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  • 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
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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
  • B01D11/02—Solvent extraction of solids
  • B01D11/0288—Applications, solvents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
  • B01D11/04—Solvent extraction of solutions which are liquid
  • B01D11/0492—Applications, solvents used
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  • 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
• • 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
  • 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
  • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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  • C09K3/00—Materials not provided for elsewhere
  • C09K3/30—Materials not provided for elsewhere for aerosols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5018—Halogenated solvents
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
  • F03C—POSITIVE-DISPLACEMENT ENGINES DRIVEN BY LIQUIDS
  • F03C99/00—Subject matter not provided for in other groups of this subclass
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
  • G06Q30/00—Commerce
  • G06Q30/018—Certifying business or products
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  • 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
• • 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
• • 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
  • C08J2203/20—Ternary blends of expanding agents
  • C08J2203/202—Ternary blends of expanding agents of physical blowing agents
• • 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
  • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
  • C08J2325/04—Homopolymers or copolymers of styrene
  • C08J2325/06—Polystyrene
• • 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
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • 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
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
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  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
  • C09K2205/122—Halogenated hydrocarbons
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  • 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
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  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/22—All components of a mixture being fluoro compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
  • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
  • Y02A40/963—Off-grid food refrigeration
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49716—Converting

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.
• 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.
• 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).
• GWP global warming potential
• R-134a 1,1,1,2-tetrafluoroethane
• R-12 1,1,1,2-tetrafluoroethane
• R-134a has a GWP of 1300. It would be desirable to find replacements for R-134a that have a lower GWP.
• 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.
• 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 but its flammability characteristics are generally regarded as acceptable for some applications including mobile air conditioning or heat pumping. In particular, when compared with R-152a, its lower flammable limit is higher, its minimum ignition energy is higher and the flame speed in air is significantly lower than that of R-152a.
• 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. So the adoption of R-1234yf to replace R-134a will consume more raw materials and result in more indirect emissions of greenhouse gases than does R-134a.
• Some existing technologies designed for R-134a may not be able to accept even the reduced flammability of some heat transfer compositions (any composition having a GWP of less than 150 is believed to be flammable to some extent).
• 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:
• compositions of the invention unless otherwise stated.
• compositions of the invention comprise up to about 60 or 70% by weight R-1234ze(E), such as from about 5 to about 50%, for example from about 10 to about 40%.
• compositions of the invention comprise up to about 50% by weight of the second component, such as from about 10 to about 40%, for example from about 15 to about 35%.
• compositions of the invention contain from about 10 to about 80% by weight of the third component, preferably from about 15 to about 70%, such as from about 20 to about 60%.
• compositions of the invention comprise from about 0 to about 15% (e.g. about 5 to about 15%) by weight of the fourth component.
• compositions of the invention comprise from about 5 to about 60% by weight of the fourth component.
• compositions herein are by weight based on the total weight of the compositions, unless otherwise stated.
• the components and the amounts of the components of the compositions of the invention typically are chosen such that the flammability of both liquid and vapour phases is reduced relative to the pure flammable component, or rendered completely non-flammable.
• the second component is R-32.
• the third component comprises a mixture of R-125 and R-134a.
• compositions of the invention comprise R-1234ze(E), R-32, R-125 and R-134a.
• An advantageous composition of the invention comprises from about 5 to about 40% by weight of R-1234ze(E), from about 20 to about 35% by weight R-32, from about 15 to about 30% by weight R-125, and from about 12 to about 50% by weight R-134a.
• compositions of the invention contain from about 10 to about 50% by weight R-1234ze(E), from about 22 to about 40% by weight R-32, from about 10 to about 30% by weight R-125, and from about 15 to about 30% by weight R-134a.
• compositions of the invention contain from about 17 to about 46% by weight R-1234ze(E), from about 26 to about 40% by weight R-32, from about 10 to about 18% by weight R-125, and from about 15 to about 30% by weight R-134a.
• compositions of the invention contain from about 14 to about 40% by weight R-1234ze(E), from about 22 to about 38% by weight R-32, from about 18 to about 28% by weight R-125, and from about 15 to about 30% by weight R-134a.
• a preferred composition of the invention consists essentially of about 20% by weight R-1234ze(E), about 30% by weight R-32, about 25% by weight R-125, and about 25% by weight R-134a.
• the invention excludes compositions that comprise or consist of approximately 1 to 16% by weight (e.g. approximately 3 to 8%) R-1234ze, approximately 8 to 20% by weight R-32 (e.g. approximately 12 to 18%), approximately 8 to 20% by weight R-125 (e.g. approximately 8 to 12%) and approximately 60 to 72% by weight R-134a (e.g. about 70 to 75%).
• the invention excludes compositions that comprise or consist of approximately 6% by weight R-1234ze, approximately 14% by weight R-32, approximately 14% by weight R-125 and approximately 66% by weight R-134a.
• compositions of the invention contain R-161 as a fourth component.
• the R-161 is present in such compositions in an amount of from about 10 to about 60% by weight.
• the R-161 is present in an amount of from 10 to about 30% by weight, for example from about 10 to about 20% by weight.
• a preferred composition of the invention comprises R-1234ze(E), R-32, R-161 and R-134a.
• An advantageous composition of the invention comprises from about 5 to about 60% by weight R-1234ze(E), from about 20 to about 50% by weight R-32, from about 10 to about 60% by weight R-161, and from about 10 to about 40% by weight R-134a.
• a preferred composition of the invention comprises from about 10 to about 60% by weight R-1234ze(E), from about 20 to about 50% by weight R-32, from about 10 to about 40% by weight R-161, and from about 10 to about 30% by weight R-134a.
• a further preferred composition of the invention comprises from about 30 to about 60% by weight R-1234ze(E), from about 20 to about 50% by weight R-32, from about 10 to about 30% by weight R-161, and from about 10 to about 25% by weight R-134a.
• Another advantageous composition of the invention comprises from about 40 to about 60% by weight R-1234ze(E), from about 20 to about 50% by weight R-32, from about 10 to about 20% by weight R-161, and from about 10 to about 25% by weight R-134a.
• a preferred composition of the invention comprises R-1234ze(E), R-32, R-161 and R-125.
• An advantageous composition of the invention comprises from about 5 to about 70% by weight R-1234ze(E), from about 15 to about 50% by weight R-32, from about 10 to about 40% by weight R-161, and from about 10 to about 40% by weight R-125.
• a preferred composition of the invention comprises from about 10 to about 65% by weight R-1234ze(E), from about 16 to about 40% by weight R-32, from about 10 to about 30% by weight R-161, and from about 10 to about 25% by weight R-125.
• a further preferred composition of the invention comprises from about 25 to about 60% by weight R-1234ze(E), from about 20 to about 40% by weight R-32, from about 10 to about 20% by weight R-161, and from about 10 to about 25% by weight R-125.
• composition of the invention comprises from about 20 to about 55% by weight R-1234ze(E), from about 16 to about 35% by weight R-32, from about 20 to about 30% by weight R-161, and from about 10 to about 25% by weight R-125.
• compositions of the invention consist essentially of any of the stated components, in any of the stated amounts.
• compositions of the invention contain substantially no other components, particularly no further (hydro)(fluoro) compounds (e.g. (hydro)(fluoro)alkanes or (hydro)(fluoro)alkenes) known to be used in heat transfer compositions.
• hydro)(fluoro) compounds e.g. (hydro)(fluoro)alkanes or (hydro)(fluoro)alkenes
• Consist of within the meaning of “consist essentially of”.
• any of the compositions of the invention described herein, including those with specifically defined amounts of components, may consist essentially of (or consist of) the components defined in those compositions.
• compositions according to the invention conveniently comprise substantially no R-1225 (pentafluoropropene), 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.
• compositions of the invention deliver acceptable properties for use in air conditioning, heat pump and low and medium temperature refrigeration systems as alternatives to existing refrigerants such as R-22, R-410A, R-407A, R-407B, R-407C, R507 and R-404a, while reducing GWP and without resulting in high flammability hazard.
• low temperature refrigeration means refrigeration having an evaporation temperature of from about ⁇ 50 to about ⁇ 20° C.
• Medium temperature refrigeration means refrigeration having an evaporation temperature of from about ⁇ 20 to about 0° C.
• IPCC Intergovemmental Panel on climate Change
• TAR Tin Assessment Report
• the compositions of the invention have a GWP less than R-22, R-410A, R-407A, R-407B, R-407C, R507 or R-404a.
• the GWP of the compositions of the invention is less than about 2800
• the GWP may be less than 2800, 2500, 2300, 2100, 2000, 1900, 1800, 1700, 1500 or 1400.
• compositions of the invention have a GWP that is less than 1500, preferably less than 1400, more preferably less than 1300, 1000, 900 or 700 or 500.
• compositions are of reduced flammability hazard when compared to the individual flammable components of the compositions, e.g. R-32, propene or propane.
• 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-32, propene, propane or R-1234yf.
• the compositions of the invention are non-flammable (or inflammable).
• 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.
• Temperature glide which can be thought of as the difference between bubble point and dew point temperatures of a zeotropic (non-azeotropic) mixture at constant pressure, is a characteristic of a refrigerant; if it is desired to replace a fluid with a mixture then it is often preferable to have similar or reduced glide in the alternative fluid.
• the compositions of the invention are zeotropic.
• the temperature glide (in the evaporator) of the compositions of the invention is less than about 10K, preferably less than about 5K.
• the volumetric refrigeration capacity of the compositions of the invention is at least 85% of the existing refrigerant fluid it is replacing, preferably at least 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-407C in medium temperature and/or low temperature application
• the compositions of the invention have a volumetric refrigeration capacity that is at least 95% of that of R-407C, 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.
• compositions of the invention preferably have energy efficiency at least 95% (preferably at least 98%) of R-407C, R-407A or R-404A under equivalent conditions, while having reduced or equivalent pressure drop characteristic and cooling capacity at 95% or higher of R-407C, R-407A or R-404A values.
• the compositions have higher energy efficiency and lower pressure drop characteristics than R-407C, R-407A or R-404A under equivalent conditions.
• the compositions also advantageously have better energy efficiency and pressure drop characteristics than R-407C, R-407A or R-404A 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.
• PABs polyalkyl benzenes
• POEs polyol esters
• PAGs polyalkylene glycols
• PAG esters polyalkylene glycol esters
• PVEs polyvinyl ethers
• poly (alpha-olefins) poly (alpha-olefins) and combinations thereof.
• 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.
• composition of the invention may be combined with a flame retardant.
• the additional 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 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.
• 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.
• a foam obtainable from the foamable composition of the invention.
• 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.
• the existing heat transfer fluid is R-134a
• the composition of the invention contains R134a, R-1234ze(E), the second component, optionally R-125, and optionally the fourth component (and optional components such as a lubricant, a stabiliser or an additional flame retardant), R-1234ze(E), the second component, any R-125 and/or the fourth component 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), the second component, etc, 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), a second component selected from R-32, propene and propane, optionally R-125, and optionally a fourth component selected from R-161, R-152a and mixtures thereof, and optional components such as a lubricant, a stabiliser or an additional flame retardant, into a heat transfer device containing an existing heat transfer fluid which is R-134a.
• R-134a is removed from the heat transfer device before introducing the R-1234ze(E), the second component, etc.
• compositions of the invention may also be prepared simply by mixing the R-1234ze(E), the second and third components, and optionally the fourth component (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.
• 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.orqlevents/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.
• these methods may be carried out on 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.
• refrigeration e.g. low and medium temperature refrigeration
• blowing agents e.g. low and medium temperature refrigeration
• aerosols or sprayable propellants gaseous dielectrics
• cryosurgery e.g., 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 a 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, R-407D, R-407F, R507, R-22 and R-404A.
• the compositions of the invention are particularly suited as replacements for R-22, R-404A, R-407A, R-407B, R-407C or R-410A.
• 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. Preferably, the existing compound or composition in the product is fully replaced by the composition of the invention.
• Blend A The performance of Blend A is shown in Tables 1 and 2 with the estimated performance of the commercially available and commonly used refrigerants R-407C, R-407A and R-404A indicated for comparison.
• the capacity, energy efficiency (as Coefficient of Performance) and suction line pressure drop are compared to a baseline of R-407C, as this refrigerant has the highest theoretical COP and lowest direct GWP of the established refrigerants.
• this composition has comparable energy efficiency than R-407C, better cooling capacity than R-407C, lower pressure drop and essentially comparable discharge temperature. Furthermore the capacity and energy efficiency of the composition is superior to R-404A.
• the composition has lower GWP than R-407C and so the total environmental warming impact (TEWI) of a system using this fluid will be lower than that achievable using R-407C or R-404A.
• the fluid further exhibits close match of performance parameters to R-407A, which is today finding increasing utility as a refrigerant to replace R-404A.
• the operating pressures are very similar to those found with R-407A, so replacement of R-407A with this composition would require little or no change to a refrigeration system control scheme.
• composition is believed to be essentially non-flammable.
• compositions of the invention comprising: R-32 in range 20-35% w/w; R-125 in range 15-30% w/w; R-134a in range 15-50% w/w and R-1234ze being the balance, using the same conditions as in Table 1 and with R-407C as the reference fluid for comparison of capacity, energy efficiency and suction line pressure drop.
• the compositions of the invention give acceptable or improved performance with lower GWP and lower overall TEWI than R-407A, R-407C or R-404A.
• 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 0-200 bar 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.aov/srd/PDFfiles/REFPROP8.PDF, and is incorporated herein by reference.
• the vapour liquid equilibrium behaviour of R-1234ze(E) was studied in a series of binary pairs with carbon dioxide, R-32, R-125, R-134a, R-152a, R-161, propane and propylene over the temperature range ⁇ 40 to +60° C., which encompasses the practical operating range of most refrigeration and air conditioning systems.
• the composition was varied over the full compositional space for each binary in the experimental programme, mixture parameters for each binary pair were regressed to the experimentally obtained data and the parameters were also incorporated into the REFPROP software model.
• the academic literature was next searched for data on the vapour liquid equilibrium behaviour of carbon dioxide with the hydrofluorocarbons R-32, R-125, R-152a, R-161 and R-152a.
• VLE data obtained from sources were then used to generate mixing parameters for the relevant binary mixtures and these were then also incorporated into the REFPROP model.
• the standard REFPROP mixing parameters for carbon dioxide with propane and propylene were also incorporated to this model.
• the resulting software model was used to compare the performance of selected fluids of the invention with R-407A in a low temperature supermarket refrigeration cycle simulation.
• the use of liquid injection to control compressor discharge temperature was included as a feature of this cycle. Liquid injection is recommended by compressor manufacturers and refrigerant suppliers if R-407A or R-22 is to be used in such applications.
• the quantity of liquid required to maintain the compressor discharge gas at or below the desired maximum temperature was estimated by assuming that the liquid to be injected to the compressor was at the same thermodynamic state as the liquid leaving the condenser and by then performing a heat balance on the machine.
• the total compression work required was then derived from knowledge of the total mass flow through the compressor and the specified outlet and inlet refrigerant states.
• the comparison of fluids was carried out assuming equivalent mean evaporating and condensing temperatures for the refrigerants, and fixed degrees of subcooling and evaporator superheat. Fixed pressure drops were assumed for R-407A in the evaporator, condenser and compressor suction gas line. The pressure drops for the fluids of the invention were then estimated for the same cycle by estimating the achieved compressor throughput with the fluid, deriving the mass flowrate of the refrigerant in the line and then calculating the pressure drop by comparison with the assumed pressure drop for the reference refrigerant.
• the compressor was assumed to be a piston type machine running at fixed speed and known piston displacement with an effective clearance volume ratio of 3% and an average adiabatic (isentropic) efficiency of 65%, operating at a constant compressor suction gas temperature of 20° C.
• the volumetric efficiency of the compressor was then estimated for each refrigerant from the pressure ratio developed over the compressor and the thermodynamic properties of the gas using the standard relationship for estimation of volumetric efficiency in such a machine.
• Mean condenser temperature ° C. 40 Mean evaporator temperature ° C. ⁇ 30 Condenser subcooling K 5 Evaporator superheat K 5 Evaporator pressure drop bar 0.10 Suction line pressure drop bar 0.20 Condenser pressure drop bar 0.10 Compressor displacement m 3 /hr 18 Liquid injection temperature ° C. 130 Compressor suction temperature ° C. 20 Compressor clearance volume ratio 3% Compressor isentropic efficiency 65%
• compositions of the invention containing 16 to 40% by weight R-32, 10 to 24% by weight R-125, 16 to 28% by weight R-134a and 8 to 56% by weight R-1234ze(E) is shown in Tables 3 to 34 below.
• R-1234ze(E) to the fluid further allows a reduction of GWP of the mixture compared to the GWP of any of the R-407 fluids and compared to R-404A.
• R1234ze(E) is unsuitable in its own right for this application given its (relatively) high boiling point of ⁇ 19° C. Surprisingly, therefore, it has proved possible to use significant quantities of R-1234ze(E) in the compositions of the invention without detrimental effect on the operating pressures of the fluids.
• the fluids of the invention offer highly unexpected significant improved environmental performance when compared to comparable known HFC refrigerants (e.g. R-407A, R407F and R-404a) on the grounds of:
• the currently most preferred fluids of the invention are those whose cooling capacity matches that of R-404A, whose condensing pressure is lower than that of R-404A and whose energy efficiency is higher than that of R-407A or R-407F when compared in this manner.
• compositions of the invention it has also been found possible with the compositions of the invention to exceed the performance of R-407D, a fluid which is used for certain refrigerated transport applications as an alternative to the CFC refrigerant R-500, for example if R-32 content in the range 16-20% is used. It is evident from the performance comparison that the capacity and COP of R-407D can be matched or bettered whilst maintaining compressor discharge pressure at or below that of R-407D. Thus the previously claimed benefits of the fluids are also achieved for this application.
• the Coefficient of Performance (COP) of the fluids is not only higher than that of R-407A in the equivalent cycle conditions but is higher than that achievable with the R32/R125/R134a/R1234ze(E) fluids of the invention.
• the use of minor quantities of R-161 in place of R-125 allows further improvement of the energy efficiency (COP), further reduction of the GWP of the refrigerant, reduction in condenser operating pressure and reduction in the amount of R-32 required to give comparable cooling capacity.
• the fluids therefore offer similar performance benefits as already stated. These fluids are especially attractive in applications and equipment where mild flammability of the refrigerant can be accepted.
• the Coefficient of Performance (COP) of the fluids is higher than that of R-407A in the equivalent cycle conditions.
• the use of minor quantities of R-161 allows improvement of the energy efficiency (COP) and reduction of the GWP of the refrigerant.
• a reduction in condenser operating pressure and pressure ratio is also observed, alongside a reduction in the amount of R-32 required to give comparable cooling capacity.
• the fluids therefore offer similar performance benefits as previously stated. These fluids are especially attractive in applications and equipment where mild flammability of the refrigerant can be accepted.

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