WO2002024829A1 - Centrifugal compression refrigerant compositions - Google Patents

Centrifugal compression refrigerant compositions Download PDF

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Publication number
WO2002024829A1
WO2002024829A1 PCT/GB2000/003596 GB0003596W WO0224829A1 WO 2002024829 A1 WO2002024829 A1 WO 2002024829A1 GB 0003596 W GB0003596 W GB 0003596W WO 0224829 A1 WO0224829 A1 WO 0224829A1
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WO
WIPO (PCT)
Prior art keywords
weight
heptafluoropropane
tetrafluoroethane
composition according
composition
Prior art date
Application number
PCT/GB2000/003596
Other languages
French (fr)
Inventor
Neil Andre Roberts
Original Assignee
Rhodia Organique Fine Limited
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 Rhodia Organique Fine Limited filed Critical Rhodia Organique Fine Limited
Priority to AU7302100A priority Critical patent/AU7302100A/en
Priority to AU2000273021A priority patent/AU2000273021B2/en
Priority to CA002424842A priority patent/CA2424842A1/en
Priority to PCT/GB2000/003596 priority patent/WO2002024829A1/en
Priority to CZ2003734A priority patent/CZ2003734A3/en
Priority to JP2002529229A priority patent/JP2004512393A/en
Priority to BRPI0017337-1A priority patent/BR0017337B1/en
Priority to EP00960853A priority patent/EP1325097A1/en
Publication of WO2002024829A1 publication Critical patent/WO2002024829A1/en

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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

Definitions

  • This invention relates to refrigerant compositions. More particularly, it relates to refrigerant compositions which can be used in place of R12 in a compression refrigeration system employing a centrifugal compressor.
  • R12 (CC1 2 F 2 ) has been used for many years as a refrigerant composition.
  • CFC gases various attempts have been made to reduce or eliminate its use.
  • R134 tetrafluoroethane
  • vapour densities are related to the molecular weight.
  • the molecular weight of R12 is 121 whereas the molecular weight of R134 is only 102. This difference would require the dimensions of the impellor used in the centrifugal compressor system to be altered as well as its speed. Clearly there is a need for a composition which can be used in an existing system without modification.
  • a further complication in the use of refrigerants using a centrifugal compressor resides in the fact that a centrifugal compressor uses a "flooded" evaporator i.e. some refrigerant liquid remains throughout the cooling cycle.
  • the formulation of the liquid composition included in the system generally differs from the formulation of the vapour circulating in the system.
  • the object of the present invention is to provide a refrigerant composition which can be used in systems employing a centrifugal compressor without the need to modify the impellor dimensions or its speed.
  • a composition which can be used in an existing system without modification is a need for a composition which can be used in an existing system without modification.
  • liquid refrigerant composition which comprises at least 35% by weight of tetrafluoroethane and at least 20% by weight of heptafluoropropane such that the concentration of tetrafluoroethane and heptafluoropropane is at least 90% by weight of the composition.
  • Tetrafluoroethane exists in two forms, namely the symmetrical 1,1,2,2- tetrafluoroethane and 1,1,1,2-tetrafluoroethane known as R134a. The latter is preferred for use in the present invention.
  • heptafluoropropane exists in two isomeric forms, namely 1,1,1 ,2,3 ,3 ,3 -heptafluoropropane, known as R227ea which is preferred, and 1,1, 1,2,2,3, 3 -heptafluoropropane, known as R227ca.
  • formulations in the vapour phase will differ from that in the liquid phase. It has been found that formulations comprising 20 to 52% by weight ofR227 and, correspondingly, 80 to 48% of R134a will provide formulations which will behave in the vapour phase in a manner similar to that of R12 with a variation of + or - 10%.
  • compositions of the present invention consist essentially of R134 and R227 (i.e. they are binary compositions), especially R134a and R227ea, but small amounts of a third component can be included.
  • Any additional component i.e. third or higher component can be present in an amount up to 10% weight, preferably up to 5%, and more preferably up to 2%, by weight of the composition. If more than one additional component is used then the total amount of these components is not more than 10% by weight. Since a principal aim of the formulation is to increase the overall molecular weight and thereby increase the vapour density, it is more usual to replace some of the R134a than replace some of the R227.
  • Possible additional components include C318 (octafluorocyclobutane), R218 (octafluoropropane) and R125 (pentafluoroethane).
  • the concentration of R134 is generally 80 to 35%>, preferably 70 to 45% and more preferably 50 to 60%, by weight.
  • the concentration of R227 is generally 20 to 65%>, preferably 30 to 55% and especially 40 to 50%, by weight.
  • a particularly preferred formulation consists of 52.5%) of R134a and 47.5% of R227ea. This preferred formulation is based on the assumption that one needs to obtain a formulation which has an overall molecular weight corresponding to that of R12 i.e. 121.
  • vapour formulation of about 60% R134a and 40% R227ea.
  • molecular weight alone does not give a complete picture of how a formulation will behave in the vapour phase. It is also necessary for it to have the correct vapour density and vapour pressure characteristics.
  • R227 contains less than or equal to 45% by weight of R227, especially 30 to 40, 42.5 or 45%, preferably 35 to 42.5 or 45% or 35 to 40%, by weight, the remainder being R134.
  • a particularly preferred formulation comprises about 63.3% by weight of R134a and about 36.7% by weight of R227ea. These formulations are cheaper to make because R227ea is more expensive than R134a.
  • the present invention also provides a method of refrigerating a body which comprises placing the object in the vicinity of a refrigeration system which employs a centrifugal compressor wherein the liquid refrigerant supplied to the compressor is a composition of the present invention, and a refrigeration system incorporating a centrifugal compressor wherein the liquid in the compressor is a composition of the present invention.
  • the formulations of Examples 2 and 4 give particularly good vapour pressure and vapour density values which are comparable to, or even better than, those of R12, especially at 30 °C to 40 °C which are generally the most important as these are the usual condensing temperatures.

Abstract

A liquid refrigerant composition is disclosed which comprises at least 35 % by weight of tetrafluoroethane and at least 20 % by weight of heptafluoropropane such that the sum of the concentrations of heptafluoroethane and heptafluoropropane is at least 90 % by weight of the composition.

Description

CENTRIFUGAL COMPRESSION REFRIGERANT COMPOSITIONS
This invention relates to refrigerant compositions. More particularly, it relates to refrigerant compositions which can be used in place of R12 in a compression refrigeration system employing a centrifugal compressor.
R12 (CC12F2) has been used for many years as a refrigerant composition. However, in view of concerns over the use of CFC gases various attempts have been made to reduce or eliminate its use. In other words, ways have been sought to replace R12 by formulations which are not damaging to the environment.
One hydrocarbon which has been used with some success instead of R12 is tetrafluoroethane (R134). This is because it has a similar pressure-temperature relationship and refrigerating effect to that of R12. Indeed in positive displacement compressors R134 is a good substitute for R12.
Unfortunately, it is not satisfactory to use R134 instead of R12 in systems involving the use of a centrifugal compressor. This is because an additional constraint is placed on the refrigerant in that, as well as having similar thermodynamic properties, it must also have similar vapour density properties.
Roughly, vapour densities are related to the molecular weight. The molecular weight of R12 is 121 whereas the molecular weight of R134 is only 102. This difference would require the dimensions of the impellor used in the centrifugal compressor system to be altered as well as its speed. Clearly there is a need for a composition which can be used in an existing system without modification.
A further complication in the use of refrigerants using a centrifugal compressor resides in the fact that a centrifugal compressor uses a "flooded" evaporator i.e. some refrigerant liquid remains throughout the cooling cycle. As a result, the formulation of the liquid composition included in the system generally differs from the formulation of the vapour circulating in the system.
The object of the present invention is to provide a refrigerant composition which can be used in systems employing a centrifugal compressor without the need to modify the impellor dimensions or its speed. Clearly there is a need for a composition which can be used in an existing system without modification.
According to the present invention it has surprisingly been found that certain liquid formulations of Rl 34 and R227 (heptafluoropropane) behave well as replacements for R12 in centrifugal compression refrigerating systems. According to the present invention there is provided a liquid refrigerant composition which comprises at least 35% by weight of tetrafluoroethane and at least 20% by weight of heptafluoropropane such that the concentration of tetrafluoroethane and heptafluoropropane is at least 90% by weight of the composition.
Tetrafluoroethane exists in two forms, namely the symmetrical 1,1,2,2- tetrafluoroethane and 1,1,1,2-tetrafluoroethane known as R134a. The latter is preferred for use in the present invention.
Likewise heptafluoropropane exists in two isomeric forms, namely 1,1,1 ,2,3 ,3 ,3 -heptafluoropropane, known as R227ea which is preferred, and 1,1, 1,2,2,3, 3 -heptafluoropropane, known as R227ca.
As indicated above the formulation in the vapour phase will differ from that in the liquid phase. It has been found that formulations comprising 20 to 52% by weight ofR227 and, correspondingly, 80 to 48% of R134a will provide formulations which will behave in the vapour phase in a manner similar to that of R12 with a variation of + or - 10%.
The preferred compositions of the present invention consist essentially of R134 and R227 (i.e. they are binary compositions), especially R134a and R227ea, but small amounts of a third component can be included. Any additional component i.e. third or higher component can be present in an amount up to 10% weight, preferably up to 5%, and more preferably up to 2%, by weight of the composition. If more than one additional component is used then the total amount of these components is not more than 10% by weight. Since a principal aim of the formulation is to increase the overall molecular weight and thereby increase the vapour density, it is more usual to replace some of the R134a than replace some of the R227. Possible additional components include C318 (octafluorocyclobutane), R218 (octafluoropropane) and R125 (pentafluoroethane). The concentration of R134 is generally 80 to 35%>, preferably 70 to 45% and more preferably 50 to 60%, by weight. The concentration of R227 is generally 20 to 65%>, preferably 30 to 55% and especially 40 to 50%, by weight. A particularly preferred formulation consists of 52.5%) of R134a and 47.5% of R227ea. This preferred formulation is based on the assumption that one needs to obtain a formulation which has an overall molecular weight corresponding to that of R12 i.e. 121. This is achieved with a vapour formulation of about 60% R134a and 40% R227ea. However, as indicated above, molecular weight alone does not give a complete picture of how a formulation will behave in the vapour phase. It is also necessary for it to have the correct vapour density and vapour pressure characteristics.
Other preferred formulations have been found which attempt to take this into account; these contain less than or equal to 45% by weight of R227, especially 30 to 40, 42.5 or 45%, preferably 35 to 42.5 or 45% or 35 to 40%, by weight, the remainder being R134. A particularly preferred formulation comprises about 63.3% by weight of R134a and about 36.7% by weight of R227ea. These formulations are cheaper to make because R227ea is more expensive than R134a. The present invention also provides a method of refrigerating a body which comprises placing the object in the vicinity of a refrigeration system which employs a centrifugal compressor wherein the liquid refrigerant supplied to the compressor is a composition of the present invention, and a refrigeration system incorporating a centrifugal compressor wherein the liquid in the compressor is a composition of the present invention.
The following Examples further illustrate the present invention:-
Figure imgf000005_0001
Saturated Liquid Vapour Pressure Comparison
Figure imgf000005_0002
Comparison of Vapour Density.
Figure imgf000005_0003
Refrigeration Performance
Figure imgf000005_0004
As can be seen, the formulations of Examples 2 and 4 give particularly good vapour pressure and vapour density values which are comparable to, or even better than, those of R12, especially at 30 °C to 40 °C which are generally the most important as these are the usual condensing temperatures.

Claims

1. A liquid refrigerant composition which comprises at least 35% by weight of tetrafluoroethane and at least 20% by weight of heptafluoropropane such that the sum of the concentrations of heptafluoroethane and heptafluoropropane is at least 90% by weight of the composition.
2. A composition according to claim 1 which consists essentially of tetrafluoroethane and heptafluoropropane.
3. A composition according to claim 1 or 2 wherein the tetrafluoroethane is 1,1,1,2-tetrafluoroethane.
4. A composition according to claim 1 wherein the heptafluoropropane is 1,1,1 ,2,3 ,3 ,3 -heptafluoropropane.
5. A composition according to claim 1 which consists essentially of 80 to 35% by weight of tetrafluoroethane and 20 to 65% by weight of heptafluoropropane.
6. A composition according to claim 5 which consists essentially of 70 to 45%o by weight of tetrafluoroethane and 30 to 55% by weight of heptafluoropropane.
7. A composition according to claim 6 which consists essentially of 60 to 50% by weight of tetrafluoroethane and 40 to 50% by weight of heptafluoropropane.
8. A composition according to claim 1 which consists essentially of about 52.5% by weight of tetrafluoroethane and about 47.5% by weight of heptafluoropropane.
9. A composition according to claim 6 which comprises less than 45% by weight of heptafluoropropane.
10. A composition according to claim 9 which consists essentially of 35 to 45% by weight of heptafluoropropane.
11. A composition according to claim 9 which consists essentially of 35 to 40% by weight of heptafluoropropane.
12. A refrigeration system incorporating a centrifugal compressor wherein the liquid in the compressor is a composition as claimed in claim 1.
13. A method of refrigerating a body which comprises placing the obj ect in the vicinity of a refrigeration system which employs a centrifugal compressor wherein the liquid refrigerant supplied to the compressor is a composition as claimed in claim 1.
PCT/GB2000/003596 2000-09-19 2000-09-19 Centrifugal compression refrigerant compositions WO2002024829A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU7302100A AU7302100A (en) 2000-09-19 2000-09-19 Centrifugal compression refrigerant compositions
AU2000273021A AU2000273021B2 (en) 2000-09-19 2000-09-19 Centrifugal compression refrigerant compositions
CA002424842A CA2424842A1 (en) 2000-09-19 2000-09-19 Centrifugal compression refrigerant compositions
PCT/GB2000/003596 WO2002024829A1 (en) 2000-09-19 2000-09-19 Centrifugal compression refrigerant compositions
CZ2003734A CZ2003734A3 (en) 2000-09-19 2000-09-19 Liquid coolant for centrifugal compressors
JP2002529229A JP2004512393A (en) 2000-09-19 2000-09-19 Refrigerant composition for centrifugal compression
BRPI0017337-1A BR0017337B1 (en) 2000-09-19 2000-09-19 liquid refrigerant composition, and, cooling system incorporating a centrifugal compressor.
EP00960853A EP1325097A1 (en) 2000-09-19 2000-09-19 Centrifugal compression refrigerant compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/GB2000/003596 WO2002024829A1 (en) 2000-09-19 2000-09-19 Centrifugal compression refrigerant compositions

Publications (1)

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WO2002024829A1 true WO2002024829A1 (en) 2002-03-28

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Country Status (7)

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EP (1) EP1325097A1 (en)
JP (1) JP2004512393A (en)
AU (2) AU2000273021B2 (en)
BR (1) BR0017337B1 (en)
CA (1) CA2424842A1 (en)
CZ (1) CZ2003734A3 (en)
WO (1) WO2002024829A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7229567B2 (en) 1997-07-15 2007-06-12 E.I. Dupont De Nemours And Company Refrigerant compositions
US7258813B2 (en) 1999-07-12 2007-08-21 E.I. Du Pont De Nemours And Company Refrigerant composition
US7276176B2 (en) 2002-10-11 2007-10-02 E. I. Du Pont De Nemours And Company Refrigerant compositions
US7641810B2 (en) 2002-11-29 2010-01-05 Neil Andre Roberts Refrigerant compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992017558A1 (en) * 1991-03-28 1992-10-15 E.I. Du Pont De Nemours And Company Azeotropic and azeotrope-like compositions of 1,1,2,2-tetrafluoroethane
WO1994000529A1 (en) * 1992-06-25 1994-01-06 Great Lakes Chemical Corporation Refrigerant blends containing 1,1,1,2,3,3,3-heptafluoropropane
WO1999025786A1 (en) * 1997-11-18 1999-05-27 Alliedsignal Inc. Hydrofluorocarbon refrigerants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992017558A1 (en) * 1991-03-28 1992-10-15 E.I. Du Pont De Nemours And Company Azeotropic and azeotrope-like compositions of 1,1,2,2-tetrafluoroethane
WO1994000529A1 (en) * 1992-06-25 1994-01-06 Great Lakes Chemical Corporation Refrigerant blends containing 1,1,1,2,3,3,3-heptafluoropropane
WO1999025786A1 (en) * 1997-11-18 1999-05-27 Alliedsignal Inc. Hydrofluorocarbon refrigerants

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7229567B2 (en) 1997-07-15 2007-06-12 E.I. Dupont De Nemours And Company Refrigerant compositions
US7258813B2 (en) 1999-07-12 2007-08-21 E.I. Du Pont De Nemours And Company Refrigerant composition
US7276176B2 (en) 2002-10-11 2007-10-02 E. I. Du Pont De Nemours And Company Refrigerant compositions
US7410595B2 (en) 2002-10-11 2008-08-12 E.I. Du Pont De Nemours And Company Refrigerant compositions
US7648642B2 (en) 2002-10-11 2010-01-19 E.I. Du Pont De Nemours And Company Refrigerant compositions
US7799240B1 (en) 2002-10-11 2010-09-21 E.I. Du Pont De Nemours And Company Refrigerant compositions
US7837894B2 (en) 2002-10-11 2010-11-23 E. I. Du Pont De Nemours And Company Refrigerant compositions
US7641810B2 (en) 2002-11-29 2010-01-05 Neil Andre Roberts Refrigerant compositions
US7713434B2 (en) 2002-11-29 2010-05-11 E.I. Du Pont De Nemours And Company Refrigerant compositions
US7771610B2 (en) 2002-11-29 2010-08-10 E.I. Du Pont De Nemours And Company Refrigerant compositions
US8246851B2 (en) 2002-11-29 2012-08-21 Roberts Neil Andre Chiller refrigerants

Also Published As

Publication number Publication date
CZ2003734A3 (en) 2003-09-17
BR0017337B1 (en) 2010-11-03
JP2004512393A (en) 2004-04-22
BR0017337A (en) 2003-07-29
AU7302100A (en) 2002-04-02
EP1325097A1 (en) 2003-07-09
AU2000273021B2 (en) 2006-09-14
CA2424842A1 (en) 2002-03-28

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