WO2008113984A1 - Composition réfrigérante - Google Patents

Composition réfrigérante Download PDF

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Publication number
WO2008113984A1
WO2008113984A1 PCT/GB2008/000911 GB2008000911W WO2008113984A1 WO 2008113984 A1 WO2008113984 A1 WO 2008113984A1 GB 2008000911 W GB2008000911 W GB 2008000911W WO 2008113984 A1 WO2008113984 A1 WO 2008113984A1
Authority
WO
WIPO (PCT)
Prior art keywords
refrigerant composition
consisting essentially
refrigerant
hermetic
composition
Prior art date
Application number
PCT/GB2008/000911
Other languages
English (en)
Inventor
John Edward Poole
Richard Powell
Original Assignee
Rpl 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
Application filed by Rpl Holdings Limited filed Critical Rpl Holdings Limited
Priority to EP08718751A priority Critical patent/EP2125986A1/fr
Priority to CA002681272A priority patent/CA2681272A1/fr
Publication of WO2008113984A1 publication Critical patent/WO2008113984A1/fr

Links

Classifications

    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • F25B9/006—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
    • 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

  • This invention relates to refrigerant compositions, particularly to refrigerant compositions which have minimal adverse effect on stratospheric ozone.
  • the invention particularly relates to compositions which are for use in new and existing refrigeration, air conditioning and heat pumping equipment. These refrigerant compositions are compatible with the new synthetic lubricants, including but not restricted to polyol ester oils and polyalkylene glycol oils.
  • chlorofluorocarbons such as CFC12 and CFC502
  • hydrochlorofluorocarbons such as HCFC22
  • CFCs chlorofluorocarbons
  • HFCs hydro fluorocarbons
  • HFCs There are six main HFCs, namely HFC134a, HFC32, HFC125, HFC143a, HFC227ea and HFC 152a, which either individually or when blended into mixtures can replace CFCs and HCFCs. While HFC 134a, HFC227ea and HFC 152a can be used to replace ODS directly, HFC32, HFC143a and HFC125 are generally found in blends as replacements for ODS. HFCs do not have adequate solubility in traditional lubricants such as mineral and alkylbenzene oils so that synthetic oxygen containing lubricants have been introduced specifically in order that HFCs can be used in new equipment.
  • traditional lubricants such as mineral and alkylbenzene oils
  • Refrigerant blends such as R404A, R507A and others have been commercialised as replacements for CFCs and HCFCs at low temperature, typically operating at around -35 0 C in the evaporator but their performance declines as the temperature rises so that they are not effective, for example, as replacements for ODS in air conditioning applications.
  • R404A and R507A have been formulated primarily to replace CFC502 at low temperatures,
  • Refrigerant blends such as R407C, R410A and others have been commercialised as replacements for CFCs and HCFCs at medium to high temperatures, typically operating at around +5 0 C in the evaporator and condensing at around +35 0 C but their performance declines as the temperature decreases so that they are not effective, for example, as replacements for ODS in refrigeration applications such as are used in supermarkets.
  • R407C and R410A have been formulated primarily to replace HCFC22 for air conditioning applications.
  • R407C is a zeotrope, not an azeotrope or near azeotrope, so its application is further restricted by having a comparatively high temperature glide in the evaporator which can cause icing at the entry of the evaporator thus reducing the energy efficiency and the capacity of the system. Furthermore, R407C, being a zeotrope, is unacceptable for flooded systems where large composition shifts would occur resulting in large compression ratios and potential over-pressurisation of the condenser.
  • An object of this invention is to provide a refrigerant blend that can be readily used to replace R22 in new & existing equipment. It is especially important that such a blend should have an adequate refrigeration capacity.
  • the capacity should be at least 90% of that of the fluid it is replacing, more preferably at least 95% of that of the fluid it is replacing and most preferably equal to or greater than that of the fluid it is replacing under similar operating conditions. It is an object of this invention to provide refrigerant compositions which have capacities similar to R22 across the range of applications for air conditioning & refrigeration from high to low temperatures where R22 is commonly found.
  • HFC refrigerant blend which has been commercialised which has a safety classification of Al according to ASHRAE Standard 34, being of low toxicity and non flammable, which can match the capacity, performance and pressures of HFCF22 across the range of applications where HCFC22 is found including refrigeration and air conditioning applications including centrifugal chillers.
  • An object of this invention is to provide refrigerant compositions with low temperature glides of less than 2 0 C that match the thermodynamic performance of HCFC22 across the temperature range of applications where HCFC22 is commonly found including refrigeration and air conditioning applications operating at evaporator temperatures ranging from +5 0 C to -40 0 C. It is known in the art that high compression ratios can result in increased energy usage and the potential for compressor damage.
  • This invention relates to refrigerant compositions which have compression ratios which should be at least no more than 10% of that of the fluid it is replacing, more preferably no more than 5% of that of the fluid it is replacing and most preferably equal to or lower than that of the fluid it is replacing under similar operating conditions.
  • Preferred aspects of this invention relate to refrigerant compositions which have compression ratios which are similar to R22 across the range of applications for air conditioning & refrigeration from high to low temperatures where R22 is commonly found.
  • Azeotrope an azeotropic blend is one containing two or more refrigerants whose equilibrium vapour and liquid phase compositions are the same at a given pressure. Azeotropic blends exhibit some segregation of components at other conditions. The extent of the segregation depends on the particular azeotrope and the application.
  • Azeotropic temperature the temperature at which the liquid and vapour phases of a blend have the same mole fractionation of each component at equilibrium for a specified pressure.
  • Near azeotrope a zeotropic blend with a temperature glide sufficiently small that it may be disregarded without consequential error in analysis for a specific application.
  • Zeotrope blends comprising multiple components of different volatilities that, when used in refrigeration cycles, change volumetric composition and saturation temperatures as they evaporate (boil) or condense at constant pressure.
  • Temperature glide the absolute value of the difference between the starting and ending temperatures of a phase-change process by a refrigerant within a component of a refrigerating system, exclusive of any subcooling or superheating. This term usually describes condensation or evaporation of a zeotrope.
  • a refrigerant composition consists of: a refrigerant composition suitable for air conditioning, refrigeration and heat pumping applications consisting essentially of: Rl 34a 10 to 20%
  • a preferred composition consists essentially of:
  • Rl 43a 50 to 20%.
  • a further preferred composition consists essentially of: Rl 34a 10 to 20%
  • a further preferred composition consists essentially of:
  • a further preferred composition consists essentially of: Rl 34a 10 to 20%
  • a further preferred composition consists essentially of: Rl 34a 15 to 20%
  • a further preferred composition consists essentially of:
  • a further preferred composition consists essentially of:
  • a further preferred composition consists essentially of: Rl 34a 15 to 20%
  • An especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • a further especially preferred composition consists essentially of:
  • compositions of this invention consist of the components mentioned above, optionally with small amounts of impurities or additives in an amount which is not sufficient to affect the essential properties of the composition. Preferably no additives are used.
  • Preferred compositions meet the criteria for safety classifications Al and A2 of ASHRAE Standard 34 or meet the criteria for safety classification Al of ASHRAE Standard 34
  • compositions may be used in an air conditioning unit with a synthetic oxygen- containing lubricant or may be used in a refrigeration unit with a synthetic oxygen containing lubricant.
  • the lubricant may be a polyol ester, a polyether or a mixture of oxygen- containing lubricants.
  • compositions may be used in a hermetic or semi-hermetic refrigeration unit providing cold temperatures in a range between about 0 0 C and about -45 0 C, or may be used in an open refrigeration unit driven by an external power source providing cold temperatures in a range between about 0 0 C and about -45 0 C.
  • the compositionsr may be used in an hermetic or semi-hermetic air conditioning unit providing cold temperatures in a range between about 0 0 C and about 20 0 C, or may be used in an hermetic or semi-hermetic heat pump unit providing warm temperatures in a range between about 15 0 C and about 50 0 C.
  • composition may also be used in an open air conditioning unit driven by an external power source providing cold temperatures in a range between about 0 0 C and about 20 0 C.
  • the composition may be used in an open heat pump unit driven by an external power source providing warm temperatures in a range between about 15 0 C and about 50 0 C.
  • compositions preferably meet the criteria for safety classification A2 of ASHRAE Standard 34 and more preferably meet the stricter Al classification.
  • compositions comprise near azeotropic and zeotropic refrigerant compositions, which are non flammable under all conditions of fractionation as defined under ASHRAE Standard 34, and which can be used to replace HCFC22 in new & existing equipment across the application ranges including refrigeration and air conditioning and centrifugal chillers.
  • These refrigerant applications are compatible with the oxygen containing synthetic lubricants including but not restricted to polyol ester, polalkylbenzene & polether oils.
  • HFC 143a and HFC32 have not received a non flammable rating by ASHRAE.
  • Preferred embodiments of this invention relate to compositions of refrigerants which cover blends of non flammable HFCs with flammable HFCs selected so that all such compositions are non flammable during fractionation while providing similar refrigerating effects and thermodynamic performances to HCFC22.
  • HFC 143a has an ASHRAE safety classification of A2 which makes limitation of the amount of HFC 143a used relative to the amounts of non- flammable components important to obtaining a non flammable rating of Al for the blend.
  • compositions in accordance with this invention may not contain any hydrocarbon compound.
  • Preferred compositions provide very similar performance to HCFC22 across the evaporating temperature range commonly associated with HCFC22.
  • Example 1 The invention is further described by means of examples but not in a limitative sense.
  • Example 1 The invention is further described by means of examples but not in a limitative sense.
  • Blends of R125, R143a and R134a were evaluated in a typical hermetic or semi- hermetic air conditioner using NIST's CYCLE D program. COOLING DUTY DELIVERED 10 kW EVAPORATOR
  • Blends of R125, R143a and R134a were evaluated in a typical open compressor refrigeration unit using NIST's CYCLE D program. COOLING DUTY DELIVERED 10 kW

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

L'invention porte sur une composition réfrigérante constituée essentiellement de trois composants hydrofluorocarbonés choisis parmi HFC134a, HFC125 et HFC143a, et qui remplace le HCFC22 dans les nouveaux appareils.
PCT/GB2008/000911 2007-03-19 2008-03-14 Composition réfrigérante WO2008113984A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08718751A EP2125986A1 (fr) 2007-03-19 2008-03-14 Composition réfrigérante
CA002681272A CA2681272A1 (fr) 2007-03-19 2008-03-14 Composition refrigerante

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0705219.4 2007-03-19
GB0705219A GB2447629A (en) 2007-03-19 2007-03-19 Refrigerant composition comprising three hydrofluorocarbon components

Publications (1)

Publication Number Publication Date
WO2008113984A1 true WO2008113984A1 (fr) 2008-09-25

Family

ID=38008668

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2008/000911 WO2008113984A1 (fr) 2007-03-19 2008-03-14 Composition réfrigérante

Country Status (4)

Country Link
EP (1) EP2125986A1 (fr)
CA (1) CA2681272A1 (fr)
GB (1) GB2447629A (fr)
WO (1) WO2008113984A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8465664B2 (en) 2006-03-03 2013-06-18 Rpl Holdings Limited Refrigerant composition
US9023231B2 (en) 2009-12-21 2015-05-05 Rpl Holdings Limited Non ozone depleting and low global warming potential refrigerants for low temperature refrigeration
US10253233B2 (en) 2015-03-27 2019-04-09 Rpl Holdings Limited Non-ozone depleting and low global warming refrigerant blends
US11459497B2 (en) 2017-11-27 2022-10-04 Rpl Holdings Limited Low GWP refrigerant blends
US11827834B2 (en) 2020-10-22 2023-11-28 Rpl Holdings Limited Thermal pump refrigerants

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5277834A (en) * 1990-07-26 1994-01-11 E. I. Du Pont De Nemours And Company Near-azeotropic blends for use as refrigerants
EP0626435A2 (fr) * 1990-04-04 1994-11-30 Daikin Industries, Limited Réfrigérant
US5494597A (en) * 1993-01-07 1996-02-27 Exxon Chemical Patents Inc. Refrigeration working fluid compositions containing difluoroethane or pentafluoroethane and a polyolester lubricant
US5616276A (en) * 1990-07-26 1997-04-01 E. I. Du Pont De Nemours And Company Azeotrope-like refrigerants with chlorodifluoromethane, pentafluoroethane, and C2 -C4 hydrocarbon
US5711158A (en) * 1995-05-15 1998-01-27 Matsushita Electric Industrial Co., Ltd. Apparatus and method for charging three-component mixed refrigerant
US20010023596A1 (en) * 1994-09-20 2001-09-27 Makoto Fujita Refrigerating apparatus

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2548411B2 (ja) * 1989-11-30 1996-10-30 松下電器産業株式会社 作動流体
JPH08100170A (ja) * 1994-09-30 1996-04-16 Asahi Glass Co Ltd 作動流体混合物
FR2860001B1 (fr) * 2003-09-19 2008-02-15 Arkema Composition a base d'hfc (hydrofluorocarbures) et son utilisation
GB0404343D0 (en) * 2004-02-27 2004-03-31 Rpl Holdings Ltd Refrigerant composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0626435A2 (fr) * 1990-04-04 1994-11-30 Daikin Industries, Limited Réfrigérant
US5277834A (en) * 1990-07-26 1994-01-11 E. I. Du Pont De Nemours And Company Near-azeotropic blends for use as refrigerants
US5616276A (en) * 1990-07-26 1997-04-01 E. I. Du Pont De Nemours And Company Azeotrope-like refrigerants with chlorodifluoromethane, pentafluoroethane, and C2 -C4 hydrocarbon
US5494597A (en) * 1993-01-07 1996-02-27 Exxon Chemical Patents Inc. Refrigeration working fluid compositions containing difluoroethane or pentafluoroethane and a polyolester lubricant
US20010023596A1 (en) * 1994-09-20 2001-09-27 Makoto Fujita Refrigerating apparatus
US5711158A (en) * 1995-05-15 1998-01-27 Matsushita Electric Industrial Co., Ltd. Apparatus and method for charging three-component mixed refrigerant

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8465664B2 (en) 2006-03-03 2013-06-18 Rpl Holdings Limited Refrigerant composition
US9062237B2 (en) 2006-03-03 2015-06-23 Rpl Holdings Limited Refrigerant composition
US9023231B2 (en) 2009-12-21 2015-05-05 Rpl Holdings Limited Non ozone depleting and low global warming potential refrigerants for low temperature refrigeration
US10253233B2 (en) 2015-03-27 2019-04-09 Rpl Holdings Limited Non-ozone depleting and low global warming refrigerant blends
US11459497B2 (en) 2017-11-27 2022-10-04 Rpl Holdings Limited Low GWP refrigerant blends
US11827834B2 (en) 2020-10-22 2023-11-28 Rpl Holdings Limited Thermal pump refrigerants

Also Published As

Publication number Publication date
CA2681272A1 (fr) 2008-09-25
GB2447629A (en) 2008-09-24
EP2125986A1 (fr) 2009-12-02
GB0705219D0 (en) 2007-04-25

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