AU655701B2 - Mixtures of 1,1,1-trifluoroethane and perfluoropropane and their applications as refrigerants, as aerosol propellants or as plastic foam-expanding agents - Google Patents
Mixtures of 1,1,1-trifluoroethane and perfluoropropane and their applications as refrigerants, as aerosol propellants or as plastic foam-expanding agents Download PDFInfo
- Publication number
- AU655701B2 AU655701B2 AU31147/93A AU3114793A AU655701B2 AU 655701 B2 AU655701 B2 AU 655701B2 AU 31147/93 A AU31147/93 A AU 31147/93A AU 3114793 A AU3114793 A AU 3114793A AU 655701 B2 AU655701 B2 AU 655701B2
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- AU
- Australia
- Prior art keywords
- perfluoropropane
- trifluoroethane
- mixtures
- refrigerants
- plastic foam
- Prior art date
- Legal status (The legal status 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 status listed.)
- Ceased
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Classifications
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- 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
- 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
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
-
- 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
- C08J2207/00—Foams characterised by their intended use
- C08J2207/04—Aerosol, e.g. polyurethane foam spray
-
- 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
- C09K2205/12—Hydrocarbons
- C09K2205/128—Perfluorinated hydrocarbons
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (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)
- Photoreceptors In Electrophotography (AREA)
- Lubricants (AREA)
Abstract
To replace chlorofluorocarbons as refrigerating fluids, the invention proposes to employ mixtures containing, on a mass basis, approximately 40 to 70 % of 1,1,1-trifluoroethane and 30 to 60 % of perfluoropropane. The mixtures according to the invention can also be employed as aerosol propellants or as blowing agents for plastic foams.
Description
I LI L r S F Ref: 228871
AUSTRALIA
PATENTS ACT 1990 655'/01o COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
Name and Address of Applicant: o r r t ~r
I
D
r Elf Atochem S.A.
4 8 Cours Michelet La Defense 92800 Puteaux
FRANCE
Sylvie Macaudiere and Jean-Claude Tanguy Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Actual Inventor(s): Address for Service: Invention Title: r Ir i
I
i r ct rrir Mixtures of 1,1,1-trifluoroethane and perfluoropropane and their Applications as Refrigerants, as Aerosol Propellants or as Plastic Foam-Expanding Agents The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845/4 2 The present invention relates to mixtures of refrigerants having a low boiling point which have little or no effect on the environment and may replace chlorofluorocarbons (CFC) in pressurised low-temperature refrigeration systems and be used as aerosol propellants or as plastic foam-expanding agents.
It has been established that, because of their significant action on ozone, CFCs will, in the shorter or longer term, be replaced by refrigerants which no longer contain chlorine and, as a result, are less aggressive with respect to the environment.
1,1,1-trifluoroethane (HFC 143a) and perfluoropropane (FC 218) have, in comparison with the completely halogenated chlorinated compounds, a very small effect on the environment. HFC 143a has, however, the disadvantage of being inflammable. With regard to FC 218, its use in refrigeration is reflected in a relatively poor refrigerating capacity, a high compression ratio and, consequently, high operating costs.
S 20 It has now been found that mixtures contaia by mass, about 40 to 70 of HFC 143a and 30 to 60 of FC 218 have a maximum vapour pressure in comparison with the vypour pressures of the pure compounds.
On the other hand, for mass fractions of HFC 143a 1 25 of between 41 and 60.3 and of FC 218 of between 39.7 and *9 the mixtures show a pseudo-azeotropic behaviour and are non-inflammable, in contrast to HFC 143 a.
3 It has also been found that the two constituents together form an azeotrope which has a minimum boiling point of about -49.8 0 C under 1.013 bar and in which the HFC 143a content at the normal boiling point is about 55 by mass and that of FC 218 about 45 Because of their low boiling point, the mixtures according to the invention may be used as refrigerants in low-temperature -50 C) applications, as in the case of low-temperature industrial or commercial refrigeration.
The azeotrope described above is a refrigerant mixture which is very particularly preferred.
In the light of their physical properties, which are close to those of the CFCs, the mixtures according to the invention may also be used as aerosol propellants or as 15 plastic foam-expanding agents.
o. The following Examples further illustrate the .oo.oo invention, without restricting it.
0 00 S EXAMPLE 1 The azeotrope according to the invention has been 20 studied experimentally at various temperatures by gas phase chromatographic analysis of the compositions of the liquid phase and of the vapour phase for various mixtures of HFC 1[ '143a and FC 218.
The pressures were measured to an accuracy of 25 greater than 0.02 bar using a HEISE manometer. The temperatures were measured to an accuracy of 0.02 0 C using a 1000 ohm platinum probe.
4 Graph 1 of the accompanying drawing shows the liquid/vapour equilibrium curve of HFC 143a/FC 218 mixtures, recorded at a temperature of In this graph, the abscissa axis indicates the mass fraction of HFC 143a and the ordinate axis the absolute pressure in bars; the black squares correspond to the experimental points.
A curve analogous to that of graph 1 is obtained for each temperature. By successive additions of HFC 143a to the FC 218, the pressure developed by the mixture increases regularly, then passes through a maximum and falls regularly, this demonstrating the existence of the azeotrope of minimum boiling point.
EXAMPLE 2 The HFC 143a/FC 218 azeotrope was also 15 demonstrated experimentally by determining the boiling point t, S under 1.013 bar for various mixtures of HFC 143a and FC 218.
The pressures were determined to a precision of greater than 0.005 bar using a HEISE manometer. The temperatures were adjusted in 0.1 0 C steps in order to obtain S 20 a pressure of 1.013 bar.
The normal boiling points determined in this way for various compositions containing HFC 143a and FC 218 are indicated in the following table: i 'indicated in the following table: 4 tic.
-99 C
T
5 TABLE 1 HFC 143a content, Normal boiling by mass, in the point composition (oC) 100 47.3 60.3 49.7 54.8 49.8 49.8 44.7 49.8 41.0 49.6 0 37.0 et.
o 0 The results in this table demonstrate a minimum normal boiling point for a mass fraction of HFC 143a of about 44.7-54.8 However, it is pointed out that the mixture behaves as a quasi-azeotrope for mass fractions of HFC 143a of 41 to 60.3 The correlation of the experimental points thus obtained was carried out in accordance with well-known techniques, using computer simulation.
The results of these correlations demonstrate the minimum normal boiling point for a mass fraction of HFC 143a of 55 this enables the azeotrope to be characterised by: its normal boiling point, which is about -49.8 0
C
its HFC 143a content, by mass, in the composition, which is about 55 Table 2 below gives the pressure/temperature relationship for a mixture containing, by mass, about 55 of 1 -1! 6 HFC 143a and 45 of FC 218, compared with that of the pure substances.
TABLE 2 ABSOLUTE PRESSURE (BAR)
TEMPERATURE
HFC 143a/FC 218 Pure Pure Azeotrope HFC 143a FC 218 40 1.59 1.42 0.87 20 3.50 3.17 2.04 0 6.74 6.21 4.16 20 11.81 11.04 7.67 40 19.45 38.27 12.98 0~ *00444 4 4.r O 1 4401 Cr The vapour pressure of the azeotrope remains higher than the vapour pressure of the pure substances over a wide temperature range. These data indicate that the mixture remains azeotropic over this entire temperature range.
EXAMPLE 3 This example illustrates the use of the mixtures according to the invention as refrigerants.
The thermodynamic performance data of various mixtures according to the invention were compared with the performance data of the two constituents on *heir own and with those of CFC 502 (azeotropic mixture containing, by mass, 48.8 of chlorodifluoromethane and 51.2 of 7chioropentafluoroethane) for a standard thermodynamic cycle defined as follows: condensation temperature: 300C evaporation temperature 4000 liquid supercooling 150C vapour superheating 25 0
C
Table 3 lists the thermodynamic performance data observed under these conditions for pure HFC 143a, pure FC 218, their mixtures ,and CFC 502.
TABLE 3 HFC 143a/FC 218 Volumetric compression Discharge composition COP refrigeeating ratio temperature capacity (~by mass) 100/0 0.981 1.080 10.3 69 20 70/30 0.958 1.100 10.0 59 60/40 0.955 1.095 9.8 56 55/45 0.951 1.085 9.8 54 50/50 0.947 1.070 9.9 53 45/55 0.936 1.035 10.0 51 25 40/60 0.925 0.995 10.2 20/80 0.872 0.780 11.6 0/100 0.925 0.590 11.7 34 30 cFC50 026 ()in relation to CFC 502 It can be seen that the mixtures according to the invention offer advantages over pure HFC 143a, pure FC 218 or CFC 502, in particular: .a lower compression ratio, improving the (It:
C
atti tell' It It 4 II 14 I I (It C I C: I CIII. C I ttt.
III.
IC
C C -9 -8volumetric efficiency of the compressor and, as a result, giving rise to lower operating costs for the installation; a discharge temperature which is lower by at least 0 C compared with CFC 502 or HFC 143a, which promotes good stability of the mixture in a refrigerating circuit; a higher available volumetric refrigerating capacity, which in practice, for a given refrigerating capacity, permits the use of a smaller compressor than that defined for the use of CFC 502.
0 6
I
f
Claims (7)
1. A mixture consisting of, by mass, about 40 to 70 of 1,1,1- trifluoroethane and 30 to 60 of perfluoropropane.
2. A mixture according to claim 1, consisting of, by mass, about 41 to 60.3 of 1,1,1-trifluoroethane and 39.7 to 59 of perfluoropropane.
3. A mixture according to claim 2, consisting of, by mass, about 55 of 1,1,1-trifiuoroethane and 45 of perfluoropropane and corresponding to an azeotropic mixture of low minimum boiling point (about -49.8oC under 1.013 bar).
4. A mixture according to claim 1 substantially as described in any one 10 of the Examples.
5. A mixture according to any one of claims 1 to 4 for use as a refrigerant.
6. A mixture according to any one of claims 1 to 4 for use as an aerosol propellant. 15
7. A mixture according to any of claims 1 to 4 for use as a plastic foam- expanding agent. Dated 17 October, 1994 Elf Atochem S.A. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON Sr -I:1 -Pt j v* /y I I S 1 t P ABSTRACT MIXTURES OF 1,1,1-TRIFLUOROETHANE AND PFRFLUOROPROPANE AND THEIR APPLICATIONS AS REFRIGERANTS, AS AEROSOL PROPELLANTS OR AS PLASTIC FOAM-EXPANDING AGENTS Mixtures containing, by mass, about 40 to 70 of 1,1,1-trifluoroethane and 30 to 60 of perfluoropropane may be used to replace chlorofluorocarbons as refrigerants and 9600 may also be used as aerosol propellants or as plastic foam- 0oo no 10 expanding agents. sc 00 00* 0 0 o oo 0D 0 0 0 0 00 0 0 0 P U
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9200260 | 1992-01-13 | ||
FR929200260A FR2686092B1 (en) | 1992-01-13 | 1992-01-13 | MIXTURES OF 1,1,1-TRIFLUOROETHANE AND PERFLUOROPROPANE AND THEIR APPLICATIONS AS REFRIGERANTS, AS AEROSOL PROPELLERS OR AS PLASTIC FOAM EXPANSION AGENTS. |
Publications (2)
Publication Number | Publication Date |
---|---|
AU3114793A AU3114793A (en) | 1993-07-15 |
AU655701B2 true AU655701B2 (en) | 1995-01-05 |
Family
ID=9425565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU31147/93A Ceased AU655701B2 (en) | 1992-01-13 | 1993-01-12 | Mixtures of 1,1,1-trifluoroethane and perfluoropropane and their applications as refrigerants, as aerosol propellants or as plastic foam-expanding agents |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0552075B1 (en) |
JP (1) | JPH07112991B2 (en) |
KR (2) | KR930016537A (en) |
AT (1) | ATE124439T1 (en) |
AU (1) | AU655701B2 (en) |
CA (1) | CA2086819A1 (en) |
DE (1) | DE69300208T2 (en) |
DK (1) | DK0552075T3 (en) |
ES (1) | ES2073950T3 (en) |
FI (1) | FI930117A (en) |
FR (1) | FR2686092B1 (en) |
IL (1) | IL104019A (en) |
NO (1) | NO924805L (en) |
ZA (1) | ZA9365B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0669966A1 (en) * | 1992-11-19 | 1995-09-06 | E.I. Du Pont De Nemours And Company | Refrigerant compositions including 1,1,2-trifluoroethane |
EP1028152A3 (en) * | 1993-02-05 | 2005-06-15 | E.I. Du Pont De Nemours And Company | Compositions of a hydrofluorocarbon and a hydrocarbon |
US5458798A (en) * | 1993-02-05 | 1995-10-17 | E. I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of a hydrofluorocarbon and a hydrocarbon |
US6173577B1 (en) | 1996-08-16 | 2001-01-16 | American Superconductor Corporation | Methods and apparatus for cooling systems for cryogenic power conversion electronics |
US6023934A (en) * | 1996-08-16 | 2000-02-15 | American Superconductor Corp. | Methods and apparatus for cooling systems for cryogenic power conversion electronics |
US5801937A (en) * | 1996-10-16 | 1998-09-01 | American Superconductor Corporation | Uninterruptible power supplies having cooled components |
DE19708157A1 (en) * | 1997-02-28 | 1998-09-03 | Peter Kwasny Gmbh | Aerosol film-forming compositions for hair- and deodorant-sprays |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2631792A (en) * | 1991-10-09 | 1993-04-22 | Elf Atochem S.A. | Mixtures of 1,1,1-trifluoroethane, perfluoropropane and propane, and their applications as refrigerant fluids, as aerosol propellants or as blowing agents for plastic foams |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1542023A (en) * | 1967-10-27 | 1968-10-11 | Union Carbide Corp | Cooling compositions |
NL7708731A (en) * | 1976-08-13 | 1978-02-15 | Montedison Spa | PROCESS FOR THE PREPARATION OF NEW DRIVER COMPOSITIONS FOR AEROSOLS. |
JPH075880B2 (en) * | 1987-09-21 | 1995-01-25 | ダイキン工業株式会社 | Coolant |
JPH01108292A (en) * | 1987-10-19 | 1989-04-25 | Daikin Ind Ltd | Refrigerant |
JP2545887B2 (en) * | 1987-11-02 | 1996-10-23 | ダイキン工業株式会社 | Coolant |
JP2847797B2 (en) * | 1989-09-06 | 1999-01-20 | ダイキン工業株式会社 | Working fluid |
JP2794818B2 (en) * | 1989-09-06 | 1998-09-10 | ダイキン工業株式会社 | Working fluid |
FR2662944B2 (en) * | 1989-11-10 | 1992-09-04 | Atochem | NEW AZEOTROPIC MIXTURE WITH LOW BOILING POINT BASED ON FLUOROALKANES AND ITS APPLICATIONS. |
DE69011287T2 (en) * | 1989-11-30 | 1994-11-17 | Matsushita Electric Ind Co Ltd | Work equipment. |
-
1992
- 1992-01-13 FR FR929200260A patent/FR2686092B1/en not_active Expired - Lifetime
- 1992-12-08 IL IL10401992A patent/IL104019A/en not_active IP Right Cessation
- 1992-12-11 NO NO92924805A patent/NO924805L/en unknown
-
1993
- 1993-01-06 CA CA002086819A patent/CA2086819A1/en not_active Abandoned
- 1993-01-06 ZA ZA9365A patent/ZA9365B/en unknown
- 1993-01-08 DK DK93400036.5T patent/DK0552075T3/en active
- 1993-01-08 AT AT93400036T patent/ATE124439T1/en not_active IP Right Cessation
- 1993-01-08 ES ES93400036T patent/ES2073950T3/en not_active Expired - Lifetime
- 1993-01-08 DE DE69300208T patent/DE69300208T2/en not_active Expired - Fee Related
- 1993-01-08 EP EP93400036A patent/EP0552075B1/en not_active Expired - Lifetime
- 1993-01-08 JP JP5001573A patent/JPH07112991B2/en not_active Expired - Lifetime
- 1993-01-12 FI FI930117A patent/FI930117A/en unknown
- 1993-01-12 AU AU31147/93A patent/AU655701B2/en not_active Ceased
- 1993-01-13 KR KR1019930000379A patent/KR930016537A/en active IP Right Grant
- 1993-02-13 KR KR1019930000379D patent/KR960006072B1/en active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2631792A (en) * | 1991-10-09 | 1993-04-22 | Elf Atochem S.A. | Mixtures of 1,1,1-trifluoroethane, perfluoropropane and propane, and their applications as refrigerant fluids, as aerosol propellants or as blowing agents for plastic foams |
Also Published As
Publication number | Publication date |
---|---|
JPH07112991B2 (en) | 1995-12-06 |
AU3114793A (en) | 1993-07-15 |
ATE124439T1 (en) | 1995-07-15 |
KR930016537A (en) | 1993-08-26 |
IL104019A (en) | 1995-10-31 |
JPH05271122A (en) | 1993-10-19 |
ES2073950T3 (en) | 1995-08-16 |
KR960006072B1 (en) | 1996-05-08 |
DE69300208T2 (en) | 1996-02-29 |
CA2086819A1 (en) | 1993-07-14 |
ZA9365B (en) | 1993-08-03 |
IL104019A0 (en) | 1993-05-13 |
NO924805D0 (en) | 1992-12-11 |
FI930117A0 (en) | 1993-01-12 |
FR2686092B1 (en) | 1994-09-16 |
FR2686092A1 (en) | 1993-07-16 |
EP0552075B1 (en) | 1995-06-28 |
EP0552075A1 (en) | 1993-07-21 |
DK0552075T3 (en) | 1995-11-13 |
NO924805L (en) | 1993-07-14 |
FI930117A (en) | 1993-07-14 |
DE69300208D1 (en) | 1995-08-03 |
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