巴西专利BR112012005251B1 Use of a binary composition and heat transfer process

专利PDF首页>>巴西专利

专利附录

专利说明

权利要求

类似技术

同族专利

引用文献

法律状态

优先权

专利摘要:
binary refrigerant fluid the present invention relates to binary compositions 2,3,3,3 tetrafluoropropene and difluoromethane and more particularly has as its object its heat transfer fluid in systems with compression with exchangers operating in countercurrent mode or in cross current with countercurrent tendency. it is also concerned with a heat transfer process.
公开号:BR112012005251B1
申请号:R112012005251-9
申请日:2010-08-17
公开日:2020-02-27
发明作者:Wissam Rached
申请人:Arkema France；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for USE OF A BINARY COMPOSITION AND HEAT TRANSFER PROCESS.
[0001] The present invention relates to binary compositions of the
2,3,3,3-tetrafluoro propene and difluoromethane and their uses as heat transfer fluids.
[0002] The problems presented by substances that deplete the atmospheric ozone layer (ODP: ozone depletion potential) were addressed in Montreal where the protocol was signed, imposing a reduction in the production and use of chlorofluoro carbides (CFC). This protocol constitutes the object of fines that imposed the abandonment of CFCs and extended the regulation to other products, including hydrochloride fluoro carbon (HCFC).
[0003] The refrigeration and air conditioning industry has invested a lot in replacing these refrigerants and this is how hydrofluoro carbides (HFCs) were commercialized.
[0004] In the automobile industry, the air conditioning systems of vehicles sold in many countries are passed from a refrigerant to chlorofluoro carbide (CFC-12) to that of hydrofluoro carbide (1,1,1,2 tetrafluoro ethane: HFC-134a) , less harmful to the ozone layer. However, in relation to the objectives set by the Kyoto protocol, HFC-134a (GWP = 1300) is considered to have a high heating power. The contribution to the greenhouse effect of a fluid is quantified by a criterion, the GWP (Global Warming Potentials) that summarizes the heating power, considering a reference value of 1 for carbon dioxide.
[0005] Carbon dioxide, being non-toxic, flammable and having a very low GWP, has been proposed as a refrigerant for air conditioning systems, replacing HFC-134a. However, the
Petition 870190110543, of 10/30/2019, p. 7/25
2/12 The use of carbon dioxide has several drawbacks, notably linked to the very high pressure of its use as a refrigerant in existing devices and technologies.
[0006] On the other hand, the R-404A mixture consisting of 44% by weight of pentafluoro ethane, 52% by weight of trifluoro ethane and 4% by weight of HFC-134a is widely used as a refrigerant for large surfaces (supermarket) ) and refrigerated transport. This mix, however, has a GWP of 3900.
[0007] JP 4110388 describes the use of hydrofluoro propenes of formula C3HmFn, with m, n representing an integer between 1 and 5 including + n = 6, as heat transfer fluids, in particular tetrafluoro propene and trifluoro propene.
[0008] WO2004 / 037913 discloses the use of compositions comprising at least one fluoroalkene, having three or four carbon atoms, notably pentafluoro propene and tetrafluoro propene, preferably having a maximum GWP of 150, as fluids of heat transfer.
[0009] WO 2006/094303 discloses an azeotropic composition containing 7.4% by weight of 2,3,3,3 tetrafluoro propene (HFO-1234yf) and 92.6% by weight of difluoromethane (HFC-32). That document also discloses quasi-azeotropic compositions containing 1 to 57% by weight of 2,3,3,3 tetrafluoro propene and 43 to 99% by weight of difluoro ethane.
[00010] A heat exchanger is a device that allows the transfer of thermal energy from one fluid to another, without mixing them. The thermal flow passes through the exchange surface that separates the fluids. Most of the time this method is applied to cool or heat a liquid or a gas that is impossible to cool or heat directly.
[00011] In compression systems, the thermal exchange between the fluid
Petition 870190110543, of 10/30/2019, p. 8/25
3/12 refrigerant and heat sources are made through heat-carrying fluids. These heat-carrying fluids are either gaseous (air in the air conditioner and refrigeration with direct expansion), liquid (water in domestic heat pumps, glycolated water) or diphasic.
[00012] There are different transfer modes:
- the two fluids are arranged in parallel and go in the same direction: co-current mode (antimetallic);
- the two fluids are arranged in parallel, but go in the opposite direction: countercurrent mode (methodical);
- the two fluids are positioned perpendicularly: cross-flow mode. The cross current may be of a co-current or counter-current tendency;
- one of the two fluids makes a half-turn in a wider conduit, which the second fluid passes through. This configuration is comparable to a co-current exchanger about half the length, and for the other half to a countercurrent exchanger: pinhead mode.
[00013] The applicant then discovered that binary compositions of the
2,3,3,3 tetrafluoro propene and difluoromethane are particularly interesting, as heat transfer fluid in compression refrigeration systems with exchangers, operating in countercurrent mode or in crosscurrent mode with a countercurrent tendency.
[00014] Thus, these compositions can be used as heat transfer fluid in heat pumps, possibly reversible up to a heating temperature of 95 ° C, in air conditioning, industrial air conditioning (paper, server room) in domestic air conditioning. household refrigeration and freezing, using systems with compression with countercurrent changers or
Petition 870190110543, of 10/30/2019, p. 9/25
4/12 in cross current mode with countercurrent tendency.
[00015] Thus, a first object of the present invention relates to the use of the binary compositions of 2,3,3,3-tetrafluoro propene and difluoromethane as heat transfer fluid in the compression refrigeration systems with countercurrent exchangers or in cross current mode with countercurrent tendency.
[00016] Preferably, the binary compositions of 2,3,3,3 tetrafluoro propene and difluoromethane are used as heat transfer fluid for the air conditioner and heat pump, with countercurrent or cross current mode exchangers. countercurrent trend.
[00017] The 2,3,3,3-tetrafluoro propene and difluoromethane binary compositions are preferably zeotropic and contain essentially 70 to 90% by weight of 2,3,3,3-tetrafluoro propene and 10 to 30% by weight of difluoromethane.
[00018] Preferably, the zeotropic compositions contain essentially 78 to 84% by weight of 2,3,3,3-tetrafluoro propene and 16 to 22% by weight of difluoromethane.
[00019] Advantageously preferred zeotropic compositions contain essentially 81 to 83% by weight of 2,3,3,3 tetrafluoro propene and 17 to 19% by weight of difluoromethane.
[00020] The binary compositions used in the present invention have, at the same time, a zero ODP and a low GWP. Its high critical temperature (> 90 ° C) allows its use in extreme conditions, namely very high ambient temperatures or to produce heat at a high temperature (in heat pumps). The coefficient of performance (COP: the relationship between the thermal power and the electrical consumption of a heat pump or air conditioner) of these binary compositions in countercurrent heat exchangers, is higher than the current refrigerant compositions. Considering the pressure level
Petition 870190110543, of 10/30/2019, p. 10/25
5/12 on condenser and compression rates, there is no need to develop new compressors; compressors existing in the marked can be convenient.
[00021] The binary compositions used in the present invention can replace R-404A and R-407C (ternary mixture containing 52% by weight of HFC-134a, 25% by weight of pentafluoro ethane and 23% by weight of difluoromethane) in systems from heat transfer to compression with exchangers operating in countercurrent mode or in cross current mode with countercurrent tendency.
[00022] In addition, binary zeotropic compositions can be used in compression systems provided with a composition variation device by controlled distillation. This device allows to improve the efficiency and to reduce the losses when starting and stopping the compressor.
[00023] Subtle binary compositions according to the present invention can be stabilized. The amount of stabilizer preferably represents a maximum of 5% by weight with respect to the binary composition.
[00024] As stabilizers, nitromethane, ascorbic acid, terephthalic acid, azoles, such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-ter-butyl-4-methyl phenol, epoxides (possibly fluorinated or perfluorinated alkyl or alkenyl or aromatic), such as n-butyl glycidyl ether, hexane diol diglycidyl ether, allyl glycidyl ether, butyl phenyl glycidyl ether, phosphites, phosphates, phosphonates, thiols and lactones.
[00025] A second object of the present invention relates to a heat transfer process, in which binary compositions of 2,3,3,3-tetrafluoro propene and difluoromethane, as defined above, are used as the refrigerant in systems with
Petition 870190110543, of 10/30/2019, p. 11/25
6/12 compression, using changers in countercurrent mode or in crosscurrent mode with countercurrent tendency. The process according to the present invention can be applied in the presence of lubricants, such as mineral oil, alkyl benzene, polyalkylene glycol, polyol ester and polyvinyl ether.
[00026] A third object of the present invention relates to a binary composition containing essentially 78 to 84% by weight of
2,3,3,3-tetrafluoro propene and from 16 to 22% by weight of difluoromethane. The preferred binary composition, according to the third object, contains essentially 81 to 83% by weight of 2,3,3,3-tetrafluoro propene and 17 to 19% by weight of difluoromethane.
[00027] Binary compositions, according to the third object of the present invention, can be stabilized. The amount of stabilizer preferably represents a maximum of 5% by weight with respect to the binary composition.
[00028] The stabilizer can be chosen from those mentioned above.
[00029] The composition according to the third object can be used as a heat transfer fluid.
[00030] A fourth object, according to the present invention, refers to a composition that comprises the binary composition, according to the third object, possibly stabilized, and at least one lubricant. The lubricant can be chosen from mineral oil, alkyl benzene, polyalkylene glycol, polyol ester and polyvinyl ether. EXPERIMENTAL PART
CALCULATION TOOLS [00031] The RK-Soave equation is used to calculate the densities, enthalpies, entropies and the vapor balance 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
Petition 870190110543, of 10/30/2019, p. 12/25
7/12 also the interaction coefficients for each binary.
[00032] The necessary data for each pure body are:
[00033] Boiling temperature, temperature and critical pressure, the pressure curve as a function of temperature, from the boiling point to the critical point, the saturated liquid and saturated vapor densities, as a function of temperature.
HFC-32 [00034] The data on HFC-32 are published in the ASHRAE Handbook 2005, chapter 20, and are also available under Refrop (Program developed by NIST to calculate the properties of refrigerants).
HFO-1234yf [00035] The data of the temperature-pressure curve of the HFO-1234yf are measured by the static method. The temperature and critical pressure are measured by a C80 calorimeter sold by Setaram. Densities, with saturation as a function of temperature, are measured by the densimeter technology with vibrating tube developed by the laboratories of the school of Mines of Paris.
Binary Interaction Coefficient of HFC-32 / HFO-1234yf:
[00036] The RK-Soave equation uses binary interaction coefficients to represent the behavior of products in mixtures. The coefficients are calculated according to the experimental data of liquid vapor balance.
[00037] The technique applied for the liquid vapor balance measures is the analytical static cell method. The balance cell comprises a saphir tube and is equipped with two electromagnetic ROLSITM samplers. It is immersed in a cryothermostat bath (HUBER HS40). A magnetic stirring with a rotating field drive at variable speed is used to accelerate the achievement of equilibrium. The analysis of the samples is done by chromatography (HP5890
Petition 870190110543, of 10/30/2019, p. 13/25
8/12 series !!) in gas phase, using a catarometer (TCD).
[00038] The liquid vapor balance measurements on the HFC32 / HFO-1234yf torque are performed by the following isotherms: -10 ° C, 30 ° C and 70 ° C.
COMPRESSION SYSTEM [00039] Consider a compression system equipped with a countercurrent evaporator and condenser, a screw compressor and a distender.
[00040] The system works with 15 ° C of superheat and 5 ° C of subcooling. The minimum temperature deviation between secondary fluid and refrigerant is considered to be around 5 ° C.
[00041] The isentropic performance of the compressors is a function of the compression rate. This yield is calculated according to the following equation:
Hisen = ab (Tc) ² - d / Te (1) [00042] For a screw compressor, the constants a, b, c, and d of equation (1) of the isentropic performance are calculated according to the standard data published in the Handbook Handbook of air conditioning and refrigeration, page 11.52. The performance coefficient (COP) is defined as the useful power supplied by the system over the power supplied or consumed by the system.
[00043] The performance coefficient (COP) and is defined as being the useful power supplied by the system over the power supplied or consumed by the system.
[00044] The Lorenz performance coefficient (COPLorenz) is a reference performance coefficient. It is a function of temperatures and is used to compare the COP of different fluids.
[00045] Lorenz's performance coefficient is defined as follows:
(T temperatures are in K)
Petition 870190110543, of 10/30/2019, p. 14/25
9/12

(2)
yspcrecto · '· (3) [00046] Lorenz's COP in the case of air conditioning and refrigeration:
COPlorenz - ríVípOreCDr iTjécJíE · (4) [00047] Lorenz's COP in case of heating:
and cDcUscssdor
COPlorenz = -----—------ y Cüi ^ CtoCSíLtor y Sl '^ ODreLtoF / 7 S £ Í5 (5) [00048] For each composition, the performance coefficient of the Lorenz cycle is calculated depending on the corresponding temperatures.
[00049] The% COP / COP Lorenz is the ratio of the system's COP to the corresponding Lorenz cycle COP.
RESULTS HEATING MODE [00050] In heating mode, the compression system operates between an inlet temperature of the refrigerant in the evaporator of -5 ° C and an inlet temperature of the refrigerant in the condenser of 50 ° C. The system provides heat at 45 ° C.
[00051] The performances of the compositions, according to the invention, under the heat pump operating conditions are given in Table 1. The values of the constituents (HFO-1234yf, HFC-32) for each composition are given in percentage by weight .
Petition 870190110543, of 10/30/2019, p. 15/25
TABLE 1
Temp. outputevap. (° C) Temp. output comp.(° C) T cond output (° C) Evap. P(Pub.) Cond P(Pub.) Rate(w / w) Glide Rend.Comp. % COP / COPLorenz R404A -5 77 50 5.2 23.0 4.4 0.38 79.7 57.7 HFO-1234yf HFC-3285 15 0 76 43 4.0 16.5 4.1 4.84 80.6 64.7 84 16 0 77 43 4.1 16.7 4.1 5.01 80.7 64.7 83 17 0 77 43 4.2 17.0 4.1 5.16 80.7 64.7 82 18 0 78 43 4.2 17.2 4.1 5.29 80.8 64.7 81 19 0 78 43 4.3 17.5 4.1 5.39 80.8 64.7 80 20 0 79 43 4.4 17.7 4.0 5.48 80.8 64.7 79 21 0 80 43 4.5 18.0 4.0 5.54 80.9 64.7 78 22 1 80 43 4.5 18.2 4.0 5.59 80.9 64.7
12/10
Petition 870190110543, of 10/30/2019, p. 16/25
12/11
RESULTS COOLING MODE [00052] In cooling mode, the compression system works between an inlet temperature of the refrigerant in the evaporator of -5 ° C and an inlet temperature of the refrigerant in the condenser of 50 ° C. The system supplies cold at 0 ° C.
[00053] The performances of the compositions, according to the invention, under cooling operating conditions are given in Table 2. The values of the constituents (HFO-1234yf, HFC-32) for each composition are given in percentage by weight.
Petition 870190110543, of 10/30/2019, p. 17/25
TABLE 2
Temp. evap output.(° C) Temp. output comp. (° C) T cond output(° C) Evap. P(Pub.) Cond P(Pub.) Rate(w / w) Glide Rend.Comp. % COP / COPLorenz R404A -5 77 50 5.2 23.0 4.4 0.38 79.7 47.9 HFO-1234yf HFC-3288 12 -1 75 44 3.7 15.7 4.2 4.20 80.3 55.9 87 13 -1 75 43 3.8 16.0 4.2 4.44 80.4 56.0 86 14 0 76 43 3.9 16.2 4.2 4.65 80.5 56.2 85 15 0 76 43 4.0 16.5 4.1 4.84 80.6 56.3 84 16 0 77 43 4.1 16.7 4.1 5.01 80.7 56.4 83 17 0 77 43 4.2 17.0 4.1 5.16 80.7 56.4 83 18 0 78 43 4.2 17.2 4.1 5.29 80, .8 56.5 81 19 0 78 43 4.3 17.5 4.0 5.39 80.8 56.5 80 20 0 79 43 4.4 17.7 4.0 5.48 80.8 56.5 79 21 1 80 43 4.5 18.0 4.0 5.54 80.9 56.6 78 22 1 804.5 18.25.59 80.9 56.6
12/12

权利要求:
Claims (9)
[1]
1. Use of a binary composition of 2,3,3,3 tetrafluoropropene, and difluoromethane, characterized by the fact that it is like heat transfer fluid in compression refrigeration systems, with counter-current or cross-current exchangers with a countercurrent tendency, in which the composition contains
70 to 90% by weight of 2,3,3,3 tetrafluoro propene and
10 to 30% by weight of difluoromethane.
[2]
2. Use according to claim 1, characterized by the fact that the composition contains
78 to 84% by weight of 2,3,3,3 tetrafluoropropene and
16 to 22% by weight of difluoromethane.
[3]
3. Use according to claim 1, characterized by the fact that the composition contains
81 to 83% by weight of 2,3,3,3 tetrafluoropropene and
17 to 19% by weight of difluoromethane.
[4]
Use according to any one of claims 1 to 3, characterized in that the binary composition is used as a heat transfer fluid for the air conditioner and heat pump.
[5]
5. Heat transfer process, characterized by the fact that it comprises using a binary composition of 2,3,3,3 tetrafluoro propene and difluoromethane, as a refrigerant in a system with compression with exchangers in countercurrent mode or in cross current mode with countercurrent trend.
[6]
6. Process, according to claim 5, characterized by the fact that the composition contains
70 to 90% by weight of 2,3,3,3 tetrafluoro propene and
Petition 870190110543, of 10/30/2019, p. 19/25
2/2
10 to 30% by weight of difluoromethane.
[7]
7. Process, according to claim 5, characterized by the fact that the composition contains
78 to 84% by weight of 2,3,3,3 tetrafluoro propene and
16 to 22% by weight of difluoromethane.
[8]
Process according to any one of claims 5 to 7, characterized in that the binary composition is stabilized.
[9]
Process according to any one of claims 5 to 8, characterized by the fact that it is applied in the presence of a lubricant.

类似技术:

公开号 | 公开日 | 专利标题

BR112012005251B1|2020-02-27|Use of a binary composition and heat transfer process

US9663697B2|2017-05-30|Use of ternary compositions

US9505968B2|2016-11-29|Ternary compositions for low-capacity refrigeration

US10316231B2|2019-06-11|Low-temperature and average-temperature refrigeration

US10035938B2|2018-07-31|Heat transfer fluid replacing R-134a

BR112012005350B1|2020-02-18|Use of ternary composition as heat transfer fluid and heat transfer process

BR112012005348B1|2020-02-27|HEAT TRANSFER FLUID IN REPLACEMENT OF R-410A

US9267064B2|2016-02-23|Ternary compositions for high-capacity refrigeration

同族专利:

公开号 | 公开日

CN102482561B|2014-12-24|

US20150353802A1|2015-12-10|

US20120151959A1|2012-06-21|

US20190023957A1|2019-01-24|

FR2950065B1|2012-02-03|

WO2011030026A1|2011-03-17|

JP2019214725A|2019-12-19|

US9133379B2|2015-09-15|

US9884984B2|2018-02-06|

CN104388048A|2015-03-04|

JP2017193711A|2017-10-26|

JP5801810B2|2015-10-28|

BR112012005251A2|2016-03-15|

RU2012114109A|2013-10-20|

EP2475734A1|2012-07-18|

CN102482561A|2012-05-30|

FR2950065A1|2011-03-18|

US20180134936A1|2018-05-17|

EP2475734B1|2021-04-07|

US10858562B2|2020-12-08|

ES2864828T3|2021-10-14|

JP6781308B2|2020-11-04|

PT2475734T|2021-04-26|

RU2543191C2|2015-02-27|

JP2016026248A|2016-02-12|

US10125296B2|2018-11-13|

JP2013504638A|2013-02-07|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

CH549772A|1972-04-29|1974-05-31|Bertrams Ag Hch|CROSS COUNTERFLOW HEAT EXCHANGER AND METHOD OF ITS MANUFACTURING.|

FR2256381A1|1973-12-27|1975-07-25|Tour Agenturer Ab|Arrangement for heating or cooling a flow medium - part of air currents diverted to a circuit containing e.g. ammonia in a heat exchanger|

US6503417B1|1998-04-13|2003-01-07|E. I. Du Pont De Nemours And Company|Ternary compositions of ammonia, pentafluoroethane and difluoromethane|

JP2000161805A|1998-11-27|2000-06-16|Daikin Ind Ltd|Refrigerating apparatus|

US6176102B1|1998-12-30|2001-01-23|Praxair Technology, Inc.|Method for providing refrigeration|

TR201908011T4|2002-10-25|2019-06-21|Honeywell Int Inc|Compositions containing fluorine-substituted olefins.|

US20040089839A1|2002-10-25|2004-05-13|Honeywell International, Inc.|Fluorinated alkene refrigerant compositions|

US7279451B2|2002-10-25|2007-10-09|Honeywell International Inc.|Compositions containing fluorine substituted olefins|

US20120097885A9|2003-10-27|2012-04-26|Honeywell International Inc.|Compositions Containing Difluoromethane and Fluorine Substituted Olefins|

US20140166923A1|2002-10-25|2014-06-19|Honeywell International Inc.|Compositions containing difluoromethane and fluorine substituted olefins|

JP4110388B2|2003-01-10|2008-07-02|荒川化学工業株式会社|Cleaning agent and rinsing agent for gold-plated parts, cleaning method and rinsing method|

US11214720B2|2009-07-29|2022-01-04|Honeywell International Inc.|Compositions containing difluoromethane and fluorine substituted olefins|

US9845419B2|2009-07-29|2017-12-19|Honeywell International Inc.|Low GWP heat transfer compositions containing difluoromethane and 1,3,3,3-tetrafluoropropene|

JP5770969B2|2008-07-30|2015-08-26|ハネウェル・インターナショナル・インコーポレーテッド|Composition containing difluoromethane and fluorine-substituted olefin|

JP2005202637A|2004-01-15|2005-07-28|Matsushita Electric Ind Co Ltd|Automatic vending machine|

US7569170B2|2005-03-04|2009-08-04|E.I. Du Pont De Nemours And Company|Compositions comprising a fluoroolefin|

US20060243944A1|2005-03-04|2006-11-02|Minor Barbara H|Compositions comprising a fluoroolefin|

JP4705157B2|2005-03-18|2011-06-22|キャリア・コマーシャル・リフリージレーション・インコーポレーテッド|Multi-element heat exchanger|

EP1763086A1|2005-09-09|2007-03-14|Interuniversitair Micro-Elektronica Centrum|Photovoltaic cell with thick silicon oxide and silicon nitride passivation and fabrication method|

EP2602299A2|2006-09-01|2013-06-12|E. I. du Pont de Nemours and Company|Method for circulating selected heat transfer fluids through a closed loop cycle|

JP2008134031A|2006-11-29|2008-06-12|Hitachi Appliances Inc|Refrigerating device using zeotropic refrigerant mixture|

WO2008085314A2|2006-12-19|2008-07-17|E. I. Du Pont De Nemours And Company|Dual row heat exchanger and automobile bumper incorporating the same|

EP3091320A1|2007-05-11|2016-11-09|The Chemours Company FC, LLC|A vapor compression heat transfer system|

KR101380581B1|2007-01-18|2014-04-01|삼성디스플레이 주식회사|Liquid crystal display panel having power supply line and liquid crystal display|

AR067115A1|2007-06-21|2009-09-30|Du Pont|METHOD FOR DETECTING LEAKS IN A HEAT TRANSFER SYSTEM|

JP2010534743A|2007-07-27|2010-11-11|イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー|Compositions containing fluoroolefins and uses thereof|

JP2009257652A|2008-02-29|2009-11-05|Daikin Ind Ltd|Refrigerating apparatus|

JP2009257655A|2008-03-04|2009-11-05|Daikin Ind Ltd|Refrigerating apparatus|

JP5176624B2|2008-03-18|2013-04-03|ダイキン工業株式会社|Refrigeration equipment|

JP2009228984A|2008-03-24|2009-10-08|Taiheiyo Cement Corp|Automatic coating removal device of combustion gas bleeding probe|

JP2009257743A|2008-03-25|2009-11-05|Daikin Ind Ltd|Refrigerating device|

JP2009257601A|2008-04-11|2009-11-05|Daikin Ind Ltd|Air conditioning device|

US8038899B2|2008-04-28|2011-10-18|Honeywell International Inc.|Refrigerant compositions having a siloxane solubilizing agent|

FR2932492B1|2008-06-11|2010-07-30|Arkema France|COMPOSITIONS BASED ON HYDROFLUOROOLEFINS|

FR2932494B1|2008-06-11|2011-02-25|Arkema France|COMPOSITIONS BASED ON HYDROFLUOROOLEFINS|

FR2932493B1|2008-06-11|2010-07-30|Arkema France|COMPOSITIONS BASED ON HYDROFLUOROOLEFINS|

JP2010002074A|2008-06-18|2010-01-07|Mitsubishi Electric Corp|Mixed refrigerant and refrigerating cycle device using the same|

WO2010002016A1|2008-07-01|2010-01-07|Daikin Industries, Ltd.|REFRIGERANT COMPOSITION COMPRISING DIFLUOROMETHANE AND 2,3,3,3-TETRAFLUOROPROPENE |

WO2010002023A1|2008-07-01|2010-01-07|Daikin Industries, Ltd.|REFRIGERANT COMPOSITION COMPRISING DIFLUOROMETHANE , 2,3,3,3-TETRAFLUOROPROPENE AND 1,1,1,2-TETRAFLUOROETHANE |

EP3093323A1|2008-07-30|2016-11-16|Honeywell International Inc.|Compositions containing difluoromethane and fluorine substituted|

FR2936806B1|2008-10-08|2012-08-31|Arkema France|REFRIGERANT FLUID|

US20170080773A1|2008-11-03|2017-03-23|Arkema France|Vehicle Heating and/or Air Conditioning Method|

FR2937906B1|2008-11-03|2010-11-19|Arkema France|METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE|

US20100122545A1|2008-11-19|2010-05-20|E. I. Du Pont De Nemours And Company|Tetrafluoropropene compositions and uses thereof|

EP2367601B1|2008-11-19|2015-10-28|E. I. du Pont de Nemours and Company|Tetrafluoropropene compositions and uses thereof|

FR2938550B1|2008-11-20|2010-11-12|Arkema France|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE|

FR2938551B1|2008-11-20|2010-11-12|Arkema France|METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE|

FR2941039B1|2009-01-14|2013-02-08|Arkema France|HEAT TRANSFER METHOD|

JP2010203759A|2009-02-04|2010-09-16|Panasonic Corp|Freezer|

FR2942237B1|2009-02-13|2013-01-04|Arkema France|METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE|

FR2950065B1|2009-09-11|2012-02-03|Arkema France|BINARY REFRIGERANT FLUID|

FR2950071B1|2009-09-11|2012-02-03|Arkema France|TERNARY COMPOSITIONS FOR LOW CAPACITY REFRIGERATION|

FR2950069B1|2009-09-11|2011-11-25|Arkema France|USE OF TERNARY COMPOSITIONS|

FR2950068B1|2009-09-11|2012-05-18|Arkema France|HEAT TRANSFER METHOD|

FR2950067B1|2009-09-11|2011-10-28|Arkema France|HEAT TRANSFER FLUID IN REPLACEMENT OF R-410A|

US10035938B2|2009-09-11|2018-07-31|Arkema France|Heat transfer fluid replacing R-134a|

FR2950066B1|2009-09-11|2011-10-28|Arkema France|LOW AND MEDIUM TEMPERATURE REFRIGERATION|

FR2950070B1|2009-09-11|2011-10-28|Arkema France|TERNARY COMPOSITIONS FOR HIGH CAPACITY REFRIGERATION|

FR2954342B1|2009-12-18|2012-03-16|Arkema France|HEAT TRANSFER FLUIDS WITH REDUCED FLAMMABILITY|

KR20120123354A|2009-12-21|2012-11-08|이 아이 듀폰 디 네모아 앤드 캄파니|Compositions comprising tetrafluoropropene and difluoromethane and uses thereof|

MX341131B|2010-01-27|2016-08-08|Daikin Ind Ltd|Refrigerant composition comprising difluoromethane and 2,3,3,3-tetrafluoropropene .|

FR2957083B1|2010-03-02|2015-12-11|Arkema France|HEAT TRANSFER FLUID FOR CENTRIFUGAL COMPRESSOR|

FR2959997B1|2010-05-11|2012-06-08|Arkema France|HEAT TRANSFER FLUIDS AND THEIR USE IN COUNTER-CURRENT HEAT EXCHANGERS|

FR2959999B1|2010-05-11|2012-07-20|Arkema France|HEAT TRANSFER FLUIDS AND THEIR USE IN COUNTER-CURRENT HEAT EXCHANGERS|

FR2959998B1|2010-05-11|2012-06-01|Arkema France|TERNARY HEAT TRANSFER FLUIDS COMPRISING DIFLUOROMETHANE, PENTAFLUOROETHANE AND TETRAFLUOROPROPENE|

CN106634851A|2010-06-22|2017-05-10|阿科玛股份有限公司|Heat transfer compositions of hydrofluorocarbons and a hydrofluoroolefin|

FR2962130B1|2010-06-30|2012-07-20|Arkema France|COMPOSITION BASED ON 2,3,3,3-TETRAFLUOROPROPENE|

FR2962442B1|2010-07-09|2016-02-26|Arkema France|STABLE 2,3,3,3-TETRAFLUOROPROPENE COMPOSITION|

FR2964975B1|2010-09-20|2012-08-24|Arkema France|COMPOSITION BASED ON 2,3,3,3-TETRAFLUOROPROPENE|

FR2971512B1|2011-02-10|2013-01-18|Arkema France|BINARY COMPOSITIONS OF 2,3,3,3-TETRAFLUOROPROPENE AND AMMONIA|

FR2974812B1|2011-05-04|2014-08-08|Arkema France|HEAT TRANSFER COMPOSITIONS HAVING IMPROVED MISCIBILITY WITH LUBRICATING OIL|

US20130093218A1|2011-10-14|2013-04-18|Lear Corporation|Seat Assembly Having a Folding Seat Bottom and Head Restraint|

FR2986007B1|2012-01-25|2015-01-23|Arkema France|HEAT TRANSFER COMPOSITIONS HAVING IMPROVED MISCIBILITY WITH LUBRICATING OIL|

FR2986236B1|2012-01-26|2014-01-10|Arkema France|HEAT TRANSFER COMPOSITIONS HAVING IMPROVED MISCIBILITY WITH LUBRICATING OIL|

KR101981035B1|2012-03-29|2019-08-28|제이엑스티지 에네루기 가부시키가이샤|Working fluid composition for refrigerator|

FR3000093B1|2012-12-26|2015-07-17|Arkema France|AZEOTROPIC OR QUASI-AZEOTROPIC COMPOSITION OF CHLOROMETHANE|

FR3000095B1|2012-12-26|2015-02-20|Arkema France|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE AND 1,2-DIFLUOROETHYLENE|

FR3000096B1|2012-12-26|2015-02-20|Arkema France|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE|

FR3003565B1|2013-03-20|2018-06-29|Arkema France|COMPOSITION COMPRISING HF AND 2,3,3,3-TETRAFLUOROPROPENE|

FR3008419B1|2013-07-11|2015-07-17|Arkema France|2,3,3,3-TETRAFLUOROPROPENE-BASED COMPOSITIONS HAVING IMPROVED MISCIBILITY|

FR3033791B1|2015-03-18|2017-04-14|Arkema France|STABILIZATION OF 1-CHLORO-3,3,3-TRIFLUOROPROPENE|

US10514296B2|2015-07-29|2019-12-24|Samsung Electronics Co., Ltd.|Spectrometer including metasurface|

BR112018067402A2|2016-02-29|2019-01-22|Chemours Co Fc Llc|composition, processes for generating cooling and heating, replacement methods, air conditioning or heat pump system and cooling system|

FR3057271B1|2016-10-10|2020-01-17|Arkema France|USE OF TETRAFLUOROPROPENE COMPOSITIONS|

FR3061905B1|2017-01-19|2019-05-17|Arkema France|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE|

FR3061906B1|2017-01-19|2019-03-15|Arkema France|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE|

JP6418284B1|2017-06-12|2018-11-07|ダイキン工業株式会社|Composition containing refrigerant, use thereof, refrigeration method using the same, and refrigerator including the same|

FR3070982B1|2017-09-12|2019-08-30|Arkema France|COMPOSITION BASED ON HYDROCHLOROFLUOROOLEFIN AND MINERAL OIL|FR2936806B1|2008-10-08|2012-08-31|Arkema France|REFRIGERANT FLUID|

FR2937328B1|2008-10-16|2010-11-12|Arkema France|HEAT TRANSFER METHOD|