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WO1997010312A1 - Fluide frigorigene hydrofluorocarbone - Google Patents

Fluide frigorigene hydrofluorocarbone Download PDF

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Publication number
WO1997010312A1
WO1997010312A1 PCT/US1996/014736 US9614736W WO9710312A1 WO 1997010312 A1 WO1997010312 A1 WO 1997010312A1 US 9614736 W US9614736 W US 9614736W WO 9710312 A1 WO9710312 A1 WO 9710312A1
Authority
WO
WIPO (PCT)
Prior art keywords
pentafluoropropane
refrigerant
hfc
mixture
composition
Prior art date
Application number
PCT/US1996/014736
Other languages
English (en)
Inventor
Ian Robert Shanklnd
David Paul Wilson
Rajiv Ratna Singh
Original Assignee
Alliedsignal Inc.
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 Alliedsignal Inc. filed Critical Alliedsignal Inc.
Priority to AU69776/96A priority Critical patent/AU6977696A/en
Priority to EP96930875A priority patent/EP0850286A1/fr
Priority to JP9512142A priority patent/JPH10511135A/ja
Publication of WO1997010312A1 publication Critical patent/WO1997010312A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • 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

Definitions

  • This invention relates to hydrofluorocarbons useful in refrigeration and heat pump applications as well as foam blowing agents. More specifically, the invention provides hydrofluorocarbons that are environmentally desirable replacements for chlorofluorocarbons and hydrochlorofluorocarbons in refrigeration applications, such as centrifugal chillers, and foam blowing agent applications.
  • Vapor compression is one type of refrigeration.
  • vapor compression involves changing the refrigerant from the liquid to the vapor phase through heat absorption at a low pressure and then from the vapor to the liquid phase through heat removal at an elevated pressure.
  • While the primary purpose of refrigeration is to remove energy at low temperature, the primary purpose of a heat pump is to add energy at higher temperature.
  • Heat pumps are considered reverse cycle systems because, for heating, the operation ofthe condenser is interchanged with that ofthe refrigeration evaporator.
  • replacement refrigerant compositions possess those properties unique to the composition being replaced including chemical stability, low toxicity, non-flammability, and efficiency-in-use.
  • the latter characteristic is important in refrigeration and air-conditioning applications especially where a loss in refrigerant thermodynamic performance or energy efficiency may have secondary environmental impacts through increased fossil fuel usage arising from an increased demand for electrical energy.
  • the ideal substitute would not require major engineering changes to conventional equipment currently used.
  • the compounds 1, 1, 1,2,3-pentafluoropropane (“HFC-245eb”), 1, 1, 1,3,3- pentafluoropropane (“HFC-245fa”), 1,1,2,3,3-pentafluoropropane (“HFC- 245ea”), and mixtures thereof are useful as refrigerants, heat transfer fluids, and blowing agents. More specifically it has been discovered that these compounds and mixtures meet the need for a nonflammable refrigerant which has a low ozone depletion potential and is a negligible contributor to green-house global warming compared with currently used refrigerants, such as R-11 and 123. Further, it has been discovered that these compounds and mixtures have COP's and capacities that render them suitable for use in refrigeration applications, including in centrifugal chillers. Also, the compounds and mixtures ofthe invention exhibit low compressor discharge temperatures.
  • centrifugal chillers refrigeration equipment that uses centrifugal compression to compress the refrigerant.
  • the invention provides a method for producing refrigeration using a compound selected from HFC-245eb, HFC-245fa, HFC- 245ea, and mixtures thereof.
  • a method for producing refrigeration using a centrifugal chiller is provided using a compound selected from
  • HFC-245eb HFC-245fa, HFC-245ea, and mixtures thereof.
  • a method for producing heating is provided using a compound selected from HFC-245eb, HFC-245fa, HFC-245ea, and mixtures thereof.
  • mixtures is meant both nonazeotropic and azeotrope-like compositions of at least two ofthe compounds.
  • this invention provides azeotrope-like compositions comprising effective amounts of at least two compounds selected from HFC-245eb, HFC -245fa, and HFC-245ea.
  • effective amount is meant an amount of each component that, when combined with the other component, results in the formation of an azeotrope or azeotrope-like mixture.
  • the invention provides azeotrope-like compositions comprising from about 10 to about 90 weight percent 245fa and from about 90 to about 10 weight percent 245ea, the compositions having a boiling point 25° C ⁇ 7° C at 760 mm Hg. More preferably, the composition comprises from about 30 to about 70 weight percent HFC-245fa and from about 70 to about 30 weight percent HFC-245ea, more preferably about 50 weight percent HFC-245fa and about 50 weight percent HFC-245ea.
  • azeotrope-like compositions are compositions that behave like azeotropic mixtures. From fundamental principles, the thermodynamic state of a fluid is defined by pressure, temperature, liquid composition, and vapor composition.
  • An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the state pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant boiling and cannot be separated during a phase change.
  • Azeotrope-like compositions behave like azeotropic mixtures, e ⁇ , or are constant boiling or essentially constant boiling.
  • the composition ofthe vapor formed during boiling or evaporation is identical, or substantially identical, to the original liquid composition
  • the liquid composition changes, if at all, only to a minimal or negligible extent.
  • nonazeotrope-like compositions in which, during boiling or evaporation, the liquid composition changes to a substantial degree.
  • the compounds and mixtures ofthe invention may be used in a method for producing refrigeration that comprises condensing a refrigerant and thereafter evaporating the refrigerant in the vicinity ofa body to be cooled.
  • the compounds and mixtures ofthe invention may be used in a method for producing heating which comprises condensing a refrigerant in the vicinity ofa body to be heated and thereafter evaporating the refrigerant.
  • the compounds and mixtures ofthe invention may be used in a method for producing refrigeration using a centrifugal chiller that comprises compressing the compound or mixture ofthe invention by centrifugal compression and evaporating the refrigerant in the vicinity of a body to be cooled.
  • the compounds and mixtures ofthe present invention may be used in a method for producing foam comprising blending a heat plasticized resin with a volatile blowing agent comprising the fluids ofthe present invention and introducing the resin/volatile blowing agent blend into a zone of lower pressure to cause foaming.
  • the compounds and mixtures ofthe present invention may also be used in a method of dissolving contaminants or removing contaminants from the surface ofa substrate which comprises the step of contacting the substrate with the compositions ofthe present invention.
  • the compounds and mixtures ofthe present invention may also be used as fire extinguishing agents.
  • the compounds and mixtures ofthe present invention are known materials.
  • the materials should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the cooling or heating properties, constant-boiling properties, or blowing agent properties ofthe system.
  • propane may be added to refrigerant compositions to aid oil solubility and may be added to the fluids ofthe present invention.
  • Nitromethane may also be added as a stabilizer. Similar materials may be added to the present compositions.
  • the critical temperature of HFC-245ea was measured by measuring the temperature where the meniscus between the liquid and vapor phase disappeared and was found to be 193.0° C.
  • EXAMPLE 4 The critical temperature of HFC-245eb was measured by measuring the temperature where the meniscus between the Liquid and vapor phase disappeared and was found to be 164.90° C.
  • EXAMPLE 5 The liquid density of material HFC-245eb was measured, as a function of temperature, using glass flotation beads of precisely known densities. The following data were obtained:
  • Example 8 This example shows that HFC-245ea, HFC-245fa and HFC-245eb have certain advantages when compared to other refrigerants which are currently used in certain refrigeration cycles.
  • the theoretical performance of a refrigerant at specific operating conditions can be estimated from the thermodynamic properties ofthe refrigerant using standard refrigeration cycle analysis techniques as described, for example, in RC Downing, Fluorocarbon Refrigerants Handbook. Chapter 3, Prentice-Hall, 1988
  • the coefficient of performance, COP is a universally accepted measure, especially useful in representing the relative thermodynamic efficiency ofa refrigerant in a specific heating or cooling cycle involving evaporation or condensation ofthe refrigerant. In refrigeration engineering, this term expresses the ratio of useful refrigeration to the energy applied by the compressor in compressing the vapor.
  • the capacity ofa refrigerant represents the volumetric efficiency ofthe refrigerant.
  • this value expresses the capability of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant.
  • a refrigerant with a higher capacity will deliver more cooling or heating power.
  • the compressor has a displacement of 1000 cubic feet per hour.
  • Such calculations were performed for HFC-245ea, HFC-245eb and HFC-245fa and for R-123.
  • R-123 is presently being used as an alternative for R- 11 in centrifugal chillers.
  • Table 6 lists the COP, discharge temperature and capacity ofthe various refrigerants.
  • HFC-245fa and 245eb have higher refrigeration capacity.
  • HFC-245fa and 245eb have lower compression ratios which ratios are advantageous from the point of increased reliability of mechanical machinery in which these refrigerants are likely to be employed.
  • HFC-245ea exhibits higher energy efficiency in comparison to the other fluids.
  • HFC-245fa Approximately 10 g HFC-245fa were added to the reference and sample arms of a differential ebulliometer to obtain boiling point measurements. See W. Swietoslawski, Ebul ⁇ ometric Measurements (1945). The system was brought to total reflux by gently heating the lower part ofthe ebulliometer. The temperature ofthe boiling liquid was measured with reference to pure HFC-245fa using a PC17US96/14736
  • Weight Percent 245ea BP (°C) Weight Percent 245ea BP ( ⁇ C)
  • the data from Table 7 may be compared to the boiling point ofthe HFC- 245fa/HFC-245ea mixture obtained according to Raoult's Law
  • the comparison, illustrated on Table 8, shows that the actual boiling point does not change as much on the addition of HFC-245ea as is predicted and the mixture, therefore, is unexpectedly constant boiling.
  • Example 10 From the data of Example 9,- the theoretical performance of mixtures of
  • HFC- 245fa HFC-245ea are calculated using the method of Example 8. The calculation is performed for a water chiller refrigeration cycle in which the condenser temperature is typically 100° F and the evaporator temperature is 30° F.
  • Compression efficiency of 80 % in a saturated cycle is assumed.
  • the compressor displacement is 1000 cubic feet per hour.
  • the results are that the compositions have refrigeration capacities closer to R-11 than either ofthe two components singly and, thus, are suitable replacements for those environmentally undesirable refrigerants currently used in chiller applications.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

L'invention concerne des hydrofluorocarbures utilisés en réfrigération et dans des applications faisant intervenir des pompes thermiques. Cette invention porte sur des hydrofluorocarbures choisis dans le groupe constitué de 1,1,2,3,3-pentafluoropropane, 1,1,13,3-pentafluoropropane, 1,1,1,2,3-pentafluoropropane ainsi que sur des mélanges de ceux-ci, aptes d'un point de vue écologique, au remplacement de chlorofluorocarbones dans des applications relevant du domaine de la réfrigération comme des dispositifs de refroidissement centrifuges.
PCT/US1996/014736 1995-09-14 1996-09-13 Fluide frigorigene hydrofluorocarbone WO1997010312A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU69776/96A AU6977696A (en) 1995-09-14 1996-09-13 Hydrofluorocarbon refrigerants
EP96930875A EP0850286A1 (fr) 1995-09-14 1996-09-13 Fluide frigorigene hydrofluorocarbone
JP9512142A JPH10511135A (ja) 1995-09-14 1996-09-13 ヒドロフルオロカーボン系冷媒

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US374195P 1995-09-14 1995-09-14
US60/003,741 1995-09-14
US69793696A 1996-09-03 1996-09-03
US08/697,936 1996-09-03

Publications (1)

Publication Number Publication Date
WO1997010312A1 true WO1997010312A1 (fr) 1997-03-20

Family

ID=26672142

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/014736 WO1997010312A1 (fr) 1995-09-14 1996-09-13 Fluide frigorigene hydrofluorocarbone

Country Status (5)

Country Link
EP (1) EP0850286A1 (fr)
JP (1) JPH10511135A (fr)
AU (1) AU6977696A (fr)
CA (1) CA2231111A1 (fr)
WO (1) WO1997010312A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998008913A1 (fr) * 1996-08-30 1998-03-05 Imperial Chemical Industries Plc Compositions refrigerantes
US6100229A (en) * 1998-01-12 2000-08-08 Alliedsignal Inc. Compositions of 1,1,1,3,3,-pentafluoropropane and chlorinated ethylenes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8574451B2 (en) * 2005-06-24 2013-11-05 Honeywell International Inc. Trans-chloro-3,3,3-trifluoropropene for use in chiller applications

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2274462A (en) * 1993-01-20 1994-07-27 Ici Plc Refrigerant composition
WO1994022973A1 (fr) * 1993-03-29 1994-10-13 E.I. Du Pont De Nemours And Company Compositions refrigerantes a base d'hexafluoropropane et d'hydrofluorocarbone
EP0661365A2 (fr) * 1991-07-22 1995-07-05 E.I. Du Pont De Nemours And Company Utilisation de 1,2,2,3,3-pentafluoropropane
WO1996015206A1 (fr) * 1994-11-16 1996-05-23 E.I. Du Pont De Nemours And Company Compositions de pentafluoropropane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661365A2 (fr) * 1991-07-22 1995-07-05 E.I. Du Pont De Nemours And Company Utilisation de 1,2,2,3,3-pentafluoropropane
GB2274462A (en) * 1993-01-20 1994-07-27 Ici Plc Refrigerant composition
WO1994022973A1 (fr) * 1993-03-29 1994-10-13 E.I. Du Pont De Nemours And Company Compositions refrigerantes a base d'hexafluoropropane et d'hydrofluorocarbone
WO1996015206A1 (fr) * 1994-11-16 1996-05-23 E.I. Du Pont De Nemours And Company Compositions de pentafluoropropane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998008913A1 (fr) * 1996-08-30 1998-03-05 Imperial Chemical Industries Plc Compositions refrigerantes
US6495060B2 (en) 1996-08-30 2002-12-17 Ineos Fluor Holdings Limited Refrigerant compositions
US6100229A (en) * 1998-01-12 2000-08-08 Alliedsignal Inc. Compositions of 1,1,1,3,3,-pentafluoropropane and chlorinated ethylenes

Also Published As

Publication number Publication date
CA2231111A1 (fr) 1997-03-20
EP0850286A1 (fr) 1998-07-01
AU6977696A (en) 1997-04-01
JPH10511135A (ja) 1998-10-27

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