WO1997007181A1 - Compositions de refrigerants - Google Patents

Compositions de refrigerants Download PDF

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Publication number
WO1997007181A1
WO1997007181A1 PCT/GB1996/001960 GB9601960W WO9707181A1 WO 1997007181 A1 WO1997007181 A1 WO 1997007181A1 GB 9601960 W GB9601960 W GB 9601960W WO 9707181 A1 WO9707181 A1 WO 9707181A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
refrigerant composition
azeotropic refrigerant
refrigerant
composition
Prior art date
Application number
PCT/GB1996/001960
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 AU67463/96A priority Critical patent/AU6746396A/en
Priority to EP96927757A priority patent/EP0845021A1/fr
Priority to JP9509032A priority patent/JPH11511192A/ja
Publication of WO1997007181A1 publication Critical patent/WO1997007181A1/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
    • C09K2205/34—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 bromotrifluoromethane (R-13B1).
  • 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-corrosivity, high stability and freedom from objectionable odour.
  • chlorofluorocarbon refrigerants such as bromotrifluoromethane (refrigerant R-13B1), trichlorofluoromethane (refrigerant R-ll), dichlorodifluoromethane (refrigerant R-12), chlorodifluoromethane (refrigerant R-22) and the azeotropic mixture of chlorodifluoromethane and chloropentafluoroethane (refrigerant R-115); the azeotrope being refrigerant R-502.
  • Refrigerant R-13B1 has been widely used in low temperature refrigeration applications.
  • 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-13B1.
  • non-azeotropic (zeotropic) refrigerant composition comprising:
  • the zeotropic refrigerant composition of the invention comprises three 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 difluoromethane (R-32) which has a boiling point of around -51.6°C.
  • the third component (component (C)) is pentafluoroethane (R-125) which has a boiling point of around -48.5°C.
  • a preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-13B1 is one comprising from 2 to 15 Z by weight C0 2 , from 25 to 50 Z by weight R-32 and from 40 to 65 Z by weight R-125.
  • a particularly preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-13B1 is one comprising from 5 to 12 Z by weight, more particularly from 8 to 12 Z by weight, C0 2> from 35 to 50 Z by weight, more particularly from 40 to 50 Z by weight, R-32 and from 40 to 55 Z by weight, more particularly from 40 to 50 Z by weight, R-125.
  • An especially preferred refrigerant composition of the invention is one comprising about 10 Z by weight C0 2 , about 43 Z by weight R-32 and about 47 Z by weight R-125.
  • the refrigerant composition of the invention may also be combined with one or more hydrocarbon compounds in an amount which is sufficient to allow the composition to transport a mineral oil or alkyl benzene type lubricant around a refrigeration circuit and return it to the compressor.
  • inexpensive lubricants based on mineral oils or alkyl benzenes may be used to lubricate the compressor.
  • Suitable hydrocarbons for use with the refrigerant composition of the invention are those containing from 2 to 6 carbon atoms, with hydrocarbons containing from 3 to 5 carbon atoms being preferred. Propane and pentane are particularly preferred hydrocarbons, with pentane being especially preferred. Where a hydrocarbon is combined with the refrigerant composition of the invention, it will preferably be present in an amount of from 1 to 10 Z by weight on the total weight of the refrigerant composition.
  • the refrigerant composition of the invention may also be used in combination with the types of lubricants which have been specially developed for use with hydrofluorocarbon based refrigerants.
  • 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.
  • 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-13B1 in low temperature refrigeration applications.
  • a composition comprising 10 Z by weight C0 2 , 43 Z by weight R-32 and 47 Z by weight R-125.
  • composition comprising 10 Z by weight C0 2 , 45 Z by weight R-32 and 45 Z by weight R-125.
  • composition comprising 5 Z by weight C0 2 , 45.6 Z by weight R-32 and 49.4 Z by weight R-125.
  • a composition comprising 10 Z by weight C0 2 , 36 Z by weight R-32 and 54 Z by weight R-125.
  • a composition comprising 10 Z by weight C0 2 , 27 Z by weight R-32 and 63 Z by weight R-125.
  • the performance parameters of the refrigerant compositions which are presented in Table 1, i.e. condenser pressure, evaporator pressure, discharge temperature, refrigeration capacity (by which is meant the cooling duty achieved per unit swept volume of the compressor), coefficient of performance (COP) (by which is meant the ratio of cooling duty (refrigeration effect) achieved to mechanical energy supplied to the compressor), and the glides in the evaporator and condenser (the temperature range over which the refrigerant composition boils in the evaporator and condenses in the condenser), are all art recognised parameters.

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

La présente invention concerne une composition de réfrigérant non azéotropique qui comprend (A) du dioxyde de carbone (CO2), (B) du difluorométhane (R-32) et (C) du pentafluoroéthane (R-125).
PCT/GB1996/001960 1995-08-18 1996-08-12 Compositions de refrigerants WO1997007181A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU67463/96A AU6746396A (en) 1995-08-18 1996-08-12 Refrigerant compositions
EP96927757A EP0845021A1 (fr) 1995-08-18 1996-08-12 Compositions de refrigerants
JP9509032A JPH11511192A (ja) 1995-08-18 1996-08-12 冷媒組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9516921.5A GB9516921D0 (en) 1995-08-18 1995-08-18 Refrigerant compositions
GB9516921.5 1995-08-18

Publications (1)

Publication Number Publication Date
WO1997007181A1 true WO1997007181A1 (fr) 1997-02-27

Family

ID=10779411

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/001960 WO1997007181A1 (fr) 1995-08-18 1996-08-12 Compositions de refrigerants

Country Status (6)

Country Link
EP (1) EP0845021A1 (fr)
JP (1) JPH11511192A (fr)
AU (1) AU6746396A (fr)
CA (1) CA2227917A1 (fr)
GB (1) GB9516921D0 (fr)
WO (1) WO1997007181A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004041957A1 (fr) * 2002-11-01 2004-05-21 Honeywell International Inc. Fluide de transfert thermique contenant difluoromethane et dioxyde de carbone
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration
EP1743010B1 (fr) 2004-04-29 2016-06-29 Honeywell International Inc. Compositions comprenant du tetrafluoropropene et du dioxyde de carbone
CN108779941A (zh) * 2016-03-16 2018-11-09 伟思环境技术有限公司 测试室
DE102017216363A1 (de) * 2017-09-08 2019-03-14 Technische Universität Dresden Kältemittel
DE102019105676A1 (de) * 2019-03-06 2020-09-10 Weiss Umwelttechnik Gmbh Kältemittel

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2910016B1 (fr) * 2006-12-19 2009-02-20 Arkema France Compositions utilisables comme fluide frigorigene

Citations (2)

* 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
WO1996002607A1 (fr) * 1994-07-14 1996-02-01 E.I. Du Pont De Nemours And Company Compositions refrigerantes

Patent Citations (2)

* 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
WO1996002607A1 (fr) * 1994-07-14 1996-02-01 E.I. Du Pont De Nemours And Company Compositions refrigerantes

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7238299B2 (en) 2002-11-01 2007-07-03 Honeywell International Inc. Heat transfer fluid comprising difluoromethane and carbon dioxide
EP2253686A3 (fr) * 2002-11-01 2013-09-18 Honeywell International Inc. Fluide de transfert thermique comportant du difluorométhane et dioxyde de carbone
WO2004041957A1 (fr) * 2002-11-01 2004-05-21 Honeywell International Inc. Fluide de transfert thermique contenant difluoromethane et dioxyde de carbone
EP1743010B2 (fr) † 2004-04-29 2019-08-28 Honeywell International Inc. Compositions comprenant du tetrafluoropropene et du dioxyde de carbone
EP1743010B1 (fr) 2004-04-29 2016-06-29 Honeywell International Inc. Compositions comprenant du tetrafluoropropene et du dioxyde de carbone
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration
US10921029B2 (en) 2016-03-16 2021-02-16 Weiss Umwelttechnik Gmbh Test chamber
CN108779941A (zh) * 2016-03-16 2018-11-09 伟思环境技术有限公司 测试室
EP3430325B1 (fr) * 2016-03-16 2022-12-28 Weiss Technik GmbH Chambre d'essai
DE102017216363A1 (de) * 2017-09-08 2019-03-14 Technische Universität Dresden Kältemittel
US11584875B2 (en) 2017-09-08 2023-02-21 Weiss Technik Gmbh Coolant
DE102019105676A1 (de) * 2019-03-06 2020-09-10 Weiss Umwelttechnik Gmbh Kältemittel
DE102019105676B4 (de) * 2019-03-06 2021-05-06 Weiss Umwelttechnik Gmbh Kältemittel und dessen Verwendung

Also Published As

Publication number Publication date
JPH11511192A (ja) 1999-09-28
GB9516921D0 (en) 1995-10-18
EP0845021A1 (fr) 1998-06-03
AU6746396A (en) 1997-03-12
CA2227917A1 (fr) 1997-02-27

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