under the trademark
Fomblin.RTM.-Y can have the formula of
CF.sub.3O(CF.sub.2CF(CF.sub.3)--O--).sub.m'(CF.sub.2--O--).sub.n'--R.sub.-
1f. Also suitable is
CF.sub.3O[CF.sub.2CF(CF.sub.3)O].sub.m'(CF.sub.2CF.sub.2O).sub.o'(CF.sub.-
2O).sub.n'--R.sub.1f. In the formulae R.sub.1f is CF.sub.3,
C.sub.2F.sub.5, C.sub.3F.sub.7, or combinations of two or more
thereof; (m'+n') is 8-45, inclusive; and m/n is 20-1000, inclusive;
o' is 1; (m'+n'+o') is 8-45, inclusive; m'/n' is 20-1000,
inclusive.
[0136] PFPE commercially available under the trademark
Fomblin.RTM.-Z can have the formula of
CF.sub.3O(CF.sub.2CF.sub.2--O--).sub.p'(CF.sub.2--O).sub.q'CF.sub.3
where (p'+q') is 40-180 and p'/q' is 0.5-2, inclusive.
[0137] Another family of PFPE, commercially available under the
trademark Demnum.TM. from Daikin Industries, Japan, can also be
used. It can be produced by sequential oligomerization and
fluorination of 2,2,3,3-tetrafluorooxetane, yielding the formula of
F-[(CF.sub.2).sub.3--O].sub.t''-R.sub.2f where R.sub.2f is
CF.sub.3, C.sub.2F.sub.5, or combinations thereof and t' is 2-200,
inclusive.
[0138] In some embodiments, the PFPE is unfunctionalized. In an
unfunctionalized perfluoropolyether, the end group can be branched
or straight chain perfluoroalkyl radical end groups. Examples of
such perfluoropolyethers can have the formula of
C.sub.r'F.sub.(2r'+1)--A--CC.sub.r'F.sub.(2r'+1) in which each r'
is independently 3 to 6; A can be
O--(CF(CF.sub.3)CF.sub.2-O).sub.w', [0139]
O--(CF.sub.2-O).sub.x'(CF.sub.2CF.sub.2--O).sub.y',
O--(C.sub.2F.sub.4--O).sub.w',
O--(C.sub.2F.sub.4--O).sub.x'(C.sub.3F.sub.6--O).sub.y', [0140]
O--(CF(CF.sub.3)CF.sub.2--O).sub.x'(CF.sub.2--O).sub.y',
O--(CF.sub.2CF.sub.2CF.sub.2--O).sub.w', [0141]
O--(CF(CF.sub.3)CF.sub.2-O).sub.x'(CF.sub.2CF.sub.2--O).sub.y'--(CF.sub.2-
--O).sub.z', or combinations of two or more thereof; preferably A
is O--(CF(CF.sub.3)CF.sub.2--O).sub.w',
O--(C.sub.2F.sub.4--O).sub.w', [0142]
O--(C.sub.2F.sub.4-O).sub.x'(C.sub.3F.sub.6--O).sub.y',
O--(CF.sub.2CF.sub.2CF.sub.2--O).sub.2', or combinations of two or
more thereof; w' is 4 to 100; x' and y' are each independently 1 to
100. Specific examples include, but are not limited to, [0143]
F(CF(CF.sub.3)--CF.sub.2-O).sub.9--CF.sub.2CF.sub.3,
F(CF(CF.sub.3)--CF.sub.2--O).sub.9--CF(CF.sub.3).sub.2, and
combinations thereof. In such PFPEs, up to 30% of the halogen atoms
can be halogens other than fluorine, such as, for example, chlorine
atoms.
[0144] In other embodiments, the two end groups of the
perfluoropolyether, independently, may be functionalized by the
same or different groups. A functionalized PFPE is a PFPE wherein
at least one of the two end groups of the perfluoropolyether has at
least one of its halogen atoms substituted by a group selected from
esters, hydroxyls, amines, amides, cyanos, carboxylic acids,
sulfonic acids or combinations thereof.
[0145] In some embodiments, representative ester end groups include
[0146] --COOCH.sub.3, --COOCH.sub.2CH.sub.3, --CF.sub.2COOCH.sub.3,
--CF.sub.2COOCH.sub.2CH.sub.3, [0147]
--CF.sub.2CF.sub.2COOCH.sub.3,
--CF.sub.2CF.sub.2COOCH.sub.2CH.sub.3,
--CF.sub.2CH.sub.2COOCH.sub.3, [0148]
--CF.sub.2CF.sub.2CH.sub.2COOCH.sub.3,
--CF.sub.2CH.sub.2CH.sub.2COOCH.sub.3,
--CF.sub.2CF.sub.2CH.sub.2CH.sub.2COOCH.sub.3.
[0149] In some embodiments, representative hydroxyl end groups
include [0150] --CF.sub.2OH, --CF.sub.2CF.sub.2OH,
--CF.sub.2CH.sub.2OH, --CF.sub.2CF.sub.2CH.sub.2OH,
--CF.sub.2CH.sub.2CH.sub.2OH,
--CF.sub.2CF.sub.2CH.sub.2CH.sub.2OH.
[0151] In some embodiments, representative amine end groups include
[0152] --CF.sub.2NR.sup.1R.sup.2,
--CF.sub.2CF.sub.2NR.sup.1R.sup.2,
--CF.sub.2CH.sub.2NR.sup.1R.sup.2,
--CF.sub.2CF.sub.2CH.sub.2NR.sup.1R.sup.2, [0153]
--CF.sub.2CH.sub.2CH.sub.2NR.sup.1R.sup.2,
--CF.sub.2CF.sub.2CH.sub.2CH.sub.2NR.sup.1R.sup.2, wherein R.sup.1
and R.sup.2 are independently H, CH.sub.3, or CH.sub.2CH.sub.3.
[0154] In some embodiments, representative amide end groups include
[0155] --CF.sub.2C(O)NR.sup.1R.sup.2,
--CF.sub.2CF.sub.2C(O)NR.sup.1R.sup.2,
--CF.sub.2CH.sub.2C(O)NR.sup.1R.sup.2, [0156]
--CF.sub.2CF.sub.2CH.sub.2C(O)NR.sup.1R.sup.2,
--CF.sub.2CH.sub.2CH.sub.2C(O)NR.sup.1R.sup.2, [0157]
--CF.sub.2CF.sub.2CH.sub.2CH.sub.2C(O)NR.sup.1R.sup.2, wherein
R.sup.1 and R.sup.2 are independently H, CH.sub.3, or
CH.sub.2CH.sub.3.
[0158] In some embodiments, representative cyano end groups include
[0159] --CF.sub.2CN, --CF.sub.2CF.sub.2CN, --CF.sub.2CH.sub.2CN,
--CF.sub.2CF.sub.2CH.sub.2CN, --CF.sub.2CH.sub.2CH.sub.2CN, and
[0160] --CF.sub.2CF.sub.2CH.sub.2CH.sub.2CN.
[0161] In some embodiments, representative carboxylic acid end
groups include --CF.sub.2COOH, --CF.sub.2CF.sub.2COOH,
--CF.sub.2CH.sub.2COOH, --CF.sub.2CF.sub.2CH.sub.2COOH,
--CF.sub.2CH.sub.2CH.sub.2COOH,
--CF.sub.2CF.sub.2CH.sub.2CH.sub.2COOH.
[0162] In some embodiments, the sulfonic acid end groups is
selected from the group consisting of --S(O)(O)OR.sup.3,
--S(O)(O)R.sup.4, --CF.sub.2OS(O)(O)OR.sup.3, [0163]
--CF.sub.2CF.sub.2OS(O)(O)OR.sup.3,
--CF.sub.2CH.sub.2OS(O)(O)OR.sup.3, [0164]
--CF.sub.2CF.sub.2CH.sub.2OS(O)(O)OR.sup.3,
--CF.sub.2CH.sub.2CH.sub.2OS(O)(O)OR.sup.3, [0165]
--CF.sub.2CF.sub.2CH.sub.2CH.sub.2OS(O)(O)OR.sup.3,
--CF.sub.2S(O)(O)OR.sup.3, --CF.sub.2CF.sub.2S(O)(O)OR.sup.3,
[0166] --CF.sub.2CH.sub.2S(O)(O)OR.sup.3,
--CF.sub.2CF.sub.2CH.sub.2S(O)(O)OR.sup.3, [0167]
--CF.sub.2CH.sub.2CH.sub.2S(O)(O)OR.sup.3,
--CF.sub.2CF.sub.2CH.sub.2CH.sub.2S(O)(O)OR.sup.3,
--CF.sub.2OS(O)(O)R.sup.4, [0168]
--CF.sub.2CF.sub.2OS(O)(O)R.sup.4,
--CF.sub.2CH.sub.2OS(O)(O)R.sup.4,
--CF.sub.2CF.sub.2CH.sub.2OS(O)(O)R.sup.4, [0169]
--CF.sub.2CH.sub.2CH.sub.2OS(O)(O)R.sup.4,
--CF.sub.2CF.sub.2CH.sub.2CH.sub.2OS(O)(O)R.sup.4, wherein R.sup.3
is H, CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CF.sub.3, CF.sub.3, or
CF.sub.2CF.sub.3, R.sup.4 is CH.sub.3, CH.sub.2CH.sub.3,
CH.sub.2CF.sub.3, CF.sub.3, or CF.sub.2CF.sub.3.
[0170] In some embodiments, the disclosed compositions include
additives that are members of the triaryl phosphate family of EP
(extreme pressure) lubricity additives, such as butylated triphenyl
phosphates (BTPP), or other alkylated triaryl phosphate esters,
e.g. Syn-O-Ad.RTM. 8478 from Akzo Chemicals, tricresyl phosphates
and related compounds. Additionally, the metal dialkyl
dithiophosphates (e.g., zinc dialkyl dithiophosphate (or ZDDP),
including the commercially available Lubrizol 1375 and other
members of this family of chemicals is used in compositions of the
disclosed compositions. Other antiwear additives include natural
product oils and asymmetrical polyhydroxyl lubrication additives,
such as the commercially available Synergol TMS (International
Lubricants).
[0171] In some embodiments, stabilizers such as antioxidants, free
radical scavengers, and water scavengers and mixtures thereof are
included. Such additives in this category can include, but are not
limited to, butylated hydroxy toluene (BHT), epoxides, and mixtures
thereof. Corrosion inhibitors include dodecyl succinic acid (DDSA),
amine phosphate (AP), oleoyl sarcosine, imidazone derivatives and
substituted sulfphonates.
[0172] In one embodiment, the compositions disclosed herein may be
prepared by any convenient method to combine the desired amounts of
the individual components. A preferred method is to weigh the
desired component amounts and thereafter combine the components in
an appropriate vessel. Agitation may be used, if desired.
[0173] In another embodiment, the compositions disclosed herein may
be prepared by a method comprising (i) reclaiming a volume of one
or more components of a refrigerant composition from at least one
refrigerant container, (ii) removing impurities sufficiently to
enable reuse of said one or more of the reclaimed components, (iii)
and optionally, combining all or part of said reclaimed volume of
components with at least one additional refrigerant composition or
component.
[0174] A refrigerant container may be any container in which is
stored a refrigerant blend composition that has been used in a
refrigeration apparatus, air-conditioning apparatus or heat pump
apparatus. Said refrigerant container may be the refrigeration
apparatus, air-conditioning apparatus or heat pump apparatus in
which the refrigerant blend was used. Additionally, the refrigerant
container may be a storage container for collecting reclaimed
refrigerant blend components, including but not limited to
pressurized gas cylinders.
[0175] Residual refrigerant means any amount of refrigerant blend
or refrigerant blend component that may be moved out of the
refrigerant container by any method known for transferring
refrigerant blends or refrigerant blend components.
[0176] Impurities may be any component that is in the refrigerant
blend or refrigerant blend component due to its use in a
refrigeration apparatus, air-conditioning apparatus or heat pump
apparatus. Such impurities include but are not limited to
refrigeration lubricants, being those described earlier herein,
particulates including but not limited to metal, metal salt or
elastomer particles, that may have come out of the refrigeration
apparatus, air-conditioning apparatus or heat pump apparatus, and
any other contaminants that may adversely effect the performance of
the refrigerant blend composition.
[0177] Such impurities may be removed sufficiently to allow reuse
of the refrigerant blend or refrigerant blend component without
adversely effecting the performance or equipment within which the
refrigerant blend or refrigerant blend component will be used.
[0178] It may be necessary to provide additional refrigerant blend
or refrigerant blend component to the residual refrigerant blend or
refrigerant blend component in order to produce a composition that
meets the specifications required for a given product. For
instance, if a refrigerant blend has three components in a
particular weight percentage range, it may be necessary to add one
or more of the components in a given amount in order to restore the
composition to within the specification limits.
[0179] Compositions of the present invention have zero ozone
depletion potential and low global warming potential (GWP).
Additionally, the compositions of the present invention will have
global warming potentials that are less than many hydrofluorocarbon
refrigerants currently in use. One aspect of the present invention
is to provide a refrigerant with a global warming potential of less
than 1000, less than 500, less than 150, less than 100, or less
than 50.
Methods of Use
[0180] The compositions disclosed herein are useful as heat
transfer compositions, aerosol propellants, foaming agents, blowing
agents, solvents, cleaning agents, carrier fluids, displacement
drying agents, buffing abrasion agents, polymerization media,
expansion agents for polyolefins and polyurethane, gaseous
dielectrics, fire extinguishing agents, and fire suppression
agents. Additionally, in liquid or gaseous form, the disclosed
compositions may act as working fluids used to carry heat from a
heat source to a heat sink. Such heat transfer compositions may
also be useful as refrigerants in a cycle wherein the fluid
undergoes phase changes; that is, from a liquid to a gas and back
or vice versa.
[0181] The compositions disclosed herein may be useful as low GWP
(global warming potential) replacements for currently used
refrigerants, including but not limited to R134a (or HFC-134a,
1,1,1,2-tetrafluoroethane), R22 (or HCFC-22,
chlorodifluoromethane), R404A, (ASHRAE designation for a blend of
44 weight percent R125, 52 weight percent R143a
(1,1,1-trifluoroethane), and 4.0 weight percent R134a), R407A,
R407B, R407C, R407D, and R407E (ASHRAE designations for blends of
R134a, R125 (pentafluoroethane), and R32 (difluoromethane) in
differing component concentrations), R408A (ASHRAE designation for
a blend of 7 weight percent R125, 46 weight percent R143a, and 47
weight percent R22); R410A (ASHRAE designation for a blend of 50
weight percent R125 and 50 weight percent R32), R413A (ASHRAE
designation for a blend containing R218, R134a, and isobutane);
R417A, (ASHRAE designation for a blend of 46.6 weight percent R125,
50.0 weight percent R134a, and 3.4 weight percent n-butane), R419A
(ASHRAE designation for a blend containing R125, R134a and DME);
R422A, R422B, R422C and R422D, (ASHRAE designation for blends of
R125, R134a, isobutane in differing component concentrations),
R423A (ASHRAE designation for a blend containing R134a and
1,1,1,2,3,3,3-heptafluoropropane (R227ea)); R424A (ASHRAE
designation for a blend containing R125, R134a, isobutane,
n-butane, and isopentane); R426A (ASHRAE designation for a blend
containing R125, R134a, n-butane, and isopentane); R427A (ASHRAE
designation for a blend of 15 weight percent R32, 25 weight percent
R125, 50 weight percent R134a, and 10 weight percent R143a); R428A
(ASHRAE designation for a blend containing R125, R143a, propane and
isobutane); R430A (ASHRAE designation for a blend containing R152a
and isobutane); R434A (ASHRAE designation for a blend containing
R125, R134a, R143a, and isobutane); R437A (ASHRAE designation for a
blend containing R125, R134a, n-butane, and n-pentane); R438A
(ASHRAE designation for a blend containing R32, R125, R134a,
n-butane, and isopentane); R507A and R507B (ASHRAE designation for
a blend of R125 and R143a in differing component concentrations);
and R508A and R508B (ASHRAE designations for blends of
trifluoromethane (R23) and hexafluoroethane (R116) in differing
component concentrations).
[0182] Additionally, the compositions disclosed herein may be
useful as replacements for R12 (CFC-12, dichlorodifluoromethane) or
R502 (ASHRAE designation for a blend of 51.2 weight percent CFC-115
(chloropentafluoroethane) and 48.8 weight percent HCFC-22).
[0183] Often replacement refrigerants are most useful if capable of
being used in the original refrigeration equipment designed for a
different refrigerant. In particular, the compositions as disclosed
herein may be useful as replacements for R12, R134a, R22, R404A,
R407A, R407C, R408A, R410A, R413A, R417A, R419A, R422A, R422B,
R422C, R422D, R423A, R424A. R426A, R428A, R430A, R434A, R437A,
R438A, R502, R507A, R507B, and R508, among others in original
equipment. Additionally, the compositions as disclosed herein may
be useful as replacements for R12, R134a, R22, R404A, R407A, R407C,
R408A, R410A, R413A, R417A, R419A, R422A, R422B, R422C, R422D,
R423A, R424A. R426A, R428A, R430A, R434A, R437A, R438A, R502,
R507A, R507B, and R508, among others, in equipment designed for
these refrigerants with some system modifications. Further, the
compositions as disclosed herein may be useful for replacing any of
the above mentioned refrigerants in equipment specifically modified
for or produced entirely for these new compositions.
[0184] In many applications, some embodiments of the disclosed
compositions are useful as refrigerants and provide at least
comparable cooling performance (meaning cooling capacity and energy
efficiency) as the refrigerant for which a replacement is being
sought.
[0185] In some embodiments, the compositions disclosed herein are
useful for any positive displacement compressor system designed for
any number of heat transfer compositions. Additionally, many of the
compositions disclosed are useful in new equipment utilizing
positive displacement compressors to provide similar performance to
the aforementioned refrigerants.
[0186] In one embodiment, disclosed herein is a process to produce
cooling comprising condensing a composition as disclosed herein and
thereafter evaporating said composition in the vicinity of a body
to be cooled.
[0187] In another embodiment, disclosed herein is a process to
produce heat comprising condensing a composition as disclosed
herein in the vicinity of a body to be heated and thereafter
evaporating said composition.
[0188] In some embodiments, the use of the above disclosed
compositions includes using the composition as a heat transfer
composition in a process for producing cooling, wherein the
composition is first cooled and stored under pressure and when
exposed to a warmer environment, the composition absorbs some of
the ambient heat, expands, and the warmer environment is thusly
cooled.
[0189] In some embodiments, the compositions as disclosed herein
may be useful in particular in air conditioning applications
including but not limited to chillers, high temperature heat pumps,
residential, commercial or industrial air conditioning systems
(including residential heat pumps), and including window, ductless,
ducted, packaged terminal, chillers, and those exterior but
connected to the building such as rooftop systems.
[0190] In some embodiments, the compositions as disclosed herein
may be useful in particular in refrigeration applications including
high, medium or low temperature refrigeration and other specific
uses such as in commercial, industrial or residential refrigerators
and freezers, ice machines, self-contained coolers and freezers,
supermarket rack and distributed systems, flooded evaporator
chillers, direct expansion chillers, walk-in and reach-in coolers
and freezers, and combination systems.
[0191] Additionally, in some embodiments, the disclosed
compositions may function as primary refrigerants in secondary loop
systems that provide cooling to remote locations by use of a
secondary heat transfer fluid.
[0192] In another embodiment is provided a method for recharging a
heat transfer system that contains a refrigerant to be replaced and
a lubricant, said method comprising removing the refrigerant to be
replaced from the heat transfer system while retaining a
substantial portion of the lubricant in said system and introducing
one of the compositions herein disclosed to the heat transfer
system.
[0193] In another embodiment, a heat exchange system comprising a
composition disclosed herein is provided, wherein said system is
selected from the group consisting of air conditioners, freezers,
refrigerators, water chillers, flooded evaporator chillers, direct
expansion chillers, walk-in coolers, heat pumps, mobile
refrigerators, mobile air conditioning units, and systems having
combinations thereof.
[0194] In another embodiment is provided a method for replacing a
high GWP refrigerant in a refrigeration, air-conditioning, or heat
pump apparatus, wherein said high GWP refrigerant is selected from
the group consisting of R134a, R22, R12, R404A, R410A, R407A,
R407C, R413A, R417A, R422A, R422B, R422C and R422D, R423A, R427A,
R507A, R507B, R502, and R437A, said method comprising providing a
composition as disclosed herein to said refrigeration,
air-conditioning, or heat pump apparatus that uses, used or is
designed to use said high GWP refrigerant; wherein said composition
is selected from the group consisting of: [0195] HFO-1234yf and
HFC-32; [0196] HFO-1234yf and HFC-134a; [0197] HFO-1234yf,
HFC-152a, and HFC-134a; [0198] HFO-1234yf, HFC-125, and HFC-152a;
[0199] HFO-1234yf, HFC-125, and HFC-134a; [0200] HFO-1234yf,
HFC-32, and HFC-134a; [0201] HFO-1234yf, HFC-32, and HFC-125;
[0202] HFO-1234yf, HFC-32, HFC-125, and HFC-134a; [0203] HFO-1234ze
and HFC-32; [0204] HFO-1234ze and HFC-125; [0205] HFO-1234ze,
HFC-125, and HFC-152a; [0206] HFO-1234ze, HFC-125, and HFC-134a;
[0207] HFO-1234ze, HFC-32, and HFC-134a; [0208] HFO-1234ze, HFC-32,
and HFC-125; and [0209] HFO-1234ze, HFC-32, HFC-125, and
HFC-134a.
[0210] In another embodiment, the method for replacing a high GWP
refrigerant may further comprise providing a composition to said
refrigeration, air-conditioning, or heat pump apparatus that uses,
used or is designed to use said high GWP refrigerant, wherein the
composition is selected from the group consisting of: [0211]
HFO-1234yf and HFC-32; [0212] HFO-1234yf and HFC-134a; [0213]
HFO-1234yf, HFC-152a, and HFC-134a; [0214] HFO-1234yf, HFC-125, and
HFC-152a; [0215] HFO-1234yf, HFC-125, and HFC-134a; [0216]
HFO-1234yf, HFC-32, and HFC-134a; [0217] HFO-1234yf, HFC-32, and
HFC-125; [0218] HFO-1234yf, HFC-32, HFC-125, and HFC-134a; [0219]
HFO-1234ze and HFC-32; [0220] HFO-1234ze and HFC-125; [0221]
HFO-1234ze, HFC-125, and HFC-152a; [0222] HFO-1234ze, HFC-125, and
HFC-134a; [0223] HFO-1234ze, HFC-32, and HFC-134a; [0224]
HFO-1234ze, HFC-32, and HFC-125; and [0225] HFO-1234ze, HFC-32,
HFC-125, and HFC-134a.
[0226] Vapor-compression refrigeration, air-conditioning, or heat
pump systems include an evaporator, a compressor, a condenser, and
an expansion device. A vapor-compression cycle re-uses refrigerant
in multiple steps producing a cooling effect in one step and a
heating effect in a different step. The cycle can be described
simply as follows. Liquid refrigerant enters an evaporator through
an expansion device, and the liquid refrigerant boils in the
evaporator, by withdrawing heat from the environment, at a low
temperature to form a gas and produce cooling. The low-pressure gas
enters a compressor where the gas is compressed to raise its
pressure and temperature. The higher-pressure (compressed) gaseous
refrigerant then enters the condenser in which the refrigerant
condenses and discharges its heat to the environment. The
refrigerant returns to the expansion device through which the
liquid expands from the higher-pressure level in the condenser to
the low-pressure level in the evaporator, thus repeating the
cycle.
[0227] In one embodiment, there is provided a heat transfer system
containing a composition as disclosed herein. In another embodiment
is disclosed a refrigeration, air-conditioning, or heat pump
apparatus containing a composition as disclosed herein. In another
embodiment, is disclosed a stationary refrigeration,
air-conditioning, or heat pump apparatus containing a composition
as disclosed herein. In yet another embodiment is disclosed a
mobile refrigeration or air conditioning apparatus containing a
composition as disclosed herein.
[0228] In another embodiment, disclosed is a method of using the
composition of the present invention as a heat transfer fluid
composition. The method comprises transporting said composition
from a heat source to a heat sink.
EXAMPLES
[0229] The concepts disclosed herein will be further described in
the following examples, which do not limit the scope of the
invention described in the claims.
Example 1
Impact of Vapor Leakage
[0230] A vessel is charged with an initial composition at a
temperature of about 23.degree. C., and the initial vapor pressure
of the composition is measured. The composition is allowed to leak
from the vessel, while the temperature is held constant, until 50
weight percent of the initial composition is removed, at which time
the vapor pressure of the composition remaining in the vessel is
measured. Results are shown in Table 2.
TABLE-US-00002 TABLE 2 After After 50% 50% Composition Initial P
Initial P Leak Leak Delta P wt % (Psia) (kPa) (Psia) (kPa) (%)
1234yf/152a/134a 40/40/20 91.0 627 90.5 624 0.5% 20/40/40 88.3 609
87.6 604 0.8% 40/20/40 93.1 642 92.7 639 0.4% 98/1/1 93.5 645 93.5
645 0.0% 1/98/1 81.6 563 81.6 563 0.0% 1/1/98 90.8 626 90.7 625
0.1% 80/10/10 95.0 655 95.0 655 0.0% 10/80/10 84.1 580 83.6 576
0.6% 10/10/80 90.6 625 90.2 622 0.4% 60/20/20 94.3 650 94.2 649
0.1% 20/60/20 86.9 599 86.1 594 0.9% 20/20/60 90.6 625 90.1 621
0.6% 45/45/10 91.2 629 90.7 625 0.5% 10/45/45 86.1 594 85.5 590
0.7% 45/10/45 94.9 654 94.7 653 0.2% 40/30/30 91.9 634 91.4 630
0.5% 30/40/30 89.8 619 89.1 614 0.8% 30/30/40 90.8 626 90.2 622
0.7% 86/4/10 95.1 656 95.0 655 0.1% 86/5/9 95.1 656 95.0 655 0.1%
65/5/30 96.2 663 96.2 663 0.0% 65/30/5 93.6 645 93.4 644 0.2%
5/65/30 84.0 579 83.6 576 0.5% 5/30/65 86.6 597 86.2 594 0.5%
30/5/65 94.5 652 94.2 649 0.3% 30/65/5 88.2 608 87.5 603 0.8%
90/5/5 94.5 652 94.5 652 0.0% 70/5/25 96.1 663 96.1 663 0.0%
1234yf/152a/125 40/40/20 103.4 713 99.0 683 4.3% 20/40/40 114.6 790
106.6 735 7.0% 40/20/40 121.8 840 114.4 789 6.1% 98/1/1 94.2 649
93.8 647 0.4% 1/98/1 82.1 566 81.8 564 0.4% 1/1/98 186.3 1285 185.1
1276 0.6% 80/10/10 101.8 702 99.0 683 2.8% 10/80/10 89.3 616 86.6
597 3.0% 10/10/80 159.8 1102 152.2 1049 4.8% 60/20/20 107.7 743
103.3 712 4.1% 20/60/20 98.4 678 93.6 645 4.9% 20/20/60 136.6 942
127.4 878 6.7% 45/45/10 97.1 669 94.6 652 2.6% 10/45/45 115.5 796
106.5 734 7.8% 45/10/45 129.6 894 121.5 838 6.3% 40/30/30 111.8 771
105.8 729 5.4% 30/40/30 108.9 751 102.7 708 5.7% 30/30/40 118.2 815
110.6 763 6.4% 86/4/10 102.0 703 98.9 682 3.0% 86/5/9 101.1 697
98.4 678 2.7% 65/5/30 118.7 818 111.7 770 5.9% 65/30/5 96.6 666
95.4 658 1.2% 5/65/30 101.2 698 94.3 650 6.8% 5/30/65 134.8 929
124.2 856 7.9% 30/5/65 149.7 1032 141.6 976 5.4% 30/65/5 90.9 627
89.2 615 1.9% 90/5/5 97.9 675 96.3 664 1.6% 70/5/25 114.5 789 108.2
746 5.5% 1234yf/125/134a 40/40/20 130.0 896 122.4 844 5.8% 20/40/40
128.8 888 121.0 834 6.1% 40/20/40 112.9 778 107.9 744 4.4% 98/1/1
94.3 650 93.9 647 0.4% 1/98/1 187.3 1291 186.6 1287 0.4% 1/1/98
91.8 633 91.4 630 0.4% 80/10/10 103.5 714 100.3 692 3.1% 10/80/10
167.5 1155 162.1 1118 3.2% 10/10/80 101.2 698 97.7 674 3.5%
60/20/20 112.9 778 107.7 743 4.6% 20/60/20 147.7 1018 140.0 965
5.2% 20/20/60 111.2 767 105.7 729 4.9% 45/45/10 134.3 926 126.2 870
6.0% 10/45/45 132.3 912 123.7 853 6.5% 45/10/45 104.8 723 102.0 703
2.7% 40/30/30 121.3 836 114.8 792 5.4% 30/40/30 129.6 894 122.1 842
5.8% 30/30/40 120.8 833 114.2 787 5.5% 86/4/10 98.3 678 96.9 668
1.4% 86/5/9 99.1 683 97.3 671 1.8% 65/5/30 100.9 696 99.4 685 1.5%
65/30/5 120.5 831 113.2 780 6.1% 5/65/30 151.1 1042 143.0 986 5.4%
5/30/65 117.8 812 109.9 758 6.7% 30/5/65 99.7 687 98.0 676 1.7%
30/65/5 153.1 1056 145.5 1003 5.0% 90/5/5 98.5 679 96.7 667 1.8%
70/5/25 100.7 694 99.1 683 1.6% 35/35/30 125.4 865 118.4 816 5.6%
50/30/20 121.4 837 114.7 791 5.5% 45/30/25 121.4 837 114.8 792 5.4%
50/25/25 117.2 808 111.3 767 5.0% 45/15/40 108.9 751 104.9 723 3.7%
50/12/38 106.6 735 103.3 712 3.1% 1234yf/32/134a 40/40/20 185.3
1278 167.8 1157 9.4% 20/40/40 176.9 1220 158.6 1094 10.3% 40/20/40
148.4 1023 128.6 887 13.3% 98/1/1 97.8 674 94.7 653 3.2% 1/98/1
231.3 1595 230.9 1592 0.2% 1/1/98 93.5 645 92.1 635 1.5% 80/10/10
130.6 900 111.0 765 15.0% 10/80/10 220.2 1518 215.7 1487 2.0%
10/10/80 117.3 809 105.3 726 10.2% 60/20/20 153.8 1060 131.2 905
14.7% 20/60/20 203.9 1406 193.0 1331 5.3% 20/20/60 142.0 979 123.4
851 13.1% 45/45/10 195.0 1344 180.0 1241 7.7% 10/45/45 179.5 1238
161.6 1114 10.0% 45/10/45 126.0 869 111.5 769 11.5% 40/30/30 168.2
1160 148.0 1020 12.0% 30/40/30 181.2 1249 163.5 1127 9.8% 30/30/40
164.6 1135 144.6 997 12.2% 86/4/10 110.7 763 100.6 694 9.1% 86/5/9
114.3 788 102.0 703 10.8% 65/5/30 114.0 786 104.0 717 8.8% 65/30/5
176.6 1218 152.9 1054 13.4% 5/65/30 202.0 1393 190.1 1311 5.9%
5/30/65 154.1 1062 134.0 924 13.0% 30/5/65 109.8 757 102.0 703 7.1%
30/65/5 214.5 1479 207.8 1433 3.1% 90/5/5 114.1 787 101.4 699 11.1%
70/5/25 110.4 761 103.8 716 6.0% 90/4/6 110.4 761 100.0 689 9.4%
10/40/50 172.3 1188 153.2 1056 11.1% 30/45/25 188.7 1301 172.8 1191
8.4% 20/45/35 184.3 1271 167.5 1155 9.1% 1234yf/134a/125/32
1/1/1/97 231.2 1594 230.9 1592 0.1% 1/1/97/1 188.8 1302 187.8 1295
0.5% 1/97/1/1 94.3 650 92.5 638 1.9% 97/1/1/1 98.6 680 95.2 656
3.4% 50/38/9/3 113.9 785 106.2 732 6.8% 50/38/8/4 116.1 800 107.2
739 7.7% 50/38/7/5 118.4 816 108.2 746 8.6% 20/20/20/40 193.8 1336
180.9 1247 6.7% 10/10/10/70 218.2 1504 213.1 1469 2.3% 5/5/5/85
226.2 1560 224.0 1544 1.0% 5/5/50/40 214.7 1480 210.4 1451 2.0%
50/5/5/40 193.4 1333 176.7 1218 8.6% 10/40/10/40 180.7 1246 163.9
1130 9.3% 37/50/10/3 113.5 783 106.1 732 6.5% 37/10/50/3 148.2 1022
137.8 950 7.0% 50/10/37/3 137.1 945 126.0 869 8.1% 10/50/37/3 132.8
916 122.7 846 7.6% 70/20/8/2 110.2 760 103.5 714 6.1% 20/70/8/2
106.6 735 101.0 696 5.3% 8/20/70/2 162.0 1117 154.3 1064 4.8%
70/8/20/2 119.4 823 110.1 759 7.8% 35/25/30/10 149.2 1029 134.7 929
9.7% 92/1/1/6 118.2 815 102.9 709 12.9% 1/92/1/6 106.3 733 98.5 679
7.3% 1/1/92/6 195.5 1348 193.7 1336 0.9% 74/10/10/6 125.3 864 110.7
763 11.7% 10/74/10/6 116.4 803 106.1 732 8.8% 10/10/74/6 177.0 1220
169.8 1171 4.1% 54/20/20/6 132.6 914 119.0 820 10.3% 20/54/20/6
127.3 878 115.7 798 9.1% 20/20/54/6 158.3 1091 147.7 1018 6.7%
34/30/30/6 138.5 955 126.2 870 8.9% 30/34/30/6 137.9 951 125.7 867
8.8% 30/30/34/6 141.4 975 129.3 891 8.6% 40/27/27/6 136.7 943 124.2
856 9.1% 27/40/27/6 134.7 929 122.8 847 8.8% 27/27/40/6 146.3 1009
134.5 927 8.1% 50/22/22/6 133.6 921 120.5 831 9.8% 22/50/22/6 129.5
893 117.7 812 9.1% 22/22/50/6 154.8 1067 143.7 991 7.2% 88/1/1/10
131.7 908 110.2 760 16.3% 1/88/1/10 115.2 794 103.6 714 10.1%
1/1/88/10 200.1 1380 198.0 1365 1.0% 70/10/10/10 137.5 948 118.6
818 13.7% 10/70/10/10 125.8 867 112.2 774 10.8% 10/10/70/10 182.3
1257 174.5 1203 4.3% 50/20/20/10 143.2 987 127.0 876 11.3%
20/50/20/10 137.1 945 122.9 847 10.4% 20/20/50/10 164.5 1134 152.5
1051 7.3% 40/25/25/10 145.7 1005 130.7 901 10.3% 25/40/40/10 142.7
984 128.4 885 10.0% 25/25/40/10 156.1 1076 142.8 985 8.5% 78/1/1/20
158.6 1094 131.4 906 17.2% 1/78/1/20 135.4 934 117.7 812 13.1%
1/1/78/20 209.3 1443 206.9 1427 1.1% 60/10/10/20 161.9 1116 139.8
964 13.7% 10/60/10/20 146.7 1011 128.7 887 12.3% 10/10/60/20 193.2
1332 184.8 1274 4.3% 40/20/20/20 165.1 1138 147.2 1015 10.8%
20/40/20/40 158.9 1096 141.9 978 10.7% 20/20/40/20 177.0 1220 163.5
1127 7.6% 30/25/25/20 166.5 1148 150.0 1034 9.9% 25/30/25/20 164.9
1137 148.6 1025 9.9% 25/25/30/20 169.4 1168 153.9 1061 9.1%
68/1/1/30 178.4 1230 154.0 1062 13.7% 1/68/1/30 153.1 1056 133.0
917 13.1% 1/1/68/30 215.9 1489 213.8 1474 1.0% 50/10/10/30 179.9
1240 160.6 1107 10.7% 10/50/10/30 164.9 1137 146.2 1008 11.3%
10/10/50/30 201.3 1388 193.3 1333 4.0% 40/15/15/30 180.7 1246 163.4
1127 9.6% 15/40/15/30 171.3 1181 153.8 1060 10.2% 15/15/40/30 193.7
1336 182.2 1256 5.9% 30/20/20/30 181.4 1251 165.6 1142 8.7%
20/30/20/30 177.6 1225 161.5 1114 9.1% 20/20/30/30 186.5 1286 173.0
1193 7.2% 59/1/1/39 191.9 1323 172.8 1191 10.0% 1/59/1/39 167.2
1153 147.4 1016 11.8% 1/1/59/39 220.3 1519 218.6 1507 0.8%
40/10/11/39 192.8 1329 177.80 1226 7.8% 10/40/11/39 180.1 1242
163.20 1125 9.4% 11/10/40/39 206.4 1423 198.70 1370 3.7%
30/15/16/39 193.0 1331 179.30 1236 7.1% 15/30/16/39 186.6 1287
171.70 1184 8.0% 16/15/30/39 199.4 1375 188.90 1302 5.3%
[0231] The compositions as listed in Table 2 are near-azeotropic
when the composition remaining after 50 weight percent is removed
is less than about 10 percent.
Example 2
Glide Reduction
[0232] The temperature glide and other cooling performance
parameters for a composition containing HFO-1234yf and HFC-32 is
determined and displayed in Table 3 as compared to R407C (ASHRAE
designation for a refrigerant blend containing 23 wt % HFC-32, 25
wt % HFC 125 and 52 wt % HFC-134a). The glide, pressures, discharge
temperatures, COP (energy efficiency) and cooling capacity are
determined for the following conditions:
TABLE-US-00003 Evaporator temperature 41.degree. F. (5.degree. C.)
Condenser temperature 104.degree. F. (40.degree. C.) Subcool amount
41.degree. F. (5.degree. C.) Return gas temperature 59.degree. F.
(15.degree. C.) Compressor efficiency is 70%
TABLE-US-00004 TABLE 3 Glide, Pres Pres Disch .degree. C. evap,
cond, Temp, Capacity (Cond/ Composition kPa kPa .degree. C. COP
(kJ/m.sup.3) Evap) R407C 584 1627 71.3 4.53 3978 5/4.8 HFO-1234yf
371 1016 54.6 4.722 2516 0 HFO-1234yf/HFC-32 421 1159 57.5 4.598
2799 3.7/2.6 (95/5wt %) HFO-1234yf/HFC-32 469 1291 60.1 4.5 3067
5.8/4.4 (90/10 wt %) HFO-1234yf/HFC-32 515 1412 62.5 4.45 3325
6.9/5.5 (85/15 wt %) HFO-1234yf/HFC-32 559 1523 64.6 4.416 3575
7.3/6 (80/20 wt %) HFO-1234yf/HFC-32 572 1556 65.3 4.408 3648
7.3/6.1 (78.5/21.5 wt %)
R407C is currently a commercial refrigerant product even with the
glide as reported in the table above. This data indicate that
HFC-32 concentrations of 15 weight percent or below more closely
approach the temperature glide for R407C, which is an amount that
has been acceptable in certain applications.
Example 3
Flammability
[0233] Flammable compounds may be identified by testing under ASTM
(American Society of Testing and Materials) E681-2004, with an
electronic ignition source. Such tests of flammability were
conducted on compositions of the present disclosure at 101 kPa
(14.7 psia), 50 percent relative humidity, and 60.degree. C. or
100.degree. C. at various concentrations in air in order to
determine if flammable and if so, find the lower flammability limit
(LFL) and the upper flammability limit (UFL). The results are given
in Table 4.
TABLE-US-00005 TABLE 4 Temperature, .degree. C. 60.degree. C.
100.degree. C. LFL UFL LFL UFL (vol % (vol % (vol % (vol %
Composition in air) in air) in air) in air) HFO-1234yf/HFC-134a
non- non- non- non- (50/50 wt %) flammable flammable flammable
flammable HFO-1234yf/HFC-134a non- non- non- non- (52.5/47.5 wt %)
flammable flammable flammable flammable HFO-1234yf/HFC-134a non-
non- 10 10 (53.75/46.25 wt %) flammable flammable
HFO-1234yf/HFC-134a non- non- 9.0 10.5 (55/45 wt %) flammable
flammable HFO-1234yf/HFC-134a non- non- 8.0 12 (57.5/42.5 wt %)
flammable flammable HFO-1234yf/HFC-134a non- non- not tested not
tested (60/40 wt %) flammable flammable HFO-1234yf/HFC-134a 10 11
not tested not tested (60.6/39.4 wt %) HFO-1234yf/HFC-134a 8.8 10.8
not tested not tested (62.5/37.5 wt %) HFO-1234yf/HFC-134a 8.0 12
not tested not tested (65/35 wt %)
[0234] The results indicate that compositions comprising no more
than about 60 weight percent HFO-1234yf and the remainder being
HFC-134a are non-flammable at 60.degree. C. Additionally,
compositions comprising no more than about 53 weight percent
HFC-1234yf and the remainder being HFC-134a are non-flammable at
100.degree. C. Those compositions comprising fluoroolefins that are
non-flammable are more acceptable candidates as refrigerant or heat
transfer fluid compositions.
Example 4
Global Warming Potentials
[0235] Values for global warming potential (GWP) for some of the
disclosed compositions are listed in Table 5 as compared to GWP
values for HCFC-22, HFC-134a, R404A, R407C, R410A and other
currently used refrigerants. The GWP for the pure components are
listed for reference. The GWP values for compositions containing
more than one component are calculated as weighted averages of the
individual component GWP values. The values for the HFCs are taken
from the "Climate Change 2007--IPCC (Intergovernmental Panel on
Climate Change) Fourth Assessment Report on Climate Change", from
the section entitled "Working Group 1 Report: "The Physical Science
Basis", Chapter 2, pp. 212-213, Table 2.14. The value for
HFO-1234yf was published in Papadimitriou et al., Physical
Chemistry Chemical Physics, 2007, vol. 9, pp. 1-13. Specifically,
the 100 year time horizon GWP values are used.
TABLE-US-00006 TABLE 5 Component or composition GWP HCFC-22 1810
HFC-134a 1430 HFC-152a 124 HFC-125 3500 HFC-32 675 HFC-143a 4470
HFO-1234ze 6 HFO-1234yf 4 R404A 3922 R407C 1802 R410A 2088
HFO-1234yf/HFC-134a (60/40 wt %) 860 HFO-1234yf/HFC-134a (50/50 wt
%) 717 HFO-1234yf/HFC-32 (78.5/21.5 wt %) 148 HFO-1234yf/HFC-32
(85/15 wt %) 105 HFO-1234yf/HFC-32 (90/10 wt %) 71
HFO-1234yf/HFC-32/HFC-125/HFC-134a (35/10/30/25 wt %) 1476
HFO-1234yf/HFC-32/HFC-125/HFC-134a (97/1/1/1 wt %) 57
HFO-1234yf/HFC-32/HFC-125/HFC-134a (1/97/1/1 wt %) 704
HFO-1234yf/HFC-32/HFC-125/HFC-134a (1/1/97/1 wt %) 3415
HFO-1234yf/HFC-32/HFC-125/HFC-134a (1/1/1/97 wt %) 1490
HFO-1234yf/HFC-32/HFC-125/HFC-134a (92/5/1/1 wt %) 87
HFO-1234yf/HFC-32/HFC-125/HFC-134a (50/40/5/5 wt %) 519
HFO-1234yf/HFC-32/HFC-125/HFC-134a (34/6/30/30 wt %) 1520
HFO-1234yf/HFC-32/HFC-125/HFC-134a (1/20/78/1 wt %) 2879
HFO-1234yf/HFC-32/HFC-125/HFC-134a (74/6/10/10 wt %) 254
HFO-1234yf/HFC-32/HFC-125/HFC-134a (27/6/27/40 wt %) 1559
HFO-1234yf/HFC-32/HFC-125 (40/10/50 wt %) 1819
HFO-1234yf/HFC-32/HFC-125 (8/50/42 wt %) 1808
HFO-1234yf/HFC-32/HFC-125 (60/30/10 wt %) 555
HFO-1234yf/HFC-32/HFC-125 (20/20/60 wt %) 2236
HFO-1234yf/HFC-32/HFC-125 (44/20/36 wt %) 1397
HFO-1234yf/HFC-32/HFC-125 (70/15/15 wt %) 629
HFO-1234yf/HFC-32/HFC-125 (70/20/10 wt %) 488
HFO-1234yf/HFC-32/HFC-125 (60/10/30 wt %) 1120
HFO-1234yf/HFC-32/HFC-134a (1/1/98 wt %) 1409
HFO-1234yf/HFC-32/HFC-134a (1/4/95 wt %) 1386
HFO-1234yf/HFC-32/HFC-134a (95/4/1 wt %) 45
HFO-1234yf/HFC-32/HFC-134a (1/98/1 wt %) 676
HFO-1234yf/HFC-32/HFC-134a (98/1/1 wt %) 25
HFO-1234yf/HFC-32/HFC-134a (54/45/1 wt %) 320
HFO-1234yf/HFC-32/HFC-134a (1/45/54 wt %) 1076
HFO-1234yf/HFC-32/HFC-134a (45/45/10 wt %) 320
HFO-1234yf/HFC-32/HFC-134a (30/45/25 wt %) 662
HFO-1234yf/HFC-32/HFC-134a (30/65/5 wt %) 511
HFO-1234yf/HFC-152a/HFC-134a (1/1/98 wt %) 1401
HFO-1234yf/HFC-152a/HFC-134a (1/98/1 wt %) 136
HFO-1234yf/HFC-152a/HFC-134a (98/1/1 wt %) 19
HFO-1234yf/HFC-125/HFC-152a (1/1/98 wt %) 157
HFO-1234yf/HFC-125/HFC-152a (98/1/1 wt %) 40
HFO-1234yf/HFC-125/HFC-152a (1/98/1 wt %) 3431
HFO-1234yf/HFC-125/HFC-134a (1/1/98 wt %) 1436
HFO-1234yf/HFC-125/HFC-134a (1/98/1 wt %) 3444
HFO-1234yf/HFC-125/HFC-134a (98/1/1 wt %) 53 HFO-1234ze/HFC-134a
(50/50 wt %) 718 HFO-1234ze/HFC-134a (80/20 wt %) 293
HFO-1234ze/HFC-125 (95/5 wt %) 184 HFO-1234ze/HFC-125 (80/20 wt %)
705 HFO-1234ze/HFC-32 (30/70 wt %) 474 HFO-1234ze/HFC-32 (60/40 wt
%) 274 HFO-1234ze/HFC-32 (80/20 wt %) 140
[0236] Many compositions as disclosed herein, such as those listed
in Table 5, provide lower GWP alternatives to HCFC-22, HFC-134a,
R404A, R407C, and/or R410A etc.
Example 5
Cooling Performance
[0237] Table 6 shows the performance of some exemplary compositions
as compared to HCFC-22, HFC-134a, HFO-1234yf, R410A, and R407C. In
Table 6, Evap Pres is evaporator pressure, Cond Pres is condenser
pressure, Comp Disch T is compressor discharge temperature, COP is
coefficient of performance (analogous to energy efficiency), and
CAP is capacity. The data are based on the following
conditions.
TABLE-US-00007 Evaporator temperature 45.degree. F. (7.2.degree.
C.) Condenser temperature 110.degree. F. (43.3.degree. C.) Subcool
amount 2.8.degree. F. (5.degree. C.) Return gas temperature
65.degree. F. (18.degree. C.) Compressor efficiency is 70%
[0238] Note that the evaporator superheat enthalpy is included in
cooling capacity and energy efficiency determinations.
TABLE-US-00008 TABLE 6 CAP COP Compr relative relative Temp Evap
Cond Disch to to Glide. Press Press Temp CAP R407C R407C .degree.
C. Composition (kPa) (kPa) (.degree. C.) (kJ/m.sup.3) (%) COP (%)
(cond/evap) R22 624 1660 85 4112 99.1 4.49 103 0 HFC-134a 377 1110
67 2709 65.3 4.58 105 0 HFO-1234yf 399 1104 59 2564 61.8 4.44 102 0
R410A 991 2589 83 5830 141 4.12 94.7 0.14/0.14 R407C 6.25 1767 76
4151 100 4.36 100 4.8/4.8 HFO-1234yf/HFC-134a 411 1164 62 2763 66.6
4.50 103 0.01 (60/40 wt %) HFO-1234yf/HFC-32 6101 1685 70 3835 92.4
4.29 98.4 7.1/6.1 (78.5/21.5 wt %) HFO-1234yf/HFC-32 578 1603 68
3654 88.0 4.31 98.9 7/5.8 (82/18 wt %) HFO-1234yf/HFC-32 549 1529
67 3493 84.1 4.32 99.3 6.8/5.4 (85/15 wt %) HFO-1234yf/HFC- 590
1638 67 3738 90.0 4.32 99.1 4.1/3.6 32/HFC-125/HFC-134a
(35/10/30/25 wt %)
[0239] Several described compositions have capacity greater than
the capacity of HFC-134a, HFO-1234yf and within 10% of the capacity
of R407C. Energy efficiency (as displayed as COP), is within 2% of
the efficiency for R407C.
Example 6
Heating Performance
[0240] Table 7 shows the performance of some exemplary compositions
as compared to HCFC-22, HFC-134a, HFO-1234yf, and R410A. In Table
7, Evap Pres is evaporator pressure, Cond Pres is condenser
pressure, Comp Disch T is compressor discharge temperature, COP is
coefficient of performance (analogous to energy efficiency), and
CAP is capacity. The data are based on the following
conditions.
TABLE-US-00009 Condenser temperature 20.degree. F. (-6.7.degree.
C.) Evaporator temperature 80.degree. F. (26.7.degree. C.) Subcool
amount 10.degree. F. (5.6.degree. C.) Return gas temperature
65.degree. F. (18.degree. C.) Compressor efficiency is 70%
TABLE-US-00010 TABLE 7 CAP COP Compr relative relative Temp Cond
Evap Disch to to Glide, Press Press Temp CAP HCFC-22 HCFC-22
.degree. C. Composition (kPa) (kPa) (.degree. C.) (kJ/m3) (%) COP
(%) (cond/evap) R22 397 1091 85 2948 100 4.85 100 0 HFC-134a 228
699 67 1897 64.3 5.02 104 0 HFO-1234yf 249 713 58 1914 64.9 5.03
104 0 R410A 393 1145 75 2965 101 4.74 97.8 0.55/0.52
HFO-1234yf/HFC-134a 251 744 63 2009 68.1 5.03 104 0/0.1 (50/50 wt
%) HFO-1234yf/HFC-32 392 1109 69 2812 95.4 4.70 96.9 7.9/6.7
(78.5/21.5 wt %) HFO-1234yf/HFC- 374 1069 66 2757 93.5 4.80 98.9
4.6/4.1 32/HFC-125/HFC-134a (35/10/30/25 wt %)
[0241] Several described compositions have capacity within 7% of
the capacity of HCFC-22. Energy efficiency (as displayed as COP)
for these compositions is better than or within 4% of the
efficiency for HCFC-22.
Example 7
Heating Performance
[0242] Table 8 shows the performance of some exemplary compositions
as compared to HCFC-22, and HFO-1234yf/HFC-32 compositions. In
Table 8, Evap Pres is evaporator pressure, Cond Pres is condenser
pressure, Comp Disch T is compressor discharge temperature, COP is
coefficient of performance (analogous to energy efficiency), and
CAP is capacity. The data are based on the following
conditions.
TABLE-US-00011 Evaporator temperature 32.degree. C. Condenser
temperature -12.degree. C. Subcool amount 9.degree. C. Return gas
temperature -9.degree. C. Compressor efficiency is 70%
TABLE-US-00012 TABLE 8 Cond/ Evap 100 yr Compr Avg GWP Cond Evap
Exit Temp COP Cap (IPCC Pressure Pressure Temp Glide Capacity Rel
to Rel to AR4) (kPa) (kPa) (.degree. C.) (.degree. C.) COP
(kJ/m{circumflex over ( )}3) R-22 R-22 HCFC-22 1810 330 1254 76.9 0
4.598 3133.4 100% 103% HFO-1234yf 4 205 824 42.7 0 4.533 1876.1 99%
62% HFO-1234yf/ 105 290 1155 52.3 6.6 4.521 2657.0 98% 88% HFC-32
(85/15 wt %) HFO-1234yf/ 111 295 1174 52.9 6.7 4.520 2703.7 98% 89%
HFC-32 (84/16 wt %) HFO-1234yf/ 125 305 1211 54.0 6.9 4.517 2795.4
98% 92% HFC-32 (82/18 wt %) HFO-1234yf/ 138 316 1247 55.1 7.1 4.513
2885.1 98% 95% HFC-32 (80/20 wt %) HFO-1234yf/ 145 321 1265 55.6
7.1 4.512 2929.1 98% 97% HFC-32 (79/21 wt %)
[0243] In heating mode, compositions of HFO-1234yf from 79-85 wt %
and HFC-32 from 15-21 wt % have equivalent energy efficiency to
R-22 and capacity from 88-97% of R-22. These compositions also have
100 year GWP less than 150 indicating they would be an excellent
low GWP replacement for R-22 in heat pumps.
Example 8
Cooling Performance
[0244] Table 9 shows the performance of some exemplary compositions
as compared to HFC-134a. In Table 9, Evap Pres is evaporator
pressure, Cond Pres is condenser pressure, Comp Disch T is
compressor discharge temperature, COP is coefficient of performance
(analogous to energy efficiency), CAP is cooling capacity, Avg.
Temp. glide is the average of the temperature glide in the
evaporator and condenser, and GWP is global warming potential. The
data are based on the following conditions.
TABLE-US-00013 Evaporator temperature -10.degree. C. Condenser
temperature 40.0.degree. C. Subcool amount 6.degree. C. Return gas
temperature 10.degree. C. Compressor efficiency is 70%
[0245] Note that the evaporator superheat enthalpy is not included
in cooling capacity and energy efficiency determinations.
TABLE-US-00014 TABLE 9 Compr CAP COP Avg. Evap Cond Disch relative
relative Temp. Press Press Temp CAP to 134a to 134a Glide,
Composition (kPa) (kPa) (.degree. C.) (kW) (%) COP (%) .degree. C.
GWP* HFC-134a 200.6 1016.5 81.4 2.231 2.742 0 1430 HFO-1234yf 220.5
1015.6 68.3 2.113 94.7 2.580 94.1 0 4 HFO-1234ze/HFC-125 156.7
814.4 76.3 1.769 79 2.756 101 1.61 184 (95/5 wt %)
HFO-1234ze/HFC-125 166.6 864.4 76.4 1.869 84 2.746 100 2.96 355
(90/10 wt %) HFO-1234ze/HFC-125 176.9 915.0 76.4 1.968 88 2.735 100
4.08 530 (85/15 wt %) HFO-1234ze/HFC-125 187.7 966.1 76.4 2.067 93
2.718 99 4.99 705 (80/20 wt %) *The GWP value for HFC-134a is taken
from the "Climate Change 2007 - IPCC (Intergovernmental Panel on
Climate Change) Fourth Assessment Report on Climate Change", from
the section entitled "Working Group 1 Report: "The Physical Science
Basis", Chapter 2, pp. 212-213, Table 2.14. The value for
HFO-1234yf was published in Papadimitriou et al., Physical
Chemistry Chemical Physics, 2007, vol. 9, pp. 1-13. Specifically,
the 100 year time horizon GWP values are used. The GWP values for
the compositions containing HFC-134a and HFO-1234yf are calculated
as weighted averages of the individual component GWP values.
[0246] The data in Table 9 indicates that the HFO-1234ze/HFC-125
compositions could serve as a replacement for HFC-134a, having
performance similar to HFC-134a. In particular, these compositions
provide matching energy efficiency (shown as COP), pressures and
temperatures in the system, with lower GWP values, and only a minor
reduction in cooling capacity. Plus, all the compositions have
relatively low temperature glide and a specific composition could
be selected based on regulatory requirements for GWP, which have
not at this time been determined.
Example 9
Cooling Performance
[0247] Table 10 shows the performance of certain compositions as
compared to CO2, R404A (ASHRAE designation for a mixture containing
HFC-125, HFC-134a, and HFC-143a), R410A (ASHRAE designation for a
mixture containing HFC-32 and HFC-125) and HFC-32. In Table 10,
Evap Pres is evaporator pressure, Cond Pres is condenser pressure,
Comp Disch T is compressor discharge temperature, COP is
coefficient of performance (analogous to energy efficiency), CAP is
capacity, Avg. Temp. glide is the average of the temperature glide
in the evaporator and condenser, and GWP is global warming
potential. The data are based on the following conditions.
TABLE-US-00015 Evaporator temperature -35.degree. C. Condenser
temperature -6.degree. C. Subcool amount 0.degree. C. Return gas
temperature -25.degree. C. Compressor efficiency is 70%
[0248] Note that the evaporator superheat enthalpy is not included
in cooling capacity and energy efficiency determinations.
TABLE-US-00016 TABLE 10 Compr Avg. Evap Cond Disch Temp. Press
Press Temp CAP Glide, Composition (kPa) (kPa) (.degree. C.) (kW)
COP .degree. C. GWP* CO.sub.2 1204.7 2960.8 57.3 12.132 4.229 0 1
R404A 168.3 449.4 20.0 2.175 4.791 0.5 3922 HFO-1234yf/HFC-32 163.6
503.5 31.5 2.271 4.875 6.7 252 (63/37 wt %) R410A 220.1 654.1 38.3
2.966 4.836 0.1 2088 HFO-1234yf/HFC-32 213.6 635.4 46.4 2.934 4.865
0.8 490 (27.5/72.5 wt %) HFO-1234yf/HFC-32 185.6 561.8 36.9 2.547
4.853 4.3 340 (50/50 wt %) HFO-1234yf/HFC-32 200.2 599.6 41.0 2.739
4.851 2.5 407 (40/60 wt %) HFO-1234yf/HFC-32 218.2 649.8 50.2 3.015
4.852 0.3 541 (20/80 wt %) HFC-32 221.0 666.3 60.8 3.126 4.833 0
675 HFO-1234ze/HFC-32 60.8 220.1 28.6 0.982 4.947 4.7 73 (90/10 wt
%) HFO-1234ze/HFC-32 74.7 266.2 33.2 1.201 4.958 7.5 140 (80/20 wt
%) HFO-1234ze/HFC-32 89.1 311.4 37.4 1.419 4.968 9.1 207 (70/30 wt
%) HFO-1234ze/HFC-32 104.1 356.1 41.4 1.637 4.958 9.8 274 (60/40 wt
%) HFO-1234ze/HFC-32 119.6 400.9 45.2 1.855 4.944 9.8 341 (50/50 wt
%) HFO-1234ze/HFC-32 135.9 446.6 48.8 2.074 4.927 9.2 407 (40/60 wt
%) HFO-1234ze/HFC-32 144.1 469.9 50.6 2.185 4.907 8.6 441 (35/65 wt
%) HFO-1234ze/HFC-32 153.0 493.8 52.4 2.298 4.892 8.0 474 (30/70 wt
%) HFO-1234ze/HFC-32 162.1 518.4 54.1 2.413 4.875 7.2 508 (25/75 wt
%) HFO-1234ze/HFC-32 171.7 543.9 55.7 2.532 4.858 6.2 541 (20/80 wt
%) HFO-1234ze/HFC-32 193.1 599.4 58.7 2.793 4.830 3.7 608 (10/90 wt
%) *The GWP value for HFCs are taken from the "Climate Change 2007
- IPCC (Intergovernmental Panel on Climate Change) Fourth
Assessment Report on Climate Change", from the section entitled
"Working Group 1 Report: "The Physical Science Basis", Chapter 2,
pp. 212-213, Table 2.14. The value for HFO-1234yf was published in
Papadimitriou et al., Physical Chemistry Chemical Physics, 2007,
vol. 9, pp. 1-13. Specifically, the 100 year time horizon GWP
values are used. The GWP values for the compositions containing
more than one component are calculated as weighted averages of the
individual component GWP values.
[0249] The composition containing 63 wt % HFO-1234yf and 37 wt %
HFC-32 actually shows improved COP and capacity relative to R404A
and also has significantly lower GWP. The composition containing
27.5 wt % HFO-1234yf and 72.5 wt % HFC-32 matches the COP and
capacity of R410A, has very low temperature glide indicating
azeotrope-like behavior and also has significantly lower GWP. Note
that all mixtures of tetrafluoropropene (both HFO-1234yf and
HFO-1234ze) and HFC-32 have improved COP (energy efficiency) as
compared to CO2, and many have improved COP as compared to R404A
and R410A as well.
* * * * *