U.S. patent application number 14/615741 was filed with the patent office on 2015-06-04 for heat transfer fluid replacing r-410a.
This patent application is currently assigned to Arkema France. The applicant listed for this patent is Arkema France. Invention is credited to Wissam RACHED.
Application Number | 20150152306 14/615741 |
Document ID | / |
Family ID | 42135950 |
Filed Date | 2015-06-04 |
United States Patent
Application |
20150152306 |
Kind Code |
A1 |
RACHED; Wissam |
June 4, 2015 |
HEAT TRANSFER FLUID REPLACING R-410A
Abstract
A heat transfer method using ternary composition containing
2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and difluoromethane,
as a heat transfer fluid in refrigeration systems, to replace the
R-410A mixture.
Inventors: |
RACHED; Wissam; (Chaponost,
FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Arkema France |
Colombes |
|
FR |
|
|
Assignee: |
Arkema France
Colombes
FR
|
Family ID: |
42135950 |
Appl. No.: |
14/615741 |
Filed: |
February 6, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13391417 |
Mar 8, 2012 |
9011711 |
|
|
PCT/FR2010/051727 |
Aug 17, 2010 |
|
|
|
14615741 |
|
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Current U.S.
Class: |
62/77 |
Current CPC
Class: |
C09K 2205/22 20130101;
C09K 5/045 20130101; C09K 2205/126 20130101; F25B 9/006 20130101;
F25B 45/00 20130101; C09K 2205/40 20130101 |
International
Class: |
C09K 5/04 20060101
C09K005/04; F25B 45/00 20060101 F25B045/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 11, 2009 |
FR |
09.56245 |
Claims
1-11. (canceled)
12. A method of modifying a heat transfer system containing R-410A
comprising removing R-410A and adding refrigerant comprising a
ternary composition of 2,3,3,3-tetrafluoropropene, difluormethane,
and 1,1-difluoroethane.
13. The method as claimed in claim 12, wherein the refrigerant
further comprises a stabilizer.
14. The method as claimed in claim 13, wherein the stabilizer is
selected from the group consisting of nitromethane, ascorbic acid,
terephthalic acid, azoles, phenolic compounds, epoxides,
phosphites, phosphates, phosphonates, thiols and lactones.
15. The method as claimed in claim 13, wherein stabilizer
represents at most 5% by weight relative to the refrigerant.
16. The method as claimed in claim 12, wherein the heat transfer
system is of the compression type.
17. The method as claimed in claim 16, wherein the heat transfer
system operates with exchangers in countercurrent mode or in
crossed-current mode with countercurrent tendency.
18. The method as claimed in claim 12, wherein the refrigerant
further comprises a lubricant.
19. The method as claimed in claim 18, wherein the lubricant is
selected from the group consisting of mineral oil, alkylbenzene,
polyalkylene glycol and polyvinyl ether.
20. A heat transfer system comprising exchangers operating in
countercurrent mode or in crossed-current mode with countercurrent
tendency and a refrigerant comprising a ternary composition of
2,3,3,3-tetrafluoropropene, difluormethane, and
1,1-difluoroethane.
21. The method as claimed in claim 20, wherein the refrigerant
further comprises a stabilizer.
22. The method as claimed in claim 21, wherein the stabilizer is
selected from the group consisting of nitromethane, ascorbic acid,
terephthalic acid, azoles, phenolic compounds, epoxides,
phosphites, phosphates, phosphonates, thiols and lactones.
23. The method as claimed in claim 21, wherein stabilizer
represents at most 5% by weight relative to the refrigerant.
24. The method as claimed in claim 20, wherein the heat transfer
system is of the compression type.
25. The method as claimed in claim 20, wherein the heat transfer
system is a compression-type low- and medium-temperature
refrigeration system.
26. The method as claimed in claim 20, wherein the refrigerant
further comprises a lubricant.
27. The method as claimed in claim 26, wherein the lubricant is
selected from the group consisting of mineral oil, alkylbenzene,
polyalkylene glycol and polyvinyl ether.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S.
application Ser. No. 13/391,417, filed on Mar. 8, 2012, which is a
U.S. National Stage of International Application No.
PCT/FR2010/051727, filed on Aug. 17, 201, which claims the benefit
of French Application No. 09.56245, filed on Sep. 11, 2009. The
entire contents of each of U.S. application Ser. No. 13/391,417,
International Application No. PCT/FR2010/051727, and French
Application No. 09.56245 are hereby incorporated herein by
reference in their entirety.
TECHNICAL FIELD
[0002] The present invention relates to the use of ternary
compositions of 2,3,3,3-tetrafluoropropene as heat transfer fluids
replacing R-410A.
BACKGROUND
[0003] The problems posed by substances with ozone depletion
potential (ODP) were discussed in Montreal, where the protocol was
signed requiring a reduction of the production and use of
chlorofluorocarbons (CFCs). Amendments have been made to this
protocol, requiring abandonment of CFCs and extending the
regulations to cover other products, including
hydrochlorofluorocarbons (HCFCs).
[0004] The refrigeration and air conditioning industry has made a
considerable investment in substitution of these refrigerants, and
accordingly hydrofluorocarbons (HFCs) were put on the market.
[0005] The (hydro)chlorofluorocarbons used as expanding agents or
solvents have also been replaced with HFCs.
[0006] In the automobile industry, the systems for air conditioning
of vehicles marketed in many countries have changed over from a
chlorofluorocarbon refrigerant (CFC-12) to a hydrofluorocarbon
refrigerant (1,1,1,2-tetrafluoroethane: HFC-134a), which is less
harmful to the ozone layer. However, with respect to the objectives
established by the Kyoto protocol, HFC-134a (GWP=1300) is
considered to have a high warming power. A fluid's contribution to
the greenhouse effect is quantified by a criterion, GWP (Global
Warming Potential), which summarizes the warming power by taking a
reference value of 1 for carbon dioxide.
[0007] As carbon dioxide is nontoxic, nonflammable and has a very
low GWP, it has been proposed as a refrigerant for air conditioning
systems in place of HFC-134a. However, the use of carbon dioxide
has several drawbacks, notably connected with the very high
pressure for its application as refrigerant in existing equipment
and technologies.
[0008] Moreover, the mixture R-410A consisting of 50 wt. % of
pentafluoroethane and 50 wt. % of HFC-134a is widely used as
refrigerant in stationary air conditioners. However, this mixture
has a GWP of 2100.
[0009] Document JP 4110388 describes the use of hydrofluoropropenes
of formula C.sub.3H.sub.mF.sub.n, with m, n representing an integer
between 1 and 5 inclusive and m+n=6, as heat transfer fluids, in
particular tetrafluoropropene and trifluoropropene.
[0010] Document WO2004/037913 discloses the use of compositions
comprising at least one fluoroalkene having three or four carbon
atoms, notably pentafluoropropene and tetrafluoropropene,
preferably having a GWP of at most 150, as heat transfer
fluids.
[0011] Document WO 2005/105947 teaches the addition to
tetrafluoropropene, preferably 1,3,3,3-tetrafluoropropene, of an
expanding co-agent such as difluoromethane, pentafluoroethane,
tetrafluoroethane, difluoroethane, heptafluoropropane,
hexafluoropropane, pentafluoropropane, pentafluorobutane, water and
carbon dioxide.
[0012] Document WO 2006/094303 discloses an azeotropic composition
containing 7.4 wt. % of 2,3,3,3-tetrafluoropropene (1234yf) and
92.6 wt. % of difluoromethane (HFC-32). This document also
discloses an azeotropic composition containing 91 wt. % of
2,3,3,3-tetrafluoropropene and 9 wt. % of difluoroethane
(HFC-152a).
[0013] A heat exchanger is a device for transferring thermal energy
from one fluid to another, without mixing them. The thermal flux
passes through the exchange surface that separates the fluids.
Mostly this method is used for cooling or heating a liquid or a gas
that cannot be cooled or heated directly.
[0014] In compression systems, heat exchange between the
refrigerant and the heat sources takes place via heat-transfer
fluids. These heat transfer fluids are in the gaseous state (the
air in air conditioning and direct-expansion refrigeration), liquid
(water in domestic heat pumps, glycol solution) or two-phase.
[0015] There are various transfer modes: [0016] the two fluids are
arranged in parallel and go in the same sense: co-current mode
(antimethodical); [0017] the two fluids are arranged in parallel
but go in the opposite sense: countercurrent mode (methodical);
[0018] the two fluids are positioned perpendicularly:
crossed-current mode. The crossed current can have co-current or
countercurrent tendency; [0019] one of the two fluids makes a
U-turn in a wider pipeline, which the second fluid passes through.
This configuration is comparable to a co-current exchanger on half
its length, and to a countercurrent exchanger for the other half:
pin-head mode.
DETAILED DESCRIPTION
[0020] The applicant has now discovered that ternary compositions
of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and
difluoromethane are particularly advantageous as heat transfer
fluid.
[0021] These compositions have both a zero ODP and a GWP below that
of existing heat transfer fluids such as R-410A.
[0022] Moreover, their performance (COP: coefficient of
performance, defined as the useful power delivered by the system to
the power supplied to or consumed by the system) is greater than
that of existing heat transfer fluids such as R-410A.
[0023] The compositions used as heat transfer fluid in the present
invention have a critical temperature above 87.degree. C. (the
critical temperature of R410A is 70.5.degree. C.). These
compositions can be used in heat pumps for supplying heat at
temperatures up to 65.degree. C. but also at higher temperatures up
to 87.degree. C. (temperature range where R-410A cannot be
used).
[0024] The compositions used as heat transfer fluid in the present
invention have temperatures at the compressor outlet equivalent to
the values given by R-410A. The pressures at the condenser are
lower than the pressures of R-410A and the compression ratios are
also lower. These compositions can use the same compressor
technology as used with R-410A.
[0025] The compositions used as heat transfer fluid in the present
invention have saturated-vapor densities below the saturated-vapor
density of R-410A. The volumetric capacities given by these
compositions are equivalent to the volumetric capacity of R-410A
(between 91 and 95%). Owing to these properties, these compositions
operate with smaller pipeline diameters and therefore less head
loss in the vapor pipelines, which increases the performance of the
installations.
[0026] These compositions are suitable preferably in
compression-type refrigeration systems with exchangers operating in
countercurrent mode or in crossed-current mode with countercurrent
tendency.
[0027] Thus, these compositions can be used as heat transfer fluid
in heat pumps, optionally reversible, in air conditioning, and in
low-temperature and medium-temperature refrigeration employing
compression systems with exchangers in countercurrent mode or in
crossed-current mode with countercurrent tendency. The present
invention therefore relates to the use of ternary compositions of
2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and difluoromethane
as heat transfer fluid in refrigeration systems replacing the
mixture R-410A.
[0028] Preferably, these compositions are used in compression-type
refrigeration systems with exchangers operating in countercurrent
mode or in crossed-current mode with countercurrent tendency.
[0029] Preferably, the compositions used in the present invention
contain essentially from 5 to 83 wt. % of
2,3,3,3-tetrafluoropropene and from 2 to 50 wt. % of
1,1-difluoroethane and from 15 to 75 wt. % of difluoromethane.
[0030] Advantageously, the compositions used contain essentially
from 5 to 63 wt. % of 2,3,3,3-tetrafluoropropene and from 2 to 25
wt. % of difluoroethane and from 35 to 70 wt.% of
difluoromethane.
[0031] The compositions that are particularly preferred contain
essentially from 40 to 58 wt. % of 2,3,3,3-tetrafluoropropene, from
40 to 50 wt. % of difluoromethane and from 2 to 10 wt. % of
1,1-difluoroethane.
[0032] The compositions used in the present invention can be
stabilized. The stabilizer preferably represents at most 5 wt. %
relative to the total composition.
[0033] As stabilizers, we may notably mention nitromethane,
ascorbic acid, terephthalic acid, azoles such as tolutriazole or
benzotriazole, phenolic compounds such as tocopherol, hydroquinone,
t-butyl hydroquinone, 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, butylphenylglycidyl ether, phosphites,
phosphates, phosphonates, thiols and lactones.
[0034] Another object of the present invention relates to a method
of heat transfer in which the aforementioned ternary compositions
of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and
difluoromethane are used as heat transfer fluid in refrigeration
systems replacing the mixture R-410A.
[0035] Preferably, the method is employed in compression-type
refrigeration systems with exchangers operating in countercurrent
mode or in crossed-current mode with countercurrent tendency.
[0036] The method according to the present invention can be
implemented in the presence of lubricants such as mineral oil,
alkylbenzene, polyalkylene glycol and polyvinyl ether.
[0037] The compositions used in the present invention are suitable
for replacing R-410A in refrigeration, air conditioning and heat
pumps with the existing installations.
EXPERIMENTAL SECTION
Tools for Calculation
[0038] The RK-Soave equation is used for calculating the densities,
enthalpies, entropies and the data on liquid-vapor equilibrium of
the mixtures. To use this equation it is necessary to know the
properties of the pure substances used in the mixtures in question
as well as the coefficients of interaction for each binary
mixture.
[0039] The data required for each pure substance are:
Boiling point, critical temperature and pressure, curve of pressure
as a function of temperature from the boiling point to the critical
point, the saturated liquid density and saturated vapor density as
a function of temperature.
HFC-32, HFC-152a:
[0040] The data for these products are published in ASHRAE Handbook
2005 chapter 20, and are also available using Refrop (software
developed by NIST for calculating the properties of
refrigerants).
HFO-1234yf:
[0041] The data for the temperature-pressure curve of HFO-1234yf
are measured by the static method. The critical temperature and
pressure are measured with a C80 calorimeter marketed by Setaram.
The densities, at saturation as a function of temperature, are
measured by the vibrating tube densimeter technology developed by
the laboratories of the Ecole de Mines ("Mining Engineering
College") in Paris.
Coefficient of Interaction of the Binary Mixtures
[0042] The RK-Soave equation uses coefficients of binary
interaction for representing the behavior of the products in
mixtures. The coefficients are calculated as a function of
experimental data for liquid-vapor equilibrium.
[0043] The technique used for the measurements of liquid-vapor
equilibrium is the static analytical cell method. The equilibrium
cell comprises a sapphire tube and is equipped with two ROLSITM
electromagnetic samplers. It is immersed in a cryothermostat bath
(HUBER HS40). Magnetic stirring driven by a field rotating at
variable speed is used for accelerating attainment of the
equilibria. The samples are analyzed by gas chromatography (HP5890
series II) using a catharometer (TCD).
HFC-32/HFO-1234yf, HFC-152a/HFO-1234yf:
[0044] The measurements of liquid-vapor equilibrium on the
HFC-32/HFO-1234yf binary mixture are performed for the following
isotherms: -10.degree. C., 30.degree. C. and 70.degree. C.
[0045] The measurements of liquid-vapor equilibrium on the
HFC-152a/HFO-1234yf binary mixture are performed for the following
isotherms: 10.degree. C.
HFC-32/HFO-152a:
[0046] The data on liquid-vapor equilibrium for the HFC-152a/HFC-32
binary mixture are available using Refprop. Two isotherms
(-20.degree. C. and 20.degree. C.) and two isobars (1 bar and 25
bar) are used for calculating the coefficients of interaction for
this binary.
Compression System
[0047] Consider a compression system equipped with an evaporator
and countercurrent condenser, a screw compressor and a pressure
reducing valve.
[0048] The system operates with 15.degree. C. of superheating and
5.degree. C. of supercooling. The minimum temperature difference
between the secondary fluid and the refrigerant is considered to be
of the order of 5.degree. C.
[0049] The isentropic efficiency of the compressors is a function
of the compression ratio.
[0050] This efficiency is calculated from the following
equation:
.eta. isen = a - b ( .tau. - c ) 2 - d .tau. - e ( 1 )
##EQU00001##
[0051] For a screw compressor, the constants a, b, c, d and e in
equation (1) of isentropic efficiency are calculated using standard
data published in the handbook "Handbook of air conditioning and
refrigeration", page 11.52.
[0052] % CAP is the percentage of the ratio of the volumetric
capacity supplied by each product to the capacity of R-410A.
[0053] The coefficient of performance (COP) is defined as the ratio
of the useful power delivered by the system to the power supplied
to or consumed by the system.
[0054] The Lorenz coefficient of performance (COP.sub.Lorenz) is a
reference coefficient of performance. It is a function of
temperature and is used for comparing the COPs of different
fluids.
[0055] The Lorenz coefficient of performance is defined as
follows:
(The temperatures T are in K)
T.sub.mean.sup.condenser=T.sub.inlet.sup.condenser-T.sub.outlet.sup.cond-
enser (2)
T.sub.mean.sup.evaporator=T.sub.outlet.sup.evaporator-T.sub.inlet.sup.ev-
aporator (3)
[0056] The COP.sub.Lorenz in the case of air conditioning and
refrigeration is:
COPlorenz = T mean evaporator T mean condenser - T mean evaporator
( 4 ) ##EQU00002##
[0057] The COP.sub.Lorenz in the case of heating is:
COPlorenz = T mean condenser T mean condenser - T mean evaporator (
5 ) ##EQU00003##
[0058] For each composition, the coefficient of performance of the
Lorenz cycle is calculated as a function of the corresponding
temperatures.
[0059] % COP/COP.sub.Lorenz is the ratio of the COP of the system
relative to the COP of the corresponding Lorenz cycle.
Results, Cooling Mode or Air Conditioning
[0060] In cooling mode, the compression system operates between a
refrigerant inlet temperature at the evaporator of -5.degree. C.
and a refrigerant inlet temperature at the condenser of 50.degree.
C. The system delivers cold at 0.degree. C.
[0061] The performance of the compositions according to the
invention in cooling operating conditions is given in Table 1. The
values of the constituents (HFO-1234yf, HFC-32, HFC-152a) for each
composition are given as percentage by weight.
TABLE-US-00001 TABLE 1 Temp Temp outlet outlet T outlet % evap comp
cond evap P cond P Ratio efficiency % COP/ (.degree. C.) (.degree.
C.) (.degree. C.) (bar) (bar) (w/w) Shift comp CAP COPLorenz R410A
-5 101 50 6.8 30.6 4.5 0.07 79.6 100 50.4 HFO- HFC- HFC- 1234yf 32
152a 50 45 5 -1 95 45 5.6 23.3 4.2 4.00 80.5 92 55.9 45 50 5 -2 99
46 5.7 24.4 4.2 3.48 80.3 95 55.4 45 45 10 -1 97 45 5.4 22.8 4.2
4.26 80.4 92 56.5 40 50 10 -1 100 46 5.6 23.9 4.3 3.87 80.2 95
56.1
Results, Heating Mode
[0062] In heating mode, the compression system operates between a
refrigerant inlet temperature at the evaporator of -5.degree. C.
and a refrigerant inlet temperature at the condenser of 50.degree.
C. The system delivers heat at 45.degree. C.
[0063] The performance of the compositions according to the
invention in operating conditions in heating mode is given in Table
2. The values of the constituents (HFO-1234yf, HFC-32, HFC-152a)
for each composition are given as percentage by weight.
TABLE-US-00002 TABLE 2 Temp Temp outlet outlet T outlet % evap comp
cond evap P cond P Ratio efficiency % COP/ (.degree. C.) (.degree.
C.) (.degree. C.) (bar) (bar) (w/w) Shift comp CAP COPLorenz R410A
-5 101 50 6.8 30.6 4.5 0.07 79.6 100 58.8 HFO- HFC- HFC- 1234yf 32
152a 45 50 5 -2 99 46 5.7 24.4 4.2 3.48 80.3 92 63.1 40 50 10 -1
100 46 5.6 23.9 4.3 3.87 80.2 91 63.6
Results, Low-Temperature Refrigeration
[0064] In low-temperature refrigeration mode, the compression
system operates between a refrigerant inlet temperature at the
evaporator of -30.degree. C. and a refrigerant inlet temperature at
the condenser of 40.degree. C. The system delivers cold at
-25.degree. C.
[0065] The performance of the compositions according to the
invention in operating conditions in refrigeration mode is given in
Table 3. The values of the constituents (HFO-1234yf, HFC-32,
HFC-152a) for each composition are given as percentage by
weight.
TABLE-US-00003 TABLE 3 Temp Temp outlet outlet T outlet % evap comp
cond evap P cond P Ratio efficiency % COP/ (.degree. C.) (.degree.
C.) (.degree. C.) (bar) (bar) (w/w) Shift comp CAP COPLorenz R410A
-30 149 40 2.7 24.2 9.0 0.06 52.3 100 33.0 HFO- HFC- HFC- 1234yf 32
152a 45 50 5 -27 137 36 2.3 19.1 8.4 3.35 56.9 93 38.8 40 50 10 -26
140 35 2.2 18.6 8.5 3.73 56.4 93 38.9
* * * * *