WO2009047535A2 - Compositions de transfert de chaleur - Google Patents

Compositions de transfert de chaleur Download PDF

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Publication number
WO2009047535A2
WO2009047535A2 PCT/GB2008/003457 GB2008003457W WO2009047535A2 WO 2009047535 A2 WO2009047535 A2 WO 2009047535A2 GB 2008003457 W GB2008003457 W GB 2008003457W WO 2009047535 A2 WO2009047535 A2 WO 2009047535A2
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WO
WIPO (PCT)
Prior art keywords
composition
composition according
heat transfer
compound
transfer device
Prior art date
Application number
PCT/GB2008/003457
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English (en)
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WO2009047535A3 (fr
Inventor
Stuart Corr
Robert Elliot Low
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Ineos Fluor Holdings Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0719989A external-priority patent/GB0719989D0/en
Priority claimed from GB0814060A external-priority patent/GB0814060D0/en
Priority claimed from GB0814051A external-priority patent/GB0814051D0/en
Application filed by Ineos Fluor Holdings Limited filed Critical Ineos Fluor Holdings Limited
Publication of WO2009047535A2 publication Critical patent/WO2009047535A2/fr
Publication of WO2009047535A3 publication Critical patent/WO2009047535A3/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
    • C08J9/127—Mixtures of organic and inorganic 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
    • 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
    • C08J2203/14—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
    • C09K2205/12—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
    • C09K2205/22—All components of a mixture being fluoro compounds

Definitions

  • the invention relates to heat transfer compositions, and in particular to heat transfer compositions which may be suitable as replacements for existing refrigerants such as R-134a, R-410A, R-407A, R-407B, R-407C, R-507, R-22 and R-404A, especially R-134a.
  • the properties preferred of 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, 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. Whilst heat transfer devices of the type to which the present invention relates are essentially closed systems, loss of refrigerant to the atmosphere can occur due to leakage during operation of the equipment or during maintenance procedures. It was important, therefore, to replace fully and partially halogenated chlorofluorocarbon refrigerants by materials having zero ozone depletion potentials.
  • R-134a 1,1 ,1,2-tetrafluoroethane
  • R-12 1,1 ,1,2-tetrafluoroethane
  • GWP greenhouse warming potential
  • R-1243zf is a low flammability refrigerant, and has a relatively low Greenhouse Warming Potential. Its boiling point, critical temperature, and other properties make it a potential alternative to higher GWP refrigerants such as R-134a.
  • difluoropropenes (designated as R-1252; the isomers and stereoisomers of difluoropropenes are encompassed by this description) also have relatively low Greenhouse Warming Potentials, and have other physical properties such as boiling points which make them suitable for use as refrigerants, especially as part of refrigerant blends.
  • 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 have a capacity and energy efficiency (which may be conveniently expressed as the "Coefficient of Performance") ideally within 20% of the values, for example of those attained using R-134a, and preferably with 10% or less (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 without entailing significant cost differences.
  • the composition should also ideally have reduced toxicity and acceptable flammability.
  • composition comprising:
  • the R- 1252 is not R-1252zc.
  • the first compound is only one of R- 1243zf, R-1252zf, R-1252yf, R-1252ye, R-1252ze and R-1252zc.
  • the second compound is only one of R- 1225ye(E), R-1225 ye(Z), R-152a, R-134a, R-227ea and R-125.
  • the second compound is selected from R-152a, R-134a, R-227ea and R-125, and mixtures thereof. Additionally the second compound may be only one of R-152a, R-134a, R-227ea and R-125.
  • the third preferred compound is only one of R-1270, R-32, R-161 , R-1234yf and CO 2 .
  • compositions according to the invention comprise R-1225ye it is preferred that the R-1225ye component is 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% 2 isomer, the balance being the E isomer.
  • a composition contains either R-1225ye (E) or R-1225ye (Z), then absent further qualification this means that the R-1225ye (E) or (Z) component of the total R-1225ye content is at least 98% of that isomer, as appropriate.
  • the R-1225ye is present at a level of 1 to 50%, preferably 3 to 35% by weight.
  • the R-1243zf and R-1252 isomers are conveniently used at levels of 10 to 95%, conveniently 10, 20, 30, 40 or 50 to 90% by weight of the composition.
  • the R-32 is conveniently used at a level of 0.5 to 60 %, such as 1 to 50%, preferably 2 to 40, 3 to 30 or 5 to 15% by weight of the composition.
  • the R-1270 is conveniently used at a level of 1 to 20%, preferably 1 to 10% by weight of the composition.
  • the CO 2 is conveniently used at a level of 1 to 40%, preferably 2 to 20% by weight of the composition.
  • the R-152a is conveniently used at a level of 4 to 80%, preferably 5 to 70% by weight of the composition.
  • the R-134a, R-227ea and R-125 are conveniently used at a level of 1 to 60 %, such as 4 to 30, 40 or 50%, preferably 5 to 20% by weight of the composition.
  • the R-161 is conveniently used at a level of 1 to 50%, preferably 10 to 50% by weight of the composition.
  • the R-1234yf is conveniently used at a level of 1 to 50%, preferably 1 to 30% by weight of the composition.
  • the second compound is R-152a.
  • the resulting compositions may be considered to have a low flammability, lower than R-1243zf on its own under the test conditions and protocol described in ASHRAE Standard 34 incorporating the ASTM Standard E-681 with test methodology as per Addendum 34p dated 2004.
  • low flammability we include lower flammability fluorocarbons (e.g. 1,1- difluoroethane, 152a and 3,3,3-trifluoropropene, 1243zf).
  • fluorocarbons e.g. 1,1- difluoroethane, 152a and 3,3,3-trifluoropropene, 1243zf.
  • flammability can be considered to be reduced/lower (compared, for example, to such fluorocarbons and hydrocarbons) if (i) the lower flammable limit (LFL) in air is increased, and/or (ii) the ignition energy required to initiate the combustion reaction is increased, and/or (iii) the speed of flame propagation is reduced.
  • LFL lower flammable limit
  • a composition of the invention with low flammability may also be non-flammable.
  • the second compound is R-1225ye (E) or (Z).
  • E ASHRAE
  • Z ASHRAE Standard 34 incorporating the ASTM Standard E-681 with test methodology as per Addendum 34p dated 2004.
  • the second compound is R-134a.
  • compositions also provide additional advantages; these include improved safety in use, improved refrigeration performance, improved heat- transfer performance and improved environmental performance through reduced greenhouse warming impact.
  • the third compound is R-32.
  • Particularly preferred blends according to the invention comprise:
  • compositions including R-32 exhibit maxima in COP as the level of R-32 is increased from zero.
  • the maxima locations vary slightly depending on other components and cycle conditions but in general they are found where the level of R-32 is constrained to between 5% and 15% by weight in the composition.
  • An object of the invention is to reduce the contribution to greenhouse warming resulting from the operation of an air conditioning system. Improved energy efficiency reduces this contribution; finding such increases in energy efficiency of the system by adding a higher GWP component (R-32) is a second benefit of the lower overall GWP compositions thus provided.
  • the R-32/R-1243zf/R-134a blend contains from about 1 to about 30 % R-32 w/w (or about 1.5 to about 20 %), preferably from about 2 to about 15 %, more preferably from about 3 to about 10 %, for example from about 4 to about 8 %.
  • the R-32/R-1243zf/R-134a blend contains a combined amount of R134a and 1243zf of from about 70 or 80 to about 99 % w/w, preferably from about 75 to about 98 %, more preferably from about 90 to about 97 %, for example from about 92 to about 96 %.
  • the ratio of R-1243zf:R-134a typically is selected so as to keep the GWP of the R-32/R-1243zf/R-134a blend below about 750, preferably below about 500 or 250, most preferably below about 150, depending on the application.
  • the ratio may be from about 20:1 to about 1 :1, preferably from about 15:1 to about 5:1, for example from about 12:1 to about 8:1.
  • the R-32/R-1243zf/R-134a blend may contain from about 0.1 to about 20 % R-134a w/w, preferably from about 0.5 to about 15 % or from about 1 to about 10 %, for example from about 3 to about 9 %; and from about 50 to about 98.9 - 99.1 % R-1243zf w/w, preferably from about 70 to about 97.5 % or from about 75 or 80 to about 96 %, for example from about 83 to about 93 %.
  • a particularly preferred R-32/R-1243zf/R-134a blend contains from about 4 to about 8 % or about 5 to about 7 % R-32 w/w (e.g.
  • R-134a e.g. about 6 %), from about 3 to about 9 % or about 4 or 5 to about 8 % R-134a (e.g. about 7 %) and from about 80 to about 90 or about 82 or 84 to about 88 or 89 % R-1243zf (e.g. about 87 %).
  • This composition range is preferred for the replacement of R- 134a, for example in air conditioning applications, particularly for automotive air conditioning.
  • R-32/R-1243zf/R-134a blend contains from about 20 to about 60 %, such as from about 30 to about 50 %, e.g. from about 35 to about 45 % R-32, from about 1 to about 20 %, such as from about 5 to about 15 % R-134a and from about 30 to about 70 %, such as from about 40 to about 65 %, e.g. from about 50 to about 60 % R-1243zf.
  • This composition range is preferred for the replacements of R-407 and/or R-22.
  • the third compound is CO 2 .
  • a further particularly preferred blend according to the invention comprises CO 2 / R-1243zf/R-134a.
  • the CO 2 /R-1243zf/R-134a blend contains from about 0.5 to about 20 % CO 2 w/w, preferably from about 1 to about 15 % or from about 1.5 to about 10 %, for example from about 2 to about 8 %.
  • the CO 2 /R-1243zf/R-134a blend may contain from about 0.1 to about 25 % R-134a w/w, preferably from about 1 to about 20 % or from about 2 to about 15 %, for example from about 3 to about 12 %.
  • the CO 2 /R-1243zf/R-134a blend contains from about 55 to about 99.5 % R-1243zf w/w, preferably from about 65 to about 98 % or from about 75 to about 96.5 %, for example from about 80 to about 95 %.
  • a particularly preferred CO 2 /R-1243zf/R-134a blend contains from about 3 to about 6 % R-32 w/w (e.g. about 4 %), from about 6 to about 12 % R-134a (e.g. about 10 %) and from about 82 to about 90 % R-1243zf (e.g. about 86 %).
  • R-1234yf can be improved by adding R1243zf or any of the R1252 isomers described above, in particular the R1252yf and R1252zf isomers.
  • the refrigerant fluid R-1225ye exhibits low acute toxicity. However, we have found in chronic 28 day toxicology testing that R-1225ye, although preferred in refrigerant blends because of the relatively high refrigeration performance, exhibits toxicological activity at exposures of 10,000 ppm. This may result in reduced occupational exposure limits for compositions comprising R-1225ye when compared to the fluids that they are intended to replace. Therefore in certain embodiments it is preferred that the refrigerant composition comprises no more than 50% R-1225ye (E) or (Z), preferably no more that 30% R-1225 (E) or (Z), preferably no more than 25% R-1225ye (E) or (Z). In some aspects, the compositions of the invention do not contain R-1225ye.
  • the resultant heat transfer composition has a GWP less than that of the fluid it is intended to replace, for example lower than that of R-134a.
  • the resultant heat transfer composition has a GWP less than 500, preferably less than 150, more preferably less than 100, more preferably less than 50.
  • the resultant heat transfer composition has a capacity greater than that of R-134a alone.
  • non-flammable refers to compounds or compositions which are determined to be non-flammable as determined in accordance with ASHRAE Standard 34 incorporating the ASTM Standard E-681 with test methodology as per Addendum 34p dated 2004, the entire content of which is incorporated herein by reference.
  • the formulation may not be necessary for the formulation to be classed as non-flammable by the ASHRAE 34 methodology; it is possible to develop fluids whose flammability limits will be sufficiently reduced in air to render them safe for use in the application, for example if it is physically not possible to make a flammable mixture by leaking the refrigeration equipment charge into the surrounds.
  • One example of such an application is that of mobile air conditioning technology embodying the secondary loop approach for isolation of the refrigerant from the passenger compartment air supply by using an intermediary heat transfer fluid such as glycol to transfer heat between air and refrigerant.
  • R-1225ye (E) or (Z) to flammable refrigerants based on a first compound comprising R-1243zf or R-1252 and a further compound selected from R-1270, R-32, R-161 and R-1234yf is to modify their flammability in mixtures with air in this manner. Additionally, the R-32/R-1243zf/R-134a blends and CO 2 /R-1243zf/R-134a blends described hereinbefore have such reduced flammability.
  • the compositions of the invention e.g. the R- 32/R-1243zf/R-134a blends or CO 2 / R-1243zf/R-134a blends
  • a lower flammability limit (as measured in accordance with the ASHRAE methodology hereinbefore defined) of at least 4% v/v in air, preferably at least 4.5% or 5%.
  • the LFL of the compositions of the invention is higher than for R-1243zf alone.
  • compositions according to the invention typically have improved capacity compared to R-1225ye, R-134a and/or R-1243zf (e.g. R-1225ye or R-1243zf) alone.
  • the invention provides the incorporation of a relatively small proportion of a further compound, which may be flammable, have a higher GWP, or both, to provide a resultant composition, preferably a heat transfer composition having both a relatively low GWP and a relatively low or substantially no flammability characteristic, and relatively small temperature "glide", yet providing 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 refrigerant blends. So if it is desired to replace a fluid with a mixture, then it is often preferable to have a blend with as small a temperature glide as possible (for example less than 10 0 C, preferably less than 7°C and more preferably less that 5°C) to avoid excessive fractionation of the components forming the blend. Refrigerant compositions exhibiting glides of this order are known to be acceptable to the refrigeration industry. Such refrigerants include R-407C.
  • the composition may comprise at least one further refrigerant in an amount of from about 1 to about 20, 30, 40 or 50 % by weight of the composition, preferably (if used) from about 1 to about 10% by weight of the composition (e.g. from about 1 to about 5 or 6% by weight of the composition).
  • the nature and amount of the further refrigerant fluid, if used, is such that the resultant ternary (or greater) mixture is non-flammable.
  • the relative amounts of R-32, R-134a and R-1243zf may or may not be altered.
  • compositions of the invention may comprise a composition comprising R-32, R-134a and R-1243zf (preferably in the amounts hereinbefore described) and a further refrigerant (preferably in the amounts hereinbefore described).
  • R-32, R-134a and R-1243zf may be replaced by the further refrigerant.
  • the further refrigerant may be added at the expense of the R-1243zf, resulting in a composition comprising 6 % R-32, 7 % R-134a, 77 % 1243zf and 10 % of the further refrigerant w/w.
  • compositions herein, including in the claims, are by weight unless otherwise stated, based on the total weight of the composition.
  • 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. In addition, they will typically have improved toxicity and improved flammability characteristics.
  • 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 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.
  • the refrigerant composition further comprises an additional 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 composition is a heat transfer composition, preferably a refrigerant composition.
  • 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.
  • automotive air conditioning systems Preferably it is an automotive 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 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.
  • the compositions it is preferred for the compositions to have a GWP of about 150 or less. However, for other applications, it may be acceptable for 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.
  • the internationally accepted GWP values for selected refrigerant fluids of the invention from the IPCC Third Assessment Report (2001) which are incorporated into European legislation on control of fluorinated gases are tabulated in the following list:
  • the additional refrigerant has a GWP lower than the desired value then the maximum amount in the composition is dictated by considerations of flammability and similarity of the resulting mixture to the fluid it is intended to replace.
  • the refrigerant compositions may be altered by the skilled man to suit the application requirements and flammability characteristics so desired.
  • he may choose to add components, for example halocarbons, such as CF 3 I, which are known to reduce or suppress flammability, to the refrigerant mixtures of the invention.
  • 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 an (automotive) air conditioning system.
  • the method further comprises the step of obtaining an allocation of greenhouse gas (e.g. carbon dioxide) emission credit.
  • 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.org/events/aars/presentations/2007papasawa.pdf).
  • LCCP Life-Cycle Carbon Production
  • 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.
  • the methods may be carried out on any suitable product, for example in the fields of air-conditioning, refrigeration, heat transfer, blowing agents, aerosols or sprayable propellants, gaseous dielectrics, cryosurgery, veterinary procedures, dental procedures, fire extinguishing, flame suppression, solvents (e.g. carriers for flavorings and fragrances), cleaners, air horns, pellet guns, topical anesthetics, and expansion applications.
  • the field is air-conditioning, especially automotive air-conditioning.
  • 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 (automotive) air conditioning unit.
  • the existing compound or composition have an environmental impact as measured by greenhouse warming potential (GWP) and/or TEWI and/or LCCP that is higher than the composition of the invention which replaces it.
  • GWP greenhouse warming potential
  • 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-410A, R-407A, R-407B, R-407C, R-507, R-22 and R-404A, preferably R-134a.
  • 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.
  • the existing compound or composition has a GWP of greater than 750 or 500 or 250 or 150 (as measured by methods described herein).
  • the replacement composition of the invention preferably has a GWP less than 750 or 500 or 250 or 150.
  • 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 certain of the fluorinated propenes were taken from reliable open literature sources; chiefly the NIST Webbook site http://webbook.nist.gov.
  • R-1234yf, R1243zf, R-1225ye(2) and R-1225ye(E) were calculated from measurements of the vapour pressure of each fluid.
  • the acentric factors for the isomers of R-1252 were estimated using the Lee-Kesler correlation.
  • Ideal gas enthalpy data for the fluorinated propenes were also estimated using Hyperchem ® molecular modelling software and the Joback group contribution method; this was subsequently checked for accuracy against measured data for R-1225ye(E) and R-1234yf.
  • 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 or measured vapour-liquid equilibrium data at temperatures close to or below 0 0 C. This approach was taken as the distribution of the refrigerant components in an air conditioning system employing a mixed refrigerant is known to be determined principally by the equilibrium pertaining in the evaporator; which will operate at temperatures typically 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. Refrig. 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 Equilib 218 (2004), pp. 95-101.
  • Binary data for R-32 with R-1270 (propene) were taken from J. Chem. Eng. Data, 50 (2), 419-424, 2OO5.Binary data for R-1270 with R-134a and R-152a were taken from Kleiber Fluid Phase Equilibria 92 (1994) 149-194.
  • the vapour liquid equilibria of selected binary pairs of fluids were measured using a static cell technique to measure the total pressure of a mixture of known composition.
  • R-32/R- 1243zf R-32/R-1234yf; R-134a/R-1234yf; R-1243zf/R-1234yf; R-152a/R- 1234yf; R-1225ye(Z)/R-1234yf; R-1224ye(Z)/R-32; R-1225ye/(Z)/R- 1225ye(E); R-1225ye(Z)/R-134a; R-1243zf/R-1225ye(Z). 5
  • the refrigerant performance characterised by the coefficient of performance (COP) and the
  • the refrigerant performance of a range of R-32/R-1243zf/R-134a blends is 25 shown in (Fig 4 and) the table below, using the following parameters: 5°C evaporator temperature, 5°C of useful superheat, 15°C suction return temperature, 50°C condenser temperature, 5°C of liquid subcool, 10m3/hr compressor displacement with 70% compressor isentropic efficiency.
  • Blend Composition (w%)
  • the lower flammability limit (LFL) of two R-32/R-1243zf/R-134a blends was measured as described hereinbefore at 60 0 C and compared against the measured LFL of 1243zf alone and a blend of 134a/R-1243zf.
  • the results0 were compared with LFL for each composition as measured using Le Chatalier's rule, which stipulates that the LFL of a mixed fuel is the volume- fraction average of the lower limits of the flammable components. The results are shown below.
  • the R-32/R-134a/R-1243zf blend has superior properties compared to R-1234yf and R-1243zf alone.
  • This blend has comparable refrigeration capacity and COP, but an increased evaporation pressure, compared to 134a alone. This is advantageous because the lower the operating pressure, the more pressure drop can be expected in the hoses or lines leading to and from the air conditioning refrigerant compressor. Increased pressure drop contributes to increased energy consumption.
  • the R-32/R-134a/R-1243zf blend has a 100-year GWP of 144 if calculated using the most recent Intergovernmental Panel on Climate Change (IPCC) data (so-called AR4 values), or 127 if calculated using the last issue of IPCC data (so-called Third Assessment Report (TAR) data) as encoded in the European F-Gas Directive.
  • IPCC Intergovernmental Panel on Climate Change
  • AR4 values the most recent Intergovernmental Panel on climate Change
  • TAR Third Assessment Report
  • the performance of the R-32/R-134a/R-1243zf (6%/7%/87% w/w) blend was evaluated in a laboratory calorimeter bench test program using the components of a standard production model of automotive air conditioning system designed for R-134a.
  • the system consisted of: a microchannel evaporator; a suction line hose; a fixed displacement compressor; a discharge line hose; a condenser unit; a liquid return line and a thermostatic control valve.
  • the system was assembled using two psychrometric wind tunnels inside calorimeter enclosures to supply air at controlled rate, temperature and humidity to the evaporator and condenser units. Pressure drops in the system hoses were balanced to ensure that they would be equivalent to those seen in an assembled system. The compressor speed could be altered by adjusting the drive pulley ratio. Cooling performance was evaluated by measuring the heat gained and lost by the air flowing through the evaporator and condenser units and by measuring the total energy balance over the calorimeter.
  • the system was operated firstly on R-134a to check that the performance at standard rating points was consistent with expected values and that the optimal refrigerant charge was as expected. Then a series of rating tests were conducted using the R-32/R-134a/R-1243zf (6%/7%/87% w/w) blend. The only alterations made to the system for the new fluid were that the optimal charge mass, determined using the same procedure as for R- 134a,was found to be 88% of the R-134a charge and that the expansion valve was adjusted by % turn to attain correct superheat values leaving the evaporator.
  • the performance of the two fluids was determined using the system operated at 35°C ambient air temperature having a relative humidity of 40% and with the compressor operated at 3 different speeds (900rpm, 2500rpm and 4000prm). Table 1 shows the measured cooling duty and coefficient of performance for the two fluids:
  • the lubricant was also tested for Total Acid Number (TAN) by titration with 0.1 M alcoholic Potassium Hydroxide solution, and colour (Hazen Units, HU) by comparative testing using Lovibond Colour Comparator.
  • the sealed autoclaves were then evacuated with a vacuum pump for several minutes before cooling (using either a freezer or dry ice). Approximately 6Og of refrigerant was then added to the autoclave by vacuum distillation before placing the autoclaves in an oven at 175 0 C for two weeks.
  • a blend was prepared containing 4%/10%/86% by weight CO 2 (R-744)/R- 134a/R-1243zf.
  • the lower flammability limit (LFL) of this blend was measured at 23 and 60 0 C and compared against the measured LFL of 1243zf alone and a blend of 134a/R-1243zf. The results are shown below.
  • Refrigerant flow required 251 319 251 237 to deliver 1OkW cooling capacity (kg/hr)
  • the CO 2 /R-134a/R-1243zf blend has superior properties compared to R-1234yf and R-1243zf alone.
  • This blend has comparable refrigeration capacity and COP, but an increased evaporation pressure, compared to 134a alone. This is advantageous because the lower the operating pressure, the more pressure drop can be expected in the hoses or lines leading to and from the air conditioning refrigerant compressor. Increased pressure drop contributes to increased energy consumption.
  • the CO 2 /R-134a/R-1243zf blend has a 100-year GWP of 146 if calculated using the most recent IPCC AR4 values, or 133 if calculated using the TAR data as encoded in the European F-Gas Directive.

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Abstract

L'invention porte sur une composition comprenant : (i) un premier composé comprenant R-1243zf, (3,3,3-trifluoropropène) ou un difluoropropène (R-1252) choisi parmi R-1252zf, R-1252yf, R-1252ye, R-1252ze et R-1252zc, et leurs mélanges ; (ii) un second composé choisi parmi R-1225ye(E), R-1225ye(Z) (à la fois 1,2,3,3,3-pentafluoropropène), R-152a (1,1-difluoroéthane), R-134a (1,1,1,2-tétrafluoroéthane), R-227ea (1,1,1,2,3,3,3-heptafluoropropane) et R-125 (pentafluoroéthane), et leurs mélanges ; et (iii) un troisième composant choisi parmi R-1270 (propylène), R-32 (difluorométhane), R-161 (fluoroéthane) et R-1234yf (2,3,3,3-tétrafluoropropène), le dioxyde de carbone (CO2) et leurs mélanges.
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US8808571B2 (en) 2010-05-20 2014-08-19 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
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EP2558544B1 (fr) 2010-04-16 2018-09-05 The Chemours Company FC, LLC Refroidisseurs contenant de composition comportant du 2,3,3,3-tétrafluoropropène et du 1,1,1,2-tétrafluoroéthane
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CN110343510A (zh) * 2018-04-02 2019-10-18 江西天宇化工有限公司 一种不可燃并具有低温室效应的混合制冷剂及其应用
CN112552876A (zh) * 2020-12-10 2021-03-26 珠海格力电器股份有限公司 一种混合制冷剂和空调系统

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US9546311B2 (en) 2008-08-19 2017-01-17 Honeywell International Inc. Azeotrope-like compositions of 1,1,1,2-tetrafluoropropene and 1,1,1,2-tetrafluoroethane
US11027249B2 (en) 2008-08-19 2021-06-08 Honeywell International Inc. Azeotrope-like compositions of 1,1,1,2-tetrafluoropropene and 1,1,1,2-tetrafluoroethane
WO2010064005A1 (fr) * 2008-12-02 2010-06-10 Ineos Fluor Holdings Limited Compositions de transfert de chaleur
US10450489B2 (en) 2010-03-02 2019-10-22 Arkema France Heat-transfer fluid for a centrifugal compressor
US9574124B2 (en) 2010-03-02 2017-02-21 Arkema France Heat-transfer fluid for a centrifugal compressor
EP2558544B1 (fr) 2010-04-16 2018-09-05 The Chemours Company FC, LLC Refroidisseurs contenant de composition comportant du 2,3,3,3-tétrafluoropropène et du 1,1,1,2-tétrafluoroéthane
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US9309450B2 (en) 2010-05-20 2016-04-12 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
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US8522606B2 (en) 2010-12-22 2013-09-03 Nuovo Pignone S.P.A. Similitude testing of compressor performance
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