WO1997007179A1 - Compositions refrigerantes - Google Patents

Compositions refrigerantes Download PDF

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Publication number
WO1997007179A1
WO1997007179A1 PCT/GB1996/001955 GB9601955W WO9707179A1 WO 1997007179 A1 WO1997007179 A1 WO 1997007179A1 GB 9601955 W GB9601955 W GB 9601955W WO 9707179 A1 WO9707179 A1 WO 9707179A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
refrigerant composition
azeotropic refrigerant
refrigerant
composition
Prior art date
Application number
PCT/GB1996/001955
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 EP96927146A priority Critical patent/EP0845019A1/fr
Priority to AU67076/96A priority patent/AU6707696A/en
Priority to JP9509029A priority patent/JPH11511190A/ja
Publication of WO1997007179A1 publication Critical patent/WO1997007179A1/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 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 i ⁇ then compressed arid 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.
  • 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) and the azeotropic mixture of chlorodifluoromethane and chloropentafluoroethane (refrigerant R-115) ; the azeotrope being refrigerant R-502.
  • Refrigerant R-502 for example, 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-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 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 pentafluoroethane (R-125) which has a boiling point of around -48.5 * C.
  • the third component (component (C) ) is 1,1, 1-trifluoroethane (R-143a) which has a boiling point of around -47.6 * C.
  • the refrigerant composition of the invention may-also contain 1, 1, 1,2-tetrafluoroethane (R-134a) which has a boiling point of around -26.5'C.
  • R-134a 1, 1, 1,2-tetrafluoroethane
  • the amounts of the C0 2 , R-125 and R-143a and the amount of the R-134a (if included) in the refrigerant composition may be varied within wide limits, but typically the refrigerant composition will comprise from 1 to 20 % by weight C0 2 , from 25 to 70 % by weight R-125, from 25 to 70 % by weight R-143a and from 0 to 25 % by weight (for example, from 1 to 25 % by weight) R-134a.
  • a preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-502 is one comprising from 2 to 15 % by weight CO., from 28 to 70 % by weight R-125 and from 28 to 70 % by weight R-143a.
  • a particularly preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-502 is one comprising from 2 to 12 % by weight, more particularly from 2 to 10 % by weight, C0 2 , from 38 to 60 % by weight, more particularly from 45 to 50 % by weight, R-125 and from 38 to 60 % by weight, more particularly from 45 to 50 % by weight, R-143a.
  • a preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-502 is one comprising from 2 to 15 % by weight CO,, from 27 to 70 % by weight R-125, from 27 to 70 % by weight R-143a and from 1 to 25 % by weight R-134a.
  • a particularly preferred refrigerant composition of the invention in terms of its suitability as a replacement for refrigerant R-502 is one comprising from 2 to 15 % by weight, more particularly from 2 to 12 % by weight, C ⁇ 2 , from 37 to 60 % by weight, more particularly from 35 to 45 % by weight, R-125, from 37 to 60 % by weight, more particularly from 43 to 53 % by weight, R-143a and from 1 to 10 % by weight, more particularly from 1 to 5 % by weight, R-134a.
  • 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.
  • a hydrocarbon is combined with the refrigerant composition of the invention, it will preferably be present in an amount of from 1 to 10 % 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 s . 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 % by weight C0 2 , 43.1 % by weight R-125, 51 % by weight R-143a and 3.9 % by weight R-134a.
  • a composition comprising 5 % by weight C0 2 , 41.8 % by weight R-125, 49.4 % by weight R-143a and 3.8 % by weight R-134a.
  • a composition comprising 10 % by weight C0 2 , 39.6 % by weight R-125, 46.8 % by weight R-143a and 3.6 % by weight R-134a.
  • a composition comprising 2 % by weight C0 2 , 49 % by weight R-125 and 49 % by weight R-143a.
  • a composition comprising 5 % by weight C0 2 , 47.5 % by weight R-125 and 47.5 % by weight R-143a.
  • 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.

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  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une composition réfrigérante non azéotropique comprenant (A) du dioxyde de carbone (CO2), (B) du pentafluoroéthane (R-125) et (C) du 1,1,1-trifluoroéthane (R-143a).
PCT/GB1996/001955 1995-08-18 1996-08-12 Compositions refrigerantes WO1997007179A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96927146A EP0845019A1 (fr) 1995-08-18 1996-08-12 Compositions refrigerantes
AU67076/96A AU6707696A (en) 1995-08-18 1996-08-12 Refrigerant compositions
JP9509029A JPH11511190A (ja) 1995-08-18 1996-08-12 冷媒組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9516920.7A GB9516920D0 (en) 1995-08-18 1995-08-18 Refrigerant compositions
GB9516920.7 1995-08-18

Publications (1)

Publication Number Publication Date
WO1997007179A1 true WO1997007179A1 (fr) 1997-02-27

Family

ID=10779410

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/001955 WO1997007179A1 (fr) 1995-08-18 1996-08-12 Compositions refrigerantes

Country Status (6)

Country Link
EP (1) EP0845019A1 (fr)
JP (1) JPH11511190A (fr)
AU (1) AU6707696A (fr)
CA (1) CA2227857A1 (fr)
GB (1) GB9516920D0 (fr)
WO (1) WO1997007179A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6113803A (en) * 1991-03-18 2000-09-05 Alliedsignal Inc. Non-azeotropic refrigerant compositions comprising difluoromethane or 1,1,1-trifluoroethane
US6604368B1 (en) 1999-10-04 2003-08-12 Refrigerant Products, Ltd. R 12 replacement refrigerant
US6606868B1 (en) 1999-10-04 2003-08-19 Refrigerant Products, Ltd. R 22 replacement refrigerant
US6629419B1 (en) 1999-10-04 2003-10-07 Refringerant Products Ltd. CFC 12 replacement refrigerant
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration
US7972528B2 (en) 2006-03-03 2011-07-05 Rpl Holdings Limited Refrigerant composition
US8551354B2 (en) 2006-03-03 2013-10-08 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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015214632A (ja) * 2014-05-09 2015-12-03 パナソニックＩｐマネジメント株式会社 混合冷媒

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016597A1 (fr) * 1991-03-18 1992-10-01 Allied-Signal Inc. Compositions refrigerantes non azeotropes comprenant du difluoromethane, du 1,1,1-trifluoroethane ou du propane
DE4116274A1 (de) * 1991-05-17 1992-11-19 Forschungszentrum Fuer Kaeltet Kaeltemittel
EP0583179A1 (fr) * 1992-08-12 1994-02-16 Elf Atochem S.A. Mélanges pseudo-azéotropiques de difluorométhane, de pentafluoroéthane et de 1,1,1-trifluoroéthane, et leur application comme fluides frigorigènes en réfrigération basse température

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016597A1 (fr) * 1991-03-18 1992-10-01 Allied-Signal Inc. Compositions refrigerantes non azeotropes comprenant du difluoromethane, du 1,1,1-trifluoroethane ou du propane
DE4116274A1 (de) * 1991-05-17 1992-11-19 Forschungszentrum Fuer Kaeltet Kaeltemittel
EP0583179A1 (fr) * 1992-08-12 1994-02-16 Elf Atochem S.A. Mélanges pseudo-azéotropiques de difluorométhane, de pentafluoroéthane et de 1,1,1-trifluoroéthane, et leur application comme fluides frigorigènes en réfrigération basse température

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6113803A (en) * 1991-03-18 2000-09-05 Alliedsignal Inc. Non-azeotropic refrigerant compositions comprising difluoromethane or 1,1,1-trifluoroethane
US6604368B1 (en) 1999-10-04 2003-08-12 Refrigerant Products, Ltd. R 12 replacement refrigerant
US6606868B1 (en) 1999-10-04 2003-08-19 Refrigerant Products, Ltd. R 22 replacement refrigerant
US6629419B1 (en) 1999-10-04 2003-10-07 Refringerant Products Ltd. CFC 12 replacement refrigerant
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration
US8465664B2 (en) 2006-03-03 2013-06-18 Rpl Holdings Limited Refrigerant composition
US7972528B2 (en) 2006-03-03 2011-07-05 Rpl Holdings Limited Refrigerant composition
US8551354B2 (en) 2006-03-03 2013-10-08 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
AU6707696A (en) 1997-03-12
EP0845019A1 (fr) 1998-06-03
CA2227857A1 (fr) 1997-02-27
GB9516920D0 (en) 1995-10-18
JPH11511190A (ja) 1999-09-28

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