WO2008009923A2 - Compositions de transfert thermique - Google Patents

Compositions de transfert thermique Download PDF

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Publication number
WO2008009923A2
WO2008009923A2 PCT/GB2007/002700 GB2007002700W WO2008009923A2 WO 2008009923 A2 WO2008009923 A2 WO 2008009923A2 GB 2007002700 W GB2007002700 W GB 2007002700W WO 2008009923 A2 WO2008009923 A2 WO 2008009923A2
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WO
WIPO (PCT)
Prior art keywords
composition
parts
composition according
1225yez
refrigerant
Prior art date
Application number
PCT/GB2007/002700
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English (en)
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WO2008009923A3 (fr
Inventor
Robert Elliot Low
Stuart Corr
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Ineos Fluor Holdings Limited
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Publication date
Priority claimed from GB0614067A external-priority patent/GB0614067D0/en
Priority claimed from GB0706994A external-priority patent/GB0706994D0/en
Application filed by Ineos Fluor Holdings Limited filed Critical Ineos Fluor Holdings Limited
Publication of WO2008009923A2 publication Critical patent/WO2008009923A2/fr
Publication of WO2008009923A3 publication Critical patent/WO2008009923A3/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
    • 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
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • 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
    • 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
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • 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
    • 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
    • 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
    • C09K2205/106—Carbon dioxide
    • 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
    • C09K2205/11—Ethers
    • 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
    • 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
    • C09K2205/10—Components
    • C09K2205/132—Components containing nitrogen

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-410A. R-407C, R-404a, R-407A and R-407B and R-507, but especially R-134a and R-407C.
  • the properties preferred in a refrigerant include low toxicity, non-flamrnability, 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 chlorofiuorocarbons, such as dichlorodifluoromethane and chlorodifluoromethane, 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. 1,1,1,2-tetrafluoroethane (refrigerant R-134a) was introduced as a replacement refrigerant for R- 12. However, despite having a low ozone depletion potential, R- 134a has a global warming potential (GWP) of 1300.
  • GWP global warming potential
  • compositions which may be heat transfer compositions comprising R-1225ye and a further refrigerant.
  • compositions include inter alia combinations of R-1225ye and R-32; R- 1225ye and R-134a; R-1225ye, R-134a and R-32; R-1225ye, R-1234yf, R-32 and R-134a; and azeotropic or near azeotropic compositions comprising 1% to 99% R- 1225ye and 99% to 1% R-134a.
  • R-1225ye is non-flammable and has low Greenhouse Warming Potential (relative to CO 2 ). Its boiling point is ca. -18 0 C (for the isomeric mixture) and its critical temperature is estimated to be 113 0 C. These properties compares closely to that of R-134a (1,1,1,2-tetrafluoroethane) which has boiling point -26.4 0 C, a critical temperature of 101 0 C, and GWP of 1300. R-1225ye is therefore a potential alternative to R- 134a.
  • this fluid alone render it not suitable as a direct replacement for R- 134a.
  • its capacity is too low, by which is meant that a refrigerator or air conditioning system having a fixed compressor displacement and designed for R- 134a will deliver less cooling when charged with R-1225ye and controlled to the same operating temperatures.
  • the capacity for air conditioning applications (evaporating temperature in the range 0 to 1O 0 C) is typically 75% that of 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 Greenhouse Warming Potential, yet has a capacity and energy efficiency (which may be conveniently expressed as the "Coefficient of Performance") ideally within 20% of the values, for example of R-134a, preferably within 10% of these values, and even more preferably within 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 without entailing significant cost differences.
  • the capacity and energy efficiency of blends according to the invention may exceed those of R- 134a.
  • composition which may be a heat transfer composition comprising: (i) R-1225ye; and
  • R-290 propene (R-1270); isobutane (R-600a); n-butane (R-600); 2,3,3,3- tetrafluoropropene (R-1234yf); 1,1-difiuorocyclopropane; 1,1,2- trifiuorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafhiorocyclopropane, or ammonia, or mixtures thereof.
  • the further refrigerant is selected from R-134a, dimethyl ether, R-161,' R-32, R-744, R-41, R-290, R-1270, ammonia, R-600 or R-
  • composition which may be a heat transfer composition comprising: (i) R-1225yeZ; (ii) R-32, R-161 or R-152a; and
  • R-290 propene (R-1270); isobutene (R-600a); n-butane (R-600); 2,3,3,3- tetrafluoropropene (R-1234yf); 1,1-difluorocyclo ⁇ ropane; 1,1,2- trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafiuorocyclopropane, pentafluoroethane (R- 125) or ammonia, or mixtures thereof.
  • the further refrigerant is R-134a or R- 125.
  • the R-32, R-161 or R- 152a is R-32, and the further refrigerant is R- 134a.
  • R-32, Rl 61 or Rl 52a is R-152a, and the further refrigerant is R-125.
  • compositions comprising R-1225yeZ, R-161 and R-134a; R-1225yeZ, R-161 and R-125; and R-1225yeZ, R-125 and R-32.
  • a composition which may be a heat transfer composition comprising:
  • At least one further compound (refrigerant) selected from carbon dioxide (R-744); fluoromethane (R-41); fluoroethane (R-161); 1,1,1- trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2- tetrafluoroethane (R- 134); dimethyl ether; heptafluoropropane (R-227ea); propane (R-290); propene (R- 1270); isobutane (R-600a); n-butane (R-600); 1,1- difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2- tetrafluorocyclopropane; pentafluorocyclopropane, pentafluorororethane (R-125) or ammonia, or mixtures thereof.
  • R-744 carbon dioxide
  • the further refrigerant is R- 134a.
  • composition which may be a heat transfer composition comprising: (i) R-1225yeZ;
  • any resultant heat transfer composition has a GWP less than the refrigerant it is intended to replace, for example R- 134a or R-407C.
  • 1225yeZ component we mean a composition having a content of R-1225yeZ in the R-1225ye component which is at least 95 % Z isomer, more preferably at least
  • compositions according to the invention are set out below (all parts for any given composition total 100 and are expressed on a weight basis):
  • R-125 (1 to 3 parts): R-152a (1 to 12 parts): R-1225yeZ (85 to 98 parts);
  • R-161 (1 to 4 parts): R-1225yeZ (92 to 98 parts);
  • R-161 (1 to 4 parts): R-134a (1 to 10 parts): R-1225yeZ (86 to 98 parts); - R-32 (1 to 3 parts): R-125 (1 to 3 parts): R152a (1 to 13 parts); R-
  • R-32 (1 to 3 parts): R-125 (1 to 3 parts): R-161 (1 to 5 parts): R-1225yeZ (89 to 91 parts).
  • R-134a (4 to 8 parts): R-1234yf (4 to 44 parts): R- 1225yeZ (48 to 89 parts);
  • R-134a (4 to 8 parts): R-1234yf (4 to 28 parts): R- 1225eZ (55 to 88 parts);
  • R-32 (4 to 9 parts); R-134a (4 to 6 parts): R-1234yf (4 to 24 parts): R- 1225yeZ (73 to 88 parts) - this composition is preferred as it offers superior capacity and COP match to R- 134a with evaporator glide less than 5 0 C;
  • R-32 (1 to 4 parts): R-134a (4 to 8 parts): R-1234yf (4 to 44 parts): R- 1225yeZ (48 to 89 parts) - this composition is preferred as it has a glide less tiian or equal to 2.5 0 C with a capacity greater than or equal to 80% of that of R-134a, with good COP match.
  • compositions comprising enhanced levels of Z isomer of R-1225ye have also been found to have other benefits.
  • the R-1225ye component of any blend comprises at least 50% or at least 80% Z isomer, optionally comprises at least 95%, 98%, 99%, or even pure Z isomer, or indeed compositions comprising at least the thermodynamic equilibrium level of Z isomer from the manufacture of the R- 1225 ye component may experience reduced toxicity levels compared to compositions which comprise higher levels of R-1225ye E isomer. Toxicity in this instance is judged by primarily cardiac sensitisation, although reduced toxicity is also apparent through reduced liver cell metabolism.
  • a method of preparing and preferably reducing the toxicity and in particular the cardiac sensitisation or the extent of liver metabolism of a R-1225ye containing composition, in particular a refrigerant composition comprising a step of increasing the proportion of Z isomer in the R-1225ye component.
  • a method of preparing and preferably reducing the toxicity and in particular the cardiac sensitisation or potential liver toxicity of a R-1225ye containing composition, in particular a refrigerant composition comprising providing a R-1225ye component comprising at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%, preferably at least 95%, preferably at least 98%, preferably at least 99%, preferably pure Z isomer.
  • Also provided according to the invention is a method of preparing a refrigerant composition comprising R-1225ye and having a cardiac sensitisation less than a refrigerant composition comprising solely R- 134a comprising preparing the composition such that the proportion of the Z isomer in the R-1225ye component has been increased, and preferably such that it contains at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%, preferably at least 95%, preferably at least 98%, preferably at least 99%, preferably pure Z isomer.
  • the invention provides a refrigerant composition, conveniently a reduced toxicity refrigerant composition "which may have reduced cardiac sensitisation, comprising R-1225ye and R-32, and optionally R-134a, wherein the R-1225ye component comprises at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%, preferably at least 95%, preferably at least 98%, preferably at least 99%, preferably pure Z isomer.
  • the composition may preferably comprise at least 85% R- 1225ye, and in some instances at least 90% R-1225ye.
  • the R-32 component may preferably comprise at least 4% R-32, and may conveniently be between 4% and 8%.
  • the R-134a component if present in such compositions, is preferably present at a level of between 5% and 9%.
  • Such a composition conveniently may have a cardiac sensitisation level less than a refrigerant composition comprising solely R- 134a.
  • an automobile having an air conditioning system containing a refrigerant composition according to the invention.
  • a method of retrofitting air conditioning systems conveniently mobile air conditioning systems, preferably for the refrigerant composition to have a toxicity (e.g. cardiac sensitisation or liver metabolism) less than that of the same system containing a refrigerant composition comprising solely R-134a, comprising preparing a R-1225ye containing refrigerant wherein the proportion of Z isomer in the R-1225ye component has been increased, and preferably such that it comprises at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%, preferably at least 95%, preferably at least 98%, preferably at least 99%, preferably pure Z isomer.
  • a toxicity e.g. cardiac sensitisation or liver metabolism
  • R-1225ye there are a variety of methods known in the art for producing R-1225ye, which include catalytic dehydrofluorination methods. Each of these will produce an isomer blend, governed by kinematic factors.
  • the invention provides a method of increasing the level of Z isomer beyond that which is produced kinematically in any given preparation, and in some embodiments may provide a level of Z isomer enhanced beyond the thermodynamic equilibrium of the two isomers at the preparative reaction conditions. Enhancement of the level of Z isomer may be achieved by known techniques, including distillation or chromatographic (e.g. GC) techniques.
  • nonflammable refers to compounds or compositions which are determined to be nonflammable as determined in accordance with ASHRAE Standard 34 incorporating the ASTM Standard E-681 methodology according to Addendum p34 dated 2004, the entire content of which is incorporated herein by reference. The test used for determination is described in Clause X.2.4.1 "Leaks under storage/shipping conditions", and represents the worst case of fractionation.
  • compositions according to the invention typically have improved capacity compared to R-1225ye alone, and also typically have improved capacity compared to R-1225yeZ.
  • the incorporation of a relatively small proportion of further refrigerant(s) (component (ii) of the composition of the broadest aspect of the invention), which further refrigerant(s) may be flammable, have a higher GWP, or both, may provide a resultant heat transfer composition having both a low GWP and substantially no flammability characteristic and relatively small temperature "glide", yet provide improved capacity and optionally improved Coefficient of Performance.
  • Temperature glide which can be thought of as the difference between bubble point and dew point temperatures of a non-azeotropic mixture at constant pressure, is a characteristic of a refrigerant; so 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.
  • Compositions according to the invention may conveniently be considered not azeotropic, “near azeotropic” or “azeotrope-like”, and indeed may be considered to be “non-azeotropic”. That is, they will exhibit temperature glide on vaporisation or condensation.
  • temperature "glide” in relation to refrigerant mixtures is the temperature change that occurs on evaporation or condensation of the refrigerant mixture in the heat exchangers of a refrigerant apparatus.
  • a standardised (simplified) vapour compression refrigeration cycle which comprises: an evaporator, a compressor, a condenser and an expansion valve, with appropriate pipework and controls etc.
  • the evaporator operates at low pressure and the condenser at high pressure.
  • the refrigerant is fed as a liquid from the condenser through the expansion valve.
  • the drop in pressure results in a portion of the liquid vaporising so that the fluid entering the evaporator is a mixture of liquid and vapour.
  • the condenser glide is the difference between the dew and bubble point temperatures of the fluid mixture at the condensing pressure.
  • the dew point temperature for a fixed pressure is the temperature at which the first drop of liquid can be condensed.
  • the bubble point temperature at the same pressure is the temperature at which the first bubble of vapour can be evaporated.
  • the dew point is higher than the bubble point for a mixture exhibiting temperature glide.
  • pressure increases then the difference between dew and bubble points decreases.
  • evaporator pressure is normally designed to be 1 atmosphere (to prevent inward leakage of air) and the highest pressure is normally selected to be 25 bar or less (the cost of pressure vessels etc. increases as pressure rises).
  • the evaporator glide is the difference between the dew point temperature and the inlet temperature to the evaporator. This inlet temperature is determined by the proportion of vaporisation that has occurred on the initial expansion of feed liquid, so the evaporator inlet temperature is between the dew and bubble points at evaporator pressure.
  • compositions herein, including in the claims, are amounts by weight unless otherwise stated.
  • the composition comprises the at least one further refrigerant in an amount of from about 1 to about 30% by weight of the composition.
  • the composition comprises the at least one further refrigerant in an amount of from about 1 to about 10% by weight of the composition.
  • the composition comprises the at least one further refrigerant in an amount of from about 1 to about 6% by weight of the composition.
  • the composition comprises the at least one refrigerant in an amount of from about 1 to about 5% by weight of the composition.
  • the composition is azeotrope-like, though in certain highly preferred embodiments the composition may be considered non-azeotropic.
  • the composition has a GWP of about 750 or less.
  • the composition has a GWP of about 500 or less.
  • the composition has a GWP of about 250 or less.
  • the composition has a GWP of about 150 or less.
  • the composition has a GWP of about 100 or less.
  • the heat transfer compositions according to the invention generally have substantially similar thermodynamic characteristics to those they might replace, but will typically have significantly lower Greenhouse Warming Potential.
  • the heat transfer compositions 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 further comprises 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-oleflns) and combinations thereof.
  • composition 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 further comprises an additional flame retardant.
  • the additional flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phos ⁇ hate, (chloro ⁇ ropyl)phosphate, tri-(2,3- dibromopropyl)-phosphate, tri-(l ,3-dichloropropyl)- ⁇ hosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fiuorinated iodocarbon, a fluorinated bromocafbon, trifluoroiodomethane, perfiuoroalkyl amines, bromo-fluoroallcyl amines and mixtures thereof.
  • the composition is a refrigerant composition.
  • a heat transfer device containing 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, heat pump systems.
  • the heat transfer device contains a compressor.
  • the compressor may be centrifugal type or may be any positive-displacement type; for example rotary vane, scroll, swash-plate, screw or piston designs.
  • 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 substance 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 substance 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 refrigeration device comprising the step of removing an existing heat transfer fluid, and introducing a composition of the invention.
  • compositions In some circumstances, it is preferred for the compositions to have a GWP of about 150 or less. However, for other applications, it may be acceptable for the composition to have a higher GWP, for example a GWP of up to 250, 500 or 750.
  • the GWP values of the candidate additional fluids dictate the maximum allowable percentages for each application.
  • Internationally accepted GWP values for selected refrigerant fluids of the invention are as follows:
  • the additional refrigerant has a GWP lower than the desired value then the maximum amount in the composition is dictated by considerations of flamrnability and similarity of the resulting mixture to the fluid it is intended to replace.
  • the GWP value may also be used to set a preferred composition range.
  • the fluid to be replaced is R- 134a and in addition the mixture is required to be non-flammable
  • the preferred compositions of selected additional refrigerants having GWP higher than 150 are as follows:
  • the desired GWP is sufficiently high (providing that it is lower than the fluid which the invention replaces) then it is possible to mitigate the fiammability of a first additive replacement by adding a second or further additive replacement to the mixture; this allows the use of somewhat higher proportions of the flammable additive.
  • R-32 10%); R-125 (10%) and R-1225ye (80%) will have a GWP of 403. Its refrigeration capacity is very similar to R- 134a (estimated as typically 100-104% that of R- 134a) and it has similar COP characteristic.
  • the existing refrigerant fluid R-407C is a ternary mixture of R-32, R- 125 and R-134a in the proportions of 23%/25%/52% by weight and has a GWP of 1652.
  • a suitable replacement fluid for this refrigerant can therefore be a mixture of R-32, R-125 and R-1225ye.
  • the additive refrigerant in this case is a mixture of R-32 and R-125, such that the mass ratio of R-125 to R-32 in the mixture is at least 1:1, which ensures non-fiammability of the resultant mixture.
  • compositions may be altered by the skilled man to suit the application requirements and flammability characteristics so desired. In particular he may choose to add components such as CF 3 I, which are known to reduce or suppress flammability, to the refrigerant mixtures of the invention. However, in many preferred aspects of the invention, because of the potential toxicity and reactivity of CF 3 I, compositions according to the invention may be substantially free (e.g. containing less than about 3%), and ideally totally free of CF 3 I.
  • compositions according to the invention were found to have surprising properties, in particular in relation to properties which are important to the performance of the composition in air conditioning, especially mobile (i.e. car) air conditioning systems, in particular when they are required to approach the performance and characteristics of R-134a.
  • a replacement fluid for R-134a in air conditioning system will have a number of desirable properties. These include:
  • compositions according to the invention are "non- azeotropic" as described above; these notably include the ternary and quaternary compositions described herein. Such compositions may also be called zeotropes, zeotropic mixtures, and non-azeotropic refrigerant mixtures (NARMS). Such compositions exhibit varying degrees of glide during boiling or condensation, and also exhibit differences in vapour and liquid composition at equilibrium.
  • Example 1 The data in Table 1 provides illustration of the performance of exemplar blends, which are not limiting, for the replacement of R- 134a.
  • the thermodynamic properties used to calculate the performance have been derived as follows:
  • the Peng Robinson equation of state has been used to calculate gas density, enthalpy and entropy data and has been used to predict latent heat of vaporisation and vapour equilibrium data for the mixtures of interest.
  • the basic properties required by this equation (critical temperature, critical pressure and acentric factor) of the fluids with the exception of the fiuorinated propenes R-1234yf and R-1225ye were taken from reliable sources; chiefly the NIST Webbook site http://webbook.nist.gov.
  • the critical properties of R-1234yf were determined by measurement using a static cell.
  • the critical properties of R-1225ye were estimated using the boiling point for the isomeric mixture of -18°C and Joback's group contribution method.
  • the acentric factor for R-1234yf was calculated from measurements of the vapour pressure.
  • the acentric factor for R-1225ye was estimated using the Lee-Kesler correlation.
  • Ideal gas enthalpy data for the propenes were also estimated using the Joback group contribution method. All of these estimation techniques are described in the text "The Properties of Gases & Liquids" by RC Reid, JM Prausnitz & BE Poling, 4 th edition, published McGraw- Hill.
  • the Peng Robinson equation uses a binary interaction constant to describe the vapour liquid equilibrium of binary pairs. This constant was set to zero where no data were available for mixture pairs; otherwise its value was chosen to give a good representation of the known equilibrium data at temperatures close to 0 0 C.
  • Binary data for pairs among the fluids R-32/R-125/R-134a were obtained from measurements published in M. Nagel, K. Bier, Int. J. Refiig. 18 (1995) 534-543.
  • Binary data for R-1225ye with R-1234yf were taken from US Patent Application US2005/0233932A1.
  • Binary data for R-32 with CO 2 were taken from Rivollet et al. Fluid Phase Equilibria 218 (2004), pp. 95-101.
  • Binary data for R-32 with propane were taken from Fluid Phase Equilibria 199 (2002) 175-183.
  • Binary data for R- 1270 (propene) with R- 134a and R- 152a were taken from Kleiber FluidPhase Equilibria 92 (1994) 149-194.
  • Other data were measured using a static cell technique to measure the total pressure of a mixture of known composition. The data were then regressed using Barker's technique with the data points weighted using the maximum likelihood principle to account for measurement errors in temperature and pressure to fit the required binary interaction parameters for use with the equation of state.
  • the ASHRAE Standard 34 (relating to safety classification of refrigerants) specifies a series of tests for flammability assessment in its Addendum p34. These require measurement or prediction using a verified computer model of the degree to which fractionation affects the concentration of flammable species in the refrigerant vapour and/or liquid phases. This work has focussed on the Addendum p34 test protocol for assessing the vapour concentration in an initially 90% filled cylinder when cooled to 1O 0 C above its bubble point at atmospheric pressure and subjected to mass removal by vapour withdrawal until the cylinder is devoid of liquid. This is because the flammable component in these blends, R-32, is also the most volatile, so it will be most highly enriched in the vapour phase during fractionation. The other test protocols specified in Addendum p34 will result in less severe fractionation of the R-32.
  • WCF weighted case formulation
  • the blend having "as-charged" formulation of R-32/R- 134a/R-1225ye (6%/7%/87% by weight) has a WCF set of mass ratios of these components of 6.5/6/86.
  • the fractionation of the blend has been modelled using the Peng Robinson equation of state to correlate the vapour liquid equilibrium of the system.
  • the equation parameters have been optimised using measured vapour liquid equilibrium data for the binary pairs R-32/R-1225ye and R-32/R-134a.
  • the equilibrium between R-134a and R-1225ye has been modelled as ideal.
  • the compositions modelled are shown in Table 2: Mixtures of R32/R134a/R1225yeZ and R32/R1225yeZ - summary
  • compositions quoted are R32/R134a/R1225yeZ in mass %
  • Cells marked * correspond to compositions where the worst case fractionated formulation at the low temperature 90% fill test case (as per ASHRAE p34) will have flammable vapour according to the specified ASHRAE p34 test protocol at 100 C
  • compositions shown in Table 2 there is a range of compositions for which a COP is found which is higher than that of R- 134a.
  • R-32 is added to the blend, the COP increases above that for R- 134a, peaks and then declines. The effect has been found to be not sensitive to the addition of R- 134a to the system.
  • the mass ratio of R-32 to R-1225yeZ in a blend containing both of them lies between 0.20 and 0.35.
  • fractionation analysis shows that blends having a mass ratio of R-32:R-1225yeZ of greater than about 0.25:1 generate flammable vapours at the -20°C fractionation analysis condition. Hence keeping the mass ratio of these two components below this threshold is beneficial.
  • the evaporator temperature glide increases as R-32 is added to the mixture. Temperature glides of 5K or lower are attained when the mass ratio of R-32 to R-1225yeZ is less than 0.15. Temperature glides of 4K or lower are attained when the ratio is less than 0.11.
  • the volumetric capacity of blends containing R-32 and R-1225yeZ is 90% or more of the capacity of R-134a when the mass ratio R-32:R-1225yeZ is 0.04:1 or higher.
  • the mass fraction R-32 should be up to 0.35 of the mass fraction of R- 1225yeZ in the composition to maximise the COP.
  • the mass fraction of R-32:R-1225yeZ should be up to about 0.25 to ensure maximised COP with a "non-flammable" classification.
  • the mass ratio of R-32:R-1225yeZ should be up to about 0.15 to keep the glide of the composition as 5 0 C or less.
  • the mass ratio of R-32:R-1225yeZ should be between 0.04 and 0.15 to keep the capacity of the composition within 10% of that of R- 134a, with a glide less than 5°C.
  • the mass ratio of R-32:R-1225yeZ should be between about 0.04 and 0.11 to provide acceptable capacity, and glide less than 4 ° C.
  • a composition comprising a mass ratio of 5 to 7 parts R-32, 6 to 8 parts R- 134a and 86 to 88 parts R-1225yeZ (the sum of all parts being 100), preferably 6:7:87 R-32:R-134a:R-1225yeZ, combines these beneficial attributes.
  • Tables 3 to 7 show similar information to that shown in the context of Example 2 for different formulations.
  • test was conducted on beagle dogs to establish the ability of the test compound to sensitise the myocardium to a titrated intravenous dose of adrenaline which had been previously shown to be close to a dose which would cause cardiac arrythrnias, although being one which causes no more than 10 ectopic beats for each dog that is used in the test.
  • NOAEL No Observed Adverse Effect Levels
  • LOAEL Lowest Observed Adverse Effect Level
  • HFP hexafiuoropropene
  • ACGIH American Conference of Industrial Hygienists
  • TLV thresehold limit value
  • 1,2,3,3, 3-pentafluoropropene (R-1225ye E isomer) produced 4 very small conjugates, 2 by addition and 2 by substitution.
  • the conjugates detected were produced in both microsomal and cytosolic samples, with no significant differences seen between samples derived from either rat or human liver. No NADPH dependant oxidative metabolites were detected.
  • results indicate reduced liver metabolic activity for the Z isomer of R-1225ye compared to the E isomer, and hence that beneficial R- 1225 ye containing compositions (e.g. refrigerant compositions) comprise a higher level of Z isomer than E isomer.
  • beneficial R- 1225 ye containing compositions e.g. refrigerant compositions
  • Refrigerant blends according to the invention were tested in freezer and refrigerator environments.
  • the blends were tested according to ISO 5155, and accordingly utilized an Electrolux larder fridge ER6641T, Electrolux Freezer EU6241T, Artificial food packages, RL22H lubricant, 2 Clock hour meters, 2 Power consumption meters, 8 K type thermocouples, 1OK type thermocouples, Datalogger, R-134a and a blend according to the invention comprising 87% wt R-1225yeZ prepared by distillation to approximately 98% isomeric purity, 7% wt R-134a and 6% wt R-32.
  • Both the fridge and the freezer were maintained 30 cm from the floor.
  • the top shelf held 5 packages, the top drawer 15 packages, the middle drawer 18 packages and the bottom drawer 18 packages.
  • the top shelf held 17 packages, the middle shelf 17 packages, the bottom shelf 17 packages and the bottom drawer 11 packages.
  • Artificial food packages were made batch wise in accordance with the recipe found in ISO 5155. The 'food' was cut into blocks of 50mm x 100mm x 100mm and wrapped in cling film. They were placed inside the cabinets in order to fill the unit.
  • Four packages contained a T type thermocouple in the centre.
  • the middle packages of each shelf in the appliances contained the thermocouples.
  • the compressor was modified to accommodate an oil drain at the sump and a charging port on the service pipe.
  • a K type thermocouple was attached to the sump, the suction line and the discharge line.
  • On K type thermocouple was fixed 30cm above the cabinet and one 30cm below the cabinet.
  • the original oil and refrigerant were removed and weighed, the oil was degassed and then weighed again. The same amount was replaced as fresh RL22H.
  • the system was evacuated for fifteen minutes before charging R- 134a.
  • the cabinets were switched on and allowed to run for five days to ensure the packages had reached the correct temperature and the system had equilibrated.
  • the cabinets were in an air-conditioned cubicle set at 25 0 C.
  • the thermocouples were connected to a data-logger.
  • the cabinets were fitted with a clock meter and plugged into a power consumption meter. The initial power and time readings were taken and the temperatures were set to record hourly.
  • the R-134a experiment was repeated at 23°C and 27 0 C to obtain a temperature correction factor.
  • the test measured run time and energy consumed over a specified total elapse time as detailed in the ISO standard.
  • the column labelled delta- KWH shows the energy consumed in operation over that time period.
  • the column labelled delta-Hours shows the amount of time for which, the refrigerant compressor was in operation over the same period. This allows derivation of the refrigeration capacity and the Coefficient of Performance (COP).
  • the raw data were corrected using the temperature calibration curve to an equivalent mean ambient temperature.
  • compositions comprising 87% wt R-1225yrZ, 7% wt R-134a and 6% wt R-32 exhibits COP values within 10% of the R- 134a values.

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Abstract

L'invention concerne une composition de transfert thermique comprenant (i) R-1225yeZ, (ii) R-32, R-161 ou R-152a, et (iii) au moins un frigorigène supplémentaire choisi parmi le dioxyde de carbone (R-744), le fluorométhane (R-41), le fluoroéthane (R-161), le 1,1,1-trifluoroéthane (R-143a), le 1,1,1,2-tétrafluoroéthane (R-134a), le 1,1,2,2-tétrafluoroéthane (R-134), le diméthyl-éther, l'heptafluoropropane (R-227ea), le propane (R-290), le propène (R-1270), l'isobutane (R-600a), le n-butane (R-600), le 2,3,3,3-tétrafluoropropène (R-1234yf), le 1,1-difluorocyclopropane, le 1,1,2-trifluorocyclopropane, le 1,1,2,2-tétrafluorocyclopropane, le pentafluorocyclopropane, le pentafluoroéthane (R-125) ou l'ammoniac ou des mélanges de ceux-ci.
PCT/GB2007/002700 2006-07-17 2007-07-17 Compositions de transfert thermique WO2008009923A2 (fr)

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CN101864277A (zh) * 2010-06-03 2010-10-20 集美大学 低gwp值的制冷剂组合物
WO2011030031A1 (fr) * 2009-09-11 2011-03-17 Arkema France Compositions ternaires pour refrigeration haute capacite
WO2011030032A1 (fr) * 2009-09-11 2011-03-17 Arkema France Compositions ternaires pour refrigeration basse capacite
US20130152626A1 (en) * 2010-08-13 2013-06-20 Carrier Corporation Fluorinated hydrocarbon compostion
WO2014085973A1 (fr) * 2012-12-04 2014-06-12 Honeywell International Inc. Compositions caloporteuses de faible potentiel de réchauffement du globe (prg)
US8808569B2 (en) 2009-09-11 2014-08-19 Arkema France Use of ternary compositions
CN110272722A (zh) * 2019-07-16 2019-09-24 杭州艾尔柯制冷剂科技有限公司 一种环保混合制冷剂
CN110746936A (zh) * 2019-10-11 2020-02-04 金华永和氟化工有限公司 一种环保混合制冷剂
CN110845997A (zh) * 2019-10-16 2020-02-28 珠海格力电器股份有限公司 一种热传递介质及适用于冷却器的组合物
CN111004609A (zh) * 2019-10-22 2020-04-14 湖北瑞能华辉能源管理有限公司 替代r-134a的制冷剂及其制备方法和应用
CN113845882A (zh) * 2021-10-21 2021-12-28 珠海格力电器股份有限公司 三元环保混合制冷剂、其制备方法及制冷系统
US20220169902A1 (en) * 2019-03-04 2022-06-02 The Chemours Company Fc, Llc Heat transfer compositions comprising r-1225ye(e), hfo-1234yf, r-32, r-125 and co2
US11592217B2 (en) * 2018-10-26 2023-02-28 The Chemours Company Fc, Llc HFO-1234ze, HFO-1225zc and HFO-1234yf compositions and processes for producing and using the compositions

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US9127191B2 (en) 2009-09-11 2015-09-08 Arkema France Use of ternary compositions
WO2011030032A1 (fr) * 2009-09-11 2011-03-17 Arkema France Compositions ternaires pour refrigeration basse capacite
FR2950070A1 (fr) * 2009-09-11 2011-03-18 Arkema France Compositions ternaires pour refrigeration haute capacite
FR2950071A1 (fr) * 2009-09-11 2011-03-18 Arkema France Compositions ternaires pour refrigeration basse capacite
CN102482556A (zh) * 2009-09-11 2012-05-30 阿克马法国公司 用于低容量制冷的三元组合物
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US9663697B2 (en) 2009-09-11 2017-05-30 Arkema France Use of ternary compositions
US9505968B2 (en) 2009-09-11 2016-11-29 Arkema France Ternary compositions for low-capacity refrigeration
US9399726B2 (en) 2009-09-11 2016-07-26 Arkema France Use of ternary compositions
US8808569B2 (en) 2009-09-11 2014-08-19 Arkema France Use of ternary compositions
RU2554180C2 (ru) * 2009-09-11 2015-06-27 Аркема Франс Трехкомпонентные композиции для охлаждения малой производительности
CN102482557B (zh) * 2009-09-11 2015-09-02 阿克马法国公司 用于高容量制冷的三元组合物
WO2011030031A1 (fr) * 2009-09-11 2011-03-17 Arkema France Compositions ternaires pour refrigeration haute capacite
CN104974719A (zh) * 2009-09-11 2015-10-14 阿克马法国公司 用于高容量制冷的三元组合物
US9175203B2 (en) 2009-09-11 2015-11-03 Arkema France Ternary compositions for low-capacity refrigeration
US9267064B2 (en) 2009-09-11 2016-02-23 Arkema France Ternary compositions for high-capacity refrigeration
CN101864277A (zh) * 2010-06-03 2010-10-20 集美大学 低gwp值的制冷剂组合物
US20130152626A1 (en) * 2010-08-13 2013-06-20 Carrier Corporation Fluorinated hydrocarbon compostion
US9353302B2 (en) * 2010-08-13 2016-05-31 Carrier Corporation Fluorinated hydrocarbon composition
WO2014085973A1 (fr) * 2012-12-04 2014-06-12 Honeywell International Inc. Compositions caloporteuses de faible potentiel de réchauffement du globe (prg)
US11913681B2 (en) 2018-10-26 2024-02-27 The Chemours Company Fc, Llc HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions
US11592217B2 (en) * 2018-10-26 2023-02-28 The Chemours Company Fc, Llc HFO-1234ze, HFO-1225zc and HFO-1234yf compositions and processes for producing and using the compositions
US11732932B2 (en) 2018-10-26 2023-08-22 The Chemours Company Fc, Llc HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions
US20220169902A1 (en) * 2019-03-04 2022-06-02 The Chemours Company Fc, Llc Heat transfer compositions comprising r-1225ye(e), hfo-1234yf, r-32, r-125 and co2
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