The present invention relates to the use of binary compositions of 2,3,3,3-tetrafluoropropene and difluoromethane as heat transfer fluids.
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).
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.
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.
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.
Moreover, the mixture R-404A consisting of 44 wt. % of pentafluoroethane, 52 wt. % of trifluoroethane and 4 wt. % of HFC-134a is widely used as refrigerant for large areas (supermarkets) and in refrigerated transport. However, this mixture has a GWP of 3900.
Document JP 4110388 describes the use of hydrofluoropropenes of formula C3HmFn, with m, n representing an integer between 1 and 5 inclusive and m+n=6, as heat transfer fluids, in particular tetrafluoropropene and trifluoropropene.
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.
Document WO 2006/094303 discloses an azeotropic composition containing 7.4 wt. % of 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 92.6 wt. % of difluoromethane (HFC-32). This document also discloses quasi-azeotropic compositions containing from 1 to 57 wt. % of 2,3,3,3-tetrafluoropropene and from 43 to 99 wt. % of difluoromethane.
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.
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.
There are various transfer modes:
The applicant has now discovered that binary compositions of 2,3,3,3-tetrafluoropropene and difluoromethane are particularly advantageous as heat transfer fluid in compression systems for low-temperature and medium-temperature refrigeration, with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.
Thus, these compositions can be used as heat transfer fluid in the refrigeration of refrigerated vehicles, in food storage and in industry (chemical industry, food industry etc.) with exchangers in countercurrent mode or in crossed-current mode with countercurrent tendency.
A first object of the present invention relates to the use of binary compositions of 2,3,3,3-tetrafluoropropene and difluoromethane as heat transfer fluid in compression systems for low-temperature and medium-temperature refrigeration, with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.
Low-temperature and medium-temperature refrigeration means the range from −45° C. to −10° C. at the evaporator.
Preferably, the binary compositions of 2,3,3,3-tetrafluoropropene and difluoromethane contain essentially from 61 to 85 wt. % of 2,3,3,3-tetrafluoropropene and from 15 to 39 wt. % of difluoromethane.
Advantageously, binary compositions contain essentially from 70 to 79 wt. % of 2,3,3,3-tetrafluoropropene and from 21 to 30 wt. % of difluoromethane.
The binary compositions used in the present invention have both a zero ODP and a low GWP. The coefficient of performance (COP: ratio of the cold power to the electricity consumption of a refrigerator) of these binary compositions in exchangers in countercurrent mode is higher than for the compositions currently used in low-temperature and medium-temperature refrigeration. Taking into account the pressure level at the condenser, it is not necessary to develop new compressors; the compressors currently on the market may be suitable.
The binary compositions used in the present invention can replace R-404A and R-407C (ternary mixture containing 52 wt. % of HFC-134a, 25 wt. % of pentafluoroethane and 23 wt. % of difluoromethane) in compression-type heat-transfer systems with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.
The binary compositions used according to the present invention can be stabilized. The amount of stabilizer preferably represents at most 5 wt. % relative to the binary composition.
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.
A second object of the present invention relates to a method of heat transfer in compression systems for low- and medium-temperature refrigeration in which binary compositions of 2,3,3,3-tetrafluoropropene and difluoromethane, as defined above, are used as refrigerant with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.
The method according to the present invention can be employed in the presence of lubricants such as mineral oil, alkylbenzene, polyalkylene glycol, polyol ester and polyvinyl ether.
Experimental Section
Tools for Calculation
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.
The data required for each pure substance are:
The data for HFC-32 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:
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 Binary Interaction of HFC-32/HFO-1234yf:
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.
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 ROLSI™ 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).
The measurements of liquid-vapor equilibrium on the HFC-32/HFO-1234yf binary mixture are performed for the following isotherms: −10° C., 30° C. and 70° C.
Compression System
Consider a compression system equipped with an evaporator and countercurrent condenser, a screw compressor and a pressure reducing valve.
The system functions with 15° C. of superheating and 5° C. of supercooling. The minimum temperature difference between the secondary fluid and the refrigerant is considered to be of the order of 5° C.
The isentropic efficiency of the compressors is a function of the compression ratio. This efficiency is calculated from the following equation:
For a screw compressor, the constants a, b, c, d and e in equation (1) of isentropic efficiency are calculated on the basis of the standard data published in the Handbook “Handbook of air conditioning and refrigeration”, page 11.52.
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.
The Lorenz coefficient of performance (COPLorenz) is a reference coefficient of performance. It is a function of temperature and is used for comparing the COPs of different fluids.
The Lorenz coefficient of performance is defined as follows:
(The Temperatures T are in K)
Tmeancondenser=Tinletcondenser−Toutletcondenser (2)
Tmeanevaporator=Toutletevaporator−Tinletevaporator (3)
The COPLorenz in the case of air conditioning and refrigeration is:
The Lorenz COP in the Case of Heating is:
For each composition, the coefficient of performance of the Lorenz cycle is calculated as a function of the corresponding temperatures.
% COP/COPLorenz is the ratio of the COP of the system relative to the COP of the corresponding Lorenz cycle.
Results, Low-Temperature Refrigeration Mode
In low-temperature mode, the compression system operates between a refrigerant inlet temperature at the evaporator of −30° C. and a refrigerant inlet temperature at the condenser of 40° C. The system delivers cold at −25° C.
The performance of the compositions according to the invention in low-temperature operating conditions is given in Table 1. The values of the constituents (HFO-1234yf, HFC-32) for each composition are given as percentage by weight.
Results, Medium-Temperature Refrigeration Mode
In medium-temperature mode, the compression system operates between a refrigerant inlet temperature at the evaporator of −15° C. and a refrigerant inlet temperature at the condenser of 35° C. The system delivers cold at −10° C.
The performance of the binary compositions in medium-temperature operating conditions is given in Table 2. The values of the constituents (HFO-1234yf, HFC-32) for each composition are given as percentage by weight.
Number | Date | Country | Kind |
---|---|---|---|
09 56242 | Sep 2009 | FR | national |
The present application is a divisional of U.S. application Ser. No. 13/391,405, now U.S. Pat. No. 9,039,922 filed on Feb. 29, 2012, which is a U.S. National Stage of International Application No. PCT/FR2010/051726, filed on Aug. 17, 2010, which claims the benefit of French Application No. 09.56242, filed on Sep. 11, 2009. The entire contents of each of U.S. application Ser. No. 13/391,405, International Application No. PCT/FR2010/051726, and French Application No. 09.56242 are hereby incorporated herein by reference in their entirety.
Number | Name | Date | Kind |
---|---|---|---|
6176102 | Novak et al. | Jan 2001 | B1 |
6503417 | Bivens | Jan 2003 | B1 |
8070977 | Rached | Dec 2011 | B2 |
8075798 | Rached | Dec 2011 | B2 |
8246850 | Rached | Aug 2012 | B2 |
8252198 | Rached | Aug 2012 | B2 |
8557135 | Rached | Oct 2013 | B2 |
8808569 | Rached | Aug 2014 | B2 |
8858824 | Boussand | Oct 2014 | B2 |
8858825 | Guerin et al. | Oct 2014 | B2 |
8992793 | Sato | Mar 2015 | B2 |
9011711 | Rached | Apr 2015 | B2 |
9028706 | Rached et al. | May 2015 | B2 |
9039922 | Rached | May 2015 | B2 |
9046348 | Abbas | Jun 2015 | B2 |
9057010 | Rached | Jun 2015 | B2 |
9127191 | Rached | Sep 2015 | B2 |
9133379 | Rached | Sep 2015 | B2 |
9175203 | Rached | Nov 2015 | B2 |
9267064 | Rached | Feb 2016 | B2 |
9315708 | Guerin et al. | Apr 2016 | B2 |
9359540 | Rached | Jun 2016 | B2 |
9399726 | Rached | Jul 2016 | B2 |
9505968 | Rached | Nov 2016 | B2 |
9512343 | 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 |
9683154 | Rached | Jun 2017 | B2 |
9683155 | Deur-Bert et al. | Jun 2017 | B2 |
9683157 | Rached | Jun 2017 | B2 |
9758709 | Shibanuma et al. | Sep 2017 | B2 |
9845419 | Yanna Motta 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 |
10023780 | Guerin et al. | Jul 2018 | B2 |
10035938 | Rached | Jul 2018 | B2 |
20060243944 | Minor et al. | Nov 2006 | A1 |
20070069175 | Thomas et al. | Mar 2007 | A1 |
20080184731 | Sienel et al. | Aug 2008 | A1 |
20080230738 | Minor et al. | Sep 2008 | A1 |
20080314073 | Minor | Dec 2008 | A1 |
20090120619 | Sievert | May 2009 | A1 |
20090267019 | Motta et al. | Oct 2009 | A1 |
20090314015 | Minor et al. | Dec 2009 | A1 |
20100044619 | Hulse et al. | Feb 2010 | A1 |
20100122545 | Minor et al. | May 2010 | A1 |
20100186432 | Perti et al. | Jul 2010 | A1 |
20100319377 | Moriwaki et al. | Dec 2010 | A1 |
20100326129 | Moriwaki et al. | Dec 2010 | A1 |
20110084228 | Rached | Apr 2011 | A1 |
20110089366 | Rached | Apr 2011 | A1 |
20110095224 | Rached | Apr 2011 | A1 |
20110186772 | Rached | Aug 2011 | A1 |
20110219791 | Rached | Sep 2011 | A1 |
20110219792 | Rached | Sep 2011 | A1 |
20110240254 | Rached | Oct 2011 | A1 |
20110284181 | Rached | Nov 2011 | A1 |
20120049104 | Rached | Mar 2012 | A1 |
20120056123 | Rached | Mar 2012 | A1 |
20120068105 | Rached et al. | Mar 2012 | A1 |
20120097885 | Hulse et al. | Apr 2012 | A9 |
20120144857 | Rached | Jun 2012 | A1 |
20120151958 | Rached | Jun 2012 | A1 |
20120151959 | Rached | Jun 2012 | A1 |
20120153213 | Rached | Jun 2012 | A1 |
20120159982 | Rached | Jun 2012 | A1 |
20120161064 | Rached | Jun 2012 | A1 |
20120167615 | Rached | Jul 2012 | A1 |
20120205574 | Rached et al. | Aug 2012 | A1 |
20120255316 | Andre et al. | Oct 2012 | A1 |
20130055733 | Rached | Mar 2013 | A1 |
20130055738 | Rached | Mar 2013 | A1 |
20130055739 | Rached | Mar 2013 | A1 |
20130061613 | Rached | Mar 2013 | A1 |
20130092869 | Boussand | Apr 2013 | A1 |
20130096218 | Rached | Apr 2013 | A1 |
20130105724 | Boussand | May 2013 | A1 |
20130186114 | Guerin et al. | Jul 2013 | A1 |
20140008565 | Rached et al. | Jan 2014 | A1 |
20140075969 | Guerin et al. | Mar 2014 | A1 |
20140166923 | Motta et al. | Jun 2014 | A1 |
20140318160 | Rached | Oct 2014 | A1 |
20140326017 | Rached | Nov 2014 | A1 |
20150027146 | Boussand | Jan 2015 | A1 |
20150152306 | Rached | Jun 2015 | A1 |
20150184051 | Rached | Jul 2015 | A1 |
20150184052 | Rached | Jul 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 |
20160024363 | Rached | Jan 2016 | A1 |
20160025394 | Rached | Jan 2016 | A1 |
20160115361 | Boussand | Apr 2016 | A1 |
20160122609 | Rached | May 2016 | A1 |
20160194541 | Guerin et al. | Jul 2016 | A1 |
20160244652 | Rached | Aug 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 |
20180134936 | Rached | May 2018 | A1 |
20180148395 | Rached et al. | May 2018 | A1 |
20180244970 | Rached | Aug 2018 | A1 |
20180282603 | Guerin | Oct 2018 | A1 |
Number | Date | Country |
---|---|---|
2149592 | Feb 2010 | EP |
2 246 649 | Nov 2010 | EP |
2182956 | Dec 1973 | FR |
2 256 381 | Jul 1975 | FR |
2256381 | Jul 1975 | FR |
2 936 806 | Apr 2010 | FR |
2 936 807 | Apr 2010 | FR |
2000-161805 | Jun 2000 | JP |
2008-134031 | Jun 2008 | JP |
4110388 | Jul 2008 | JP |
2008-531836 | Aug 2008 | JP |
2009-532520 | Sep 2009 | JP |
2009-222362 | Oct 2009 | JP |
2009-228984 | Oct 2009 | JP |
2009-257601 | Oct 2009 | JP |
2009-257655 | Nov 2009 | JP |
2010-002074 | Jan 2010 | JP |
2010-047754 | Mar 2010 | JP |
2010-526982 | Aug 2010 | JP |
2189544 | Sep 2002 | RU |
WO 2004037913 | May 2004 | WO |
WO 2005105947 | Nov 2005 | WO |
WO 2005105947 | Nov 2005 | WO |
WO 2006094303 | Sep 2006 | WO |
WO 2006101563 | Sep 2006 | WO |
WO 2006101563 | Sep 2006 | WO |
WO 2007126414 | Nov 2007 | WO |
WO 2007126414 | Nov 2007 | WO |
WO 2008027555 | Mar 2008 | WO |
WO 2008027555 | Mar 2008 | WO |
WO 2008085314 | Jul 2008 | WO |
WO 2008140809 | Nov 2008 | WO |
WO 2009107364 | Sep 2009 | WO |
WO 2009110228 | Sep 2009 | WO |
WO 2010000993 | Jan 2010 | WO |
WO 2010000993 | Jan 2010 | WO |
WO 2010000994 | Jan 2010 | WO |
WO 2010002016 | Jan 2010 | WO |
WO 2010002023 | Jan 2010 | WO |
WO 2010040928 | Apr 2010 | WO |
WO 2010059677 | May 2010 | WO |
WO 2010059677 | May 2010 | WO |
WO 2010061084 | Jun 2010 | WO |
WO 2010081990 | Jul 2010 | WO |
WO 2011030029 | Mar 2011 | WO |
WO 2011030031 | Mar 2011 | WO |
WO 2011030032 | Mar 2011 | WO |
WO 2011073934 | Jun 2011 | WO |
WO 2011141654 | Nov 2011 | WO |
WO 2011141654 | Nov 2011 | WO |
WO 2011141655 | Nov 2011 | WO |
WO 2011141655 | Nov 2011 | WO |
Entry |
---|
U.S. Appl. No. 14/651,855, Collier, et al. |
U.S. Appl. No. 14/651,925, Deur-Bert, et al. |
U.S. Appl. No. 14/655,500, Deur-Bert, et al. |
U.S. Appl. No. 14/823,430, Rached. |
U.S. Appl. No. 14/830,130, Rached. |
U.S. Appl. No. 14/772,950, Bonnet, et al. |
U.S. Appl. No. 14/873,855, Rached. |
U.S. Appl. No. 14/873,891, Rached. |
Collier, Bertrand, et al., U.S. Appl. No. 14/651,855 entitled “Composition Including 2,3,3,3-Tetrafluoropropene,” filed Jun. 12, 2015. |
Deur-Bert, Dominique, et al., U.S. Appl. No. 14/651,925 entitled “Composition Containing 2,3,3,3-Tetrafluoropropene and 1,2-Difluoroethylene,” filed Jun. 12, 2015. |
Deur-Bert, Dominique, et al., U.S. Appl. No. 14/655,500 entitled “Azeotropic or Quasi-Azeotropic Composition of Chloromethane,” filed Jun. 25, 2015. |
Rached, Wissam, U.S. Appl. No. 14/823,430 entitled “Use of Ternary Compositions,” filed Aug. 11, 2015. |
Rached, Wissam, U.S. Appl. No. 14/830,130 entitled “Binary Refrigerating Fluid,” filed Aug. 19, 2015. |
Bonnet, Phillippe, et al., U.S. Appl. No. 14/772,950 entitled “Composition Comprising HF and 2,3,3,3-Tetrafluoropropene,” filed Sep. 4, 2015. |
Rached, Wissam, U.S. Appl. No. 14/873,855 entitled “Heat Transfer Fluid,” filed Oct. 2, 2015. |
Rached, Wissam, U.S. Appl. No. 14/873,891 entitled “Ternary Compositions for Low-Capacity Refrigeration,” filed Oct. 2, 2015. |
U.S. Appl. No. 14/615,741, Rached. |
International Search Report issued in PCT/FR2010/051726, dated Jan. 25, 2011, EPO, Rijswijk, NL, 4 pages (English/French language versions). |
CAS Reg. No. 754-12-1, Nov. 16, 1984, 1 page. |
CAS Reg. No. 75-10-5, Nov. 16, 1984, 1 page. |
Rached, Wissam, U.S. Appl. No. 14/615,741 entitled “Heat Transfer Fluid Replacing R-410A,” filed Feb. 6, 2015. |
Third Party Observation in corresponding EP 2475735, submitted Mar. 13, 2016 with European Patent Office, 74 pages. |
Third Party Observation in corresponding Application No. EP 10 762 990.9, submitted Feb. 29, 2016 with European Patent Office, 40 pages. |
Bigot, G., et al., “Optimized Design of Heat Exchangers for “Reversible” Heat Pump Using R-407C,” Paper 463, Eighth International Refrigeration and Air Conditioning Conference at Purdue University, West Lafayette, IN, USA, Jul. 25-28, 2000, pp. 38-46, Purdue University, Purdue e-Pubs, http://docs.lib.purdue.edu/iracc/463. |
Liu, X., “Efficiency of Non-Azeotropic Refrigerant Cycle,” International Refrigeration and Air Conditioning Conference, Paper 396, 1998, pp. 108-114, Purdue University, Purdue e-Pubs, http://docs.lib.purdue.edu/iracc/396. |
U.S. Appl. No. 14/903,461, Guerin et al. |
U.S. Appl. No. 14/990,159, Boussand, et al. |
U.S. Appl. No. 14/992,387, Rached. |
U.S. Appl. No. 15/070,955, Guerin et al. |
U.S. Appl. No. 15/073,108, Rached et al. |
Guérin, Sophie, et al., U.S. Appl. No. 14/903,461 entitled, “2,3,3,3-Tetrafluoropropene Compositions Having Improved Miscibility,” filed Jan. 7, 2016. |
Boussand, Beatrice, et al., U.S. Appl. No. 14/990,159, entitled “Stable 2,3,3,3-Tetrafluoropropene Composition,” filed Jan. 7, 2016. |
Rached, Wissam, U.S. Appl. No. 14/992,387 entitled, “Ternary Compositions for High-Capacity Refrigeration,” filed Jan. 11, 2016. |
Guerin, Sophie, et al., U.S. Appl. No. 15/070,955, entitled “Heat-Transfer Compositions Exhibiting Improved Miscibility with the Lubricating Oil,” filed Mar. 15, 2016. |
Rached, Wissam, et al., U.S. Appl. No. 15/073,108 entitled “Stabilization of 1-Chloro-3,3,3-Trifluoropropene,” filed Mar. 17, 2016. |
U.S. Appl. No. 15/297,569, Rached et al. |
Rached, Wissam, et al., U.S. Appl. No. 15/297,569 entitled “Compositions Based on 2,3,3,3-Tetrafluoropropene,” filed Oct. 19, 2016. |
U.S. Appl. No. 15/189,936, Rached. |
U.S. Appl. No. 15/238,883, Rached. |
Rached, Wissam, U.S. Appl. No. 15/189,936 entitled “Use of Ternary Compositions,” filed Jun. 22, 2016. |
Rached, Wissam, U.S. Appl. No. 15/238,883 entitled “Heat Transfer Fluid Replacing R-134a,” filed Aug. 17, 2016. |
U.S. Appl. No. 15/481,815, Collier et al. |
U.S. Appl. No. 15/481,873, Deur-Bert et al. |
U.S. Appl. No. 15/490,541, Deur-Bert et al. |
U.S. Appl. No. 15/491,717, Rached. |
Notice of Opposition in corresponding EP Patent No. 2 475 735 B1, Opponent: Daikin Industries, Ltd., Feb. 24, 2017, 10 pages. |
Notice of Opposition to a European Patent in corresponding EP Patent No. 2 475 735 B1, Opponent: The Chemours Company FC, LLC, Feb. 17, 2017, 19 pages. |
Minor, Barbara Haviland, et al., Certified U.S. Appl. No. 61/116,029, filed Nov. 19, 2008, 60 pages, including cover page. |
Minor, Barbara Haviland, et al., Certified U.S. Appl. No. 61/180,201, filed May 21, 2009, 63 pages, including cover page. |
Rademacher, R., et al., “Vapor Compression Heat Pumps with Refrigerant Mixtures,” 2005, 4 pages, CRC Press, Taylor & Francis Group, Boca Raton, FL. |
Collier, Bertrand, et al., U.S. Appl. No. 15/481,815 entitled “Composition Including 2,3,3,3-Tetrafluoropropene,” filed Apr. 7, 2017. |
Deur-Bert, Dominque, et al. , U.S. Appl. No. 15/481,873 entitled “Azeotropic or Quasi-Azeotropic Composition? of Chloromethane,” filed Apr. 7, 2017. |
Deur-Bert, Dominique, et al., U.S. Appl. No. 15/490,541 entitled “Composition Containing 2,3,3,3-Tetrafluoropropene and 1,2-Difluoroethylene,” filed Apr. 18, 2017. |
Rached, Wissam, U.S. Appl. No. 15/491,717 entitled “Heat Transfer Method,” filed Apr. 19, 2017. |
U.S. Appl. No. 15/368,347, Rached. |
Rached, Wissam, et al., U.S. Appl. No. 15/368,347 entitled “Vehicle Heating and/or Air Conditioning Method”, filed Dec. 2, 2016. |
U.S. Appl. No. 15/396,855, Rached. |
Rached, Wissam, U.S. Appl. No. 15/396,855 entitled “Heat Transfer Fluid,” filed Jan. 3, 2017. |
U.S. Appl. No. 15/809,164, Rached. |
U.S. Appl. No. 15/820,996, Rached. |
Rached, Wissam, U.S. Appl. No. 15/809,164, entitled “Vehicle Heating and/or Air Conditioning Method,” filed Nov. 10, 2017. |
Rached, Wissam, U.S. Appl. No. 15/820,996, entitled “Method for Heating and/or Air Conditioning a Vehicle,” filed Nov. 22, 2017. |
U.S. Appl. No. 15/856,703, Rached. |
U.S. Appl. No. 15/878,794, Rached. |
Rached, Wissam, U.S. Appl. No. 15/856,703 entitled “Binary Refrigerating Fluid,” filed Dec. 28, 2017. |
Rached, Wissam, et al., U.S. Appl. No. 15/878,794 entitled “Stabilization of 1-Chloro-3,3,3-Trifluoropropene,” filed Jan. 24, 2018. |
U.S. Appl. No. 15/997,077, Guerin, et al. |
U.S. Appl. No. 16/034,539, Brossand. |
Guerin, Sophie, et al., U.S. Appl. No. 15/997,077 entitled “2,3,3,3-Tetrafluoropropene Compositions Having Improved Miscibility,” filed Jun. 4, 2018. |
Boussand, Beatrice, U.S. Appl. No. 16/034,539 entitled “Stable 2,3,3,3-Tetrafluoropropene Composition,” filed Jul. 13, 2018. |
U.S. Appl. No. 16/142,492, Rached. |
U.S. Appl. No. 16/143,518, Rached. |
Excerpt from Römpp Chemistry Encyclopedia, Editors: Prof. Dr. Jürgen Falbe, Prof Dr. Manfred Regitz, “binary system”, 1996, three pages including p. 432, Georg Thieme Verlang, Stuttgart, DE. |
Excerpt from Heat and Mass Transfer, Second, revised Edition, Editors: Hans Dieter Baehr, Karl Stephan, 2006, 21 pages, including pp. 40-57, Springer, Berlin-Heidelberg-New York. |
Rached, Wissam, U.S. Appl. No. 16/142,492 entitled “Heat Transfer Fluid,” filed Sep. 26, 2018. |
Rached, Wissam, U.S. Appl. No. 16/143,518 entitled “Binary Refrigerating Fluid,” filed Sep. 27, 2018. |
Number | Date | Country | |
---|---|---|---|
20150152307 A1 | Jun 2015 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13391405 | US | |
Child | 14615780 | US |