Heat transfer method

Information

  • Patent Grant
  • 10858561
  • Patent Number
    10,858,561
  • Date Filed
    Thursday, July 5, 2018
    5 years ago
  • Date Issued
    Tuesday, December 8, 2020
    3 years ago
Abstract
A method of heat transfer by means of a composition containing hydrochlorofluoroolefins. A heat transfer method including, successively, a step of evaporation of a coolant fluid, a compression step, a step of condensation of said fluid at a temperature of greater than or equal to 70° C. and a step of expansion of said fluid, characterized in that that coolant fluid includes at least one hydrochlorofluoroolefin.
Description
TECHNICAL FIELD

The present invention relates to a heat transfer process using a composition containing hydrochlorofluoroolefins. It relates more particularly to the use of a composition containing hydrochlorofluoroolefins in heat pumps.


BACKGROUND

The problems posed by substances which deplete the atmospheric ozone layer (ODP: ozone depletion potential) were tackled at 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 This protocol has been the subject of amendments which have required that CFCs be withdrawn and have extended regulatory control to other products.


The refrigeration industry and the air conditioning industry have invested a great deal in the replacement of these refrigerant fluids.


In the automotive industry, the air conditioning systems for vehicles sold in many countries have changed from a chlorofluorocarbon (CFC-12) refrigerant fluid to a hydrofluorocarbon (1,1,1,2-tetrafluoroethane: HFC-134a) refrigerant fluid 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 regarded as having 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.


As carbon dioxide is non-toxic and non-flammable and has a very low GWP, it has been proposed as a refrigerant fluid for air conditioning systems as a replacement for HFC-134a. However, there are several disadvantages to the use of carbon dioxide, related in particular to the very high pressure of the use thereof as a refrigerant fluid in existing devices and technologies.


Document JP 4110388 describes the use of hydro-fluoropropenes of formula C.sub.3H.sub.mF.sub.n with m and n representing an integer between 1 and 5 inclusive and m+n=6, as heat transfer fluids, in particular tetrafluoropropene and trifluoropropene.


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.


In document WO 2007/002625, fluorohaloalkenes having from to 6 carbon atoms, in particular tetrafluoropropenes, pentafluoropropenes and chlorotrifluoropropenes, have been described as capable of being used as a heat transfer fluid.


In the field of heat pumps, substitutes for dichlorotetrafluoroethane (HCFC-114), used under conditions of high condensing temperature, have been proposed. Thus, document U.S. Pat. No. 6,814,884 describes a composition comprising 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and at least one compound chosen from 1,1,1,2-tetrafluoroethane, pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). However, these compounds have a high GWP.







DETAILED DESCRIPTION

The applicant has now discovered that compositions containing hydrochlorofluoroolefins are very particularly suitable as heat transfer fluid in heat pumps, in particular heat pumps that operate at a high condensing temperature. Moreover, these compositions have a negligible ODP and a GWP below that of existing heat transfer fluids.


The term “hydrochlorofluoroolefins” is understood to mean olefins having from 3 to 4 carbon atoms that comprise one chlorine atom and at least one fluorine atom. Preferably, the chlorine atom is borne by the unsaturated carbon.


A heat pump is a thermodynamic device allowing the transfer of heat from the coldest medium to the hottest medium. The heat pumps used for heating are referred to as compression heat pumps and the operation is based on the principle of the compression cycle of fluids, referred to as refrigerant fluids. These heat pumps operate with compression systems comprising a single or several stage(s). At a given stage, when the refrigerant fluid is compressed and passes from the gaseous state to the liquid state, an exothermic reaction (condensation) takes place that produces heat. Conversely, if the fluid is expanded by passing it from the liquid state to the gaseous state, an endothermic reaction (evaporation) takes place, which produces a cold sensation. Everything therefore relies on the change of state of a fluid used in a closed circuit.


Each stage of a compression system comprises (i) a step of evaporation during which, in contact with heat drawn from the surroundings, the refrigerant fluid, by virtue of its low boiling point, changes from the liquid state to the gaseous state, (ii) a step of compression during which the gas from the preceding step is brought to high pressure, (iii) a step of condensation during which the gas will transmit its heat to the heating circuit; the refrigerant, still compressed, becomes liquid again and (iv) a step of expansion during which the pressure of the fluid is reduced. The fluid is ready for a new absorption of heat from the cold environment.


One subject of the present invention is a heat transfer process using a compression system having at least one stage successively comprising a step of evaporation of a refrigerant fluid, a step of compression, a step of condensation of said fluid at a temperature greater than or equal to 70° C. and a step of expansion of said fluid characterized in that the refrigerant fluid comprises at least one hydrochlorofluoroolefin.


Preferably, the condensing temperature of the refrigerant fluid is between 70 and 140° C., and advantageously between 95 and 125° C.


Preferably, the hydrochlorofluoroolefins comprise at least three fluorine atoms.


Particularly advantageous hydrochlorofluoroolefins are chlorotrifluoropropenes (HCFO-1233), in particular 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). The 1-chloro-3,3,3-trifluoropropene may be in either cis form or trans form.


Besides the hydrochlorofluoroolefin(s), the refrigerant fluid may comprise at least one hydrofluorocarbon.


As hydrofluorocarbons, mention may especially be made of 1,1,1,3,3-pentafluorobutane, 1,1,1,2-tetrafluoroethane, pentafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2,3-pentafluoropropane, 1,1,1,2,2-penta-fluoropropane and 1,1,1,2,3,3,3-heptafluoropropane.


The refrigerant fluid may also comprise at least one fluoroether, preferably at least one hydrofluoroether and advantageously at least one hydrofluoroether having from three to six carbon atoms.


As hydrofluoroethers, mention may especially be made of heptafluoromethoxypropane, nonafluoromethoxybutane and nonafluoroethoxybutane.


The hydrofluoroether is available in several isomeric forms such as 1,1,1,2,2,3,3,4,4-nonafluoroethoxybutane, 1,1,1,2,3,3-hexafluoro-2-(trifluoromethyl)-3-ethoxybutane, 1,1,1,2,2,3,3,4,4-nonafluoromethoxybutane and 1,1,1,2,3,3-hexafluoro-2-(trifluoromethyl)-3-methoxybutane.


The refrigerant fluid may also comprise at least one fluoroalkene having from 3 to 6 carbon atoms. Preferably, the fluoroalkene is chosen from fluoropropenes, in particular trifluoropropenes such as 1,1,1-trifluoropropene, tetrafluoropropenes such as 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene and fluorobutenes. Fluoromethylpropenes may be suitable.


Preferably, the refrigerant fluid comprises at least 10% by weight of hydrochlorofluoroolefins.


The refrigerant fluid used in the present invention may comprise a stabilizer of the hydrochlorofluoroolefin. The stabilizer represents at most 5% by weight relative to the total composition of the fluid.


As stabilizers, mention may especially be made of nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butylhydroguinone, 2,6-di-cert-butyl-4-methylphenol, epoxides (alkyl, optionally fluorinated or perfluorinated, or alkenyl or aromatic epoxides) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether or butylphenyl glycidyl ether, phosphites, phosphates, phosphonates, thiols and lactones.


The refrigerant used in the process according to the present invention may comprise lubricants such as mineral oil, alkylbenzene, polyalkylene glycol and polyvinyl ether.


EXPERIMENTAL SECTION

In what follows:


Evap P is the pressure at the evaporator


Cond P is the pressure at the condenser


T cond is the condensing temperature


Te comp is the compressor inlet temperature


Ratio: the compression ratio


T outlet comp is the compressor outlet temperature


COP: coefficient of performance and is defined, where a heat pump is concerned, as being the useful heat power provided the system over the power taken in or consumed by the system


CAP: volumetric capacity, heat capacity per unit volume (kJ/m.sup.3)


% CAP or COP is the ratio of the value of the CAP or COP of the fluid relative to that obtained with HCFC-114.


Example 1

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 10° C. and that at the condenser to 100° C. are given below.


For HCFC-114, the nominal operating pressure is 14.19 bar, the volumetric capacity is 785 kJ/m.sup.3 and the COP is 2.07 under the following operating conditions:


Isentropic efficiency of the compressor: 80%




















HCFO-
HFC-365mfc/



HCFC-114
HFC-365mfc
1233zd
HFC-227ea




















Temp evap (° C.)
10
10
10
10


T e comp
15
15
15
15


Evap P (kPa)
129
30
76


Cond P (kPa)
1419
590
1048


Ratio (p/p)
11.04
19.81
13.72
27.1


T cond (° C.)
100
100
100
100


T outlet comp
100
100
103


(° C.)


CAP (kJ/m3)
785
260
630
374


COP
2.07
2.30
2.42
2.40


% CAP
100
33
80
48


% COP
100
111
117
116









Example 2

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 50° C. and that at the condenser to 80° C. are given below.


For HCFC-114, the nominal operating pressure is 9.3 bar, the volumetric capacity is 3321 kJ/m.sup.3 and the COP is 8.19 under the following operating conditions:


Isentropic efficiency of the compressor: 80%

















HCFC-114
HFC-365mfc
HCFO-1233zd



















Temp outlet evap (° C.)
50
50
50


T e comp (° C.)
65
65
65


Evap P (kPa)
447
142
298


Cond P (kPa)
930
352
663


Ratio (p/p)
2.08
2.48
2.22


T cond (° C.)
80
80
80


T outlet comp (° C.)
90
87
94


CAP (kJ/m3)
3321
1394
2554


COP
8.19
8.60
8.53


% CAP
100
42
77


% COP
100
105
104









Example 3

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 50° C. and the temperature at the condenser to 95° C. are given below.


For HCFC-114, the nominal operating pressure is 12.82 bar, the volumetric capacity is 2976 kJ/m.sup.3 and the COP is 5.19 under the following operating conditions:


Isentropic efficiency of the compressor: 80%




















HCFO-




HCFC-114
HFC-365mfc
1233zd
HFO-1234yf




















Temp evap (° C.)
50
50
50
50


T e comp (° C.)
65
65
65
65


Evap P (kPa)
447
142
298
1283


Cond P (kPa)
1282
522
939
3345


Ratio (p/p)
2.87
3.67
3.15
2.61


T cond (° C.)
95
95
95
95


T outlet comp (° C.)
103
98
107
113


CAP (kJ/m3)
2976
1284
2379
4065


COP
5.19
5.56
5.56
2.80


% CAP
100
43
80
137


% COP
100
107
107
54









Example 4

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 50° C. and that at the condenser to 110° C. are given below.


For HCFC-114, the nominal operating pressure is 17.26 bar, the volumetric capacity is 2573 kJ/m.sup.3 and the COP is 3.56 under the following operating conditions:


Isentropic efficiency of the compressor: 80%

















HCFC-114
HFC-365mfc
HCFO-1233zd



















Temp evap (° C.)
50
50
50


T e comp (° C.)
65
65
65


Evap P (kPa)
447
142
298


Cond P (kPa)
1726
748
1294


Ratio (p/p)
3.86
5.26
4.34


T cond (° C.)
110
110
110


T outlet comp (° C.)
116
110
121


CAP (kJ/m3)
2573
1157
2172


COP
3.56
3.97
4.00


% CAP
100
45
84


% COP
100
111
112









Example 5

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 50° C. and that at the condenser to 120° C. are given below.


For HCFC-114, the nominal operating pressure is 20.82 bar, the volumetric capacity is 2257 kJ/m.sup.3 and the COP is 2.79 under the following operating conditions:


Isentropic efficiency of the compressor: 80%

















HCFC-114
HFC-365mfc
HCFO-1233zd



















Temp evap (° C.)
50
50
50


T e comp
65
65
65


Evap P (kPa)
447
142
298


Cond P (kPa)
2082
936
1581


Ratio (p/p)
4.66
6.58
5.30


T cond (° C.)
120
120
120


T outlet comp (° C.)
125
120
130


CAP (kJ/m3)
2257
1063
2015


COP
2.79
3.25
3.29


% CAP
100
47
89


% COP
100
116
118









Example 6

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 80° C. and that at the condenser to 110° C. are given below.


For HCFC-114, the nominal operating pressure is 17.26 bar, the volumetric capacity is 5475 kJ/m.sup.3 and the COP is 7.94 under the following operating conditions:


Isentropic efficiency of the compressor: 80%

















HCFC-114
HFC-365mfc
HCFO-1233zd



















Temp evap (° C.)
80
80
80


T e comp (° C.)
90
90
90


Evap P (kPa)
930
352
663


Cond P (kPa)
1726
748
1294


Ratio (p/p)
1.86
2.12
1.95


T cond (° C.)
110
110
110


T outlet comp (° C.)
116
111
117


CAP (kJ/m3)
5475
2872
4705


COP
7.94
8.83
8.72


% CAP
100
52
86


% COP
100
111
110









Example 7

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 80° C. and that at the condenser to 120° C. are given below.


For HCFC-114, the nominal operating pressure is 20.82 bar, the volumetric capacity is 4810 kJ/m.sup.3 and the COP is 5.45 under the following operating conditions:


Isentropic efficiency of the compressor: 80%

















HCFC-114
HFC-365mfc
HCFO-1233zd



















Temp evap (° C.)
80
80
80


T e comp (° C.)
90
90
90


Evap P (kPa)
930
352
663


Cond P (kPa)
2082
936
1581


Ratio (p/p)
2.24
2.66
2.38


T cond (° C.)
120
120
120


T outlet comp (° C.)
126
120
127


CAP (kJ/m3)
4810
2648
4360


COP
5.45
6.36
6.24


% CAP
100
55
91


% COP
100
117
114









Example 8

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 80° C. and that at the condenser to 130° C. are given below.


For HCFC-114, the nominal operating pressure is 24.92 bar, the volumetric capacity is 4027 kJ/m.sup.3 and the COP is 3.79 under the following operating conditions:


Isentropic efficiency of the compressor: 80%

















HCFC-114
HFC-365mfc
HCFO-1233zd



















Temp evap (° C.)
80
80
80


T e comp (° C.)
90
90
90


Evap P (kPa)
930
352
663


Cond P (kPa)
2492
1157
1913


Ratio (p/p)
2.68
3.28
2.88


T cond (° C.)
130
130
130


T outlet comp (° C.)
136
130
136


CAP (kJ/m3)
4027
2403
3967


COP
3.79
4.81
4.71


% CAP
100
60
99


% COP
100
127
124









Example 9

The performances of the refrigerant fluid under the heat pump operating conditions and by setting the temperature at the evaporator to 80° C. and that at the condenser to 140° C. are given below.


For HCFC-114, the nominal operating pressure is 29.61 bar, the volumetric capacity is 2971 kJ/m.sup.3 and the COP is 2.46 under the following operating conditions:


Isentropic efficiency of the compressor: 80%

















HCFC-114
HFC-365mfc
HCFO-1233zd



















Temp evap (° C.)
80
80
80


T e comp (° C.)
90
90
90


Evap P (kPa)
930
352
663


Cond P (kPa)
2961
1417
2295


Ratio (p/p)
3.19
4.02
3.46


T cond (° C.)
140
140
140


T outlet comp (° C.)
147
140
147


CAP (kJ/m3)
2971
2134
3520


COP
2.46
3.73
3.62


% CAP
100
72
118


% COP
100
152
147








Claims
  • 1. A heat transfer process using a compression system comprising successively a step of evaporation of a refrigerant fluid, a step of compression of said refrigerant fluid, a step of condensation of said refrigerant fluid at a temperature greater than or equal to 110° C. and a step of expansion of said refrigerant fluid, wherein the refrigerant comprises at least 10% by weight of trans-1-chloro-3,3,3-trifluoropropene and at least 10% by weight a fluoroalkene.
  • 2. The process as claimed in claim 1, wherein the temperature is between 110 and 140° C.
  • 3. The process as claimed in claim 1, wherein the refrigerant fluid comprises at least one hydrofluoroether.
  • 4. The process as claimed in claim 1, wherein the temperature is between 110 and 125° C.
  • 5. The process as claimed in claim 1, wherein the refrigerant fluid comprises at least 10% by weight a hydrofluorocarbon.
  • 6. The process as claimed in claim 1, wherein the temperature is between 120 and 140° C.
  • 7. The process as claimed in claim 1, wherein the temperature is between 130 and 140° C.
  • 8. A heat transfer process using a compression system comprising successively a step of evaporation of a refrigerant fluid, a step of compression of said refrigerant fluid, a step of condensation of said refrigerant fluid at a temperature greater than or equal to 110° C. and a step of expansion of said refrigerant, wherein the refrigerant comprises trans-1-chloro-3,3,3-trifluoropropene.
  • 9. The process as claimed in claim 8, wherein the temperature is greater than or equal to 130° C.
  • 10. The process as claimed in claim 8, wherein the temperature is greater than or equal to 120° C.
  • 11. The process as claimed in claim 8, wherein the refrigerant fluid comprises at least one hydrofluorocarbon.
  • 12. The process as claimed in claim 8, wherein the refrigerant fluid comprises at least one hydrofluoroether.
  • 13. The process as claimed in claim 8, wherein the refrigerant fluid comprises at least one fluoroalkene.
Priority Claims (1)
Number Date Country Kind
08 57032 Oct 2008 FR national
CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No. 13/122,890, filed on Apr. 6, 2011, which is a U.S. National stage of International Application No. PCT/FR2009/051943, filed on Oct. 13, 2009, which claims the benefit of French Application No. 0857032, filed on Oct. 16, 2008. The entire contents of each of U.S. application Ser. No. 13/122,890, International Application No. PCT/FR2009/051943, and French Application No. 0857032 are hereby incorporated herein by reference in their entirety.

US Referenced Citations (215)
Number Name Date Kind
5065990 Durfee Nov 1991 A
5363674 Powell Nov 1994 A
6013846 Wismer et al. Jan 2000 A
6646020 Nyberg et al. Nov 2003 B2
6814884 Jannick et al. Nov 2004 B2
7438826 Chen et al. Oct 2008 B1
7442321 Chen et al. Oct 2008 B1
7674756 Johnson Mar 2010 B2
7795480 Merkel et al. Sep 2010 B2
8070977 Rached Dec 2011 B2
8075798 Rached Dec 2011 B2
8217208 Hulse et al. Jul 2012 B2
8246850 Rached Aug 2012 B2
8252198 Rached Aug 2012 B2
8323524 Flynn et al. Dec 2012 B2
8450537 Rao et al. May 2013 B2
8454853 Van Horn Jun 2013 B2
8541478 Singh et al. Sep 2013 B2
8557135 Rached Oct 2013 B2
8790539 Abbas Jul 2014 B2
8808569 Rached Aug 2014 B2
8858824 Boussand Oct 2014 B2
8858825 Guerin et al. Oct 2014 B2
9011711 Rached Apr 2015 B2
9028706 Rached et al. May 2015 B2
9039922 Rached May 2015 B2
9127191 Rached Sep 2015 B2
9133379 Rached Sep 2015 B2
9157018 Rached et al. Oct 2015 B2
9175203 Rached Nov 2015 B2
9255045 Pigamo et al. Feb 2016 B2
9267064 Rached Feb 2016 B2
9267065 Van Horn Feb 2016 B2
9279074 Rached Mar 2016 B2
9315708 Guerin et al. Apr 2016 B2
9399726 Rached Jul 2016 B2
9505968 Rached Nov 2016 B2
9512343 Rached et al. Dec 2016 B2
9528038 Rached et al. Dec 2016 B2
9599381 Rached Mar 2017 B2
9650551 Collier et al. May 2017 B2
9650553 Deur-Bert et al. May 2017 B2
9663697 Rached May 2017 B2
9676984 Guerin et al. Jun 2017 B2
9683155 Deur-Bert et al. Jun 2017 B2
9683157 Rached Jun 2017 B2
9834499 Pigamo et al. Dec 2017 B2
9884984 Rached Feb 2018 B2
9908828 Rached et al. Mar 2018 B2
9969918 Deur-Bert et al. May 2018 B2
9982178 Rached et al. May 2018 B2
10023780 Guerin et al. Jul 2018 B2
10035938 Rached Jul 2018 B2
10036285 Rached Jul 2018 B2
10077221 Bonnet et al. Sep 2018 B2
10119055 Boussand Nov 2018 B2
10125296 Rached Nov 2018 B2
10131829 Deur-Bert et al. Nov 2018 B2
10252913 Bonnet et al. Apr 2019 B2
10266465 Bonnet et al. Apr 2019 B2
10316231 Rached Jun 2019 B2
10343963 Bonnet Jul 2019 B2
10358592 Rached Jul 2019 B2
10377935 Guerin et al. Aug 2019 B2
10399918 Rached Sep 2019 B2
10407603 Rached et al. Sep 2019 B2
10427998 Pigamo et al. Oct 2019 B2
10450488 Boussand Oct 2019 B2
10532965 Pigamo et al. Jan 2020 B2
10604690 Collier et al. Mar 2020 B2
10618861 Rached Apr 2020 B2
10662357 Boussand May 2020 B2
10669465 Rached Jun 2020 B2
20040180978 Dreier Sep 2004 A1
20050156135 Minor et al. Jul 2005 A1
20050285079 Minor Dec 2005 A1
20060106263 Miller et al. May 2006 A1
20060142173 Johnson et al. Jun 2006 A1
20060266976 Minor et al. Nov 2006 A1
20070100173 Miller et al. May 2007 A1
20070100175 Miller et al. May 2007 A1
20070145325 Minor Jun 2007 A1
20080051612 Knapp et al. Feb 2008 A1
20080098755 Singh et al. May 2008 A1
20080125505 Bowman et al. May 2008 A1
20090095014 Sun et al. Apr 2009 A1
20090099274 Van Der Puy et al. Apr 2009 A1
20090127496 Rao et al. May 2009 A1
20090253820 Bowman et al. Oct 2009 A1
20090305876 Singh et al. Dec 2009 A1
20090318323 Johnson et al. Dec 2009 A1
20100004155 Ishihara et al. Jan 2010 A1
20100072415 Rao Mar 2010 A1
20100102273 Basu et al. Apr 2010 A1
20100105788 Chen et al. Apr 2010 A1
20100113629 Van Horn et al. May 2010 A1
20100154444 Hulse et al. Jun 2010 A1
20100181524 Elsheikh et al. Jul 2010 A1
20100187088 Merkel et al. Jul 2010 A1
20100237279 Hulse et al. Sep 2010 A1
20110037016 Singh et al. Feb 2011 A1
20110041529 Chen et al. Feb 2011 A1
20110084228 Rached Apr 2011 A1
20110095224 Rached Apr 2011 A1
20110112340 Smith et al. May 2011 A1
20110186772 Rached Aug 2011 A1
20110197602 Abbas et al. Aug 2011 A1
20110218369 Elsheikh et al. Sep 2011 A1
20110219791 Rached Sep 2011 A1
20110219792 Rached Sep 2011 A1
20110240254 Rached Oct 2011 A1
20110284181 Rached Nov 2011 A1
20110309287 Chen et al. Dec 2011 A1
20110309288 Chen et al. Dec 2011 A1
20110315915 Abbas et al. Dec 2011 A1
20120012591 Bowman et al. Jan 2012 A1
20120041239 Suzuki et al. Feb 2012 A1
20120049104 Rached Mar 2012 A1
20120053369 Hulse et al. Mar 2012 A1
20120053372 Hulse et al. Mar 2012 A1
20120056122 Hulse et al. Mar 2012 A1
20120056123 Rached Mar 2012 A1
20120068105 Rached et al. Mar 2012 A1
20120117990 Rached May 2012 A1
20120128964 Hulse May 2012 A1
20120138847 Van Horn et al. Jun 2012 A1
20120144857 Rached Jun 2012 A1
20120145955 Abbas et al. Jun 2012 A1
20120151958 Rached Jun 2012 A1
20120151959 Rached Jun 2012 A1
20120153213 Rached Jun 2012 A1
20120159982 Rached Jun 2012 A1
20120161063 Singh Jun 2012 A1
20120161064 Rached Jun 2012 A1
20120167615 Rached Jul 2012 A1
20120205574 Rached et al. Aug 2012 A1
20120226081 Elsheikh et al. Sep 2012 A1
20120329893 Abbas Dec 2012 A1
20130004435 Cook et al. Jan 2013 A1
20130037058 Abbas Feb 2013 A1
20130092869 Boussand Apr 2013 A1
20130105724 Boussand May 2013 A1
20130119300 Van Horn et al. May 2013 A1
20130186114 Guerin et al. Jul 2013 A1
20130231399 Basu et al. Sep 2013 A9
20140008565 Rached et al. Jan 2014 A1
20140012052 Pham et al. Jan 2014 A1
20140070129 Kennoy et al. Mar 2014 A1
20140075969 Guerin et al. Mar 2014 A1
20140318160 Rached Oct 2014 A1
20140326017 Rached Nov 2014 A1
20150027146 Boussand Jan 2015 A1
20150034523 Kopkalli et al. Feb 2015 A1
20150152235 Abbas Jun 2015 A1
20150152306 Rached Jun 2015 A1
20150152307 Rached Jun 2015 A1
20150197467 Pigamo et al. Jul 2015 A1
20150231527 Singh Aug 2015 A1
20150322317 Collier et al. Nov 2015 A1
20150322321 Deur-Bert et al. Nov 2015 A1
20150344761 Rached Dec 2015 A1
20150353799 Deur-Bert et al. Dec 2015 A1
20150353802 Rached Dec 2015 A1
20160009555 Bonnet et al. Jan 2016 A1
20160009973 Rached et al. Jan 2016 A1
20160023034 Elsheikh et al. Jan 2016 A1
20160023176 Bonnet et al. Jan 2016 A1
20160023974 Bonnet et al. Jan 2016 A1
20160024363 Rached Jan 2016 A1
20160025394 Rached Jan 2016 A1
20160031773 Bonnet et al. Feb 2016 A1
20160046548 Bonnet et al. Feb 2016 A1
20160115104 Pigamo et al. Apr 2016 A1
20160115361 Boussand Apr 2016 A1
20160122609 Rached May 2016 A1
20160194541 Guerin et al. Jul 2016 A1
20160244652 Rached Aug 2016 A1
20160257867 Chen et al. Sep 2016 A1
20160272561 Rached et al. Sep 2016 A1
20160298014 Rached Oct 2016 A1
20160355718 Rached Dec 2016 A1
20160376484 Guerin et al. Dec 2016 A1
20170037291 Rached et al. Feb 2017 A1
20170080773 Rached Mar 2017 A1
20170145276 Rached May 2017 A1
20170210960 Deur-Bert et al. Jul 2017 A1
20170210962 Collier et al. Jul 2017 A1
20170218241 Deur-Bert et al. Aug 2017 A1
20170218242 Rached Aug 2017 A1
20180086173 Rached Mar 2018 A1
20180093934 Pigamo et al. Apr 2018 A1
20180126348 Bonnet et al. May 2018 A1
20180134936 Rached May 2018 A1
20180148394 Pigamo et al. May 2018 A1
20180148395 Rached et al. May 2018 A1
20180244970 Rached Aug 2018 A1
20180282603 Guerin et al. Oct 2018 A1
20180320560 Rached Nov 2018 A1
20180327645 Boussand Nov 2018 A1
20180354875 Bonnet Dec 2018 A1
20190016937 Andre et al. Jan 2019 A1
20190023957 Rached Jan 2019 A1
20190040292 Rached Feb 2019 A1
20190048518 Wong et al. Feb 2019 A1
20190203094 Rached Jul 2019 A1
20190249057 Rached Aug 2019 A1
20190276721 Rached Sep 2019 A1
20190284500 Rached Sep 2019 A1
20190337874 Rached et al. Nov 2019 A1
20190359870 Rached Nov 2019 A1
20190367789 Rached Dec 2019 A1
20190375698 Pigamo et al. Dec 2019 A1
20200048518 Rached Feb 2020 A1
20200087555 Rached Mar 2020 A1
20200216734 Rached et al. Jul 2020 A1
Foreign Referenced Citations (35)
Number Date Country
101155892 Apr 2008 CN
0 940 382 Sep 1999 EP
S62-225860 Oct 1987 JP
H02-120338 May 1990 JP
H03-168566 Jul 1991 JP
H04-110388 Apr 1992 JP
H06-272978 Sep 1994 JP
2002-501035 Jan 2002 JP
2008-133438 Jun 2008 JP
2008-524433 Jul 2008 JP
2011-037912 Feb 2011 JP
2011-510119 Mar 2011 JP
2012-506944 Mar 2012 JP
WO 9937598 Jul 1999 WO
WO 0240613 May 2002 WO
WO 2004037913 May 2004 WO
WO 2004037913 May 2004 WO
WO 2006069362 Jun 2006 WO
WO 2006069362 Jun 2006 WO
WO 2007002625 Jan 2007 WO
WO 2007002625 Jan 2007 WO
WO 2007053736 May 2007 WO
WO 2008002500 Jan 2008 WO
WO 2009003165 Dec 2008 WO
WO 2009089511 Jul 2009 WO
WO 2009089511 Jul 2009 WO
WO 2009140231 Nov 2009 WO
WO 2010043807 Apr 2010 WO
WO 2010059493 May 2010 WO
WO 2010062572 Jun 2010 WO
WO 2010062572 Jun 2010 WO
WO 2010085397 Jul 2010 WO
WO 2010088196 Aug 2010 WO
WO 2010088196 Aug 2010 WO
WO 2014158663 Oct 2014 WO
Non-Patent Literature Citations (23)
Entry
U.S. Appl. No. 16/102,320, Bonnet, et al.
International Search Report issued in PCT/FR2009/051943, dated Feb. 8, 2010, 5 pages, European Patent Office, Rijswijk, NL (English and French versions).
Official Action issued in JP 2011-531537, dated Jan. 20, 2016, 7 pages, Japan Patent Office, JP.
Official Action issued in JP 2015-026010, dated Mar. 1, 2016, 6 pages (3 pages JP OA; 3 pages Machine English-language translation), Japanese Patent Office, JP.
Bonnet, Philippe, et al., U.S. Appl. No. 16/102,320 entitled “Composition Comprising HF and E-3,3,3-Trifluoro-1-Chloropropene,” filed Aug. 13, 2018.
U.S. Appl. No. 16/333,003, Rached.
Official Action issued in CN 201610607752.3, dated Sep. 26, 2018, 6 pages (English-language translation only), State Intellectual Property Office of the People's Republic of China, CN.
Zheng, Zuyi, Application of Heat Pump Technology in Air Conditioning, China Mechanical Press, 1st edition, Jul. 1998, five pages including page 9, title page, publisher information, and English-language translation of page 9.
Xiuling Yuan, Editor, Refrigeration and Air-Conditioning Apparatus, Xi'an Jiaotong University Press, 1st edition, Mar. 2001, four pages including page 37, title page, publisher information, and English-language translation of page 37.
Rached, Wissam, U.S. Appl. No. 16/333,003 entitled “Composition Comprising 1-Chloro-3,3,3-Trifluoropropene,” filed Mar. 13, 2019.
Notice of Opposition mailed in EP 2 334 750, Jan. 17, 2019, 15 pages, European Patent Office, Munich, DE.
Yamamoto, Hiroyasu, et al., “Compression Type Heat Pump”, Application and Economy of Heat Pump, Technical Report, No. 52, Chapter 4, Feb. 27, 1984, pp. 117-134 (22 pages including Partial English-language translation).
U.S. Appl. No. 16/545,294, Pigamo, et al.
Pigamo, Anne, et al., U.S. Appl. No. 16/545,294 entitled “Compositions Based on 1,1,3,3-Tetrachloropropene,” filed Aug. 20, 2019.
U.S. Appl. No. 16/641,024, Rached, et al.
Rached, Wissam, et al., U.S. Appl. No. 16/641,024, entitled “Composition on the Basis of Hydrochlorofluoroolefin and Mineral Oil,” filed Feb. 21, 2020.
“Earth's Atmosphere,” Concise Science Dictionary, 1984, three pages including p. 218, Oxford University Press, Oxford, England.
U.S. Appl. No. 14/615,900, Wissam Rached, filed Feb. 6, 2015, (Cited herein as US Patent Application Publication No. 2015/0152235 A1 of Jun. 4, 2015).
U.S. Appl. No. 16/102,320, Philippe Bonnet, Bertrand Collier, Dominique Deur-Bert and Laurent Wendlinger, filed Aug. 13, 2018.
U.S. Appl. No. 15/809,477, Anne Pigamo, John Wismer, Bertrand Collier and Philippe Bonnet, filed Nov. 10, 2017, (Cited herein as US Patent Application Publication No. 2018/0093934 A1 of Apr. 5, 2018).
U.S. Appl. No. 15/575,980, Anne Pigamo and Bertrand Collier, filed Nov. 21, 2017, (Cited herein as US Patent Application Publication No. 2018/0148394 A1 of May 31, 2018).
U.S. Appl. No. 16/641,024, Wissam Rached and Pascale Kindler, filed Feb. 21, 2020.
U.S. Appl. No. 16/514,241, Wissam Rached, Sophie Guérin, Pascale Kindler, filed Jul. 17, 2019, (Cited herein as US Patent Application Publication No. 2019/0337874 A1 of Nov. 7, 2019).
Related Publications (1)
Number Date Country
20190048241 A1 Feb 2019 US
Continuations (1)
Number Date Country
Parent 13122890 US
Child 16027743 US