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WO1997007180A1 - Compositions de refrigerants - Google Patents

Compositions de refrigerants Download PDF

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Publication number
WO1997007180A1
WO1997007180A1 PCT/GB1996/001956 GB9601956W WO9707180A1 WO 1997007180 A1 WO1997007180 A1 WO 1997007180A1 GB 9601956 W GB9601956 W GB 9601956W WO 9707180 A1 WO9707180 A1 WO 9707180A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
refrigerant composition
refrigerant
azeotropic refrigerant
composition
Prior art date
Application number
PCT/GB1996/001956
Other languages
English (en)
Inventor
Richard Llewellyn Powell
Stuart Corr
Frederick Thomas Murphy
James David Morrison
Original Assignee
Imperial Chemical Industries Plc
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 Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to AU67077/96A priority Critical patent/AU6707796A/en
Priority to EP96927147A priority patent/EP0845020A1/fr
Priority to JP9509030A priority patent/JPH11511191A/ja
Publication of WO1997007180A1 publication Critical patent/WO1997007180A1/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
    • 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
    • C09K2205/122—Halogenated 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
    • C09K2205/34—The mixture being non-azeotropic

Definitions

  • the present invention relates to non-azeotropic refrigerant compositions and more particularly to non-azeotropic refrigerant compositions which can be used in the low temperature refrigeration applications currently satisfied by refrigerant R-502 which is an azeotropic mixture of chlorodifluoromethane (refrigerant R-22) and chloropentafluoroethane (refrigerant R-115).
  • refrigerant R-502 which is an azeotropic mixture of chlorodifluoromethane (refrigerant R-22) and chloropentafluoroethane (refrigerant R-115).
  • 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 heat transfer fluid.
  • the resulting vapour is then compressed and passes to a condenser where it condenses and gives off heat to another heat transfer fluid.
  • 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-corrosivit , high stability and freedom from objectionable odour.
  • the present invention provides a non-azeotropic refrigerant composition comprising a mixture of compounds having low or zero ozone depletion potentials which can be used in the low temperature refrigeration applications currently satisfied by refrigerant R-502.
  • the non-azeotropic refrigerant composition of the invention can exhibit an advantageously high refrigeration capacity.
  • non-azeotropic (zeotropic) refrigerant composition comprising:
  • the zeotropic refrigerant composition of the invention comprises four separate components.
  • the first component (component (A)) is carbon dioxide (C0 2 ) which exhibits a low temperature refrigeration action subliming at around -78.5°C.
  • the second component (component (B)) is pentafluoroethane (R-125) which has a boiling point of around -48.5°C.
  • the third component (component (C)) is propane (R-290) which has a boiling point of around -42.1°C.
  • the fourth component (component (D) ) is chlorodifluoromethane (R-22) which has a boiling point of around -40.8°C.
  • the amounts of the various components in the refrigerant composition may be varied within wide limits, but typically the refrigerant composition will comprise from 1 to 20 1 by weight C0 2 , from 25 to 70 Z by weight R-125, from 0.5 to 15 Z by weight R-290 and from 25 to 70 Z by weight R-22.
  • a preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-502 is one comprising from 1 to 15 2 by weight C0 2 , from 30 to 65 Z by weight R-125, from 0.5 to 10 Z by weight R-290 and from 30 to 65 Z by weight R-22.
  • a particularly preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-502 is one comprising from 1 to 15 I by weight, more particularly from 2 to 10 Z by weight, C0 2 , from 50 to 65 % by weight, more particularly from 50 to 60 Z by weight, R-125, from 0.5 to 10 Z by weight, more particularly from 1 to 5 Z by weight, R-290 and from 30 to 45 X by weight, more particularly from 30 to 40 X by weight, R-22.
  • An especially preferred refrigerant composition of the invention is one comprising from 2 to 5 X by weight C0 2 , from 55 to 60 Z by weight R-125, from 1 to 3 Z by weight R-290 and from 35 to 40 X by weight R-22.
  • Another particularly preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-502 is one comprising from 1 to 15 Z by weight, more particularly from 2 to 10 Z by weight, C0 2 , from 30 to 45 Z by weight, more particularly from 30 to 40 Z by weight, R-125, from 0.5 to 10 Z by weight, more particularly from 1 to 5 Z by weight, R-290 and from 50 to 65 Z by weight, more particularly from 50 to 60 Z by weight, R-22.
  • An especially preferred refrigerant composition of the invention is one comprising from 2 to 5 Z by weight C0 2 , from 35 to 40 X by weight R-125, from 1 to 3 2 by weight R-290 and from 55 to 60 Z by weight R-22.
  • the refrigerant composition of the invention may be used in combination with the types of lubricants which have been specially developed for use with hydrofluorocarbon based refrigerants.
  • Such 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.
  • lubricants which have been developed for use with hydrofluorocarbon based refrigerants and which may be used in combination with the present refrigerant compositions are those comprising a neopentyl polyol ester base oil derived from the reaction of at least one neopentyl polyol and at least one aliphatic carboxylic acid or an esterifiable derivative thereof.
  • 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. Preferred acids are selected from the C 5 _ 8 , particularly the C 5 _ 7 , linear alkanoic acids and the C 5 _ 10 , particularly the C 5 _ 9 , branched alkanoic acids.
  • a minor proportion of an aliphatic polycarboxylic acid may also be used in the synthesis of the ester in order to increase the viscosity thereof.
  • an aliphatic polycarboxylic acid e.g. an aliphatic dicarboxylic acid
  • 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.
  • the zeotropic refrigerant composition of the present invention may be used to provide the desired cooling in heat transfer devices such as low temperature refrigeration systems by a method which involves condensing the refrigerant composition and thereafter evaporating it in a heat exchange relationship with a heat transfer fluid to be cooled.
  • the refrigerant composition of the invention may be employed as a replacement for refrigerant R-502 in low temperature refrigeration applications.
  • a composition comprising 2 X by weight C0 2 , 58.8 X by weight R-125, 2 Z by weight R-290 and 37.2 1 by weight R-22.
  • composition comprising 5 Z by weight C0 2 , 57 Z by weight R-125, 1.9 Z by weight R-290 and 36.1 Z by weight R-22.
  • composition comprising 10 Z by weight C0 2 , 54 Z by weight R-125, 1.8 Z by weight R-290 and 34.2 Z by weight R-22.
  • a composition comprising 2 Z by weight C0 2 , 37.2 Z by weight R-125, 2 Z by weight R-290 and 58.8 Z by weight R-22.
  • a composition comprising 5 Z by weight C0 2 , 36.1 Z by weight R-125, 1.9 Z by weight R-290 and 57 Z by weight R-22.
  • a composition comprising 10 Z by weight C0 2 , 34.2 X by weight R-125, 1.8 X by weight R-290 and 54 Z by weight R-22.

Landscapes

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

Abstract

L'invention concerne une composition de réfrigérant non azéotropique comprenant (A) du dioxyde de carbone (CO2), (B) du pentafluoroéthane (R-125), (C) du propane (R-290) et (D) du chlorodifluorométhane (R-22).
PCT/GB1996/001956 1995-08-18 1996-08-12 Compositions de refrigerants WO1997007180A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU67077/96A AU6707796A (en) 1995-08-18 1996-08-12 Refrigerant compositions
EP96927147A EP0845020A1 (fr) 1995-08-18 1996-08-12 Compositions de refrigerants
JP9509030A JPH11511191A (ja) 1995-08-18 1996-08-12 冷媒組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9516919.9A GB9516919D0 (en) 1995-08-18 1995-08-18 Refrigerant compositions
GB9516919.9 1995-08-18

Publications (1)

Publication Number Publication Date
WO1997007180A1 true WO1997007180A1 (fr) 1997-02-27

Family

ID=10779409

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/001956 WO1997007180A1 (fr) 1995-08-18 1996-08-12 Compositions de refrigerants

Country Status (6)

Country Link
EP (1) EP0845020A1 (fr)
JP (1) JPH11511191A (fr)
AU (1) AU6707796A (fr)
CA (1) CA2227910A1 (fr)
GB (1) GB9516919D0 (fr)
WO (1) WO1997007180A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1431684A1 (fr) * 2002-12-20 2004-06-23 Sanyo Electric Co., Ltd. Mélange réfrigérant nonazeotrope, cycle de réfrigération et dispositif de réfrigération
EP1431683A3 (fr) * 2002-12-20 2004-10-13 Sanyo Electric Co., Ltd Dispositif de réfrigération
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4116274A1 (de) * 1991-05-17 1992-11-19 Forschungszentrum Fuer Kaeltet Kaeltemittel
EP0568115A2 (fr) * 1990-07-26 1993-11-03 E.I. Du Pont De Nemours And Company Mélanges quasi-azéotropes destinés à être utilisés comme refrigérants
WO1994011458A1 (fr) * 1992-11-06 1994-05-26 Intermagnetics General Corporation Refrigerant compose d'hydrocarbures pour systemes de refrigeration a cycle ferme
EP0638623A1 (fr) * 1993-08-13 1995-02-15 AUSIMONT S.p.A. Mélanges quasi-azéotropes utilisables comme fluides frigorifiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0568115A2 (fr) * 1990-07-26 1993-11-03 E.I. Du Pont De Nemours And Company Mélanges quasi-azéotropes destinés à être utilisés comme refrigérants
DE4116274A1 (de) * 1991-05-17 1992-11-19 Forschungszentrum Fuer Kaeltet Kaeltemittel
WO1994011458A1 (fr) * 1992-11-06 1994-05-26 Intermagnetics General Corporation Refrigerant compose d'hydrocarbures pour systemes de refrigeration a cycle ferme
EP0638623A1 (fr) * 1993-08-13 1995-02-15 AUSIMONT S.p.A. Mélanges quasi-azéotropes utilisables comme fluides frigorifiques

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1431684A1 (fr) * 2002-12-20 2004-06-23 Sanyo Electric Co., Ltd. Mélange réfrigérant nonazeotrope, cycle de réfrigération et dispositif de réfrigération
EP1431683A3 (fr) * 2002-12-20 2004-10-13 Sanyo Electric Co., Ltd Dispositif de réfrigération
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration

Also Published As

Publication number Publication date
AU6707796A (en) 1997-03-12
GB9516919D0 (en) 1995-10-18
EP0845020A1 (fr) 1998-06-03
JPH11511191A (ja) 1999-09-28
CA2227910A1 (fr) 1997-02-27

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