EP0680503A1 - Refrigerant compositions - Google Patents

Refrigerant compositions

Info

Publication number
EP0680503A1
EP0680503A1 EP94904250A EP94904250A EP0680503A1 EP 0680503 A1 EP0680503 A1 EP 0680503A1 EP 94904250 A EP94904250 A EP 94904250A EP 94904250 A EP94904250 A EP 94904250A EP 0680503 A1 EP0680503 A1 EP 0680503A1
Authority
EP
European Patent Office
Prior art keywords
component
ether
refrigerant
composition
boiling
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
EP94904250A
Other languages
German (de)
French (fr)
Inventor
Richard Llewellyn Powell
Stuart Corr
Frederick Thomas Murphy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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 GB939301004A external-priority patent/GB9301004D0/en
Priority claimed from GB939322307A external-priority patent/GB9322307D0/en
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0680503A1 publication Critical patent/EP0680503A1/en
Ceased legal-status Critical Current

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
    • 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
    • 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
    • C09K2205/112—Halogenated 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
    • C09K2205/128—Perfluorinated 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
    • 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
    • C09K2205/32—The mixture being azeotropic

Definitions

  • the present invention relates generally to non-azeotropic refrigerant compositions and in particular to non-azeotropic refrigerant compositions which are designed to replace chlorodifluoromethane (Refrigerant R-22).
  • Heat transfer devices of the mechanical compression type such as refrigerators, freezers, heat pumps and air conditioning systems are well known.
  • a refrigerant liquid of a suitable boiling point evaporates at low pressure taking heat from a surrounding zone.
  • the resulting vapour is then compressed and passes to a condenser where it condenses and gives off heat to a second zone.
  • the condensate is then returned through an expansion valve to the evaporator so completing the cycle.
  • the mechanical energy required for compressing the vapour and pumping the liquid may be provided by an electric motor or an internal combustion engine.
  • the properties preferred of a refrigerant include low toxicity, non- flammability , non-corrosivity , high stability and freedom from objectionable odour.
  • heat transfer devices have tended to use fully and partially halogenated chlorofluorocarbon refrigerants such as trichlorofluoromethane (Refrigerant R-ll), dichlorodifluoromethane (Refrigerant R-12), chlorodifluoromethane (Refrigerant R-22), or the azeotropic mixture of chlorodifluoromethane and chloropentafluoroethane (Refrigerant R-115); the azeotrope being Refrigerant R-502.
  • Refrigerant R-22 for example, is widely used in air conditioning systems.
  • the present invention provides a non-azeotropic refrigerant composition which is a blend of compounds having low or zero ozone depletion potentials.
  • the refrigerant composition of the invention can exhibit a wide boiling point range and may be used as a replacement for R-22 in air conditioning units.
  • non-azeotropic (zeotropic) refrigerant composition comprising:
  • a (hydro ) fluorocarbon is a compound selected from the group consisting of the hydrofluorocarbons and the perfluorocarbons
  • a (hydro ) fluorocarbon ether is a compound selected from the group consisting of the hydrofluorocarbon ethers and the perfluorocarbon ethers.
  • the low boiling first component typically has a boiling point in the range of from -90 to -30°C, preferably in the range of from -70 to -40°C and particularly preferably in the range of from -60 to -45°C.
  • a preferred hydrocarbon for the low boiling first component is propane.
  • the preferred (hydro )fluorocarbons and (hydro ) fluorocarbon ethers for the low boiling first component are selected from the group consisting of trifluoromethane (CHF3), fluoromethane (CH3F), difluoromethane (CH2F2)! pentafluoroethane (CF3CHF2), 1 , 1 , 1-trifluoroethane (CF3CH3), perfluoropropane (CF3CF2CF3), trifluoromethyl difluoromethyl ether (CF3OCF2H) and bis (trifluoromethyl ) ether (CF3OCF3) .
  • the low boiling first component may consist of a single refrigerant compound or it may comprise a mixture of such compounds. Where mixtures of refrigerant compounds are employed for the low boiling first component, they will preferably form an azeotropic or azeotrope-like composition.
  • Preferred azeotropic or azeotrope-like compositions for the low boiling first component include the following:
  • the azeotropic or azeotrope-like composition comprising a mixture, preferably an essentially equimolar mixture, of difluoromethane and pentafluoroethane .
  • the azeotropic or azeotrope-like composition comprising a mixture, preferably an essentially equimolar mixture, of 1 , 1 , 1-trifluoroethane and pentafluoroethane .
  • the azeotropic or azeotrope-like composition comprising a mixture, e.g. an essentially equimolar mixture, of pentafluoroethane and propane .
  • the azeotropic or azeotrope-like composition comprising a mixture, e.g. an essentially equimolar mixture, of trifluoromethyl difluoromethyl ether and propane.
  • the azeotropic or azeotrope-like composition comprising a mixture, e.g. an essentially equimolar mixture, of trifluoromethyl difluoromethyl ether and difluoromethane .
  • the azeotropic or azeotrope-like composition comprising a mixture, e.g. an essentially equimolar mixture, of perfluoropropane and propane .
  • the low boiling first component comprises at least one refrigerant compound selected from difluoromethane , pentafluoroethane and 1 , 1 , 1-trifluoroethane .
  • Difluoromethane has a boiling point of around -51.7°C
  • pentafluoroethane has a boiling point of around -48.5°C and 1 , 1
  • 1-trifluoroethane has a boiling point of around -47.6°C.
  • the low boiling first component consists essentially of difluoromethane or an azeotropic or azeotrope-like composition in which difluoromethane is a component.
  • the high boiling second component typically has a boiling point in the range of from -40 to +20°C, preferably in the range of from -30 to +10°C and particularly preferably in the range of from -20 to +10°C.
  • the preferred (hydro )fluorocarbons and (hydro )fluorocarbon ethers for the high boiling second component are selected from the group consisting of 1 , 1-difluoroethane (CHF2CH3) ,
  • the high boiling second component may consist of a single refrigerant compound or it may comprise a mixture of such compounds, for example an azeotropic or azeotrope-like mixture.
  • the high boiling second component comprises at least one refrigerant compound selected from pentafluoroethyl difluoromethyl ether, 1 , 1 , 1 , 2-tetrafluoroethyl trifluoromethyl ether, trifluoromethyl fluoromethyl ether, bis (difluoromethyl ) ether, pentafluoroethyl methyl ether, 1 , 1 , 2 , 2-tetrafluoroethyl trifluoromethyl ether, 1,1,1,2,3,3-hexafluoropropane, 1,1, 1,2,2, 3-hexafluoro ⁇ propane and 1 , 1 , 1 , 3 , 3 , 3-hexafluoropropane .
  • refrigerant compound selected from pentafluoroethyl difluoromethyl ether, 1 , 1 , 1 , 2-tetrafluoroethyl trifluoromethyl ether, trifluoromethyl fluoromethyl
  • Pentafluoroethyl difluoromethyl ether has a boiling point of around -12°C, 1 , 1 , 1 , 2-tetrafluoroethyl trifluoromethyl ether has a boiling point of around -8°C, trifluoromethyl fluoromethyl ether has a boiling point of around -20°C, bis (difluoromethyl ) ether has a boiling point of around +2°C, pentafluoroethyl methyl ether has a boiling point of around +5°C, 1 , 1 , 2 , 2-tetrafluoroethyl trifluoromethyl ether has a boiling point of around -2°C, 1 , 1 , 1 , 2 , 3 , 3-hexafluoro ⁇ propane has a boiling point of around +6.6°C, 1 , 1 , 1 , 2 , 2 , 3-hexafluoropropane has a boiling point of around -1.4°C and
  • the respective boiling points of the low boiling first component and the high boiling second component are separated by at least 30°C, preferably by at least 40°C.
  • Azeotropic compositions boil at a constant temperature in the evaporator under constant pressure conditions.
  • the refrigerant composition of the invention is a non-azeotropic (zeotropic) composition which boils over a temperature range rather than at a constant temperature, and it is this property which tends to reduce the energy required to operate the heat transfer device.
  • the temperature range over which the refrigerant composition of the invention boils is comparatively wide in view of the fairly large difference between the boiling points of the low boiling first component (A) and the high boiling second component (B).
  • the refrigerant composition of the invention boils over a temperature range of at least 7°C, more preferably over a temperature range of at least 10°C, and in an especially preferred embodiment the refrigerant composition of the invention will boil over a temperature range of at least 13°C.
  • the refrigerant is used in combination with a lubricant.
  • the lubricant circulates around the device along with the refrigerant and provides for continual lubrication of the compressor.
  • the properties desired of a lubricant include good hydrolytic stability and good thermal stability.
  • the lubricant should be compatible with the refrigerant, which in practice means that the lubricant and refrigerant should possess a degree of mutual solubility, i.e. the lubricant and the refrigerant should be at least partially soluble in one another.
  • a refrigerant/lubricant composition comprising: (1) a non-azeotropic (zeotropic) refrigerant composition comprising:
  • Suitable lubricants include those comprising a polyoxyalkylene glycol base oil.
  • Suitable polyoxyalkylene glycols include hydroxyl group initiated polyoxyalkylene glycols, e.g. ethylene and/or propylene oxide oligomers /polymers initiated on mono- or polyhydric alcohols such as methanol, butanol, pentaerythritol and glycerol.
  • Such polyoxyalkylene glycols may also be end-capped with suitable terminal groups such as alkyl, e.g. methyl groups.
  • Preferred lubricants are those comprising an ester base oil which comprises at least one neopentyl polyol ester derived from the reaction of at least one neopentyl polyol and at least one aliphatic carboxylic acid or an esterifiable derivative thereof.
  • the preference for these lubricants is due, inter alia, to their generally high level of thermal stability.
  • Suitable neopentyl polyols for the formation of the ester base oil include pentaerythritol , polypentaerythritols such as di- and tripentaerythritol , trimethylol alkanes such as" trimethylol ethane and trimethylol propane, and neopentyl glycol.
  • the esters may be formed with linear and/or branched aliphatic carboxylic acids, such as linear and/or branched alkanoic acids.
  • a minor proportion of an aliphatic polycarboxylic acid, e.g. an aliphatic dicarboxylic acid may also be used in the synthesis of the ester in order to increase the viscosity thereof.
  • the amount of the carboxylic acid(s) which is used in the synthesis will be sufficient to esterify all of the hydroxyl groups contained in the polyol, although residual hydroxyl functionality may be acceptable. It will be appreciated that esterifiable derivatives of carboxylic acids may be used in the synthesis if desired.
  • the refrigerant/lubricant compositions of the invention will typically comprise a major amount of the refrigerant and a minor amount of the synthetic lubricant.
  • the refrigerant /lubricant compositions of the invention will comprise from 50 to 99 Z by weight, more preferably from 70 to 99 X by weight, of the refrigerant and from 1 to 50 2 by weight, more preferably from 1 to 30 % by weight, of the lubricant based on the total weight thereof.

Abstract

A non-azeotropic refrigerant composition comprising (A) a first component which is a low boiling refrigerant comprising at least one compound selected from the group consisting of the (hydro)fluorocarbons, (hydro)fluorocarbon ethers, hydrocarbons and CO2 and (B) a second component which is a high boiling refrigerant comprising at least one compound selected from the group consisting of the (hydro)fluorocarbons and (hydro)fluorocarbon ethers, the first component (A) and the second component (B) having boiling points which are separated by at least 20 °C.

Description

REFRIGERANT COMPOSITIONS
The present invention relates generally to non-azeotropic refrigerant compositions and in particular to non-azeotropic refrigerant compositions which are designed to replace chlorodifluoromethane (Refrigerant R-22).
Heat transfer devices of the mechanical compression type such as refrigerators, freezers, heat pumps and air conditioning systems are well known. In such devices a refrigerant liquid of a suitable boiling point evaporates at low pressure taking heat from a surrounding zone. The resulting vapour is then compressed and passes to a condenser where it condenses and gives off heat to a second zone. The condensate is then returned through an expansion valve to the evaporator so completing the cycle. The mechanical energy required for compressing the vapour and pumping the liquid may be provided by an electric motor or an internal combustion engine.
In addition to having a suitable boiling po'int and a high latent heat of vaporisation, the properties preferred of a refrigerant include low toxicity, non- flammability , non-corrosivity , high stability and freedom from objectionable odour.
Hitherto, heat transfer devices have tended to use fully and partially halogenated chlorofluorocarbon refrigerants such as trichlorofluoromethane (Refrigerant R-ll), dichlorodifluoromethane (Refrigerant R-12), chlorodifluoromethane (Refrigerant R-22), or the azeotropic mixture of chlorodifluoromethane and chloropentafluoroethane (Refrigerant R-115); the azeotrope being Refrigerant R-502. Refrigerant R-22, for example, is widely used in air conditioning systems.
However, the fully and partially halogenated chlorofluorocarbons have been implicated in the destruction of the earth's protective ozone layer and as a result the use and production thereof is to be severely limited by international agreement.
Whilst heat transfer devices of the type to which the present invention relates are essentially closed systems, loss of refrigerant to the atmosphere can occur due to leakage during operation of the equipment or during maintenance procedures. It is important, therefore, to replace fully and partially halogenated chlprofluorocarbon refrigerants by materials having low or zero ozone depletion potentials.
In addition to the possibility of ozone depletion, it has been suggested that significant concentrations of chlorofluorocarbon refrigerants in the atmosphere might contribute to global warming (the so-called greenhouse effect). It is desirable, therefore, to use refrigerants which have relatively short atmospheric lifetimes as a result of their ability to react with other atmospheric constituents such as hydroxyl radicals .
Replacements for certain of the chlorofluorocarbon refrigerants presently in use have been developed. These replacement refrigerants tend to comprise selected hydrofluoroalkanes , i.e. compounds which contain only carbon, hydrogen and fluorine atoms in their structure. Thus, refrigerant R-12 is generally being replaced by 1 , 1 , 1 , 2-tetrafluoroethane (HFC-134a).
Although replacement refrigerants for R-22 having the required low or zero ozone depletion potential have been proposed, the present inventors realised that in certain heat transfer systems it would be beneficial to replace Refrigerant R-22 with a non-azeotropic refrigerant blend which not only exhibits a low or zero ozone depletion potential but also boils over a reasonably wide temperature range, since in this way the energy efficiency of the system may be improved leading to a reduction in indirect global warming. Non-azeotropic mixtures of this type may, in particular, be usefully employed as the heat transfer fluid in air conditioning units.
The present invention provides a non-azeotropic refrigerant composition which is a blend of compounds having low or zero ozone depletion potentials. The refrigerant composition of the invention can exhibit a wide boiling point range and may be used as a replacement for R-22 in air conditioning units.
According to the present invention there is provided a non-azeotropic (zeotropic) refrigerant composition comprising:
(A) a first component which is a low boiling refrigerant comprising at least one compou'nd selected from the group consisting of the (hydro ) fluorocarbons , (hydro ) fluorocarbon ethers, hydrocarbons and CO2; and
(B) a second component which is a high boiling refrigerant comprising at least one compound selected from the group consisting of the (hydro ) fluorocarbons and (hydro ) fluorocarbon ethers , wherein the low boiling first component and the high boiling second component have boiling points which are separated by at least 20°C.
In this specification, a (hydro ) fluorocarbon is a compound selected from the group consisting of the hydrofluorocarbons and the perfluorocarbons and a (hydro ) fluorocarbon ether is a compound selected from the group consisting of the hydrofluorocarbon ethers and the perfluorocarbon ethers.
The low boiling first component typically has a boiling point in the range of from -90 to -30°C, preferably in the range of from -70 to -40°C and particularly preferably in the range of from -60 to -45°C.
A preferred hydrocarbon for the low boiling first component is propane.
The preferred (hydro )fluorocarbons and (hydro ) fluorocarbon ethers for the low boiling first component are selected from the group consisting of trifluoromethane (CHF3), fluoromethane (CH3F), difluoromethane (CH2F2)! pentafluoroethane (CF3CHF2), 1 , 1 , 1-trifluoroethane (CF3CH3), perfluoropropane (CF3CF2CF3), trifluoromethyl difluoromethyl ether (CF3OCF2H) and bis (trifluoromethyl ) ether (CF3OCF3) .
The low boiling first component may consist of a single refrigerant compound or it may comprise a mixture of such compounds. Where mixtures of refrigerant compounds are employed for the low boiling first component, they will preferably form an azeotropic or azeotrope-like composition. Preferred azeotropic or azeotrope-like compositions for the low boiling first component include the following:
(1) The azeotropic or azeotrope-like composition comprising a mixture, preferably an essentially equimolar mixture, of difluoromethane and pentafluoroethane .
(2) The azeotropic or azeotrope-like composition comprising a mixture, preferably an essentially equimolar mixture, of 1 , 1 , 1-trifluoroethane and pentafluoroethane .
(3) The azeotropic or azeotrope-like composition comprising a mixture, e.g. an essentially equimolar mixture, of pentafluoroethane and propane .
(4) The azeotropic or azeotrope-like composition comprising a mixture, e.g. an essentially equimolar mixture, of trifluoromethyl difluoromethyl ether and propane.
(5) The azeotropic or azeotrope-like composition comprising a mixture, e.g. an essentially equimolar mixture, of trifluoromethyl difluoromethyl ether and difluoromethane . (6) The azeotropic or azeotrope-like composition comprising a mixture, e.g. an essentially equimolar mixture, of perfluoropropane and propane .
In a preferred embodiment, the low boiling first component comprises at least one refrigerant compound selected from difluoromethane , pentafluoroethane and 1 , 1 , 1-trifluoroethane . Difluoromethane has a boiling point of around -51.7°C, pentafluoroethane has a boiling point of around -48.5°C and 1 , 1 , 1-trifluoroethane has a boiling point of around -47.6°C. In a particularly preferred embodiment, the low boiling first component consists essentially of difluoromethane or an azeotropic or azeotrope-like composition in which difluoromethane is a component. The high boiling second component typically has a boiling point in the range of from -40 to +20°C, preferably in the range of from -30 to +10°C and particularly preferably in the range of from -20 to +10°C. The preferred (hydro )fluorocarbons and (hydro )fluorocarbon ethers for the high boiling second component are selected from the group consisting of 1 , 1-difluoroethane (CHF2CH3) ,
1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3) , 1,1,1,2,2,3 , 3-heptafluoropropane (CF3CF2CHF2), 1 , 1 , 1 , 2 , 2-pentafluoropropane (CF3CF2CH3) , 1,1,2,2-tetrafluoroethane (CHF2CHF2) , 1,1,1,2,3, 3-hexafluoropropane (CF3CHFCHF2) , 1 , 1 , 1 ,2 ,2, 3-hexafluoropropane (CF3CF2CH2F) , 1,1,1,3,3, 3-hexafluoropropane (CF3CH2CF3) , 1,1,2,2,3, 3-hexafluoropropane (CHF2CF2CHF2 ) , 1 , 1 , 2-trifluoroethane (CHF2CH2F) , 1,1,2,2-tetrafluoropropane (CHF2CF2CH3) , pentafluoroethyl difluoromethyl ether (CF3CF2OCHF2) , 1 , 1 , 1 , 2-tetrafluoroethyl trifluoromethyl ether (CF3CHFOCF3 ) , trifluoromethyl fluoromethyl ether (CF3OCH2F), bis (difluoromethyl) ether (CHF20CHF2), pentafluoroethyl methyl ether (CF3CF2OCH3 ) , 1 , 1 , 2 , 2-tetrafluoroethyl trifluoromethyl ether (CHF2CF2OCF3 ) and perfluorocyclobutane (C F8) .
The high boiling second component may consist of a single refrigerant compound or it may comprise a mixture of such compounds, for example an azeotropic or azeotrope-like mixture.
In a preferred embodiment, the high boiling second component comprises at least one refrigerant compound selected from pentafluoroethyl difluoromethyl ether, 1 , 1 , 1 , 2-tetrafluoroethyl trifluoromethyl ether, trifluoromethyl fluoromethyl ether, bis (difluoromethyl ) ether, pentafluoroethyl methyl ether, 1 , 1 , 2 , 2-tetrafluoroethyl trifluoromethyl ether, 1,1,1,2,3,3-hexafluoropropane, 1,1, 1,2,2, 3-hexafluoro¬ propane and 1 , 1 , 1 , 3 , 3 , 3-hexafluoropropane . Pentafluoroethyl difluoromethyl ether has a boiling point of around -12°C, 1 , 1 , 1 , 2-tetrafluoroethyl trifluoromethyl ether has a boiling point of around -8°C, trifluoromethyl fluoromethyl ether has a boiling point of around -20°C, bis (difluoromethyl ) ether has a boiling point of around +2°C, pentafluoroethyl methyl ether has a boiling point of around +5°C, 1 , 1 , 2 , 2-tetrafluoroethyl trifluoromethyl ether has a boiling point of around -2°C, 1 , 1 , 1 , 2 , 3 , 3-hexafluoro¬ propane has a boiling point of around +6.6°C, 1 , 1 , 1 , 2 , 2 , 3-hexafluoropropane has a boiling point of around -1.4°C and 1 , 1 , 1 , 3 , 3 , 3-hexafluoropropane has a boiling point of around -1.1°C.
In a preferred embodiment, the respective boiling points of the low boiling first component and the high boiling second component are separated by at least 30°C, preferably by at least 40°C.
Azeotropic compositions boil at a constant temperature in the evaporator under constant pressure conditions. In contrast, the refrigerant composition of the invention is a non-azeotropic (zeotropic) composition which boils over a temperature range rather than at a constant temperature, and it is this property which tends to reduce the energy required to operate the heat transfer device. The temperature range over which the refrigerant composition of the invention boils is comparatively wide in view of the fairly large difference between the boiling points of the low boiling first component (A) and the high boiling second component (B). Preferably, the refrigerant composition of the invention boils over a temperature range of at least 7°C, more preferably over a temperature range of at least 10°C, and in an especially preferred embodiment the refrigerant composition of the invention will boil over a temperature range of at least 13°C.
In a heat transfer device, the refrigerant is used in combination with a lubricant. The lubricant circulates around the device along with the refrigerant and provides for continual lubrication of the compressor. In addition to possessing good lubricity in the presence of the refrigerant, the properties desired of a lubricant include good hydrolytic stability and good thermal stability. Moreover, in order to provide for the return of the lubricant to the compressor, the lubricant should be compatible with the refrigerant, which in practice means that the lubricant and refrigerant should possess a degree of mutual solubility, i.e. the lubricant and the refrigerant should be at least partially soluble in one another.
Thus, in accordance with a further aspect of the present invention there is provided a refrigerant/lubricant composition comprising: (1) a non-azeotropic (zeotropic) refrigerant composition comprising:
(A) a first component which is a low boiling refrigerant comprising at least one compound selected from the group consisting of the (hydro Jfluorocarbons , (hydro )fluorocarbon ethers, hydrocarbons and CO2; and
(B) a second component which is a high boiling refrigerant comprising at least one compound selected from the group consisting of the (hydro ) fluorocarbons and (hydro )fluorocarbon ethers , the low boiling first component and the high boiling second component having boiling points which are separated by at least 20°C; and (2) sufficient to provide lubrication of a lubricant.
Suitable lubricants include those comprising a polyoxyalkylene glycol base oil. Suitable polyoxyalkylene glycols include hydroxyl group initiated polyoxyalkylene glycols, e.g. ethylene and/or propylene oxide oligomers /polymers initiated on mono- or polyhydric alcohols such as methanol, butanol, pentaerythritol and glycerol. Such polyoxyalkylene glycols may also be end-capped with suitable terminal groups such as alkyl, e.g. methyl groups.
Preferred lubricants are those comprising an ester base oil which comprises at least one neopentyl polyol ester derived from the reaction of at least one neopentyl polyol and at least one aliphatic carboxylic acid or an esterifiable derivative thereof. The preference for these lubricants is due, inter alia, to their generally high level of thermal stability.
Suitable neopentyl polyols for the formation of the ester base oil include pentaerythritol , polypentaerythritols such as di- and tripentaerythritol , trimethylol alkanes such as" trimethylol ethane and trimethylol propane, and neopentyl glycol. The esters may be formed with linear and/or branched aliphatic carboxylic acids, such as linear and/or branched alkanoic acids. A minor proportion of an aliphatic polycarboxylic acid, e.g. an aliphatic dicarboxylic acid, may also be used in the synthesis of the ester in order to increase the viscosity thereof. Usually, the amount of the carboxylic acid(s) which is used in the synthesis will be sufficient to esterify all of the hydroxyl groups contained in the polyol, although residual hydroxyl functionality may be acceptable. It will be appreciated that esterifiable derivatives of carboxylic acids may be used in the synthesis if desired.
The refrigerant/lubricant compositions of the invention will typically comprise a major amount of the refrigerant and a minor amount of the synthetic lubricant. Preferably, the refrigerant /lubricant compositions of the invention will comprise from 50 to 99 Z by weight, more preferably from 70 to 99 X by weight, of the refrigerant and from 1 to 50 2 by weight, more preferably from 1 to 30 % by weight, of the lubricant based on the total weight thereof.

Claims

C l a ims :
1. A non-azeotropic refrigerant composition comprising :
(A) a first component which is a low boiling refrigerant comprising at least one compound selected from the group consisting of the (hydro ) fluorocarbons , (hydro ) fluorocarbon ethers, hydrocarbons and CO2 and
(B) a second component which is a high boiling refrigerant comprising at least one compound selected from the group consisting of the (hydro ) fluorocarbons and (hydro ) fluorocarbon ethers , wherein the low boiling first component and the high boiling second component have boiling points which are separated by at least 20°C.
2. A refrigerant composition as claimed in claim 1 wherein the low boiling first component (A) has a boiling point in the range of from -90 to -30°C.
3. A refrigerant composition as claimed in claim 1 or claim 2 wherein the low boiling first component (A) comprises propane.
4. A refrigerant composition as claimed in any one of claims 1 to 3 wherein the low boiling first component
(A) comprises at least one compound selected from the group consisting of trifluoromethane , fluoromethane , difluoromethane , pentafluoroethane, 1,1,1-trifluoroethane, perfluoropropane, trifluoromethyl difluoromethyl ether and bis ( trifluoromethyl ) ether.
5. A refrigerant composition as claimed in claim 4 wherein the low boiling first component (A) comprises at least one refrigerant compound selected from difluoromethane , pentafluoroethane and 1,1, 1-trifluoroethane .
6. A refrigerant composition as claimed in claim 4 or claim 5 wherein the low boiling first component (A) consists essentially of difluoromethane or an azeotropic or azeotrope-like composition in which difluoromethane is a component.
7. A refrigerant composition as claimed in claim 4 wherein the low boiling first component (A) is an azeotropic or azeotrope-like composition comprising a mixture of difluoromethane and pentafluoroethane.
8. A refrigerant composition as claimed in claim 4 wherein the low boiling first component (A) is an azeotropic or azeotrope-like composition comprising a mixture of 1 , 1 , 1-trifluoroethane and pentafluoroethane.
9. A refrigerant composition as claimed in claim 4 wherein the low boiling first component (A) is an azeotropic or azeotrope-like composition comprising a mixture of pentafluoroethane and propane. ιo. A refrigerant composition as claimed in claim 4 wherein the low boiling first component (A) is an azeotropic or azeotrope-like composition comprising a mixture of trifluoromethyl difluoromethyl ether and propane . 11. A refrigerant composition as claimed in claim 4 wherein the low boiling first component (A) is an azeotropic or azeotrope-like composition comprising a mixture of trifluoromethyl difluoromethyl ether and difluoromethane. 12. A refrigerant composition as claimed in claim 4 wherein the low boiling first component (A) is an azeotropic or azeotrope-like composition comprising a mixture of perfluoropropane and propane. • 13. A refrigerant composition as claimed in any one of claims 1 to 12 wherein the high boiling second component (B) has a boiling point in the range of from -40 to +20°C. -* 14. A refrigerant composition as claimed in any one of claims 1 to 13 wherein the high boiling second component (B) comprises at least one compound selected from the group consisting of 1 , 1-difluoroethane (CHF2CH3) , 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3), 1, 1 ,1,2,2, 3 , 3-heptafluoropropane
(CF3CF2CHF2) , 1 , 1 ,1 , 2 , 2-pentafluoropropane (CF3CF2CH3), 1,1,2, 2-tetrafluoroethane (CHF2CHF2) , 1,1,1,2,3, 3-hexafluoropropane (CF3CHFCHF2) , 1 ,1 , 1 , 2 , 2 , 3-hexafluoropropane (CF3CF2CH2F) , 1 , 1 , 1, 3 , 3 , 3-hexafluoropropane (CF3CH2CF3),
1,1,2,2,3,3-hexafluoropropane (CHF2CF2CHF2) ,
1 , 1,2-trifluoroethane (CHF2CH2F) ,
1 , 1 , 2 , 2-tetrafluoropropane (CHF2CF2CH3) , pentafluoroethyl difluoromethyl ether (CF3CF2OCHF2 ) , 1 , 1 , 1 , 2-tetrafluoroethyl trifluoromethyl ether
( CF3CHFOCF3 ) , trifluoromethyl fluoromethyl ether (CF3OCH2F), bis (difluoromethyl ) ether (CHF2OCHF2), pentafluoroethyl methyl ether (CF3CF2OCH3 ) , 1 , 1 , 2 , 2-tetrafluoroethyl trifluoromethyl ether (CHF2CF2OCF3 ) and perfluorocyclobutane (C4F8).
15. A refrigerant composition as claimed in claim 14 wherein the high boiling second component (B) comprises at least one compound selected from the group consisting of pentafluoroethyl difluoromethyl ether, 1 , 1 , 1 , 2-tetrafluoroethyl trifluoromethyl ether, trifluoromethyl fluoromethyl ether, bis ( difluoromethyl ) ether, pentafluoroethyl methyl ether,
1 , 1 , 2 , 2-tetrafluoroethyl trifluoromethyl ether, 1,1,1,2,3,3-hexafluoropropane, 1,1,1,2,2, 3-hex fluoro- propane and 1 , 1 , 1 , 3 , 3 , 3-hexafluoropropane .
16. A refrigerant composition as claimed in any one of claims 1 to 15 wherein the respective boiling points of the low boiling first component (A) and the high boiling second component (B) are separated by at least 30°C.
17. A refrigerant composition as claimed in claim 16 wherein the respective boiling points of the low boiling first component (A) and the high boiling second component (B) are separated by at least 40°C.
EP94904250A 1993-01-20 1994-01-13 Refrigerant compositions Ceased EP0680503A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9301004 1993-01-20
GB939301004A GB9301004D0 (en) 1993-01-20 1993-01-20 Refrigerant compositions
GB939322307A GB9322307D0 (en) 1993-10-29 1993-10-29 Refrigerant compositions
GB9322307 1993-10-29
PCT/GB1994/000066 WO1994017153A1 (en) 1993-01-20 1994-01-13 Refrigerant compositions

Publications (1)

Publication Number Publication Date
EP0680503A1 true EP0680503A1 (en) 1995-11-08

Family

ID=26302313

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94904250A Ceased EP0680503A1 (en) 1993-01-20 1994-01-13 Refrigerant compositions

Country Status (7)

Country Link
EP (1) EP0680503A1 (en)
JP (1) JPH08505657A (en)
KR (1) KR960700323A (en)
AU (1) AU686129B2 (en)
BR (1) BR9406264A (en)
CA (1) CA2153072A1 (en)
WO (1) WO1994017153A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5605882A (en) * 1992-05-28 1997-02-25 E. I. Du Pont De Nemours And Company Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane
WO1994011460A1 (en) * 1992-11-19 1994-05-26 E.I. Du Pont De Nemours And Company Refrigerant compositions including 1,1,2-trifluoroethane
US5417871A (en) * 1994-03-11 1995-05-23 E. I. Du Pont De Nemours And Company Hydrofluorocarbon compositions
US6001273A (en) 1994-03-11 1999-12-14 Minor; Barbara Haviland Binary azeotropes of difluoromethane and hydrocarbons
GB9414133D0 (en) * 1994-07-13 1994-08-31 Ici Plc Refrigerant compositions
GB9414134D0 (en) * 1994-07-13 1994-08-31 Ici Plc Refrigerant compositions
GB9414136D0 (en) * 1994-07-13 1994-08-31 Ici Plc Refrigerant compositions
GB9414110D0 (en) * 1994-07-13 1994-08-31 Ici Plc Refrigeration compositions
DE69506550D1 (en) * 1994-07-14 1999-01-21 Du Pont COOLING COMPOSITIONS
US5688431A (en) * 1994-09-29 1997-11-18 E. I. Du Pont De Nemours And Company Octafluorobutane compositions
US5705471A (en) * 1994-09-29 1998-01-06 E. I. Du Pont De Nemours And Company 1,1,2,2,3,3,4,4-octaflourobutane compositions
US5562853A (en) * 1994-09-29 1996-10-08 E. I. Du Pont De Nemours And Company 1,1,2,2,3,3,4,4,-octafluorobutane compositions
US5562855A (en) * 1994-09-29 1996-10-08 E. I. Du Pont De Nemours And Company Octafluorobutane compositions
US5558810A (en) * 1994-11-16 1996-09-24 E. I. Du Pont De Nemours And Company Pentafluoropropane compositions
US5681501A (en) * 1995-10-11 1997-10-28 E. I. Du Pont De Nemours And Company Compositions including a hydrofluoropropane
US6688118B1 (en) 1996-03-01 2004-02-10 E. I. Du Pont De Nemours And Company Azeotropic compositions of cyclopentane
US5954995A (en) * 1996-03-22 1999-09-21 Goble; George H. Drop-in substitutes for 1,1,1,2-tetrafluoroethane (R-134a) refrigerant
US5730894A (en) * 1996-04-16 1998-03-24 E. I. Du Pont De Nemours And Company 1,1,2,2,3,3,4,4-octafluorobutane azeotropic (like) compositions
GB9618207D0 (en) * 1996-08-30 1996-10-09 Ici Plc Refrigerant compositions
JP4153590B2 (en) * 1998-06-26 2008-09-24 株式会社三愛 Working fluid
US6056891A (en) * 1998-09-01 2000-05-02 Goble; George H. Drop-in performance increasing substitute for 1,1,1,2-tetrafluoroethane refrigerant
US6881354B2 (en) * 1998-12-30 2005-04-19 Praxair Technology, Inc. Multicomponent refrigerant fluids for low and cryogenic temperatures
WO2002001120A1 (en) 2000-06-28 2002-01-03 Igc Polycold Systems, Inc. Nonflammable mixed refrigerants (mr) for use with very low temperature throttle-cycle refrigeration systems
JP3934140B2 (en) * 2002-12-03 2007-06-20 日本フリーザー株式会社 Non-azeotropic refrigerant

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3508624A1 (en) * 1985-03-11 1986-09-11 Siemens AG, 1000 Berlin und 8000 München Heat pump
US4810403A (en) * 1987-06-09 1989-03-07 E. I. Du Pont De Nemours And Company Halocarbon blends for refrigerant use
US4961321A (en) * 1989-02-28 1990-10-09 W. R. Grace & Co.-Conn. Bis (difluoromethyl) ether refrigerant
EP0430169B1 (en) * 1989-11-30 1994-08-17 Matsushita Electric Industrial Co., Ltd. Working fluid
EP0602022B1 (en) * 1990-07-26 1997-05-21 E.I. Du Pont De Nemours And Company Near-azeotropic blends for use as refrigerants
CN1029625C (en) * 1990-12-17 1995-08-30 纳幕尔杜邦公司 Constant boiling compositions of fluorinated hydrocarbons
CA2105565C (en) * 1991-03-18 2003-11-04 Robert Gerard Richard Non-azeotropic refrigerant compositions comprising difluoromethane; 1,1,1-trifluoroethane; or propane
JP2568774B2 (en) * 1991-10-28 1997-01-08 松下電器産業株式会社 Working fluid
GB9200521D0 (en) * 1992-01-10 1992-02-26 Ici Plc Compositions useful as refrigerants
DE69303603D1 (en) * 1992-03-03 1996-08-14 Univ Moncton Res Centre NON-AZEOTROPE REFRIGERANT MIXTURE FROM R23, R125 AND R32

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9417153A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration

Also Published As

Publication number Publication date
AU5838594A (en) 1994-08-15
JPH08505657A (en) 1996-06-18
WO1994017153A1 (en) 1994-08-04
BR9406264A (en) 1996-01-30
CA2153072A1 (en) 1994-08-04
KR960700323A (en) 1996-01-19
AU686129B2 (en) 1998-02-05

Similar Documents

Publication Publication Date Title
AU686129B2 (en) Refrigerant compositions
US10377935B2 (en) 2,3,3,3-tetrafluoropropene compositions having improved miscibility
US6117356A (en) Refrigerant compositions
US6106740A (en) Non-azeotropic refrigerant composition of CO2, R-125, R-143a and R-22
EP0770113B1 (en) Refrigerant compositions
EP0845019A1 (en) Refrigerant compositions
EP0770112B1 (en) Refrigerant compositions
JP4143127B2 (en) Refrigerant composition
EP0845021A1 (en) Refrigerant compositions
EP0922077B1 (en) Refrigerant compositions
WO1996003472A1 (en) Refrigerant compositions
EP0922075B1 (en) Refrigerant compositions
WO1996002603A1 (en) Refrigerant compositions
CA2227910A1 (en) Refrigerant compositions
WO1996002605A1 (en) Refrigerant compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950614

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 19960513

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19990809