WO1996002603A1 - Compositions refrigerantes - Google Patents

Compositions refrigerantes Download PDF

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Publication number
WO1996002603A1
WO1996002603A1 PCT/GB1995/001592 GB9501592W WO9602603A1 WO 1996002603 A1 WO1996002603 A1 WO 1996002603A1 GB 9501592 W GB9501592 W GB 9501592W WO 9602603 A1 WO9602603 A1 WO 9602603A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
weight
refrigerant composition
azeotropic
composition
Prior art date
Application number
PCT/GB1995/001592
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 AU28048/95A priority Critical patent/AU2804895A/en
Publication of WO1996002603A1 publication Critical patent/WO1996002603A1/fr

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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
    • C09K2205/22—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
    • C09K2205/34—The mixture being non-azeotropic

Definitions

  • the present invention relates to non-azeotropic refrigerant compositions and more particularly to non-azeotropic refrigerant compositions which boil over a wide temperature range and thus provide wide temperature glides in the heat exchangers of the heat transfer devices in which they are used.
  • 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.
  • the present invention provides a non-azeotropic refrigerant composition which comprises a mixture of compounds having low or zero ozone depletion potentials.
  • the refrigerant composition of the invention can boil over a wide temperature range and this property can be exploited to increase the energy efficiency of the equipment in which the composition is used.
  • the temperature range over which the refrigerant composition of the invention boils i.e. the so-called temperature glide, can be adjusted by appropriate selection of the components and the amounts thereof forming the composition and in this way it is possible to tailor the composition to its intended application.
  • a non-azeotropic (zeotropic) refrigerant composition comprising: (A) a first component comprising fluoromethane (R-41 ) optionally together with carbon dioxide (CO_); (B) a second component comprising at least one hydrofluorocarbon selected from the group consisting of 1,1,1, 2-tetraf.uoroethane (R-134a) and 1,1,2,2-tetrafluoroethane (R-134); and optionally
  • the zeotropic refrigerant composition of the invention comprises at least the first and second components defined above.
  • the first component comprises fluoromethane (R-41 ) or a mixture of R-41 and carbon dioxide (CO 2 ). Both of these compounds have a low temperature refrigeration action, with CO 2 subliming at around -78.5°C and R-41 having a boiling point of around -78.4 °C.
  • the second component comprises at least one hydrofluorocarbon selected from the group consisting of 1,1,1,2-tetrafluoroethane (R-134a) and 1,1,2,2-tetrafluoroethane (R-134) which have boiling points of around -26.5°C and -19.7°C respectively. It is apparent that the boiling points of both R-134a and R-134 are appreciably higher than the boiling point of the R-41 and the sublimation temperature of the CO- (if included) making up the first component which means that the refrigerant composition of the invention is capable of boiling and condensing over a wide temperature range, i.e. it can exhibit a wide temperature glide in both the evaporator and condenser.
  • the second component may contain a mixture of R-134a and R-134, it will preferably contain just one of these compounds and more preferably will contain just R-134a.
  • the refrigerant composition of the invention may also contain a third component (component (C)) comprising at least one hydrofluorocarbon selected from the group consisting of difluoromethane (R-32), 1,1,1 -trifluoroethane (R-143 a) and pentafluoroethane (R-125) which have boiling points of around -51.6°C, -47.6°C and -48.5°C respectively.
  • the third component (if included) may contain just one of the three specified compounds or it may comprise a mixture, for example an azeotropic or azeotrope-like mixture, of any two or all three of these compounds.
  • the third component (if included) is R-32, R-125 or a mixture comprising R-32 and R-125.
  • the amounts of the first and second components and the amount of the third component (if included) in the refrigerant composition may be varied within wide limits, but typically the refrigerant composition will comprise from 2 to 45 % by weight of the first component, from 15 to 98 % by weight of the second component and from 0 to 60 % by weight (for example, from 2 to 60 % by weight) of the third component.
  • the refrigerant composition will comprise from 2 to 35 % by weight of the first component, from 25 to 98 % by weight of the second component and from 0 to 50 % by weight (for example, from 2 to 50 % by weight) of the third component.
  • the refrigerant composition preferably comprises from 2 to 25 % by weight, more preferably from 2 to 10 % by weight, of the first component and from 75 to 98 % by weight, more preferably from 90 to 98 % by weight, of the second component.
  • the refrigerant composition preferably comprises from 2 to 30 % by weight, more preferably from 2 to 15 % by weight, of the first component and from 70 to 98 % by weight, more preferably from 85 to 98 % by weight, of the second component.
  • the refrigerant composition preferably comprises from 2 to 25 % by weight, more preferably from 2 to 15 % by weight, of the first component, from 35 to 96 % by weight, more preferably from 75 to 96 % by weight, of the second component and from 2 to 40 % by weight, more preferably from 2 to 20 % by weight, of the third component.
  • 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. In this way, 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 % 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 s . infrastructure particularly the C 5 . 7 , linear alkanoic acids and the C ⁇ . Q , 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 single fluid refrigerants and azeotropic refrigerant blends which are used in conventional heat transfer devices boil at a constant temperature in the evaporator under constant pressure conditions, and so produce an essentially constant temperature profile across the evaporator.
  • the temperature of the heat transfer fluid being cooled which may be air or water for example, drops fairly rapidly on first contacting the cold surfaces provided by the refrigerant evaporating in the evaporator owing to the large difference in temperature between that fluid and the evaporating refrigerant.
  • the temperature of the heat transfer fluid is progressively reduced as it passes along the length of the evaporator, there is a progressive reduction in the temperature differential between the fluid and the evaporating refrigerant and a consequent reduction in the heat transfer or cooling rate.
  • the refrigerant composition of the invention is a non-azeotropic (zeotropic) composition which boils over a temperature range under constant pressure conditions so as to create a temperature glide in the evaporator which can be exploited to reduce the energy required to operate the heat transfer device, e.g. by making use of the Lorentz cycle.
  • One technique for exploiting the temperature glide involves the use of a heat transfer device equipped with a counter current flow evaporator and/or condenser in which the refrigerant and the heat transfer fluid are caused to flow counter currently to each other. With such an arrangement, it is possible to minimise the temperature difference between the evaporating and condensing refrigerant whilst maintaining a sufficiently high temperature difference between the refrigerant and the external fluid(s) to cause the required heat transfer to take place.
  • the zeotropic refrigerant composition of the present invention may be used to provide the desired cooling in heat transfer devices such as air conditioning and 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 usefully employed as a replacement for refrigerant R-22.
  • a composition comprising 5 % by weight R-41 and 95 % by weight R-134a.
  • a composition comprising 10 % by weight R-41 and 90 % by weight R-134a.
  • a composition comprising 5 % by weight R-41, 5 % by weight R-125 and 90% by weight R-134a.
  • a composition comprising 5 % by weight R-41, 10 % by weight R-125 and 85 % by weight R-134a.
  • a composition comprising 5 % by weight R-41, 5 % by weight R-32 and 90 % by weight R-134a.
  • a composition comprising 5 % by weight R-41, 5 % by weight R-32, 5 % by weight R-125 and 85 % by weight R-134a.
  • a composition comprising 10 % by weight R-41, 5 % by weight R-125 and 85 % by weight R-134a.
  • 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 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)

Abstract

L'invention concerne une composition réfrigérante non azéotrope (zéotrope) comprenant (A) un premier composant comportant du fluorométhane (R-41), (B) un deuxième composant comportant au moins un hydrofluocarbone choisi dans le groupe comprenant 1,1,1,2-tétrafluoroéthane (R-134a) et 1,1,2,2-tétrafluoréthane (R-134), et éventuellement (C) un troisième composant comportant au moins un hydrofluorocarbone choisi dans le groupe constitué de difluorométhane (R-32), de 1,1,1-trifluoroéthane (R-143a) et de pentafluoroéthane (R-125).
PCT/GB1995/001592 1994-07-13 1995-07-06 Compositions refrigerantes WO1996002603A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU28048/95A AU2804895A (en) 1994-07-13 1995-07-06 Refrigerant compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9414136A GB9414136D0 (en) 1994-07-13 1994-07-13 Refrigerant compositions
GB9414136.3 1994-07-13

Publications (1)

Publication Number Publication Date
WO1996002603A1 true WO1996002603A1 (fr) 1996-02-01

Family

ID=10758265

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1995/001592 WO1996002603A1 (fr) 1994-07-13 1995-07-06 Compositions refrigerantes

Country Status (3)

Country Link
AU (1) AU2804895A (fr)
GB (1) GB9414136D0 (fr)
WO (1) WO1996002603A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5800730A (en) * 1990-07-26 1998-09-01 E. I. Du Pont De Nemours And Compnay Near-azeotropic blends for use as refrigerants
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration
CN113913158A (zh) * 2021-10-26 2022-01-11 珠海格力电器股份有限公司 一种非共沸制冷剂，其制备方法及其在制冷装置中的应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299614A2 (fr) * 1987-06-09 1989-01-18 E.I. Du Pont De Nemours And Company Mélanges d'hydrocarbures halogénés à usage frigorifique
DE4116274A1 (de) * 1991-05-17 1992-11-19 Forschungszentrum Fuer Kaeltet Kaeltemittel
WO1993014174A1 (fr) * 1992-01-10 1993-07-22 Imperial Chemical Industries Plc Compositions utilisees comme refrigerants
WO1994017153A1 (fr) * 1993-01-20 1994-08-04 Imperial Chemical Industries Plc Compositions refrigerantes
US5340490A (en) * 1993-07-14 1994-08-23 Alliedsignal Inc. Azeotrope-like compositions of trifluoromethane and carbon dioxide or hexafluoroethane and carbon dioxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299614A2 (fr) * 1987-06-09 1989-01-18 E.I. Du Pont De Nemours And Company Mélanges d'hydrocarbures halogénés à usage frigorifique
DE4116274A1 (de) * 1991-05-17 1992-11-19 Forschungszentrum Fuer Kaeltet Kaeltemittel
WO1993014174A1 (fr) * 1992-01-10 1993-07-22 Imperial Chemical Industries Plc Compositions utilisees comme refrigerants
WO1994017153A1 (fr) * 1993-01-20 1994-08-04 Imperial Chemical Industries Plc Compositions refrigerantes
US5340490A (en) * 1993-07-14 1994-08-23 Alliedsignal Inc. Azeotrope-like compositions of trifluoromethane and carbon dioxide or hexafluoroethane and carbon dioxide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5800730A (en) * 1990-07-26 1998-09-01 E. I. Du Pont De Nemours And Compnay Near-azeotropic blends for use as refrigerants
US7861541B2 (en) 2004-07-13 2011-01-04 Tiax Llc System and method of refrigeration
CN113913158A (zh) * 2021-10-26 2022-01-11 珠海格力电器股份有限公司 一种非共沸制冷剂，其制备方法及其在制冷装置中的应用

Also Published As

Publication number Publication date
GB9414136D0 (en) 1994-08-31
AU2804895A (en) 1996-02-16

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