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WO1993014173A1 - Compositions utilisees comme refrigerants - Google Patents

Compositions utilisees comme refrigerants Download PDF

Info

Publication number
WO1993014173A1
WO1993014173A1 PCT/GB1992/002382 GB9202382W WO9314173A1 WO 1993014173 A1 WO1993014173 A1 WO 1993014173A1 GB 9202382 W GB9202382 W GB 9202382W WO 9314173 A1 WO9314173 A1 WO 9314173A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
tetrafluoroethane
refrigerant
refrigerant composition
ether
Prior art date
Application number
PCT/GB1992/002382
Other languages
English (en)
Inventor
Richard Llewellyn Powell
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 BR9207035A priority Critical patent/BR9207035A/pt
Priority to AU31687/93A priority patent/AU666694B2/en
Priority to JP5512216A priority patent/JPH07502774A/ja
Priority to EP93900352A priority patent/EP0620837A1/fr
Priority to KR1019940702373A priority patent/KR940703902A/ko
Publication of WO1993014173A1 publication Critical patent/WO1993014173A1/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
    • 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
    • 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
    • C09K2205/22—All components of a mixture being fluoro compounds

Definitions

  • the present invention relates generally to
  • refrigerant compositions for cooling and heating applications and to the use of such compositions in heat transfer devices. More particularly, the present invention is concerned with refrigerant compositions which are designed to replace dichlorodifluoromethane (Refrigerant R-12).
  • 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 refrigerant composition which may be used as a replacement for Refrigerant R-12.
  • the composition contains refrigerant compounds which have essentially zero ozone depletion potentials and comparatively low direct global warming potentials.
  • the present invention provides a refrigerant composition
  • a refrigerant composition comprising a mixture of
  • 1,1,1,2-tetrafluoroethane (CF 3 CH 2 F) and at least one fluorinated ether selected from trifluoromethyl methyl ether (CF 3 OCH 3 ) and fluoromethyl trifluoromethyl ether (CF 3 OCH 2 F).
  • Refrigerant compositions in accordance with the present invention typically contain from 5 to 952 by weight of 1,1,1,2-tetrafluoroethane and from 95 to 5% by weight of the ether. Additionally, the refrigerant compositions of the invention may contain other materials.
  • refrigerant compounds which have low and preferably zero ozone depletion potentials, for example other hydrofluoroalkanes and/or other fluorinated ethers containing residual hydrogen atoms.
  • hydrofluoroalkanes which may be incorporated in the refrigerant compositions of the invention include difluoromethane (R-32), 1,1,1-trifluoroethane (R-143a), 1,1,2,2-tetrafluoroethane (R-134), pentafluoroethane (R-125) and 1,1-difluoroethane (R-152a).
  • fluorinated ethers which may be included in the refrigerant compositions of the invention are the fluorinated dimethyl ethers containing residual
  • the refrigerant compositions of the invention may comprise other refrigerant compounds
  • the preferred refrigerant compositions of the invention consist essentially of 1,1,1,2-tetrafluoroethane and at least one fluorinated ether selected from
  • refrigerant compositions of the invention may be zeotropic they are preferably
  • the refrigerant composition comprises a mixture of
  • compositions of this type are one which consists essentially of the stated components. Such compositions will typically comprise from 25 to 75 2 by weight of 1,1,1,2-tetrafluoroethane and from 75 to 25 % by weight of fluoromethyl
  • compositions of the invention comprising 1,1,1,2-tetrafluoroethane and fluoromethyl trifluoromethyl ether as essential
  • compositions may suitably replace Refrigerant R-12 in many applications.
  • compositions may be particularly useful as a replacement for R-12 in heat pumps and automotive air conditioners.
  • Heat pumps and automotive air conditioners operate with high discharge temperatures, typically around 80 °C, which tends to result in fairly high pressures in the condenser.
  • Table 1 shows the performance of a number of refrigerant compositions of the invention comprising 1,1,1,2-tetrafluoroethane (R-134a in the Table) and fluoromethyl trifluoromethyl ether (E-134a in the
  • fluoromethyl trifluoromethyl ether 25 % by weight of 1,1,1,2-tetrafluoroethane and 75 % by weight of fluoromethyl trifluoromethyl ether were evaluated.
  • the operating conditions which were selected for the evaluation are representative of those existing in a domestic refrigeration system. Specifically, these conditions were as follows:
  • compositions which are presented in the Table, i.e.
  • evaporator (the temperature range over which the refrigerant composition boils in the evaporator), are all art recognised parameters.
  • 1,1,1,2-tetrafluoroethane which is the generally accepted replacement for Refrigerant R-12, under identical operating conditions are also shown in Table 1 by way of comparison.
  • trifluoromethyl ether can exhibit a performance in a refrigeration system which is not too far removed from that of Refrigerant R-12. Furthermore, the glide in the evaporator was only 0.2°C for all the mixed refrigerant compositions evaluated showing that such compositions are azeotrope like.
  • the refrigerant composition comprises a mixture of 1,1,1,2-tetrafluoroethane and
  • trifluoromethyl methyl ether optionally together with fluoromethyl trifluoromethyl ether and/or at least one other fluorinated ether containing residual hydrogen atoms and/or at least one other hydrofluoroalkane.
  • compositions consisting essentially of
  • Refrigerant compositions comprising a mixture of 1,1,1,2-tetrafluoroethane and trifluoromethyl methyl ether have been found to exhibit a similar performance to Refrigerant R-12 in a refrigeration cycle. In consequence, such compositions may be used in place of Refrigerant R-12 which is at present widely used as a working fluid in refrigeration systems and related heat transfer devices. Furthermore, compositions comprising 1,1,1,2-tetrafluoroethane and trifluoromethyl methyl ether benefit from the particularly short atmospheric lifetime of trifluoromethyl methyl ether (ca 3.6 years) and, thus, can exhibit a low direct global warming potential.
  • 1,1,1,2-tetrafluoroethane and trifluoromethyl methyl ether comprise from 5 to 75 % by weight of
  • compositions of this type comprise from 5 to 60 % by weight of 1,1,1,2-tetrafluoroethane and from 95 to 40 % by weight of trifluoromethyl methyl ether, with compositions comprising from 25 to 50 % by weight of 1,1,1,2-tetrafluoroethane and from 75 to 50 % by weight of trifluoromethyl methyl ether being especially preferred.
  • the preferred compositions are therefore characterised by the presence of a substantial amount of trifluoromethyl methyl ether which confers on the composition a lower direct global warming potential.
  • such compositions also exhibit a performance in a refrigeration system which is
  • Trifluoromethyl methyl ether is slightly flammable and our research suggests that mixed refrigerant compositions comprising in excess of 40 % by weight of this ether and less than 60 % by weight of
  • 1,1,1,2-tetrafluoroethane may also be flammable. It is believed that the potential flammability of such refrigerant compositions may not be a problem in practice, bearing in mind that heat transfer devices are essentially closed systems and that certain
  • compositions containing from 70 to 95 % by weight of 1,1,1,2-tetrafluoroethane and from 30 to 5 % by weight of trifluoromethyl methyl ether are preferred, with compositions containing from 70 to 85 % by weight of 1,1,1,2-tetrafluoroethane and from 30 to 15 % by weight of trifluoromethyl methyl ether being
  • Table 2 shows the performance of a number of refrigerant compositions of the invention comprising 1,1,1,2-tetrafluoroethane (R-134a in the Table) and trifluoromethyl methyl ether (E-143a in the Table). The percentage by weight of each component in the
  • refrigerant compositions evaluated is given in the second row of the Table.
  • compositions which are presented in the Table i.e. condenser pressure, evaporator pressure, discharge temperature, return gas temperature, volumetric flow, system efficiency (coefficient of performance, by which is meant the ratio of cooling duty achieved to
  • evaporator (the temperature range over which the refrigerant composition boils in the evaporator), are all art recognised parameters.
  • 1,1,1,2-tetrafluoroethane which is the generally accepted replacement for Refrigerant R-12, under identical operating conditions are also shown in Table 2 by way of comparison.
  • compositions tested showing that such compositions are azeotrope like.
  • the refrigerant compositions of the invention may be prepared by a simple mixing process.
  • compositions are useful in all types of compression cycle heat transfer devices. Thus, they may be used to provide cooling by a method involving condensing the refrigerant composition and thereafter evaporating it in a heat exchange relationship with a body to be cooled. They may also be used to provide heating by a method involving condensing the
  • refrigerant composition in a heat exchange relationship with a body to be heated and thereafter evaporating it.
  • compositions of the invention provide a good compromise between capacity and efficiency combined with low atmospheric lifetime and essentially zero ozone depletion. They are especially suitable for applications currently satisfied by Refrigerant R-12, for example domestic refrigeration, automobile

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition réfrigérante comprenant un mélange de 1,1,1,2-tétrafluoroéthane et d'au moins un éther fluoré sélectionné à partir d'un éther méthyle trifluorométhyle et d'un éther trifluorométhyle fluorométhyle.
PCT/GB1992/002382 1992-01-10 1992-12-23 Compositions utilisees comme refrigerants WO1993014173A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR9207035A BR9207035A (pt) 1992-01-10 1992-12-23 Composição refrigerante dispositivo de transferência térmica processo para prover resfriamento e processo para prover aquecimento
AU31687/93A AU666694B2 (en) 1992-01-10 1992-12-23 Compositions useful as refrigerants
JP5512216A JPH07502774A (ja) 1992-01-10 1992-12-23 冷媒として有用な組成物
EP93900352A EP0620837A1 (fr) 1992-01-10 1992-12-23 Compositions utilisees comme refrigerants
KR1019940702373A KR940703902A (ko) 1992-01-10 1992-12-23 냉매로서 유용한 조성물(compositions useful as refrigerants)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9200521.4 1992-01-10
GB929200521A GB9200521D0 (en) 1992-01-10 1992-01-10 Compositions useful as refrigerants

Publications (1)

Publication Number Publication Date
WO1993014173A1 true WO1993014173A1 (fr) 1993-07-22

Family

ID=10708415

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1992/002382 WO1993014173A1 (fr) 1992-01-10 1992-12-23 Compositions utilisees comme refrigerants

Country Status (8)

Country Link
EP (1) EP0620837A1 (fr)
JP (1) JPH07502774A (fr)
KR (1) KR940703902A (fr)
AU (1) AU666694B2 (fr)
BR (1) BR9207035A (fr)
CA (1) CA2126185A1 (fr)
GB (1) GB9200521D0 (fr)
WO (1) WO1993014173A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994017153A1 (fr) * 1993-01-20 1994-08-04 Imperial Chemical Industries Plc Compositions refrigerantes
US5605882A (en) * 1992-05-28 1997-02-25 E. I. Du Pont De Nemours And Company Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane
US5650089A (en) * 1991-12-03 1997-07-22 The United States Of America, As Represented By The Administrator Of The U.S. Environmental Protection Agency Refrigerant compositions with fluorinated dimethyl ether and either difluoroethane or cyclopropane, and use thereof
US5713211A (en) * 1995-10-20 1998-02-03 Minnesota Mining And Manufacturing Company Hydrofluoroethers as low temperature refrigerants
US5819549A (en) * 1996-10-16 1998-10-13 Minnesota Mining And Manufacturing Company Secondary loop refrigeration system
USRE37054E1 (en) 1996-10-16 2001-02-20 Minnesota Mining And Manufacturing Company Secondary loop refrigeration system
CN110591650A (zh) * 2019-09-12 2019-12-20 珠海格力电器股份有限公司 一种适用于离心式制冷机组的热传递组合物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620839A1 (fr) * 1992-01-10 1994-10-26 Imperial Chemical Industries Plc Compositions utilisees comme agents refrigerants

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0385737A1 (fr) * 1989-02-28 1990-09-05 Hampshire Chemical Corporation Réfrigérant à base de bis(difluorométhyl)éther
WO1991013968A1 (fr) * 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Composition azeotrope de 1,1,1,2-tetrafluoroethane et d'ether dimethylique

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620839A1 (fr) * 1992-01-10 1994-10-26 Imperial Chemical Industries Plc Compositions utilisees comme agents refrigerants
US5605882A (en) * 1992-05-28 1997-02-25 E. I. Du Pont De Nemours And Company Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0385737A1 (fr) * 1989-02-28 1990-09-05 Hampshire Chemical Corporation Réfrigérant à base de bis(difluorométhyl)éther
WO1991013968A1 (fr) * 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Composition azeotrope de 1,1,1,2-tetrafluoroethane et d'ether dimethylique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Week 9221, Derwent Publications Ltd., London, GB; AN 92-172537 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5650089A (en) * 1991-12-03 1997-07-22 The United States Of America, As Represented By The Administrator Of The U.S. Environmental Protection Agency Refrigerant compositions with fluorinated dimethyl ether and either difluoroethane or cyclopropane, and use thereof
US6063305A (en) * 1991-12-03 2000-05-16 The United States Of America As Represented By The Administrator Of The Environmental Protection Agency Refrigerant compositions containing a hydrofluoropropane and a hydrofluorocarbon
US5605882A (en) * 1992-05-28 1997-02-25 E. I. Du Pont De Nemours And Company Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane
US5648016A (en) * 1992-05-28 1997-07-15 E. I. Du Pont De Nemours And Company Azeotrope (like) composition with fluoromethyl trifluoromethyl ether and 1,1-difluoroethane
US6905630B2 (en) 1992-05-28 2005-06-14 E. I. Du Pont De Nemours And Company Compositions of a hydrofluoroether and a hydrofluorocarbon
US5779931A (en) * 1992-05-28 1998-07-14 E. I. Du Pont De Nemours And Company Azeotrope (like) compositions with difluoromethoxytetrafluoro-propane and pentafluoropropane, and methods of use
US6835321B2 (en) 1992-05-28 2004-12-28 E. I. Du Pont De Nemours And Company Compositions of a hydrofluoroether and a hydrofluorocarbon
US6830703B2 (en) 1992-05-28 2004-12-14 E. I. Du Pont De Nemours And Company Compositions of a hydrofluoroether and a hydrofluorocarbon
WO1994017153A1 (fr) * 1993-01-20 1994-08-04 Imperial Chemical Industries Plc Compositions refrigerantes
USRE37119E1 (en) 1995-10-20 2001-04-03 3M Innovative Properties Company Hydrofluoroethers as low temperature refrigerants
US5713211A (en) * 1995-10-20 1998-02-03 Minnesota Mining And Manufacturing Company Hydrofluoroethers as low temperature refrigerants
USRE37054E1 (en) 1996-10-16 2001-02-20 Minnesota Mining And Manufacturing Company Secondary loop refrigeration system
US5819549A (en) * 1996-10-16 1998-10-13 Minnesota Mining And Manufacturing Company Secondary loop refrigeration system
CN110591650A (zh) * 2019-09-12 2019-12-20 珠海格力电器股份有限公司 一种适用于离心式制冷机组的热传递组合物
CN110591650B (zh) * 2019-09-12 2020-09-25 珠海格力电器股份有限公司 一种适用于离心式制冷机组的热传递组合物

Also Published As

Publication number Publication date
KR940703902A (ko) 1994-12-12
EP0620837A1 (fr) 1994-10-26
CA2126185A1 (fr) 1993-07-22
BR9207035A (pt) 1995-12-06
AU3168793A (en) 1993-08-03
JPH07502774A (ja) 1995-03-23
GB9200521D0 (en) 1992-02-26
AU666694B2 (en) 1996-02-22

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