U.S. patent application number 13/393640 was filed with the patent office on 2012-06-28 for ternary compositions for low-capacity refrigeration.
This patent application is currently assigned to Arkema France. Invention is credited to Wissam Rached.
Application Number | 20120159982 13/393640 |
Document ID | / |
Family ID | 42077109 |
Filed Date | 2012-06-28 |
United States Patent
Application |
20120159982 |
Kind Code |
A1 |
Rached; Wissam |
June 28, 2012 |
TERNARY COMPOSITIONS FOR LOW-CAPACITY REFRIGERATION
Abstract
The invention relates to compositions containing
2,3,3,3-tetrafluoropropene and to the uses thereof as heat transfer
fluid, expansion agents, solvents and aerosol. The invention
specifically relates to compositions essentially containing between
10 and 90 wt. % of 2,3,3,3-tetrafluoropropene, between 5 and 80 wt.
% of HFC-134a and between 5 and 10 wt. % of HFC-32.
Inventors: |
Rached; Wissam; (Chaponst,
FR) |
Assignee: |
Arkema France
Colombes
FR
|
Family ID: |
42077109 |
Appl. No.: |
13/393640 |
Filed: |
August 20, 2010 |
PCT Filed: |
August 20, 2010 |
PCT NO: |
PCT/FR10/51747 |
371 Date: |
March 1, 2012 |
Current U.S.
Class: |
62/468 ;
252/182.12; 252/364; 252/67; 252/68; 62/498 |
Current CPC
Class: |
C08J 9/146 20130101;
C09K 2205/22 20130101; C09K 2205/40 20130101; C09K 5/045 20130101;
C09K 3/00 20130101; C08J 2207/04 20130101; C09K 3/30 20130101; B01F
17/0085 20130101; F25B 13/00 20130101; C09K 2205/126 20130101 |
Class at
Publication: |
62/468 ; 252/67;
252/68; 252/182.12; 252/364; 62/498 |
International
Class: |
F25B 1/00 20060101
F25B001/00; C09K 3/00 20060101 C09K003/00; F25B 41/00 20060101
F25B041/00; C09K 5/00 20060101 C09K005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 11, 2009 |
FR |
0956249 |
Claims
1. A composition consisting essentially of from 10 to 90% by weight
of 2,3,3,3-tetrafluoropropene, from 5 to 80% by weight of HFC-134a
and from 5 to 10% by weight of HFC-32.
2. The composition as claimed in claim 1, characterized in that it
consists essentially of from 10 to 45% by weight of
2,3,3,3-tetrafluoropropene, from 50 to 80% by weight of HFC-134a
and from 5 to 10% by weight of HFC-32.
3. The composition as claimed in claim 1, characterized in that it
further contains a stabilizer.
4. A heat-transfer fluid comprising the composition as claimed in
claim 1.
5. A compression refrigeration systems, with exchangers operating
in counterflow mode containing a heat-transfer fluid as claimed in
claim 4..
6. (canceled)
7. The compression refrigeration system as claimed in claim 4
characterized in that it further contains a lubricant.
8. Blowing agents comprising the composition as claimed in claim
1.
9. Solvents comprising the composition as claimed in claim 1.
10. Aerosols comprising the composition as claimed in claim 1.
Description
[0001] The present invention relates to compositions containing
2,3,3,3-tetrafluoropropene and uses thereof as heat-transfer
fluids, blowing agents, solvents and aerosols.
[0002] The problems posed by substances which delete the
atmospheric ozone layer (ODP: ozone depletion potential) were
addressed in Montreal, where the protocol imposing a reduction in
the production and use of chlorofluorocarbons (CFCs) was signed.
This protocol has been the subject of amendments which have
required that CFCs be withdrawn and have extended regulatory
control to other products, including hydrochlorofluorocarbons
(HCFCs).
[0003] The refrigeration and air-conditioning industry has invested
a great deal in the replacement of these refrigerants, and as a
result, hydrofluorocarbons (HFCs) have been marketed.
[0004] The (hydro)chlorofluorocarbons used as blowing agents or
solvents have also been replaced with HFCs.
[0005] In the automotive industry, the air-conditioning systems for
vehicles sold in many countries have changed from a
chlorofluorocarbon (CFC-12) refrigerant to a hydrofluorocarbon
(1,1,1,2-tetrafluoroethane: HFC-134a) refrigerant which is less
harmful to the ozone layer. However, from the viewpoint of the
objectives set by the Kyoto protocol, HFC-134a (GWP=1300) is
considered to have a high warming potential. The contribution to
the greenhouse effect of a fluid is quantified by a criterion, the
GWP (global warming potential) which indexes the warming potential
by taking a reference value of 1 for carbon dioxide.
[0006] Since carbon dioxide is non-toxic and non-flammable and has
a very low GWP, it has been proposed as a refrigerant in
air-conditioning systems as a replacement for HFC-134a. However,
the use of carbon dioxide has several drawbacks, in particular
linked to the very high pressure at which it is used as a
refrigerant in the existing apparatuses and technologies.
[0007] Document WO 2004/037913 discloses the use of compositions
comprising at least one fluoroalkene having three or four carbon
atoms, in particular pentafluoropropene and tetrafluoropropene,
preferably having a GWP at most of 150, as heat-transfer
fluids.
[0008] Document WO 2005/105947 teaches the addition to
tetrafluoropropene, preferably 1,3,3,3-tetrafluoropropene, of a
blowing coagent such as difluoromethane, pentafluoroethane,
tetrafluoroethane, difluoroethane, heptafluoropropane,
hexafluoropropane, pentafluoropropane, pentafluorobutane, water and
carbon dioxide.
[0009] Document WO 2006/094303 discloses binary compositions of
2,3,3,3-tetrafluoropropene (HFO-1234yf) with difluoromethane
(HFC-32), and of 2,3,3,3-tetrafluoropropene with
1,1,1,2-tetrafluoroethane (HFC-134a).
[0010] Quaternary mixtures comprising 1,1,1,2,3-pentafluoro-propene
(HFO-1225ye) in combination with difluoromethane,
2,3,3,3-tetrafluoropropene and HFC-134a were disclosed in this
document. However, 1,1,1,2,3-pentafluoropropene is toxic.
[0011] Quaternary mixtures comprising 2,3,3,3-tetrafluoropropene in
combination with iodotrifluoromethane (CF.sub.3I), HFC-32 and
HFC-134a have also been disclosed in document WO 2006/094303.
However, CF.sub.3I has a non-zero ODP and poses stability and
corrosion problems.
[0012] The applicant has now developed 2,3,3,3-tetrafluoropropene
compositions which do not have the abovementioned drawbacks and
have both a zero ODP and a GWP which is lower than that of the
existing heat-transfer fluids such as and HFC-134a.
[0013] The compositions used as heat-transfer fluid in the present
invention have values for the temperatures at the compressor
outlet, and pressure levels, equivalent to the values given by
HFC-134a. The compression ratios are lower. These compositions can
replace HFC-134a without changing compressor technology.
[0014] The compositions used as a heat-transfer fluid in the
present invention have volume capacities which are greater than the
volume capacity of HFC-134a (between 116 and 133%). By virtue of
these properties, these compositions can use smaller compressors
and have the same heating or cooling capacity.
[0015] The compositions according to the present invention are
characterized in that they essentially contain from 10 to 90% by
weight of 2,3,3,3-tetrafluoropropene, from 5 to 80% by weight of
HFC-134a and from 5 to 10% by weight of HFC-32.
[0016] Preferably, the compositions essentially contain from 10 to
45% by weight of 2,3,3,3-tetrafluoropropene, from 50 to 80% by
weight of HFC-134a and from 5 to 10% by weight of HFC-32.
[0017] The compositions according to the present invention can be
used as heat-transfer fluids, preferably in compression systems and
advantageously with exchangers operating in counterflow mode or in
cross-flow mode with counterflow tendency. They are particularly
suitable for systems of low-capacity refrigeration per unit volume
swept by the compressor.
[0018] In compression systems, the heat exchange between the
refrigerant and the heat sources takes place by means of
heat-transfer fluids. These heat-transfer fluids are in the gaseous
state (the air in air-conditioning and direct expansion
refrigeration), liquid state (the water in domestic heat pumps,
glycolated water) or two-phase state.
[0019] There are various modes of transfer: [0020] the two fluids
are arranged in parallel and travel in the same direction: co-flow
(antimethodic) mode; [0021] the two fluids are arranged in parallel
but travel in the opposite direction: counterflow (methodic) mode;
[0022] the two fluids are positioned perpendicularly: cross-flow
mode. The cross-flow may be with co-flow or counterflow tendency;
[0023] one of the two fluids makes a U-turn in a wider pipe, which
the second fluid passes through. This configuration is comparable
to a co-flow exchanger over half the length, and for the other
half, to a counterflow exchanger: pinhead mode.
[0024] The compositions according to the present invention are
advantageously used in stationary air conditioning and heat pumps,
preferably as a replacement for HFC-134a.
[0025] The compositions according to the present invention can be
stabilized. The stabilizer preferably represents at most 5% by
weight relative to the total composition.
[0026] As stabilizers, mention may in particular be made of
nitromethane, ascorbic acid, terephthalic acid, azoles such as
tolutriazole or benzotriazole, phenolic compounds such as
tocopherol, hydroquinone, t-butyl hydroquinone or
2,6-di-tert-butyl-4-methylphenol, epoxides (alkyl, optionally
fluorinated or perfluorinated, or alkenyl or aromatic) such as
n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl
ether or butylphenyl glycidyl ether, phosphites, phosphates,
phosphonates, thiols and lactones.
[0027] The compositions according to the present invention, as a
heat-transfer agent, can be employed in the presence of lubricants
such as mineral oil, alkylbenzene, polyalkylene glycol and
polyvinyl ether.
[0028] The compositions according to the present invention can also
be used as blowing agents, aerosols and solvents.
EXPERIMENTAL SECTION
[0029] Calculation Tools
[0030] The RK-Soave equation is used for calculating the densities,
enthalpies, entropies and liquid/vapor equilibrium data of the
mixtures. The use of this equation requires knowledge of the
properties of the pure bodies used in the mixtures in question and
also the interaction coefficients for each binary mixture.
[0031] The data required for each pure body are:
[0032] The boiling point, the critical temperature and the critical
pressure, the curve of pressure as a function of temperature
starting from the boiling point up to the critical point, and the
saturated liquid and saturated vapor densities as a function of
temperature.
[0033] HFC-32, HFC-134a:
[0034] The data on these products aer published in the ASHRAE
Handbook 2005 chapter 20, and are also available from Refrop
(software developed by NIST for calculating the properties of
refrigerants).
[0035] HFO-1234yf:
[0036] The data of the temperature-pressure curve for HFO-1234yf
are measured by the static method. The critical temperature and the
critical pressure are measured using a C80 calorimeter sold by
Setaram. The densities, at saturation as a function of temperature,
are measured using the vibrating tube densitometer technology
developed by the laboratories of the Ecole des Mines of Paris.
[0037] Interaction Coefficient of the Binary Mixtures
[0038] The RK-Soave equation uses binary interaction coefficients
to represent the behavior of the products in mixtures. The
coefficients are calculated as a function of the experimental
liquid/vapor equilibrium data.
[0039] The technique used for the liquid/vapor equilibrium
measurements is the static-cell analytical method. The equilibrium
cell comprises a sapphire tube and is equipped with two
electromagnetic ROLSI.TM. samplers. It is immersed in a
cryothermostat bath (HUBER HS40). A magnetic stirrer with a field
drive rotating at varying speed is used to accelerate reaching the
equilibria. The analysis of the samples is carried out by gas
chromatography (HP5890 series II) using a katharometer (TCD).
[0040] HFC-32/HFO-1234yf, HFC-134a/HFO-1234yf:
[0041] The liquid/vapor equilibrium measurements on the binary
mixture HFC-32/HFO-1234yf are carried out for the following
isotherms: -10.degree. C., 30.degree. C. and 70.degree. C.
[0042] The liquid/vapor equilibrium measurements on the binary
mixture HFC-134a/HFO-1234yf are carried out for the following
isotherms: 20.degree. C.
[0043] HFC-32/HFO-134a:
[0044] The liquid/vapor equilibrium data for the binary mixture
HFC-134a/HFC-32 are available from Refprop. Two isotherms
(-20.degree. C. and 20.degree. C.) and one isobar (30 bar) are used
to calculate the interaction coefficients for this binary
mixture.
[0045] Compression System
[0046] A compression system equipped with a counterflow condenser
and evaporator, with a screw compressor and with an expansion valve
is considered.
[0047] The system operates with 15.degree. C. of overheat and
5.degree. C. of undercooling. The minimum temperature difference
between the secondary fluid and the refrigerant is considered to be
about 5.degree. C.
[0048] The isentropic efficiency of the compressors depends on the
compression ratio. This efficiency is calculated according to the
following equation:
.eta. isen = a - b ( .tau. - c ) 2 - d .tau. - e . ( 1 )
##EQU00001##
[0049] For a screw compressor, the constants a, b, c, d and e of
the isentropic efficiency equation (1) are calculated according to
the standard data published in the "Handbook of air conditioning
and refrigeration, page 11.52".
[0050] The % CAP is the percentage of the ratio of the volumetric
capacity supplied by each product over the capacity of
HFC-134a.
[0051] The coefficient of performance (COP) is defined as being the
useful power supplied by the system over the power provided or
consumed by the system.
[0052] The Lorenz coefficient of performance (COPLorenz) is a
reference coefficient of performance. It is a function of
temperatures and is used for comparing the COPs of various
fluids.
[0053] The Lorenz coefficient of performance is defined as
follows:
[0054] (The temperatures T are in K)
T.sub.average.sup.condenser=T.sub.inlet.sup.condenser-T.sub.outlet.sup.c-
ondenser (2)
T.sub.average.sup.evaporator=T.sub.outlet.sup.evaporator-T.sub.inlet.sup-
.evaporator (3)
[0055] The Lorenz COP in the case of air-conditioning and
refrigeration is:
COPlorenz = T average evaporator T average conderser - T average
evaporator ( 4 ) ##EQU00002##
[0056] The Lorenz COP in the case of heating is:
COPlorenz = T average condensor T average condenser - T average
evaporator ( 5 ) ##EQU00003##
[0057] For each composition, the coefficient of performance of the
Lorenz cycle is calculated as a function of the corresponding
temperatures.
The %COP/COPLorenz is the ratio of the COP of the system relative
to the COP of the corresponding Lorenz cycle.
[0058] Heating Mode Results
[0059] In heating mode, the compression system operates between a
temperature for inlet of the refrigerant into the evaporator of
-5.degree. C. and a temperature for inlet of the refrigerant into
the condenser of 50.degree. C. The system supplies heat at
45.degree. C.
[0060] The performance levels of the compositions according to the
invention under the heating mode operating conditions are given in
table 1. The values of the constituents (HFO-1234yf, HFC-32,
HFC-134a) for each composition are given as percentage by
weight.
TABLE-US-00001 TABLE 1 HFC-134a HFO- HFC- HFC- Evap outlet Comp
outlet Cond outlet Evap P Cond P Ratio Comp % COP/ 1234yf 32 134a
temp (.degree. C.) temp (.degree. C.) T (.degree. C.) (bar) (bar)
(w/w) Glide efficiency % CAP COPLorenz -5 81 50 2.4 13.2 5.4 0.00
75.9 100 63.3 50 10 40 -2 78 46 3.4 15.6 4.5 2.66 79.4 130 64.7 25
10 65 -2 82 47 3.3 15.4 4.7 2.55 78.7 128 65.0 10 10 80 -3 84 47
3.1 15.1 4.8 2.44 78.3 126 65.1
[0061] Cooling or Air-Conditioning Mode Results
[0062] In cooling mode, the compression system operates between a
temperature for inlet of the refrigerant into the evaporator of
-5.degree. C. and a temperature for inlet of the refrigerant into
the condenser of 50.degree. C. The system supplies refrigeration at
0.degree. C.
[0063] The performance levels of the compositions according to the
invention under the cooling mode operating conditions are given in
table 2. The values of the constituents (HFO-1234yf, HFC-32,
HFC-134a) for each composition are given as percentage by
weight.
TABLE-US-00002 TABLE 2 HFC-134a HFO- HFC- HFC- Evap outlet Comp
outlet Cond outlet Evap P Cond P Ratio Comp % COP/ 1234yf 32 134a
temp (.degree. C.) temp (.degree. C.) T (.degree. C.) (bar) (bar)
(w/w) Glide efficiency % CAP COPLorenz -5 81 50 2.4 13.2 5.4 0.00
75.9 100 54.1 65 10 25 -2 76 45 3.5 15.5 4.4 2.87 79.7 133 55.8 50
10 40 -2 78 46 3.4 15.6 4.5 2.66 79.4 133 56.0 25 10 65 -2 82 47
3.3 15.4 4.7 2.55 78.7 132 56.5 15 5 80 -4 81 48 2.9 14.3 5.0 1.38
77.6 116 55.6 10 10 80 -3 84 47 3.1 15.1 4.8 2.44 78.3 130 56.7
* * * * *