• 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:
    heat transfer fluid to replace r-410a. the present invention relates to a heat transfer process, in which ternary compositions of 2,3,3,3 tetrafluoro propene, 1,1 – difluoro ethane and difluoro methane are used as heat transfer fluid in systems cooling system to replace the r-410a mixture.
    公开号:BR112012005348B1
    申请号:R112012005348-5
    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:

    Invention Patent Descriptive Report for R-410A REPLACEMENT HEAT TRANSFER FLUID. [0001] The present invention relates to the use of 2,3,3,3-tetrafluoro propene ternary compositions as heat transfer fluids in place of R-410A.
    [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 [0004] The (hydro) chlorofluoro carbides used as blowing agents or solvents have been replaced by HFCs.
    [0005] 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.
    [0006] Carbon dioxide, being non-toxic, flammable and having a very low GWP, has been proposed as a refrigerant for
    Petition 870190112075, of 11/01/2019, p. 5/22
    2/11 the air conditioning systems, replacing the HFC-134a. However, the use of carbon dioxide presents several drawbacks, notably linked to the very high pressure of its use as a refrigerant in existing devices and technologies.
    [0007] On the other hand, the R-410A mixture consisting of 50% by weight of pentafluoro ethane, 50% by weight of HFC-134a is widely used as a refrigerant in stationary air conditioning. This mixture, however, has a GWP of 2100. 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 fluid transfer fluids heat, 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 2005/105947 teaches the addition of tetrafluoro propene, preferably 1,3,3,3 tetrafluoro propene, to a co-blowing agent, such as difluoro methane, pentafluoro ethane, tetrafluoro ethane , difluoro ethane, heptafluoro propane, hexafluoro propane, pentafluoro propane, pentafluoro butane, water and carbon dioxide.
    [00010] WO 2006/094303 discloses an azeotropic composition containing 7.4% by weight of 2,3,3,3 tetrafluoro propene (1234yf) and 92.6% by weight of difluoro methane (HFC-32). That document also discloses an azeotropic composition containing 91% by weight of 2,3,3,3 tetrafluoro propene and 9% by weight of difluoro ethane (HFC-152a).
    [00011] A heat exchanger is a device that allows to transfer
    Petition 870190112075, of 11/01/2019, p. 6/22
    3/11 the 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. [00012] In compression systems, the thermal exchange between the refrigerant fluid and the heat sources is done through the 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.
    [00013] 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 co-current or countercurrent;
    - 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.
    [00014] The applicant then discovered that ternary compositions of 2,3,3,3 tetrafluoro propene, 1,1-difluoro ethane and difluoro methane are particularly interesting as a heat transfer fluid.
    [00015] These compositions have at the same time a zero ODP and a GWP lower than that of the existing heat transfer fluids with the R-410A.
    Petition 870190112075, of 11/01/2019, p. 7/22
    4/11 [00016] In addition, their performances (COP: defined performance coefficient, as the useful power supplied by the system over the power supplied or consumed by the system) are superior to those of existing heat transfer fluids such as R- 410A.
    [00017] The compositions used as heat transfer fluid in the present invention have a critical value greater than 87 ° C (Critical temperature of R-410A is 70.5 ° C). These compositions can be used in heat pumps to provide heat at temperatures up to 65 ° C, but also at higher temperatures up to 87 ° C (temperature range in which R-410A cannot be used).
    [00018] The compositions used as heat transfer fluid in the present invention have temperatures at the outlet of the compressor equivalent to the values determined by R-410A. The condenser pressures are lower than the pressures of the R-410A and the compression rates are also lower. These compositions can use the same technology as the compressors used by the R-410A.
    [00019] The compositions used as heat transfer fluid in the present invention have lower vapor saturation density than the R-410A vapor saturated density. The volume capacities determined by these compositions are equivalent to the volume capacity of R-410A (between 91 and 95%). Thanks to these properties, these compositions work with smaller pipe diameters and, therefore, less pressure loss in the steam pipes, which increases the performances of the installations.
    [00020] These compositions are convenient, preferably, in compression refrigeration systems with exchangers operating in countercurrent mode or in cross current mode with tendency
    Petition 870190112075, of 11/01/2019, p. 8/22
    5/11 countercurrent.
    [00021] Thus, these compositions can be used as heat transfer fluid in heat pumps, possibly reversible, in air conditioning, and in low and medium temperature refrigeration, using systems with compression with exchangers in countercurrent or in cross current mode. with a counter-current trend. The present invention therefore has as its object the use of the ternary compositions of 2,3,3,3 tetrafluoro propene, 1,1-difluoro ethane and difluoro methane as heat transfer fluid in refrigeration systems instead of the mixture R-410A.
    [00022] Preferably, these compositions are used in compression refrigeration systems with exchangers that operate in countercurrent mode or in cross current mode with a countercurrent tendency.
    [00023] Preferably, the compositions used in the present invention contain essentially 5 to 83% by weight of 2,3,3,3tetrafluoro propene and 2 to 50% by weight of 1,1-difluoro ethane and 15 to 75 % by weight of difluoro methane.
    [00024] Advantageously, the compositions used contain essentially 5 to 63% by weight of 2,3,3,3 tetrafluoro propene and 2 to 25% by weight of difluoro ethane and 35 to 70% by weight of difluoro methane.
    [00025] Particularly preferred compositions contain essentially 40 to 58% by weight of 2,3,3,3 tetrafluoro propene, 40 to 50% by weight of difluoro methane and 2 to 10% by weight of 1,1-difluoro ethane.
    [00026] The compositions used in the present invention can be stabilized. The stabilizer preferably represents a maximum of 5% by weight in relation to the total composition.
    [00027] As stabilizers, nitro can be mentioned
    Petition 870190112075, of 11/01/2019, p. 9/22
    6/11 methane, ascorbic acid, terephthalic acid, azoles, such as tolutriazole or benzotriazole, phenolic compounds, such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert -butyl-4methyl phenol, epoxides (possibly fluorinated or perfluorinated alkyl or alkylenyl 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.
    [00028] Another object of the present invention relates to a heat transfer process, in which ternary compositions of 2,3,3,3-tetrafluoro propene, 1,1-difluoro ethane and difluoro methane pre- cited as heat transfer fluid in refrigeration systems in place of the R-410A mixture.
    [00029] Preferably, the process is applied in compression refrigeration systems with exchangers, operating in countercurrent mode or in crosscurrent mode with a countercurrent tendency.
    [00030] The process, according to the present invention, can be applied in the presence of lubricants, such as mineral oil, alkyl benzene, polyalkylene glycol and polyvinyl ether.
    [00031] The compositions used in the present invention are suitable for the replacement of R-410A in refrigeration, air conditioning and heat pumps with current installations.
    EXPERIMENTAL PART
    Calculation tools [00032] The RK-Soave equation is used to calculate the densities, enthalpies, entropies and the vapor balance data for mixtures. The use of this equation requires knowledge of the properties of the pure bodies used in the mixtures in question and also the interaction coefficients for each torque.
    [00033] The necessary data for each pure body are:
    Petition 870190112075, of 11/01/2019, p. 10/22
    7/11 [00034] 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 densities and saturated vapor, as a function of temperature.
    HFC-32, HFC-152a [00035] The data on these products 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 [00036] 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 [00037] 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.
    [00038] The technique applied for the liquid vapor balance measures is the static analytical 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 gas chromatography (HP5890 series !!), using a catarometer (TCD).
    Petition 870190112075, of 11/01/2019, p. 11/22
    8/11 [00039] HFC-32 / HFO -1234yf, HFC-152a / HFO-1234yf.
    [00040] The liquid vapor balance measurements on the HFC32 / HFO-1234yf torque are performed for the following isotherms: -10 ° C, 30 ° C and 70 ° C.
    [00041] The liquid vapor balance measurements on the HFC152a / HFO-1234yf torque are performed for the following isotherms: 10 ° C. [00042] HFC-32 / HFO-152a:
    [00043] The liquid vapor balance data for the HFC152a / HFC-32 torque are available under Refprop. Two isotherms (-20 ° C and 20 ° C) and two isobars (1 bar and 25 bar) are used to calculate the interaction coefficients for that torque.
    Compression system [00044] Consider a compression system equipped with a countercurrent evaporator and condenser, a screw compressor and a distender.
    [00045] The system works with 15 ° C superheat and 5 ° C sub-cooling. The minimum temperature deviation between secondary fluid and refrigerant is considered to be around 5 ° C.
    [00046] 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) [00047] For a screw compressor, the constants a, b, c, and d of equation (1) of the isentropic performance are calculated according to the type data published in the Handbook Handbook of air conditioning and refrigeration, page 11.52. The% CAP is the percentage of the ratio of the volume capacity provided by each product to the capacity of the R-410A.
    [00048] The performance coefficient (COP) and is defined as the net power delivered by the system over the power delivered
    Petition 870190112075, of 11/01/2019, p. 12/22
    9/11 or consumed by the system.
    [00049] 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.
    [00050]
    Lorenz's performance coefficient is defined as follows:
    (T temperatures are in K) p Average condenser = p condenser input _ p condenser output (2) (3) [00051] O
    Lorenz COP for air conditioning and refrigeration:
    [medium evaporator
    COPlorenz - —-------------, [condenser _ yevaporator average medium (4) [00052] Lorenz's COP in case of heating:
    [average capacitor
    COP / nrpn = --------------- [condenser_ [average evaporator average (5) [00053] For each composition, the performance coefficient of the Lorenz cycle is calculated as a function of the corresponding temperatures.
    [00054] The% COP / COP Lorenz is the ratio of the system's COP to the COP of the corresponding Lorenz cycle.
    Results in cooling mode or Air conditioning [00055] 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.
    [00056] The performances of the compositions, according to the invention, in the cooling operating conditions are given in Table 1. The values of the constituents (HFO-1234yf, HFC-32, HFCPetition 870190112075, from 11/01/2019, pg. 13/22
    11/10
    152a) for each composition are given in weight percent.
    Table 1
    Evap exit temp. (° C) Temp. Out of comp. (° C) Exit to con d(° C) Eva p. P (bar.) Con d P (bar.) Tax a(w / w) Glid and RendWithP. %HEREP % COP /COPLorenz R410A -5 101 50 6.8 30.6 4.5 0.07 79.6 100 50.4 HFO-1234y f HFÇ-32 HF C-152 to 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 55.445 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
    Heating mode results [00057] 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.
    [00058] The performances of the compositions, according to the invention in the operating conditions in heating mode are given in Table 2. The values of the constituents (HFO-1234yf, HFC32, HFC-152a) for each compositions are given in percentage by weight .
    Table 2
    Evap exit temp.(° C) Temp. Out of comp.(° C) Output with d (° C) Eva p. P (bar.) Con d P (bar.) Tax a(w / w) Glid and RendWith p. % CAP % COP / COPLore nz R410A -5 101 50 6.8 30.6 4.5 0.07 79.6 100 58.8 HFO1234 yf HF C32 HF C-152 to 5 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
    Low temperature cooling results
    Petition 870190112075, of 11/01/2019, p. 14/22
    11/11 [00059] In low temperature refrigeration mode, the compression system operates between an inlet temperature of the refrigerant in the evaporator of -30 ° C and an inlet temperature of the refrigerant in the condenser of 40 ° C. The system supplies cold at 25 ° C.
    [00060] The performances of the compositions, according to the invention, in the refrigerated operating conditions are given in Table 3. The values of the constituents (HFO-1234yf, HFC-32, HFC-152a) for each composition are given in percentage by weight.
    Table 3
    Evap exit temp. (° C) Temp. Out of comp. (° C) Exit to con d(° C) Eva p. P (bar.) Con d P (bar.) Tax a(w / w) Glid and RendWithP. %HEREP % COP /COPLorenz R410A -30 149 40 2.7 24.2 9.0 0.06 52.3 100 33.0 HFO1234 yf HFÇ-32 HFÇ-152The 45 50 5 -27 137 36 2.3 19.1 8.4 3.35 56.9 93 38.8 45 50 10 -26 140 35 2.2 18.6 8.5 3.73 56.4 93 38.9
    Petition 870190112075, of 11/01/2019, p. 15/22
    权利要求:
    Claims (11)
    [1]
    1. Use of a ternary composition of 2,3,3,3 tetrafluoro propene, 1,1-difluoro ethane and difluoro methane as heat transfer fluid in refrigeration systems to replace the R-410A mixture.
    [2]
    2. Use according to claim 1, characterized in that the ternary composition contains from 5 to 83% by weight of 2,3,3,3 tetrafluoro propene and from 15 to 75% by weight of difluoro methane and 2 to 40% by weight of difluoro ethane.
    [3]
    3. Use according to claim 1, characterized in that the ternary composition contains from 5 to 63% by weight of 2,3,3,3 tetrafluoro propene and from 35 to 70% by weight of difluoro methane and 2 to 25% by weight of difluoro ethane.
    [4]
    4. Use according to claim 1, characterized in that the composition contains 40 to 58% by weight of 2,3,3,3 tetrafluoro propene and 40 to 50% by weight of difluoro methane and 2 to 10% by weight of difluoro ethane.
    [5]
    5. Use according to any one of claims 1 to
    4, characterized by the fact that the composition is stabilized.
    [6]
    6. Use according to any one of claims 1 to
    5, characterized by the fact that they are compression refrigeration systems.
    [7]
    7. Use, according to claim 6, characterized by the fact that the systems operate with changers in countercurrent mode or in crosscurrent mode with a countercurrent tendency.
    [8]
    8. Heat transfer process, in which ternary compositions of 2,3,3,3 tetrafluoro propene, 1,1-difluoro ethane and difluoro methane are used as heat transfer fluid in the refrigeration systems instead of mixture R-410A.
    [9]
    9. Process according to claim 8,
    Petition 870190112075, of 11/01/2019, p. 16/22
    2/2 characterized by the fact that the refrigeration systems are of compression, operating, preferably with exchangers in countercurrent mode or in cross current mode with a countercurrent tendency.
    [10]
    Process according to claim 8 or 9, characterized in that the composition contains from 40 to 58% by weight of 2,3,3,3 tetrafluoro propene and from 40 to 50% by weight of difluoro methane and 2 to 10% by weight of difluoro ethane.
    [11]
    11. Process according to any one of claims 6 to 10, characterized in that it is applied in the presence of a lubricant.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012005348B1|2020-02-27|HEAT TRANSFER FLUID IN REPLACEMENT OF R-410A
    US9663697B2|2017-05-30|Use of ternary compositions
    JP6546563B2|2019-07-17|Three-component composition for low capacity cooling
    BR112012005350B1|2020-02-18|Use of ternary composition as heat transfer fluid and heat transfer process
    US10035938B2|2018-07-31|Heat transfer fluid replacing R-134a
    JP6138205B2|2017-05-31|High capacity refrigeration ternary composition
    JP2019214725A|2019-12-19|Binary refrigerating fluid
    BR112012005257B1|2020-02-27|Use of a binary composition and heat transfer process
    同族专利:
    公开号 | 公开日
    RU2012114165A|2013-10-20|
    US9011711B2|2015-04-21|
    JP2013504640A|2013-02-07|
    FR2950067B1|2011-10-28|
    CN105018036B|2020-03-03|
    JP5657669B2|2015-01-21|
    ES2562955T3|2016-03-09|
    US20150152306A1|2015-06-04|
    EP2475736B1|2016-01-13|
    FR2950067A1|2011-03-18|
    BR112012005348A2|2016-03-29|
    CN102482560A|2012-05-30|
    RU2544687C2|2015-03-20|
    CN105018036A|2015-11-04|
    PL2475736T3|2016-07-29|
    EP2475736A1|2012-07-18|
    CN102482560B|2015-07-22|
    US20120161064A1|2012-06-28|
    WO2011030028A1|2011-03-17|
    HK1211614A1|2016-05-27|
    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|
    JPH04110388A|1990-08-31|1992-04-10|Daikin Ind Ltd|Fluid for heat transfer|
    US20090253820A1|2006-03-21|2009-10-08|Honeywell International Inc.|Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming|
    US9005467B2|2003-10-27|2015-04-14|Honeywell International Inc.|Methods of replacing heat transfer fluids|
    US7279451B2|2002-10-25|2007-10-09|Honeywell International Inc.|Compositions containing fluorine substituted olefins|
    TR201908011T4|2002-10-25|2019-06-21|Honeywell Int Inc|Compositions containing 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|
    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|
    CN110003858A|2005-03-04|2019-07-12|科慕埃弗西有限公司|Composition comprising 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|
    TWI657070B|2005-06-24|2019-04-21|美商哈尼威爾國際公司|Compositions containing fluorine substituted olefins and uses thereof|
    GB0614080D0|2006-07-17|2006-08-23|Ineos Fluor Holdings Ltd|Heat transfer compositions|
    AR067115A1|2007-06-21|2009-09-30|Du Pont|METHOD FOR DETECTING LEAKS IN A HEAT TRANSFER SYSTEM|
    WO2009151669A1|2008-03-07|2009-12-17|Arkema Inc.|Halogenated alkene heat transfer compositions with improved oil return|
    FR2932493B1|2008-06-11|2010-07-30|Arkema France|COMPOSITIONS BASED ON HYDROFLUOROOLEFINS|
    FR2932492B1|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|
    FR2936806B1|2008-10-08|2012-08-31|Arkema France|REFRIGERANT FLUID|
    FR2937906B1|2008-11-03|2010-11-19|Arkema France|METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE|
    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|
    FR2942237B1|2009-02-13|2013-01-04|Arkema France|METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE|
    FR2950071B1|2009-09-11|2012-02-03|Arkema France|TERNARY COMPOSITIONS FOR LOW CAPACITY REFRIGERATION|
    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|
    FR2950069B1|2009-09-11|2011-11-25|Arkema France|USE OF TERNARY COMPOSITIONS|
    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|
    FR2950065B1|2009-09-11|2012-02-03|Arkema France|BINARY REFRIGERANT FLUID|
    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|
    FR2986007B1|2012-01-25|2015-01-23|Arkema France|HEAT TRANSFER COMPOSITIONS HAVING IMPROVED MISCIBILITY WITH LUBRICATING OIL|FR2936806B1|2008-10-08|2012-08-31|Arkema France|REFRIGERANT FLUID|
    FR2937328B1|2008-10-16|2010-11-12|Arkema France|HEAT TRANSFER METHOD|
    US20170080773A1|2008-11-03|2017-03-23|Arkema France|Vehicle Heating and/or Air Conditioning Method|
    FR2950071B1|2009-09-11|2012-02-03|Arkema France|TERNARY COMPOSITIONS FOR LOW CAPACITY REFRIGERATION|
    FR2950065B1|2009-09-11|2012-02-03|Arkema France|BINARY REFRIGERANT FLUID|
    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|
    FR2950066B1|2009-09-11|2011-10-28|Arkema France|LOW AND MEDIUM TEMPERATURE REFRIGERATION|
    FR2950069B1|2009-09-11|2011-11-25|Arkema France|USE OF TERNARY COMPOSITIONS|
    FR2950070B1|2009-09-11|2011-10-28|Arkema France|TERNARY COMPOSITIONS FOR HIGH CAPACITY REFRIGERATION|
    US10035938B2|2009-09-11|2018-07-31|Arkema France|Heat transfer fluid replacing R-134a|
    FR2954342B1|2009-12-18|2012-03-16|Arkema France|HEAT TRANSFER FLUIDS WITH REDUCED FLAMMABILITY|
    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|
    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|
    US20120119136A1|2010-11-12|2012-05-17|Honeywell International Inc.|Low gwp heat transfer compositions|
    EP2972014A4|2013-03-15|2016-10-26|Honeywell Int Inc|Low gwp heat transfer compositions|
    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|
    TWI585065B|2011-08-26|2017-06-01|杜邦股份有限公司|Compositions comprising tetrafluoropropene and methods of use thereof|
    CN102516946A|2011-12-20|2012-06-27|集美大学|Green mixed refrigerant|
    FR2986236B1|2012-01-26|2014-01-10|Arkema France|HEAT TRANSFER COMPOSITIONS HAVING IMPROVED MISCIBILITY WITH LUBRICATING OIL|
    US9783721B2|2012-08-20|2017-10-10|Honeywell International Inc.|Low GWP heat transfer compositions|
    EP2920285A1|2012-11-16|2015-09-23|Basf Se|Lubricant compositions comprising epoxide compounds|
    FR2998302B1|2012-11-20|2015-01-23|Arkema France|REFRIGERANT COMPOSITION|
    US8940180B2|2012-11-21|2015-01-27|Honeywell International Inc.|Low GWP heat transfer compositions|
    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|
    FR3000093B1|2012-12-26|2015-07-17|Arkema France|AZEOTROPIC OR QUASI-AZEOTROPIC COMPOSITION OF CHLOROMETHANE|
    US9982180B2|2013-02-13|2018-05-29|Honeywell International Inc.|Heat transfer compositions and methods|
    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|
    FR3010415B1|2013-09-11|2015-08-21|Arkema France|HEAT TRANSFER FLUIDS COMPRISING DIFLUOROMETHANE, PENTAFLUOROETHANE, TETRAFLUOROPROPENE AND POSSIBLY PROPANE|
    BR112017009812A2|2014-11-11|2018-02-27|Trane Int Inc|refrigerant compositions and methods of use|
    FR3033791B1|2015-03-18|2017-04-14|Arkema France|STABILIZATION OF 1-CHLORO-3,3,3-TRIFLUOROPROPENE|
    FR3057271B1|2016-10-10|2020-01-17|Arkema France|USE OF TETRAFLUOROPROPENE COMPOSITIONS|
    FR3070982B1|2017-09-12|2019-08-30|Arkema France|COMPOSITION BASED ON HYDROCHLOROFLUOROOLEFIN AND MINERAL OIL|
    FR3077572B1|2018-02-05|2021-10-08|Arkema France|TERNARY AZEOTROPIC OR QUASI-AZEOTROPIC COMPOSITION COMPRISING HF, 2,3,3,3-TETRAFLUOROPROPENE AND 1,1,1,2,2, -PENTAFLUOROPROPANE.|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-05| B06T| Formal requirements before examination|
    2019-08-06| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-12-31| B09A| Decision: intention to grant|
    2020-02-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/08/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FR0956245|2009-09-11|
    FR0956245A|FR2950067B1|2009-09-11|2009-09-11|HEAT TRANSFER FLUID IN REPLACEMENT OF R-410A|
    PCT/FR2010/051727|WO2011030028A1|2009-09-11|2010-08-17|Heat transfer fluid replacing r-410a|
    [返回顶部]