WO1994011459A1 - Compositions de type azeotrope de difluoromethane, de pentafluroethane et de 1,1,1-trifluoroethane - Google Patents

Compositions de type azeotrope de difluoromethane, de pentafluroethane et de 1,1,1-trifluoroethane Download PDF

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Publication number
WO1994011459A1
WO1994011459A1 PCT/US1993/010362 US9310362W WO9411459A1 WO 1994011459 A1 WO1994011459 A1 WO 1994011459A1 US 9310362 W US9310362 W US 9310362W WO 9411459 A1 WO9411459 A1 WO 9411459A1
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WO
WIPO (PCT)
Prior art keywords
weight percent
compositions
hfc
azeotrope
composition
Prior art date
Application number
PCT/US1993/010362
Other languages
English (en)
Inventor
Earl August Eugene Lund
Ian Robert Shankland
Rajiv Ratna Singh
Original Assignee
Allied-Signal 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 Allied-Signal Inc. filed Critical Allied-Signal Inc.
Priority to EP93925106A priority Critical patent/EP0668897A1/fr
Priority to JP6512123A priority patent/JPH08503461A/ja
Priority to KR1019950701865A priority patent/KR100218062B1/ko
Publication of WO1994011459A1 publication Critical patent/WO1994011459A1/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
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • 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
    • 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
    • C09K2205/32—The mixture being azeotropic

Definitions

  • Fluorocarbon based fluids have found widespread use in industry for refrigeration, air conditioning and heat pump applications.
  • 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 inter ⁇ changed with that of the refrigeration evaporator.
  • Certain fluorocarbons and in particular chlorofluorocarbons (CFC's), have gained widespread use in refrigeration applications including air conditioning and heat pump applications owing to their unique combination of chemical and physical properties.
  • the majority of refrigerants utilized in vapor compression systems are either single component fluids or azeotropic mixtures. Single component fluids and azeotropic mixtures are characterized as constant- boiling because they exhibit isothermal and isobaric evaporation and condensation.
  • the use of azeotropic mixtures as refrigerants is known in the art. See, for example, R.C. Downing, "Fluorocarbon Refrigerants Handbook", pp. 139-158, Prentice-Hall, 1988, and U.S. Patents 2,101,993 and 2,641,579.
  • Azeotropic or azeotrope-like compositions are desired because they do not fractionate upon boiling or evaporation. 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, and unless the refrigerant composition is constant boiling, i.e., is azeotrope- like, fractionation and segregation will occur upon evaporation and condensation and undesirable refrigerant distribution may act to upset cooling or heating.
  • fluorocarbon based azeotrope-like mixtures which offer alternatives for refrigeration and heat pump applications.
  • fluorocarbons which contain little or no chlorine are of particular interest because they are considered to be environmentally acceptable substitutes for the fully halogenated CFC's which are suspected of causing environmental problems associated with the depletion of the earth's protective ozone layer.
  • HFC-32 has been proposed as an environmentally acceptable refrigerant however, it is not a particularly efficient refrigerant especially at higher condensing temperatures, because it has a relatively low critical temperature. It is also flammable. HFC- 143a is a good refrigerant on a thermodynamic basis but has a lower vapor pressure than HFC-32. This results in a lower refrigeration capacity than HFC-32. HFC- 143a is also flammable. HFC-125 also has a lower capacity than HFC-32 but it is nonflammable. Applicants have surprisingly discovered that when these compounds are combined in effective amounts, an azeotrope-like composition results which has a higher refrigeration capacity than HFC-32, HFC-143a and HFC-125 and which is nonflammable in certain proportions.
  • compositions of the invention are useful as blowing agents for extruded thermal plastic foams such as polyethylene and polystyrene foams.
  • thermal plastic foams such as polyethylene and polystyrene foams.
  • the compositions of the invention may be used alone or in combination with another liquid blowing agent such as 1,1-dichloro-l- fluoroethane (HCFC-141b) or other hydrochloro- fluorocarbon or hydrofluorocarbon liquids.
  • compositions of the preferred and more preferred azeotrope-like compositions of the invention are summarized in Table I below. Note that the composition ranges reported are in weight percent and the term "about” is understood to preface each range disclosed.
  • azeotrope-like 25 composition is intended to mean that the composition behaves like a true azeotrope in terms of its constant boiling characteristics or tendency not to fractionate upon boiling or evaporation.
  • the composition of the vapor formed during evaporation 30 is identical or substantially identical to the original liquid composition.
  • the liquid composition if it changes at all, changes only slightly. This is contrasted with non-azeotrope-like compositions in which the liquid and vapor compositions change substantially during evaporation or condensation.
  • 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 the body to be cooled.
  • the azeotrope-like compositions of the invention may be used in a method for producing heating which comprises condensing a refrigerant in the vicinity of the body to be heated and thereafter evaporating the refrigerant.
  • the azeotrope-like compositions of the invention may be used as a blowing agent in a process for making extruded thermal plastic foams comprising blending heat plasticized polyolefin resin with a bloving agent and introducing the resin/blowing agent blend into a zone of lower pressure to cause foaming.
  • a process for making extruded thermal plastic foams comprising blending heat plasticized polyolefin resin with a bloving agent and introducing the resin/blowing agent blend into a zone of lower pressure to cause foaming.
  • about 1 - 15 parts of blowing agent are utilized per 100 parts resin.
  • the difluoromethane, pentafluoroethane and 1,1,1- trifluoroethane components of the novel azeotrope-like compositions of the invention are known materials. Preferably they should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the constant boiling properties of the system.
  • a 150-plate packed distillation column with a liquid nitrogen condensed vapor dividing head was used for this example.
  • the distillation column was charged with a 29/43.8/27.2 weight percent blend of HFC-32/HFC- 125/HFC-143a respectively.
  • the composition was heated under total reflux for about an hour to ensure equilibration.
  • Vapor samples were taken from the top of the condenser and analyzed using gas chromatography. The averages of the vapor sample compositions and the overhead temperatures were quite constant within the uncertainty associated with determining the compositions, indicating that the mixtures are constant-boiling or azeotrope-like.
  • the averages of the vapor sample compositions and the overhead temperatures are quite constant with the. uncertainty associated with determining the composition, indicating that the compositions are constant-boiling or azeotrope-like.
  • the theoretical performance of a refrigerant at speci ic operating conditions can be estimated from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques. See, for example, "Fluorocarbons Refrigerants Handbook", ch. 3, Prentice-Hall, (1988) by R.C. Downing.
  • the coefficient of performance, COP is a universally accepted measure, especially useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the 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 of a refrigerant represents the volumetric efficiency of the 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 COP of the 75/4/21 weight percent HFC-32/HFC-125/HFC-143a blend was 1.66.
  • the COP for each of HFC-32 and HFC-125 was 1.63 and 1.57 respectively.
  • the energy efficiency of the mixture was higher than that of pure HFC-32 and HFC-125.
  • the capacity of the azeotropic blend was higher than that of HFC-32, HFC- 125 and HFC-143a by 4%, 15% and 17% respectively.
  • a small 304 grade stainless steel pressure vessel is constructed using schedule 40 pipe which is 4 inches in length and 2 inches in diameter.
  • the vessel has top and bottom flanges which are used to close the ends of the cell.
  • a pressure tight seal is maintained between the ends of the pipe and the flanges using Teflon o-rings.
  • the vessel is closed by tightening 4 bolts which run the length of the cell through the top and bottom flanges.
  • the design pressure limit for the apparatus is 1700 psi at 200°C; the operational limit is set at 1000 psi.
  • Example 1 Twenty two and one half grams of the composition of Example 1 is charged into the sealed vessel. The vessel is placed in a 250°F oven overnight. The vessel is removed from the oven, rapidly depressurized and then immersed in water. The glass jar is removed from the vessel. The resulting foam has a density of 3 - 4 lbs/ft 3 indicating that the composition of Example 1 is a good blowing agent for thermal plastic foam.
  • compositions of HFC-32, HFC-125 and HFC-143a are azeotrope-like, useful as blowing agents for thermal plastic foam and polyurethane foam and exhibit improved refrigeration properties.
  • Example 4 The experiment outlined in Example 4 above is repeated using each of compositions a)- d) of Example 2. In each case, the resulting foam has a density of 3 - 4 lbs/ft 3 indicating that each of compositions a) - d) is a good blowing agent for thermal plastic foam.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Compositions, de type azéotrope, de difluorométhane, de pentafluoroéthane et de 1,1,1-trifluoroéthane qui sont utiles en tant que réfrigérants pour des applications de chauffage et de réfrigération, et en tant que gonflants pour la préparation de mousses thermoplastiques.
PCT/US1993/010362 1992-11-10 1993-10-28 Compositions de type azeotrope de difluoromethane, de pentafluroethane et de 1,1,1-trifluoroethane WO1994011459A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP93925106A EP0668897A1 (fr) 1992-11-10 1993-10-28 Compositions de type azeotrope de difluoromethane, de pentafluroethane et de 1,1,1-trifluoroethane
JP6512123A JPH08503461A (ja) 1992-11-10 1993-10-28 ジフルオロメタン、ペンタフルオロエタンおよび１，１，１−トリフルオロエタンからなる共沸様組成物
KR1019950701865A KR100218062B1 (ko) 1992-11-10 1993-10-28 디플루오로메탄, 펜타플루오로에탄 및 1,1,1-트리플루오로에탄을 포함하는 공비성 조성물

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US97549992A 1992-11-10 1992-11-10
US975,499 1992-11-10

Publications (1)

Publication Number Publication Date
WO1994011459A1 true WO1994011459A1 (fr) 1994-05-26

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Application Number Title Priority Date Filing Date
PCT/US1993/010362 WO1994011459A1 (fr) 1992-11-10 1993-10-28 Compositions de type azeotrope de difluoromethane, de pentafluroethane et de 1,1,1-trifluoroethane

Country Status (5)

Country Link
EP (1) EP0668897A1 (fr)
JP (1) JPH08503461A (fr)
KR (1) KR100218062B1 (fr)
CA (1) CA2148698A1 (fr)
WO (1) WO1994011459A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0738773A1 (fr) * 1995-04-20 1996-10-23 Elf Atochem S.A. Mélanges pseudo-azéotropiques à base de difluorométhane et de pentafluoroéthane, et leurs applications comme fluides frigorigènes
FR2756294A1 (fr) * 1996-11-27 1998-05-29 Atochem Elf Sa Utilisation de melanges a base de difluoromethane et de pentafluoroethane comme fluides frigorigenes en refrigeration tres basse temperature
US5800730A (en) * 1990-07-26 1998-09-01 E. I. Du Pont De Nemours And Compnay Near-azeotropic blends for use as refrigerants
FR2860001A1 (fr) * 2003-09-19 2005-03-25 Arkema Composition a base d'hfc (hydrofluorocarbures) et son utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4943388A (en) * 1989-06-28 1990-07-24 Allied-Signal Inc. Azeotrope-like compositions of pentafluoroethane; 1,1,1-trifluoroethane; and chlorodifluoromethane
JPH03170583A (ja) * 1989-11-30 1991-07-24 Matsushita Electric Ind Co Ltd 作動流体
JPH03170588A (ja) * 1989-11-30 1991-07-24 Matsushita Electric Ind Co Ltd 作動流体
WO1992001762A1 (fr) * 1990-07-26 1992-02-06 E.I. Du Pont De Nemours And Company Melanges quasi-azeotropes destines a etre utilises en tant que refrigerants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4943388A (en) * 1989-06-28 1990-07-24 Allied-Signal Inc. Azeotrope-like compositions of pentafluoroethane; 1,1,1-trifluoroethane; and chlorodifluoromethane
JPH03170583A (ja) * 1989-11-30 1991-07-24 Matsushita Electric Ind Co Ltd 作動流体
JPH03170588A (ja) * 1989-11-30 1991-07-24 Matsushita Electric Ind Co Ltd 作動流体
WO1992001762A1 (fr) * 1990-07-26 1992-02-06 E.I. Du Pont De Nemours And Company Melanges quasi-azeotropes destines a etre utilises en tant que refrigerants

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9136, Derwent World Patents Index; Class E16, AN 91-262356 *
DATABASE WPI Section Ch Week 9136, Derwent World Patents Index; Class E16, AN 91-262358 *

Cited By (10)

* 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
EP0738773A1 (fr) * 1995-04-20 1996-10-23 Elf Atochem S.A. Mélanges pseudo-azéotropiques à base de difluorométhane et de pentafluoroéthane, et leurs applications comme fluides frigorigènes
FR2733242A1 (fr) * 1995-04-20 1996-10-25 Atochem Elf Sa Melanges pseudo-azeotropiques a base de difluoromethane et de pentafluoroethane, et leurs applications comme fluides frigorigenes
FR2756294A1 (fr) * 1996-11-27 1998-05-29 Atochem Elf Sa Utilisation de melanges a base de difluoromethane et de pentafluoroethane comme fluides frigorigenes en refrigeration tres basse temperature
EP0845519A1 (fr) * 1996-11-27 1998-06-03 Elf Atochem S.A. Utilisation de mélanges à base de difluorométhane et de pentafluoroéthane comme fluides frigorigènes en réfrigération tres basse température
US6093340A (en) * 1996-11-27 2000-07-25 Elf Atochem S.A. Use of mixtures based on difluoromethane and on pentafluorethane as cryogenic fluids in very low temperature refrigeration
FR2860001A1 (fr) * 2003-09-19 2005-03-25 Arkema Composition a base d'hfc (hydrofluorocarbures) et son utilisation
WO2005028586A2 (fr) * 2003-09-19 2005-03-31 Arkema Composition a base d'hfc (hydrofluorocarbures) et son utilisation
WO2005028586A3 (fr) * 2003-09-19 2005-06-30 Arkema Composition a base d'hfc (hydrofluorocarbures) et son utilisation
US7504043B2 (en) 2003-09-19 2009-03-17 Arkema France Hydrofluorocarbon-based composition and use thereof

Also Published As

Publication number Publication date
JPH08503461A (ja) 1996-04-16
KR100218062B1 (ko) 1999-09-01
CA2148698A1 (fr) 1994-05-26
EP0668897A1 (fr) 1995-08-30
KR950704438A (ko) 1995-11-20

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