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• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
  • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
  • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/143—Halogen containing compounds
  • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
  • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/017—Mixtures of compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/30—Materials not provided for elsewhere for aerosols
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
  • F25B13/00—Compression machines, plants or systems, with reversible cycle
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2207/00—Foams characterised by their intended use
  • C08J2207/04—Aerosol, e.g. polyurethane foam spray
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
  • C09K2205/126—Unsaturated fluorinated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/22—All components of a mixture being fluoro compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/40—Replacement mixtures

Definitions

• the present invention relates to compositions comprising 2,3,3,3-tetrafluoropropene and their uses as heat transfer fluids, blowing agents, solvents and aerosols.
• ODP ozone depletion potential
• HFCs hydrofluorocarbons
• HFC-134a hydrofluorocarbon (1, 1, 1, 2 tetrafluoroethane: HFC-134a ), less harmful for the ozone layer.
• CFC-12 chlorofluorocarbon
• HFC-134a hydrofluorocarbon (1, 1, 1, 2 tetrafluoroethane: HFC-134a )
• GWP 1300
• the contribution to the greenhouse effect of a fluid is quantified by a criterion, the GWP (Global Warming Potentials) which summarizes the warming potential by taking a reference value of 1 for carbon dioxide.
• Carbon dioxide being non-toxic, non-flammable and having a very low GWP, has been proposed as a refrigerant for air conditioning systems replacing HFC-134a.
• the use of carbon dioxide has several disadvantages, particularly related to the very high pressure of its implementation as a refrigerant in existing devices and technologies.
• WO2004 / 037913 discloses the use of compositions comprising at least one fluoroalkene having three or four carbon atoms, especially pentafluoropropene and tetrafluoropropene, preferably having a GWP of at most 150, as heat transfer fluids.
• WO 2005/105947 teaches the addition to tetrafluoropropene, preferably 1, 3,3,3 tetrafluoropropene, of a co-blowing agent such as difluoromethane, pentafluoroethane, tetrafluoroethane, difluoroethane, heptafluoropropane, hexafluoropropane, pentafluoropropane, pentafluorobutane, water and carbon dioxide.
• a co-blowing agent such as difluoromethane, pentafluoroethane, tetrafluoroethane, difluoroethane, heptafluoropropane, hexafluoropropane, pentafluoropropane, pentafluorobutane, water and carbon dioxide.
• WO 2006/094303 discloses binary compositions of 2,3,3,3-tetrafluoropropene (HFO-1234yf) with difluoromethane (HFC-32), and 2,3,3,3-tetrafluoropropene with 1,1,1 , 2 tetrafluoroethane (HFC-134a).
• Quaternary mixtures comprising 1,1,1,2,3 pentafluoropropene (HFO-1225ye) in combination with difluoromethane, 2,3,3,3-tetrafluoropropene and HFC-134a have been disclosed herein. However, 1,1,1,2,3 pentafluoropropene is toxic.
• CF 3 I Quaternary mixtures comprising 2,3,3,3-tetrafluoropropene in combination with iodotrifluoromethane (CF 3 I), HFC-32 and HFC-134a have also been disclosed in WO 2006/094303.
• CF 3 I has a non-zero ODP and poses problems of stability and corrosion.
• compositions containing 2,3,3,3-tetrafluoropropene do not have the aforementioned drawbacks and having both a zero ODP and a GWP lower than existing heat transfer fluids such as HFC 134a.
• compositions used as the heat transfer fluid in the present invention have compressor outlet temperature values, pressure levels, equivalent to the values given by HFC-134a.
• the compression ratios are lower. These compositions can replace HFC-134a without changing compressor technology.
• compositions used as the heat transfer fluid in the present invention have volumetric capacities greater than the volume capacity of HFC-134a (between 1 16 and 133%). Thanks to these properties, these compositions can use smaller size compressors and have the same heating or cooling capacity.
• compositions according to the present invention are characterized in that they contain essentially from 10 to 90% by weight of 2,3,3,3-tetrafluoropropene, from 5 to 80% by weight of HFC-134a and from 5 to 10% by weight. by weight of HFC-32.
• compositions contain essentially from 10 to 45% by weight of 2,3,3,3-tetrafluoropropene, from 50 to 80% by weight of HFC-134a and from 5 to 10% by weight of HFC-32.
• compositions according to the present invention can be used as heat transfer fluids, preferably in compression systems and advantageously with exchangers operating in counter-current or cross-current counter-current mode. They are particularly suitable for low capacity refrigeration systems per unit volume swept from the compressor.
• heat transfer fluids In compression systems, the heat exchange between the refrigerant and the heat sources takes place via the heat transfer fluids. These heat transfer fluids are in the gaseous state (air in conditioned air and direct expansion refrigeration), liquid (water in domestic heat pumps, brine) or diphasic.
• co-current mode antimethodic
• counter-current mode methodical
• Cross flow may be in a co-current or countercurrent trend
• one of the two fluids makes a half-turn in a wider duct, which the second fluid passes through.
• This configuration is comparable to a co-current exchanger on half of the length, and for the other half to a counter-current heat exchanger: pinhead mode.
• compositions according to the present invention are advantageously used in stationary air conditioning and heat pumps, preferably as a replacement for HFC-134a.
• compositions according to the present invention can be stabilized.
• the stabilizer preferably represents at most 5% by weight relative to the total composition.
• nitromethane ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenol compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2 , 6-di-tert-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphates, phosphonates, thiols and lactones.
• epoxides optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic
• compositions according to the present invention as a heat transfer fluid, can be carried out in the presence of lubricant such as mineral oil, alkylbenzene, polyalkylene glycol and polyvinyl ether.
• lubricant such as mineral oil, alkylbenzene, polyalkylene glycol and polyvinyl ether.
• compositions according to the present invention are furthermore usable as blowing agents, aerosols and solvents.
• the RK-Soave equation is used to calculate densities, enthalpies, entropies and vapor-liquid equilibrium data of 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 binary.
• the necessary data for each pure body are:
• Boiling temperature, Temperature and critical pressure the pressure versus temperature curve from the boiling point to the critical point, saturated liquid and saturated vapor densities as a function of temperature.
• HFC-32, HFC-134a
• 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 marketed by Setaram.
• the saturation densities as a function of temperature are measured by the vibrating tube densimeter technology developed by the laboratories of the autoimmune des Mines de Paris.
• the RK-Soave equation uses binary interaction coefficients to represent the behavior of products in mixtures. The coefficients are calculated based on the experimental vapor equilibrium data.
• the technique used for liquid vapor equilibrium measurements is the analytical static cell method.
• the balance cell includes a sapphire tube and is equipped with two electromagnetic ROLSITM samplers. It is immersed in a cryothermostat bath (HUBER HS40). Variable speed rotary field driving magnetic stirring is used to accelerate equilibrium attainment.
• the analysis of the samples is carried out by chromatography (HP5890 seriesll) in the gas phase using a katharometer (TCD).
• the liquid vapor equilibrium data for the HFC-134a / HFC-32 binary is available under Refprop. Two isotherms (-20 ° C and 20 ° C) and one isobar (30bar) are used to calculate the interaction coefficients for this binary.
• the system operates with 15 ° C overheating and 5 ° C sub cooling.
• the minimum temperature difference between the secondary fluid and the refrigerant is considered to be of the order of 5 ° C.
• The% CAP is the percentage of the ratio of the volume capacity provided by each product to the capacity of HFC-134a.
• the coefficient of performance is defined as the useful power provided by the system on the power supplied or consumed by the system.
• the Lorenz coefficient of performance (COPLorenz) is a benchmark coefficient of performance. It is temperature dependent and is used to compare the COPs of different fluids.
• the performance coefficient of Lorenz is defined as follows:
• The% COP / COPLorenz is the ratio of the system COP to the COP of the corresponding Lorenz cycle.
• the compression system In heating mode, the compression system operates between a refrigerant inlet temperature at the evaporator of -5 ° C and a refrigerant inlet temperature at the condenser of 50 ° C.
• the system provides heat at 45 ° C.
• compositions according to the invention under the conditions of operation in heating mode are given in Table 1.
• constituent values (HFO-1234yf, HFC-32, HFC-134a) for each composition are given in percent by weight.
• the compression system In cooling mode, the compression system operates between a refrigerant inlet temperature at the evaporator of -5 ° C and a refrigerant inlet temperature at the condenser of 50 ° C.
• the system provides cold at 0 ° C.

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