WO1995000600A1 - Compositions de tetrafluorethane et de gaz ammoniac analogues a des azeotropes - Google Patents

Compositions de tetrafluorethane et de gaz ammoniac analogues a des azeotropes Download PDF

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Publication number
WO1995000600A1
WO1995000600A1 PCT/US1994/006784 US9406784W WO9500600A1 WO 1995000600 A1 WO1995000600 A1 WO 1995000600A1 US 9406784 W US9406784 W US 9406784W WO 9500600 A1 WO9500600 A1 WO 9500600A1
Authority
WO
WIPO (PCT)
Prior art keywords
azeotrope
ammonia
compositions
tetrafluoroethane
weight percent
Prior art date
Application number
PCT/US1994/006784
Other languages
English (en)
Inventor
Earl August Eugene Lund
Ian Robert Shankland
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 AU72469/94A priority Critical patent/AU7246994A/en
Publication of WO1995000600A1 publication Critical patent/WO1995000600A1/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
    • C09K2205/10—Components
    • C09K2205/132—Components containing nitrogen
    • 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
    • C09K2205/32—The mixture being azeotropic

Definitions

  • This invention relates to azeotrope-like or constant-boiling mixtures of 1 ,1 , 1 ,2-tetrafluoroethane (HFC-134a) or 1 , 1 ,2,2-tetrafluoroethane (HFC- 134) and ammonia. These mixtures are useful as refrigerants for heating and cooling. HFC-134a and HFC-134 shall collectively be referred to herein as "tetrafluoroethane”.
  • Vapor compression is one form 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 of the condenser is interchanged with that of the refrigeration evaporator.
  • chlorofluoromethane and chlorofluoroethane derivatives have gained widespread use as refrigerants in applications including air conditioning and heat pump applications owing to their unique combination of chemical and physical properties.
  • Ammonia is often used in industrial refrigeration.
  • the majority of refrigerants utilized in vapor compression systems are either single component fluids or azeotropic mixtures.
  • Azeotropic or azeotrope-like compositions are desired as refrigerants because they do not fractionate upon boiling. This behavior is desirable because in the previously described vapor compression equipment with which these refrigerants are employed, condensed material is generated in preparation for cooling or for heating purposes. Unless the refrigerant composition exhibits a constant boiling point, i.e. is azeotrope-like, fractionation and segregation will occur upon evaporation and condensation and undesirable refrigerant distribution may act to upset the cooling or heating.
  • Fluorocarbon and hydrofluorocarbon based azeotrope-like mixtures are of particular interest because they are considered to be environmentally safe substitutes for the presently used fully halogenated chlorofluorocarbons (CFC's) which are suspected of causing environmental problems in connection with the earth's protective ozone layer.
  • CFC's fully halogenated chlorofluorocarbons
  • Ammonia is a well known refrigerant however its flammability properties and high discharge temperatures, when used in vapor compression machines, are of some disadvantage.
  • Refrigerants ideally must possess properties like chemical stability, low toxicity, non-flammability, and efficiency in-use. The latter characteristic is important in refrigeration and air-conditioning 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. Furthermore, the ideal CFC refrigerant substitute should not require major engineering changes to conventional vapor compression technology currently used with ammonia or CFC refrigerants.
  • azeotrope-like as used herein is intended to mean that the composition behaves like an azeotrope, i.e. has constant-boiling characteristics or a tendency not to fractionate upon boiling or evaporation.
  • the composition of the vapor formed during boiling or evaporation is identical or substantially identical to the original liquid composition.
  • the liquid composition if it changes at all, changes only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree.
  • the azeotrope-like compositions of the invention are advantageous for the following reasons. Each component is a negligible contributor to ozone depletion. Also, because the present compositions exhibit essentially constant-vapor pressure characteristics as the liquid mixture is evaporated and show relatively minor shifts in composition during evaporation, the compositions are shown advantageous in a vapor compression cycle as they mimic the performance of a constant-boiling single component or azeotropic mixture refrigerant. This is to be contrasted with the performance of the non-azeotropic composition of HFC-134 and ammonia disclosed in U.S. patent 3,732, 150.
  • the tetrafluoroethane azeotrope-like compositions have boiling points which are lower than that of ammonia (-33.3°C) or that of the tetrafluoro ⁇ ethane component.
  • the cooling capacity of the azeotrope-like compositions is therefore higher than that of either component.
  • certain compositions of ammonia and tetrafluoroethane mixtures are also nonflammable. Addition of tetrafluoroethane to ammonia also causes the discharge temperature of the compressor in a vapor compression machine to decrease, an advantage from the refrigeration engineer's point of view.
  • Additional components may be added to the mixture to tailor the properties of the mixture according to the need.
  • propane has been added to refrigerant compositions to aid oil solubility, but is not considered to substantially affect the refrigeration properties of the mixture.
  • the azeotrope-like compositions of the invention may be used in a method for producing refrigeration which comprises condensing a refrigerant comprising the azeotrope-like compositions and thereafter evaporating the refrigerant in the vicinity of a body to be cooled.
  • the azeotrope compositions of the invention may be used in a method for producing heating which comprises condensing a refrigerant comprising the azeotrope- like compositions in the vicinity of a body to be heated and thereafter evaporating the refrigerant.
  • the tetrafluoroethane and ammonia components of the novel azeotrope-like compositions of the invention are known materials and are commercially available or may be manufactured by procedures well known in the art.
  • the materials should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the cooling or heating properties or constant-boiling properties of the system.
  • the ebulliometer was first charged with a weighed amount of ammonia.
  • the condenser was cooled with dry-ice and ethanol mixture.
  • the temperature was measured with a platinum resistance thermometer.
  • the boiling temperature and pressure were recorded after steady state was achieved.
  • An aliquot of HFC-134a was introduced into the ebulliometer and the temperature recorded after the attainment of equilibrium. The process was repeated again with addition of additional aliquots.
  • the boiling point data showed a minimum at a -37°C. _ ⁇ . 1 °C at 14.7 psia., about 4°C below the boiling point of ammonia, in the boiling temperature versus composition curve, i.e., ammonia and HFC-134a form a positive azeotrope.
  • Example shows that HFC-134 and ammonia also form an azeotrope.
  • the experiment was done in a manner identical to the one in Example 1 , except that HFC-134 was used instead of HFC-134a.
  • the boiling point data showed a minimum at a -33.6°C. ⁇ _ .1 at 14.7 psia, about 0.3° C below the boiling point of ammonia, in the boiling temperature versus compositions curve, i.e., ammonia and HFC-134 also form a positive azeotrope.

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

Abstract

L'invention se rapporte à des compositions analogues à des azéotropes comprenant du 1,1,1,2-tétrafluoroéthane (HFC-134a) ou du 1,1,2,2-tétrafluoroéthane (HFC-134) et du gaz ammoniac, ces compositions étant stables et utiles comme réfrigérants pour chauffer ou refroidir.
PCT/US1994/006784 1993-06-17 1994-06-15 Compositions de tetrafluorethane et de gaz ammoniac analogues a des azeotropes WO1995000600A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU72469/94A AU7246994A (en) 1993-06-17 1994-06-15 Azeotrope-like compositions of tetrafluoroethane and ammonia

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7869593A 1993-06-17 1993-06-17
US08/078,695 1993-06-17

Publications (1)

Publication Number Publication Date
WO1995000600A1 true WO1995000600A1 (fr) 1995-01-05

Family

ID=22145662

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/006784 WO1995000600A1 (fr) 1993-06-17 1994-06-15 Compositions de tetrafluorethane et de gaz ammoniac analogues a des azeotropes

Country Status (2)

Country Link
AU (1) AU7246994A (fr)
WO (1) WO1995000600A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6503417B1 (en) 1998-04-13 2003-01-07 E. I. Du Pont De Nemours And Company Ternary compositions of ammonia, pentafluoroethane and difluoromethane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5813687A (ja) * 1981-07-17 1983-01-26 Showa Denko Kk 冷凍作用流体組成物
JPS61255977A (ja) * 1985-05-10 1986-11-13 Asahi Glass Co Ltd 熱安定化された作動媒体組成物
WO1994007971A1 (fr) * 1992-09-25 1994-04-14 E.I. Du Pont De Nemours And Company Compositions azeotropiques ou analogues a des azeotropes de gaz ammoniaque et d'hydrofluorocarbures

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5813687A (ja) * 1981-07-17 1983-01-26 Showa Denko Kk 冷凍作用流体組成物
JPS61255977A (ja) * 1985-05-10 1986-11-13 Asahi Glass Co Ltd 熱安定化された作動媒体組成物
WO1994007971A1 (fr) * 1992-09-25 1994-04-14 E.I. Du Pont De Nemours And Company Compositions azeotropiques ou analogues a des azeotropes de gaz ammoniaque et d'hydrofluorocarbures

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7138, Derwent World Patents Index; AN 71-61135S *
DATABASE WPI Week 8310, Derwent World Patents Index; AN 83-23340K *
DATABASE WPI Week 8652, Derwent World Patents Index; AN 86-342476 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6503417B1 (en) 1998-04-13 2003-01-07 E. I. Du Pont De Nemours And Company Ternary compositions of ammonia, pentafluoroethane and difluoromethane

Also Published As

Publication number Publication date
AU7246994A (en) 1995-01-17

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