WO2014072712A1 - Compositions de transfert thermique - Google Patents

Compositions de transfert thermique Download PDF

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Publication number
WO2014072712A1
WO2014072712A1 PCT/GB2013/052913 GB2013052913W WO2014072712A1 WO 2014072712 A1 WO2014072712 A1 WO 2014072712A1 GB 2013052913 W GB2013052913 W GB 2013052913W WO 2014072712 A1 WO2014072712 A1 WO 2014072712A1
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Prior art keywords
composition
heat transfer
transfer device
weight
composition according
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PCT/GB2013/052913
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English (en)
Inventor
Robert E. Low
Original Assignee
Mexichem Amanco Holding S.A. De C.V.
Mexichem Uk Limited
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Publication of WO2014072712A1 publication Critical patent/WO2014072712A1/fr

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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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • 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
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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

Definitions

  • the invention relates to heat transfer compositions, and in particular to heat transfer compositions which may be suitable as replacements for existing refrigerants such as R- 134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R-407B, R-407C, R507 and R-404a.
  • a refrigerant liquid evaporates at low pressure taking heat from the surrounding zone.
  • the resulting vapour is then compressed and passed to a condenser where it condenses and gives off heat to a second zone, the condensate being returned through an expansion valve to the evaporator, so completing the cycle.
  • Mechanical energy required for compressing the vapour and pumping the liquid is provided by, for example, an electric motor or an internal combustion engine.
  • the properties preferred in a refrigerant include low toxicity, non-flammability, non-corrosivity, high stability and freedom from objectionable odour.
  • Other desirable properties are ready compressibility at pressures below 25 bars, low discharge temperature on compression, high refrigeration capacity, high efficiency (high coefficient of performance) and an evaporator pressure in excess of 1 bar at the desired evaporation temperature.
  • Dichlorodifluoromethane (refrigerant R-12) possesses a suitable combination of properties and was for many years the most widely used refrigerant. Due to international concern that fully and partially halogenated chlorofluorocarbons were damaging the earth's protective ozone layer, there was general agreement that their manufacture and use should be severely restricted and eventually phased out completely. The use of dichlorodifluoromethane was phased out in the 1990's.
  • Chlorodifluoromethane (R-22) was introduced as a replacement for R-12 because of its lower ozone depletion potential. Following concerns that R-22 is a potent greenhouse gas, its use is also being phased out. Whilst heat transfer devices of the type to which the present invention relates are essentially closed systems, loss of refrigerant to the atmosphere can occur due to leakage during operation of the equipment or during maintenance procedures. It is important, therefore, to replace fully and partially halogenated chlorofluorocarbon refrigerants by materials having zero ozone depletion potentials.
  • R-410A and R-407 refrigerants have been introduced as a replacement refrigerant for R-22.
  • R-22, R-410A and the R-407 refrigerants all have a high global warming potential (GWP, also known as greenhouse warming potential).
  • R-134a 1 ,1 ,1,2-tetrafluoroethane
  • R-134a is an energy efficient refrigerant, used currently for automotive air conditioning. However it is a greenhouse gas with a GWP of 1430 relative to C0 2 (GWP of CO2 is 1 by definition).
  • GWP of CO2 is 1 by definition.
  • the proportion of the overall environmental impact of automotive air conditioning systems using this gas, which may be attributed to the direct emission of the refrigerant, is typically in the range 10-20%.
  • Legislation has been passed in the European Union to rule out use of refrigerants having GWP of greater than 150 for new models of car.
  • the car industry operates global technology platforms, and in any event emission of greenhouse gas has global impact, thus there is a need to find fluids having reduced environmental impact (e.g. reduced GWP) compared to HFC-134a.
  • R-152a (1,1-difluoroethane) has been identified as an alternative to R-134a. It is somewhat more efficient than R-134a and has a greenhouse warming potential of 120. However the flammability of R-152a is judged too high, for example to permit its safe use in mobile air conditioning systems. In particular it is believed that its lower flammable limit in air is too low, its flame speeds are too high, and its ignition energy is too low. Thus there is a need to provide alternative refrigerants having improved properties such as low flammability. Fluorocarbon combustion chemistry is complex and unpredictable.
  • the refrigerant is a blend.
  • the exact flammability properties of a blend comprising a relatively flammable refrigerant and a relatively non-flammable refrigerant may not be predictable.
  • the refrigerant blend is stored in a vessel, if that vessel develops a leak, the refrigerant will often leak from the vessel at different proportionate rates, meaning that as the refrigerant escapes, the composition of the blend remaining in the vessel may change.
  • the differential leakage rates can also vary with temperature. This change in composition can lead to the refrigerant contained in the vessel changing from a non-flammable composition to a flammable composition as a proportion of it leaks. It would be advantageous to obtain blended refrigerant compositions which were still considered non-flammable even if the vessel in which the blend is stored leaked.
  • R-1234yf (2,3,3,3-tetrafluoropropene) has been identified as a candidate alternative refrigerant to replace R-134a in certain applications, notably the mobile air conditioning or heat pumping applications. Its GWP is about 4. R-1234yf is flammable and its flammability characteristics are regarded in some quarters as not being acceptable for certain applications such as mobile air conditioning.
  • R-1234yf The energy efficiency and refrigeration capacity of R-1234yf have been found to be significantly lower than those of R-134a and in addition the fluid has been found to exhibit increased pressure drop in system pipework and heat exchangers. A consequence of this is that to use R-1234yf and achieve energy efficiency and cooling performance equivalent to R-134a, increased complexity of equipment and increased size of pipework is required, leading to an increase in indirect emissions associated with equipment. Furthermore, the production of R-1234yf is thought to be more complex and less efficient in its use of raw materials (fluorinated and chlorinated) than R-134a. Current projections of long term pricing for R-1234yf is in the range 10-20 times greater than R-134a.
  • a principal object of the present invention is therefore to provide a heat transfer composition which is usable in its own right or suitable as a replacement for existing refrigeration usages which should have a reduced GWP, yet have a capacity and energy efficiency (which may be conveniently expressed as the "Coefficient of Performance") ideally within 10% of the values, for example of those attained using existing refrigerants (e.g. R-134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R-407B, R-407C, R507 and R- 404a), and preferably within less than 10% (e.g. about 5%) of these values. It is known in the art that differences of this order between fluids are usually resolvable by redesign of equipment and system operational features.
  • the composition should also ideally have reduced toxicity and acceptable flammability.
  • the subject invention addresses the above deficiencies by the provision of a heat transfer composition
  • a heat transfer composition comprising from about 71 to about 79 % by weight frans-1 , 3,3,3- tetrafluoropropene (R-1234ze(E)), and from about 21 to about 29 % by weight 1,1 ,1 ,2- tetrafluoroethane (R-134a).
  • All of the chemicals herein described are commercially available.
  • the fluorochemicals may be obtained from Apollo Scientific (UK).
  • all % amounts mentioned in compositions herein, including in the claims, are by weight based on the total weight of the compositions, unless otherwise stated.
  • compositions of the invention comprise from about 72 to about 78 % by weight R-1234ze(E) and from about 22 to about 28 % by weight R-134a.
  • compositions of the invention comprise from about 73 to about 77 % by weight R-1234ze(E) and from about 23 to about 27 % by weight R-134a.
  • compositions of the invention comprise from about 74 to about 76 % by weight R-1234ze(E) and from about 24 to about 26 % by weight R-134a.
  • the invention comprises about 71 to about 73% by weight R-1234ze(E) and from about 27 to about 29% by weight R-134a, highly preferably about 71 to about 72% by weight R-1234ze(E) and from about 28 to about 29% weight R-134a.
  • the compositions of the invention comprise: from about 72 to about 77 % by weight R-1234ze(E) and from about 23 to about 28 % by weight R-134a;
  • R-1234ze(E) from about 72 to about 76 % by weight R-1234ze(E) and from about 24 to about 28 % by weight R-134a; from about 74 to about 78 % by weight R-1234ze(E) and from about 22 to about 26 % by weight R-134a; or from about 71 to about 72% by weight R-1234ze(E) and from about 28 to 29% by weight R-134a.
  • compositions of the invention are substantially free of any other component that has heat transfer properties.
  • the compositions of the invention are substantially free of (i) any other hydrofluorocarbon compound (other than R-1234ze(E) and R-134a), and/or (ii) carbon dioxide, and/or (iii) any hydrocarbon.
  • compositions of the invention described herein may consist essentially of (or consist of) the amounts of R-1234ze(E) and R-134a defined in those compositions.
  • compositions of the invention contain substantially no other components, particularly no further hydrofluorocarbon compounds known to be used in heat transfer compositions (e.g. hydrofluoroalkanes or hydrofluoroalkenes, hydrocarbons and carbon dioxide).
  • hydrofluoroalkanes or hydrofluoroalkenes, hydrocarbons and carbon dioxide e.g. hydrofluoroalkanes or hydrofluoroalkenes, hydrocarbons and carbon dioxide.
  • compositions according to the invention conveniently comprise substantially no R-1225 (pentafluoropropene), for example conveniently substantially no R-1225ye (1 ,2,3,3,3- pentafluoropropene) or R-1225zc (1 ,1 ,3,3,3-pentafluoropropene), which compounds may have associated toxicity issues.
  • compositions of the invention contain 0.5% by weight or less of the stated component, preferably 0.1% or less, based on the total weight of the composition.
  • compositions of the invention may contain substantially no:
  • compositions of the invention have zero ozone depletion potential.
  • R-134a has a GWP of 1430 according to the IPCC (Intergovernmental Panel on Climate Change) "AR4" assessment and R-1234ze(E) has a GWP of about 6. Accordingly, the compositions of the invention have a GWP between 295 and 430, typically from about 300 to about 420. In one embodiment, the compositions of the invention have a GWP of from about 310 to about 410, for example from about 320 to about 400.
  • compositions of the invention are non-flammable at a test temperature of 60°C using the ASHRAE-34 methodology.
  • the mixtures of vapour that exist in equilibrium with the compositions of the invention at any temperature between about -20°C and 60°C are also non-flammable.
  • compositions are of reduced flammability hazard when compared to R-1234ze(E) alone, R-1234yf alone, or a binary mixture of R-134a and R-1234yf that possesses the same proportion of R-134a as the compositions of the invention.
  • Flammability may be determined in accordance with ASHRAE Standard 34 incorporating the ASTM Standard E-681 with test methodology as per Addendum 34p dated 2004, the entire content of which is incorporated herein by reference.
  • the compositions have one or more of (a) a higher lower flammable limit; (b) a higher ignition energy; or (c) a lower flame velocity compared to R-1234ze(E) alone, R-1234yf alone, or a corresponding binary mixture of R-134a and R-1234yf.
  • the compositions of the invention are non-flammable.
  • the mixtures of vapour that exist in equilibrium with the compositions of the invention at any temperature between about -20°C and 60°C are also nonflammable.
  • the compositions of the invention are less flammable compared to R- 1234ze(E), R-1234yf or an equivalent binary mixture of R-134a/R-1234yf in one or more of the following respects: lower flammable limit at 23°C; lower flammable limit at 60°C; breadth of flammable range at 23°C or 60°C; auto-ignition temperature (thermal decomposition temperature); minimum ignition energy in dry air or flame speed.
  • the flammable limits being determined according to the methods specified in ASHRAE-34 and the auto-ignition temperature being determined in a 500ml glass flask by the method of ASTM E659-78.
  • the formulation may not be necessary for the formulation to be classed as nonflammable by the ASHRAE-34 methodology; it is possible to develop fluids whose flammability limits will be sufficiently reduced in air to render them safe for use in the application, for example if it is physically not possible to make a flammable mixture by leaking the refrigeration equipment charge into the surrounds.
  • compositions of the invention exhibit a completely unexpected combination of low-/non-flammability, low GWP and improved refrigeration performance properties. Some of these refrigeration performance properties are explained in more detail below.
  • the volumetric refrigeration capacity of the compositions of the invention is at least 80% of the existing refrigerant fluid it is replacing, preferably at least 85%, 90% or even at least 95%.
  • compositions of the invention typically have a volumetric refrigeration capacity that is at least 90% of that of R-1234yf.
  • the compositions of the invention have a volumetric refrigeration capacity that is at least 95% of that of R-1234yf, for example from about 95% to about 120% of that of R-1234yf.
  • the cycle efficiency (Coefficient of Performance, COP) of the compositions of the invention is within about 5% or even better than the existing refrigerant fluid it is replacing
  • the compressor discharge temperature of the compositions of the invention is within about 15K of the existing refrigerant fluid it is replacing, preferably about 10K or even about 5K.
  • the compositions of the invention preferably have energy efficiency at least 95% (preferably at least 98%) of R-134a under equivalent conditions, while having reduced or equivalent pressure drop characteristics and cooling capacity at 95% or higher of R-134a values.
  • the compositions have higher energy efficiency and lower pressure drop characteristics than R-134a under equivalent conditions.
  • the compositions also advantageously have better energy efficiency and pressure drop characteristics than R-1234yf alone.
  • the heat transfer compositions of the invention are suitable for use in existing designs of equipment, and are compatible with all classes of lubricant currently used with established HFC refrigerants. They may be optionally stabilized or compatibilized with mineral oils by the use of appropriate additives.
  • the composition of the invention when used in heat transfer equipment, is combined with a lubricant.
  • the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinations thereof.
  • PAGs and POEs are currently preferred lubricants for the compositions of the invention.
  • the lubricant further comprises a stabiliser.
  • the stabiliser is selected from the group consisting of diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.
  • the composition of the invention may be combined with a flame retardant.
  • the flame retardant is selected from the group consisting of tri-(2- chloroethyl)-phosphate, (chloropropyl) phosphate, tri-(2,3-dibromopropyl)-phosphate, tri- (1 ,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoro iodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.
  • the heat transfer composition is a refrigerant composition.
  • the invention provides a heat transfer device comprising a composition of the invention.
  • the heat transfer device is a refrigeration device.
  • the heat transfer device is selected from the group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, and commercial or residential heat pump systems.
  • the heat transfer device is a refrigeration device or an air-conditioning system.
  • compositions of the invention are particularly suitable for use in mobile air- conditioning applications, such as automotive air-conditioning systems (e.g. heat pump cycle for automotive air-conditioning).
  • the heat transfer device contains a centrifugal-type compressor.
  • the invention also provides the use of a composition of the invention in a heat transfer device as herein described.
  • a blowing agent comprising a composition of the invention.
  • a foamable composition comprising one or more components capable of forming foam and a composition of the invention.
  • the one or more components capable of forming foam are selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene, and epoxy resins.
  • the foamable composition of the invention there is provided.
  • the foam comprises a composition of the invention.
  • a sprayable composition comprising a material to be sprayed and a propellant comprising a composition of the invention.
  • a method for cooling an article which comprises condensing a composition of the invention and thereafter evaporating said composition in the vicinity of the article to be cooled.
  • a method for heating an article which comprises condensing a composition of the invention in the vicinity of the article to be heated and thereafter evaporating said composition.
  • a method for extracting a substance from biomass comprising contacting the biomass with a solvent comprising a composition of the invention, and separating the substance from the solvent.
  • a method of cleaning an article comprising contacting the article with a solvent comprising a composition of the invention.
  • a method for extracting a material from an aqueous solution comprising contacting the aqueous solution with a solvent comprising a composition of the invention, and separating the material from the solvent.
  • a method for extracting a material from a particulate solid matrix comprising contacting the particulate solid matrix with a solvent comprising a composition of the invention, and separating the material from the solvent.
  • a mechanical power generation device containing a composition of the invention.
  • the mechanical power generation device is adapted to use a Rankine Cycle or modification thereof to generate work from heat.
  • a method of retrofitting a heat transfer device comprising the step of removing an existing heat transfer fluid, and introducing a composition of the invention.
  • the heat transfer device is a refrigeration device or (a static) air conditioning system.
  • the method further comprises the step of obtaining an allocation of greenhouse gas (e.g. carbon dioxide) emission credit.
  • an existing heat transfer fluid can be fully removed from the heat transfer device before introducing a composition of the invention.
  • An existing heat transfer fluid can also be partially removed from a heat transfer device, followed by introducing a composition of the invention.
  • R- 1234ze(E) can be added to the R-134a in the heat transfer device, thereby forming the compositions of the invention, and the heat transfer device of the invention, in situ.
  • Some of the existing R-134a may be removed from the heat transfer device prior to adding the R-1234ze(E) to facilitate providing the components of the compositions of the invention in the desired proportions.
  • the invention provides a method for preparing a composition and/or heat transfer device of the invention comprising introducing R-1234ze(E) and optional components such as a lubricant, a stabiliser and/or flame retardant, into a heat transfer device containing an existing heat transfer fluid which is R-134a.
  • R-1234ze(E) and optional components such as a lubricant, a stabiliser and/or flame retardant, into a heat transfer device containing an existing heat transfer fluid which is R-134a.
  • at least some of the R-134a is removed from the heat transfer device before introducing the R-1234ze(E).
  • compositions of the invention may also be prepared simply by mixing the R-1234ze(E) and R-134a (and optional components such as a lubricant, a stabiliser or an additional flame retardant) in the desired proportions.
  • the compositions can then be added to a heat transfer device (or used in any other way as defined herein) that does not contain R-134a or any other existing heat transfer fluid, such as a device from which R-134a or any other existing heat transfer fluid have been removed.
  • a method for reducing the environmental impact arising from operation of a product comprising an existing compound or composition comprising replacing at least partially the existing compound or composition with a composition of the invention.
  • this method comprises the step of obtaining an allocation of greenhouse gas emission credit.
  • environmental impact we include the generation and emission of greenhouse warming gases through operation of the product.
  • this environmental impact can be considered as including not only those emissions of compounds or compositions having a significant environmental impact from leakage or other losses, but also including the emission of carbon dioxide arising from the energy consumed by the device over its working life.
  • Such environmental impact may be quantified by the measure known as Total Equivalent Warming Impact (TEWI). This measure has been used in quantification of the environmental impact of certain stationary refrigeration and air conditioning equipment, including for example supermarket refrigeration systems (see, for example, http://en.wikipedia.org/wiki/Total equivalent warming impact).
  • the environmental impact may further be considered as including the emissions of greenhouse gases arising from the synthesis and manufacture of the compounds or compositions.
  • the manufacturing emissions are added to the energy consumption and direct loss effects to yield the measure known as Life-Cycle Carbon Production (LCCP, see for example http://www.sae.org/events/aars/presentations/2007papasavva.pdf).
  • LCCP Life-Cycle Carbon Production
  • the use of LCCP is common in assessing environmental impact of automotive air conditioning systems.
  • a method for generating greenhouse gas emission credit(s) comprising (i) replacing an existing compound or composition with a composition of the invention, wherein the composition of the invention has a lower GWP than the existing compound or composition; and (ii) obtaining greenhouse gas emission credit for said replacing step.
  • the use of the composition of the invention results in the equipment having a lower Total Equivalent Warming Impact, and/or a lower Life-Cycle Carbon Production than that which would be attained by use of the existing compound or composition.
  • any suitable product for example in the fields of air-conditioning, refrigeration (e.g. low and medium temperature refrigeration), heat transfer, blowing agents, aerosols or sprayable propellants, gaseous dielectrics, cryosurgery, veterinary procedures, dental procedures, fire extinguishing, flame suppression, solvents (e.g. carriers for flavorings and fragrances), cleaners, air horns, pellet guns, topical anesthetics, and expansion applications.
  • the field is air- conditioning or refrigeration.
  • suitable products include heat transfer devices, blowing agents, foamable compositions, sprayable compositions, solvents and mechanical power generation devices.
  • the product is a heat transfer device, such as a refrigeration device or an air-conditioning unit.
  • the existing compound or composition has an environmental impact as measured by GWP and/or TEWI and/or LCCP that is higher than the composition of the invention which replaces it.
  • the existing compound or composition may comprise a fluorocarbon compound, such as a perfluoro-, hydrofluoro-, chlorofluoro- or hydrochlorofluoro-carbon compound or it may comprise a fluorinated olefin.
  • the existing compound or composition is a heat transfer compound or composition such as a refrigerant.
  • refrigerants that may be replaced include R-134a, R-152a, R-1234yf, R-410A, R-407A, R-407B, R-407C, R507, R-22 and R-404A.
  • the compositions of the invention are particularly suited as replacements for R- 134a, R-152a or R-1234yf, especially R-134a or R-1234yf.
  • Any amount of the existing compound or composition may be replaced so as to reduce the environmental impact. This may depend on the environmental impact of the existing compound or composition being replaced and the environmental impact of the replacement composition of the invention.
  • the existing compound or composition in the product is fully replaced by the composition of the invention.
  • R-1234ze(E) required to model refrigeration cycle performance, namely critical point, vapour pressure, liquid and vapour enthalpy, liquid and vapour density and heat capacities of vapour and liquid were accurately determined by experimental methods over the pressure range 0-200bar and temperature range -40 to 200°C, and the resulting data used to generate Helmholtz free energy equation of state models of the Span-Wagner type for the fluid in the NIST REFPROP Version 8.0 software, which is more fully described in the user guide www.nist.gov/srd/PDFfiles/REFPROP8.PDF. and is incorporated herein by reference.
  • the generated performance data for selected compositions of the invention is set out in the following Tables.
  • the tables show key parameters of the air conditioning cycle, including operating pressures, volumetric cooling capacity, energy efficiency (expressed as coefficient of performance for cooling COP) compressor discharge temperature and pressure drops in pipework.
  • the volumetric cooling capacity of a refrigerant is a measure of the amount of cooling which can be obtained for a given size of compressor operating at fixed speed.
  • the coefficient of performance (COP) is the ratio of the amount of heat energy removed in the evaporator of the heat pump cycle to the amount of work consumed by the compressor.
  • Table 2 Theoretical Performance Data of R-134a/R-1234ze(E) blends
  • R-134a The performance of R-134a is taken as the reference point for comparison of cooling capacity, energy efficiency and pressure drop.
  • This fluid is used as a reference for comparison of the ability of the fluids of the invention to be used in air conditioning. It should be noted in passing that the utility of fluids of the invention is not limited to automotive systems. Indeed these fluids can be used in so-called stationary (residential or commercial) equipment.
  • fluids of the invention can provide improved energy efficiency compared to R-134a.
  • compositions are especially attractive since they have non-flammable liquid and vapour phases at 23°C, and selected compositions are also wholly non-flammable at 60°C and/or exhibit significantly higher auto-ignition temperature than that of R- 1234ze(E) or R-1234yf.
  • the software was used with input parameters for modelling R-1234ze(E) and the vapour liquid equilibrium of R-134a and R-1234ze(E).
  • the input parameters for R-1234ze(E) were derived by performing measurements of vapour and liquid density, vapour pressure and vapour and liquid heat capacity to allow correlation of the thermophysical properties of the fluid to a Helmholtz energy equation of state as implemented in the NIST REFPROP and REFLEAK software packages.
  • the phase equilibrium between R-134a and R-1234ze(E) was studied at a range of temperatures between -40°C and +60°C using a static-dynamic equilibrium cell apparatus to measure vapour pressure and phase compositions. The measured data were then used to fit the binary interaction parameters used in the NIST software packages to best present the experimental data.
  • the REFLEAK software was then used to model vapour and liquid removal from a cylinder at a range of initial fill conditions and test temperatures as described in ASHRAE Std.34-2007.
  • a vapour leak from an initially 90% liquid filled cylinder at 54.4°C was explored for a range of starting compositions of R-134a in R-1234ze(E).
  • the remaining liquid composition in the cylinder after the leak is the Worst Case Formulation for Flammability (WCFF) required to be tested under ASHRAE-34 for flammability classification of a blended refrigerant.
  • WCFF Worst Case Formulation for Flammability
  • the invention provides new compositions that exhibit a surprising combination of advantageous properties including good refrigeration performance, low flammability, low GWP, and/or miscibility with lubricants compared to existing refrigerants such as R-134a and the proposed refrigerant R-1234yf.

Abstract

L'invention porte sur une composition de transfert thermique comprenant essentiellement environ 71 à environ 79% en poids de trans-1,3,3,3-tétrafluoropropène (R-1234ze(E)) et environ 21 à environ 29% en poids de 1,1,1,2-tétrafluoroéthane (R-134a).
PCT/GB2013/052913 2012-11-06 2013-11-06 Compositions de transfert thermique WO2014072712A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110162410A1 (en) * 2007-10-12 2011-07-07 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
GB2477865A (en) * 2010-02-16 2011-08-17 Ineos Fluor Holdings Ltd Heat transfer compositions
EP2431442A2 (fr) * 2010-09-20 2012-03-21 Arkema France Composition à base de 1,3,3,3-tetrafluoropropène
WO2012082941A1 (fr) * 2010-12-14 2012-06-21 E. I. Du Pont De Nemours And Company Utilisation de réfrigérants comprenant e-1,3,3,3-tétrafluoropropène et au moins un tétrafluoroéthane pour le refroidissement

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110162410A1 (en) * 2007-10-12 2011-07-07 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
GB2477865A (en) * 2010-02-16 2011-08-17 Ineos Fluor Holdings Ltd Heat transfer compositions
EP2431442A2 (fr) * 2010-09-20 2012-03-21 Arkema France Composition à base de 1,3,3,3-tetrafluoropropène
WO2012082941A1 (fr) * 2010-12-14 2012-06-21 E. I. Du Pont De Nemours And Company Utilisation de réfrigérants comprenant e-1,3,3,3-tétrafluoropropène et au moins un tétrafluoroéthane pour le refroidissement

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds

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