GB2435747A

GB2435747A - Heat transfer composition

Info

Publication number: GB2435747A
Application number: GB0619503A
Authority: GB
Inventors: Robert Elliott Low; Stuart Corr
Original assignee: Ineos Fluor Holdings Ltd
Current assignee: Ineos Fluor Holdings Ltd
Priority date: 2006-07-17
Filing date: 2006-10-03
Publication date: 2007-09-05
Also published as: GB0614067D0; GB0619503D0; GB2437373A; GB0619504D0

Abstract

Heat transfer compositions comprise <SL> <LI>(i) R-1225ye; <LI>(ii) at least one further refrigerant selected from carbon dioxide (R-744); fluoromethane (R-41); difluoromethane (R32); fluoroethane (R-161); 1,1,1 -trifluoroethane (R- 143a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethylether; heptafluoropropane (R-227ea); propane (R-290); propene (R-1270); isobutane (R-600a); n-butane (R-600) 2,3,3,3-tetrafluoropropene (R-1234yf); 1,1-difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, pentafluoroethane (R-125) or ammonia. Further similar mixtures form the basis of preferred embodiments including compositions based on the isomer R-1225yeE and similar co-refrigerants in differing combinations. The compositions are used for conventional refrigeration applications such as automobile air conditioning or as aerosol propellants or in vapour phase heating or cooling applications. </SL>

Description

HEAT TRANSFER COMPOSITIONS

The invention relates to heat transfer compositions, and in particular to heat transfer compositions which may be suitable as replacements for existing refrigerants such as R-134a, R-410A. R-407C, R-404a arid R-507, but especially R-134a and R-407C.

Mechanical refrigeration systems (and related heat transfer devices such as heat pumps and air-conditioning systems) are well known. In such systems, a refrigerant liquid evaporates at low pressure taking heat from the surrounding zone. The resulting vapour is then compressed and passed to a condenser where it condenses and gives off heat to a second zone, the condensate being returned through an expansion valve to the evaporator, so completing the cycle.

Mechanical energy required for compressing the vapour and pumping the liquid is provided by, for example, an electric motor or an internal combustion engine.

In addition to having a suitable boiling point and a high latent heat of vaporisation, the properties preferred in a refrigerant include low toxicity, non-flammability, non-corrosivity, high stability and freedom from objectionable odour. Other desirable properties are ready compressibility at pressures below 25 bars, low discharge temperaturc on compression, high refrigeration capacity, high efficiency (high coefficient of performance) and an evaporator pressure in excess of 1 bar at the desired evaporation temperature. * **

Dichlorodifluorometha.ne (refrigerant R-12) possesses a suitable combination of properties and was for many years the most widely used refrigerant. Due to * * international concern that fully and partially halogenated chiorofluorocarbons, * :: such as dichiorodifluoromethane and chiorodifluoromethane, were damaging the earth's protective ozone layer, there was general agreement that their manufacture *** : 30 and use should be severely restricted and eventually phased out completely. The **** use of dichiorofluoromethane was phased out in the 1990's.

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1,1,1,2-tetrafluoroethane (refrigerant R-I 34a) was introduced as a replacement refrigerant for R-12. However, despite having a ow ozone depletion potential, R-I 34a has a global warming potential (GWP) of 1300. )

Whilst heat transfer devices of the type to which the present invention relates are essentially closed systems, loss of refrigerant to the atmosphere can occur due to leakage during operation of the equipment or during maintenance procedures. It is important, therefore, to replace fully and partially halogenated chiorofluorocarbon refrigerants by materials having zero ozone depletion potentials.

In addition to the possibility of ozone depletion, it has been suggested that significant concentrations of halocarbon refrigerants in the atmosphere might contribute to global warming (the so-called greenhouse effect). It is desirable, therefore, to use refrigerants which have relatively short atmospheric lifetimes as a result of their ability to react with other atmospheric constituents such as hydroxyl radicals or as a result of ready degradation through photolytic processes.

There is a need to provide alternative refrigerants having improved properties, such as low flammability. There is also a need to provide alternative refrigerants that may be used in existing devices such as refrigeration devices with little or no modification.

US 2004/0127383 (US-B2-6858571) (Honeywell International, Inc.) describes the use of pentafluoropropene (R-1225), especially R-1 225ye, in combination with R-S....' 1243zf,R-l52aandR-1234ze. ...

* US 2004/0119047 and US 2004/0256594 (Honeywell International, Inc.) discloses *.

* heat transfer compositions comprising a fluoroalkene of formula XCFZ R3.., where : .30 x is a C2 or C3 unsaturated, substituted or unsubstituted alkyl radical, R is Cl, F, ** * * *s..

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Br, I or H and z is I to 3, the compositions having a reduced global warming potential (GWP).

US-A-70981 76 B and US 2006/0022 166 (Honeywell International, Inc.) disclose s azeotrope-like compositions comprising effective amounts of R-1234yf and R-1225yeZ.

WO 2006/0943 03 (DuPont) discloses compositions which may be heat transfer compositions comprising R-1225ye and a further refrigerant. Specifically disclosed compositions include inter alia combinations of R-1225ye and R-32; R- 1225ye and R-134a; R-1225ye, R-134a and R-32; R-1225ye, R-1234yf, R-32 and R-1 34a; and azeotropic or near azeotropic compositions comprising 1 % to 99% R- 1225ye and 99% to 1% R-134a.

R-1 225ye (also known as HFC-I 225ye) is 1,2,3,3,3-pentafluoropropene (CF3-CF=CHF). It can exist as two stereoisomers Z and E, which are known to have very similar boiling points. Our reference to R-1225ye encompasses both isomers, and also mixtures thereof. In some embodiments, preferably the isomers are present in a mass ratio of Z to E such that at last 50% of the R-1225ye exists as the Z isomer, even more preferably at least 80%.

R-1225ye is non-flammable and has low Greenhouse Warming Potential (relative to C02). its boiling point is ca. -18 C (for the isomeric mixture) and its critical * temperature is estimated to be 113 C. These properties compares closely to that of R-134a (1,1,1,2-tetrafluoroethane) which has boiling point -26.4 C, a critical *** temperature of 101 C, and G\VP of 1300. R-1225ye is therefore a potential * alternative to R-134a.

*S..*S * S *5S**S * However, the properties of this fluid alone render it not suitable as a direct S..

*.. : 30 replacement for R-1 34a. In particular, its capacity is too low, by which is meant S...

that a refrigerator or air conditioning system having a fixed compressor ( displacement and designed for R-I 34a will deliver less cooling when charged with R-1225ye and controlled to the same operating temperatures. The capacity for air conditioning applications (evaporating temperature in the range 0 to 10 C) is typically 75% that of R-134a.

A principal object of the present invention is therefore to provide a heat transfer composition which is usable in its own right or suitable as a replacement for existing refrigeration usages which should have a reduced Greenhouse Warming Potential, yet has a capacity and energy efficiency (which may be conveniently expressed as the "Coefficient of Performance") ideally within 20% of the values, for example of R-I 34a, preferably within 10% of these values, and even more preferably within 5% of these valies. It is known in the art that differences of this order between fluids are usually resolvable by redesign of equipment and system operational features without entailing significant cost differences.

In certain preferred embodiments, the capacity and energy efficiency of blends according to the invention may exceed those of R-1 34a.

In accordance with one aspect of the invention, there is provided a composition which may be a heat transfer composition comprising: (i) R-1225ye; and (ii) at least one further compound (refrigerant) selected from carbon dioxide (R-744); fluoromethane (R-41); difluoromethane (R-32); fluoroethane (R- 161); 1,1,1 -trifluoroethane (R- 3 43a); 1,1,1,2-tetrafluoroethane (R-1 34a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoropropane (R-227ea); propane S...

(R-290); propene (R-1270); isobutane (R-600a); n-butane (R-600); 2,3,3,3- tetrafluoropropene (R-1 234yf); 1,1 -difluorocyclopropane; 1,1,2-* : * * trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, or ammonia. or mixtures thereof. *.. * * . S. *

S (.

In a preferred embodiment, the further refrigerant is selected from R-134a, dimethyl ether, R-161, R-32, R-744, R-41, R-290, R-1270, ammonia, R-600 or R-1243zf.

In further preferred aspect of the invention, there is provided a composition which may be heat transfer composition comprising: (i) R-l225yeE; (ii) R-32,R-161 orR-152a; and (iii) at least one further compound (refrigerant) selected from carbon i 0 dioxide (R-744); fluoromethane (R-4 1); fluoroethane (R-161); 1,1,1 - trifluoroethane (R-I 43a); 1,1,1,2-tetrafluoroethane (R-1 34a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoropropane (R-227ea); propane (R-290); propene (R-l 270); isobutene (R-600a); n-butane (R-600); 2,3,3,3-tetrafluoropropene (R-1234yf); 1,1 -difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, pentafluoroethane (R-125) or ammonia, or mixtures thereof.

In a preferred aspect of this embodiment, the further refrigerant is R-I 34a or 125.

In a highly preferred aspect, the R-32, R-161 or R-152a is R-32, and the further refrigerant is R-1 34a.

* In a further preferred aspect, the R-32, R-161 or R-152a is R-152a, and the further refrigerantisR-125. * . *.

* : * In further preferred aspects, there may be provided ternary heat transfer compositions comprising R-1225yeE, R-161 and R-134a; R-1225yeE, R-161 and * R-125; and R-l22SyeE, R-125 and R-32. *** * 30 *. S *.** * S *** (

In yet a further preferred aspect of the invention, there is provided a composition which may be a heat transfer composition comprising: (1) R-1225yeE; (ii) R-32; (iii) R-1234yf; and (iv) at least one further compound (refrigerant) selected from carbon dioxide (R-744); fluoromethane (R-41); fluoroethane (R-161); 1,1,1- trifluoroethane (R-143 a); I,1,1,2-tetrafiuoroethane (R-1 34a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoroproane (R-227ea); propane (R-290); propene (R-1270); isobutane (R-600a); n-butane (R-600); 1,1- difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, pentafluoroethane (R-125) or ammonia, or mixtures thereof.

In a preferred facet of this aspect of the invention, the further refrigerant is R-134a In yet a further preferred aspect of the invention, there is provided a composition which may be a heat transfer composition comprising: (i) R-l225yeE; (ii) R-32; (iii) R-125; and (iv) R-161 orR-152a Preferably, any resultant heat transfer composition has a GWP less than the refrigerant it is intended to replace, for example R-134a or R-407C. * * *.

In the context of the invention, unless otherwise specified, when we refer to a R-*.*.** l225yeE component we mean a composition having a content of R-l225yeE in the R-I 225ye component which is at least 95% E isomer, more preferably at least 98% E isomer, more preferably at least 99% E isomer, and which may in some * 0 **

I

instances be pure E isomer. The remaining minor component of any such R-l225yeE or R-1225ye composition will be the Z isomer.

Some particularly preferred specific heat transfer compositions according to the invention are set out below (all parts for any given composition total 100 and are expressed on a weight basis): -R-125 (Ito 3 parts): R-152a (Ito 12 parts): R-1225yeE (85 to 98 parts); -R-125 (ito 4 parts): R-161 (Ito 3 parts): R-1225yeE (93 to 98 parts); * R-161 (Ito 3 parts): R-134a (ito 10 parts): R-1225yeE (87 to 98 parts); -R-32 (1 to 3 parts): R-125 (1 to 3 parts): R-125a (1 to 12 parts); R-i225yeE (82 to 97 parts); -R-32 (I to 3 parts): R-125 (1 to 3 parts): R-161 (1 to 5 parts): R-1225yeE.

(89 to 97 parts).

In addition to these the following specific heat transfer compositions are also preferred: -R-32 (1 to 9 parts): R-34a (4 to 8 parts): R-1234yf (4 to 52 parts): R- 1225yeE (39 to 78 parts); -R-32 (3 to 9 parts): R-134a (4 to 8 parts): R-1234yf (4 to 24 parts): R- 1225eE (59 to 79 parts) -this composition is preferred as it provides the best capacity and COP match with evaporator glide of less than 5 C; -R-32 (3 to 7 parts); R-134a (4 to 6 parts): R-1234yf (4 to 28 parts): R-l225yeE (59 to 78 parts) -this composition is preferred as it has a GWP less or equal to 120 with a strict COP greater than or equal to 100; -R-32 (I to 3 parts): R-i34a (4 to 6 parts): R-1234yf (4 to 52 parts): R-I...

l22SyeE (39 to 78 parts) -this composition is preferred as it has an evaporator *: glide less than or equal to 2.5 C with a capacity of greater than or equal to 80% of that of R-1 34a and with good COP match. * I a..

: 30 Preferably, the nature and amount of the further refrigerant is such that the a... . ****** resultant binary (or greater) mixture is non-flammable. As used herein, "non-( flammable" refers to compounds or compositions which are determined to be non-flammable as determined in accordance with ASHRAE Standard 34 incorporating the ASTM Standard E-681 methodology according to Addendum p34. dated 2004, the entire content of which is incorporated herein by reference. The test used for determination is described in Clause X.2.4.l "Leaks under storage/shipping conditions", and represents the worst case of fractionation.

Compositions according to the invention typically have improved capacity compared to R-1225ye alone, and also typically have improved capacity compared to R-l225yeE. In one facet, the incorporation of a relatively small proportion of further refrigerant(s) (component (ii) of the composition of the broadest aspect of the invention), which further refrigerant(s) may be flammable, have a higher GWP, or both, may provide a resultant heat transfer composition having both a low GWP and substantially no flammability characteristic and relatively small Is temperature "glide", yet provide improved capacity and optionally improved Coefficient of Performance.

Temperature glide, which can be thought of as the difference between bubble point and dew point temperatures of a non-azeotropic mixture at constant pressure, is a characteristic of a refrigerant; so if it is desired to replace a fluid with a mixture then it is often preferable to have similar or reduced glide in the alternative fluid.

Compositions according to the invention may conveniently be considered not azeotropic, "near azeotropic" or "azeotrope-like", and indeed may be considered to be "non-azeotropic". That is, they will exhibit temperature glide on * vaporisation or condensation. * .

****** * To this end, temperature "glide" in relation to refrigerant mixtures is the *** .. : 30 temperature change that occurs on evaporation or condensation of the refrigerant mixture in the heat exchangers of a refrigerant apparatus. (

We refer in this context to a standardised (simplified) vapour compression refrigeration cycle, which comprises: an evaporator, a compressor, a condenser and an expansion valve, with appropriate pipework and controls etc. The evaporator operates at low pressure and the condenser at high pressure. The refrigerant is fed as a liquid from the condenser through the expansion valve. The drop in pressure results in a portion of the liquid vaporising so that the fluid entering the evaporator is a mixture of liquid and vapour.

The condenser glide is the difference between the dew and bubble point Jo temperatures of the fluid mixture at the condensing pressure. The dew point temperature for a fixed pressure is the temperature at which the first drop of liquid can be condensed. The bubble point temperature at the same pressure is the temperature at which the first bubble of vapour can be evaporated.

The dew point is higher than the bubble point for a mixture exhibiting temperature glide. As pressure increases then the difference between dew and bubble points decreases. In refrigeration systems the lowest pressure (evaporator pressure) is normally designed to be I atmosphere (to prevent inward leakage of air) and the highest pressure is normally selected to be 25 bar or less (the cost of pressure vessels etc. increases as pressure rises).

The evaporator glide is the difference between the dew point temperature and the inlet temperature to the evaporator. This inlet temperature is determined by the * proportion of vaporisation that has occurred on the initial expansion of feed liquid, * 25 so the evaporator inlet temperature is between the dew and bubble points at *..

S's... evaporator pressure.

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* Conveniently, the composition comprises the at least one further refrigerant in an amount of from about 1 to about 30% by weight of the composition. *S. * * I *. S *.. S... (

Advantageously, the composition comprises the at least one further refrigerant in an amount of from about 1 to about 10% by weight of the composition.

Preferably, the composition comprises the at least one further refrigerant in an amount of from about Ito about 6% by weight of the composition.

Advantageously, the composition comprises the at least one refrigerant in an amount of from about 1 to about 5% by weight of the composition.

In some embodiments the composition is azeotrope-like, though in certain highly preferred embodiments the composition may be considered non-azeotropic.

Conveniently, the composition has a GWP of about 750 or less.

Advantageously, the composition has a GWP of about 500 or less.

Preferably, the composition has a GWP of about 250 or less.

Conveniently, the composition has a GWP of about 150 or less.

Advantageously, the composition has a GWP of about 100 or less.

The heat transfer compositions according to the invention generally have * substantially similar thermodynamic characteristics to those they might replace, but will typically have significantly lower Greenhouse Warming Potential. * *

The heat transfer compositions are suitable for use in existing designs of * equipment, and are compatible with all classes of lubricant currently used with established HFC refrigerants. They may be optionally stablized or compatibilized : 30 with mineral oils by the use of appropriate additives. * .*. * * *4.. r

Preferably, the composition further comprises a lubricant.

Conveniently, the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (P\'Es), poly (alpha-olefms) and combinations thereof.

Advantageously, the composition further comprises a stabiliser.

Preferably, the stabiliser is selected from the group consisting of diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.

Conveniently, the composition further comprises an additional flame retardant.

Advantageously, the additional flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phosphate, (chloropropyl)phosphate, tri-(2,3-dibromopropyl)-phosphate, tri-( I,3-dichloropropyl)-phosphate, diarnmonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, thfluoroiodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.

Preferably, the composition is a refrigerant composition.

:.:::e 25 According to another aspect of the invention, there is provided a heat transfer device containing a composition of the invention.

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*5*45* * Preferably, the heat transfer device is a refrigeration device.

a.. 55 * . 5.S.

: 30 Conveniently, the heat transfer device is selected from group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, heat pump systems.

Advantageously, the heat transfer device contains a compressor. The compressor may be centrifugal type or may be any positive- displacement type; for example rotary vane, scroll, swash-plate, screw or piston designs.

According to a further aspect of the invention, there is provided a blowing agent comprising a composition of the invention.

According to another aspect of the invention, there is provided a foamable composition comprising one or more components capable of forming foam and a composition of the invention.

Preferably, the one or more components capable of forming foam are selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene, and epoxy resins.

According to a further aspect of the invention, there is provided a foam obtainable from the foamable composition of the invention.

Preferably the foam comprises a composition of the invention.

: , 25 According to another aspect of the invention, there is provided a sprayable composition comprising a material to be sprayed and a propellant comprising a * composition of the invention. Sf.. * S

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*5*.S* * 1 According to a further aspect of the invention, there is provided a method for * 30 cooling an article which compnses condensing a composition of the mvention and thereafter evaporating said composition in the vicinity of the article to be cooled.

According to another aspect of the invention, there is provided a method for heating an article which comprises condensing a composition of the invention in the vicinity of the article to be heated and thereafter evaporating said composition.

According to a further aspect of the invention, there is provided a method for extracting a substance from biomass comprising contacting the biomass with a solvent comprising a composition of the invention, and separating the substance from the solvent.

According to another aspect of the invention, there is provided a method of cleaning an article comprising contacting the article with a solvent comprising a composition of the invention.

According to a further aspect of the invention, there is provided a method for extracting a material from an aqueous solution comprising contacting the aqueous solution with a solvent comprising a composition of the invention, and separating the substance from the solvent.

According to another aspect of the invention, there is provided a method for extracting a material from a particulate solid matrix comprising contacting the particulate solid matrix with a solvent comprising a composition of the invention, and separating the substance from the solvent.

: * * 25 According to a further aspect of the invention, there is provided a mechanical ***** power generation device containing a composition of the invention. ****

* : * Preferably, the mechanical power generation device is adapted to use a Rankine Cycle or modification thereof to generate work from heat.

S.. 30 * S * S. *

S *55S r

According to another aspect of the invention, there is provided a method of retrofitting a refrigeration device comprising the step of removing an existing heat transfer fluid, and introducing a composition of the invention.

In some circumstances, it is preferred for the compositions to have a GWP of about 150 or less. However, for other applications, it may be acceptable for the composition to have a higher OWP, for example a GWP of up to 250, 500 or 750.

The GWP values of the candidate additional fluids dictate the maximum allowable percentages for each application. Internationally accepted GWP values for selected refrigerant fluids of the invention are as follows: Fluid GWP Fluid GWP R-134a 1300 R-152a 140 R-161 12 R-1270 3 R-41 140 R-227ea 3500 R-125 3400 R-143a 4300 CO2 I R-32 550 R-óOOa 3 R- 290 3 If the additional refrigerant has a GWP lower than the desired value then the maximum amount in the composition is dictated by considerations of flammability and similarity of the resulting mixture to the fluid it is intended to replace.

::. 25 If the additional refrigerant has a GWP higher than the desired value then the *: :: * GWP value may also be used to set a preferred composition range. S..

* For example, if a GWP of less than 150 is required and the fluid to be replaced is R-134a and in addition the mixture is required to be non-flammable then the * * 30 preferred compositions of selected additional refrigerants having GWP higher than are as follows: S...

R-32 6% weight basis; R-134a 9% weight basis; R-227ea 4% weight basis; R-125 4% weight basis.

If the desired GWP is sufficiently high (providing that it is lower than the fluid which the invention replaces) then it is possible to mitigate the flammability of a first additive replacement by adding a second or further additive replacement to the mixture; this allows the use of somewhat higher proportions of the flammable additive. Jo

For example a mixture of R-32 (10%); R-125 (10%) and R-1225ye (80%) will have a GWP of 403. Its refrigeration capacity is very similar to R-134a (estimated as typically 100-104% that of R-134a) and it has similar COP characteristic.

is For example, the existing refrigerant fluid R-407C is a ternary mixture of R-32, R-and R-134a in the proportions of 23%/25%/52% by weight and has a GWP of 1650. A suitable replacement fluid for this refrigerant can therefore be a mixture of R-32, R-125 and R-1225ye. The additive refrigerant in this case is a mixture of R-32 and R-125, such that the mass ratio of R-125 to R-32 in the mixture is at least 1:1, which ensures non-flammability of the resultant mixture. If a non-flammable mixture of R-32/R-125/R-1225ye is used to replace the 52% of R-134a in the R-407C composition, the resulting mixture will have a similar performance to R-407C but will have a GWP that is substantially lowered compared to that of R-407C.

: .. 25 *....* The above example teaches that the optimal matching of replacement properties * 5S.

may require the use of more than one additional fluid, so the replacements of the invention can encompass ternary or higher mixtures.

*ss*s5 * * The refrigerant compositions may be altered by the skilled man to suit the :::: application requirements and flammability characteristics so desired. In particular *.*e he may choose to add components such as CF3I, which are known to reduce or suppress flammability, to the refrigerant mixtures of the invention. However, in many preferred aspects of the invention, because of the potential toxicity and reactivity of CF3I, compositions according to the mvention may be substantially free (e.g. containing less than about 3%), and ideally totally free of CF3I.

For the ternary and quatemary compositions according to the invention, such compositions were found to have surprising properties, in particular in relation to properties which are important to the performance of the composition in air conditioning, especially mobile (i.e. car) air conditioning systems, in particular when they are required to approach the performance and characteristics of R-134a.

Flammability measurements have been carried out on mixtures of R-32 in air with R-1225yeE and R-134a as flammable diluents. It has been found that the maximum concentration of R-32 in R-1225yeE to ensure the mixture is non-flammable in air under test conditions at 100 C test temperature is 69% R-32 by volume. The maximum amount of R-32 in R-1 34a at the same test temperature that give non-flammable mixtures in air is 72% R-32 by volume. A conservative assessment criterion has therefore been used; the maximum concentration of R-32 in the fluid vapour should be 68% vol/vol to ensure non-flammability.

This assessment has been carried out for blends containing R-134a between 0 and 10% by weight in the blend. Higher levels of R-134a have notbeen used in this assessment as the total OW? is desired to be lower than 150. The GWP figures : *** 25 used in this study are: R-32 550, R-134a = 1300 and R-1225ye = 10. *.*S * * *S**

A replacement fluid for R-134a in air conditioning system will have a number of desirable properties. These include: *.SS$* * * * A volumetric capacity within 90% of R-134a; I... * . ****

* Energy efficiency (expressed as Coefficient of Performance) within 95% of R- 1 34a, or ideally comparable or better than R-I 34a; * Operating pressures similar (preferably within about 10%); * Compressor discharge temperature similar (within 10 degrees Celsius); * Non- flammable according to requirements of ASHRAE standard 34 Addendum p34 (2004 version); * Temperature "glide" lower than about 5 degrees Centigrade; and * (3WP less than 150 for European F-Gas directive compliance in mobile air conditioning (MAC) applications.

In many embodiments preferred compositions according to the invention are "non-azeotropic" as described above; these notably include the ternary and quaternary compositions described herein. Such compositions may also be called zeotropes, zeotropic mixtures, and non-azeotropic refrigerant mixtures (NARMS). Such Is compositions exhibit varying degrees of glide during boiling or condensation, and also exhibit differences in vapour and liquid composition at equilibrium.

Examples

Example I

The data in Table I provides illustration of the performance of exemplar blends, which are not limiting, for the replacement of R-I 34a. The thermodynamic properties used to calculate the performance have been derived as follows: * The Peng Robinson equation of state has been used to calculate gas density, * :.. enthalpy and entropy data and has been used to predict latent heat of vaporisation I...

and vapour equilibrium data for the mixtures of interest. The basic properties required by this equation (critical temperature, critical pressure and acentric *: factor) of the fluids with the exception of the fluorinated propenes R-1234yf and R-1225ye were taken from reliable sources; chiefly the NIST Webbook site *.* : htt://webbook.nistgov. The critical properties of R-1234yf were determined by **** ,* 30 measurement using a static cell. The critical properties of R-1225ye were r estimated using the boiling point for the isomeric mixture of -18 C and Joback's group contribution method. The acentric factor for R-I 234yf was calculated from measurements of the vapour pressure. The acentric factor for R-1225ye was estimated using the Lee-Kesler correlation. Ideal gas enthalpy data for the propenes were also estimated using the Joback group contribution method. All of these estimation techniques are described in the text "The Properties of Gases & Liquids" by RC Reid, JM Prausnitz & BE Poling, 4th edition, published McGraw-Hill.

The Peng Robinson equation uses a binary interaction constant to describe the vapour liquid equilibrium of binary pairs. This constant was set to zero where no data were available for mixture pairs; otherwise its value was chosen to give a good representation of the known equilibrium data at temperatures close to 0 C.

Binary data for pairs among the fluids R-321R-125/R-134a were obtained from measurements published in M. Nagel, K. Bier, mt. J. Refrig. 18 (1995) 534-543.

Binary data for R-1225ye with R-1234yf were taken from US Patent Application 1JS2005/0233932A1. Binary data for R-32 with CO2 were taken from Rivollet et a!. Fluid Phase Equilibria 218 (2004), 95-101. Binary data for R-32 with propane were taken from Fluid Phase Equilibria 199 (2002) 175-183. Binary data for R-1270 (propene) with R-134a and R-152a were taken from Kleiber FluidPhase Equilibria 92 (1994) 149-194. Other data were measured using a static cell technique to measure the total pressure of a mixture of known composition. The data were then regressed using Barker's technique with the data points weighted using the maximum likelihood principle to account for * measurement errors in temperature and pressure to fit the required binary ** 25 interaction parameters for use with the equation of state. **S* * S ***S

All references to literature and publication sources are included herein by *.S* * reference in the relevant part. 5.555 * . * S * ** * S... * * 5**S

S S I * ** I * ** ** . S S * ) *. S. 55. *** S * Table 1: Compositions suitable for replacement of R-134a Calculations are based on these conditions Heat duty of cycle io.oo kW Condenser mean temperature 45 degC Evaporator mean temperature 5 degC Subcool 0 K Useful superheat o K Suction tcmpcrature 25 degC Isentropic efficiency 65% Clearance ratio 4% Capacity COP Suction -Discharge l)ischarge Weight relative to relative to pressure pressure temperatur Evaporator Condenser Blend Components fractions GWP R134a R-134a barn barn e degC glide K glide K R-134a 100% 1300 100% 100% 3.48 11.61 82.6 0.0 0 R-32fR-1225ye 5%/95% 37 83% 101% 2. 84 9.68 77.3 2.7 4.8 R-32/R-125/R-1225ye 10%/l0%/80% 403 103% 101% 3.57 12. 05 85.9 5.9 8.6 R32fR-134a/R-1225ye 6%/7%/87% 133 87% 101% 2.99 10.19 78.7 3.1 5.3 R-321R-161/R-1225ye 5%15%/90% 37 89% 101% 3.06 10.30 78.7 3.3 5.1 R-161/CF3I/R-1225ye lO%120%170% 6 87% 100% 3.07 10.35 79.3 1.8 2.3 R-290/CF3I/R-1225ye lO%/30%/60% 5 86% 101% 3.06 9.80 77.7 2.1 2.3 R-1270/R-1225ye 10%/90% 6 88% 101% 3.12 10.20 76.7 3.1 3.7 C02/R-1225ye 2%198% 7 82% 98% 2.76 10.06 78.6 3.2 10.3 R-12701R-1225ye 4%/96% 7 78% 100% 2.73 9.10 74.9 1.5 2

Example 2

The ASHRAE Standard 34 (relating to safety classification of refrigerants) specifies a series of tests for flammability assessment in its Addendum p34. These require measurement or prediction using a verified computer model of the degree to which fractionation affects the concentration of flammable species in the refrigerant vapour and/or liquid phases. This work has focussed on the Addendum p34 test protocol for assessing the vapour concentration in an initially 90% filled cylinder when cooled to 10 C above its bubble point at atmospheric pressure and subjected to mass removal by vapour withdrawal until the cylinder is devoid of liquid. This is because the flammable component in these blends, R-32, is also the most volatile, so it will be most highly enriched in the vapour phase during fractionation. The other test protocols specified in Addendum p34 will result in less severe fractionation of the R-32.

Fractionation assessment has been carried out by computer model according to the conditions specified in the p34 protocol. The "worst case formulation" (WCF) has been estimated by taking the nominal "as-charged" mass ratios of each component in the blend, adding 0.5% to the mass of flammable component (R-32) and subtracting 1% from the mass of the non-flammable components (R-134a and R- 1225ye). For example the blend having "as-charged" formulation of R-321R- 134afR-1225ye (6%/7%/87% by weight) has a WCF set of mass ratios of these components of 6.5/6/8 6.

The fractionation of the blend has been modelled using the Peng Robinson :* :i equation of state to correlate the vapour liquid equilibrium of the system. The *.. equation parameters have been optimised using measured vapour liquid equilibrium data for the binary pairs R-32/R-1225ye and R-32/R-134a. The * equilibrium between R-134a and R-l225ye has been modelled as ideal. * * .* *. S * S S...

* . . . * * * * * ** * *.** I I ** * *1 The compositions modelled are shown in Table 2: Assessment of cycle performance for ternary blends of R-32/R-134a/R-1225ye(E) -summary Compositions quoted are P32/RI 34a/RI 225yeE in mass Cells marked * correspond to compositions where the worst case fractionated fonnulation at the low temperature 90% fill test case (as per ASH RAE p34) will have flammable vapour according to the specified ASHRAE p34 test protocol at 100 C Actual R32:R1225ye Evaporator Condenser Discharge volumetric Evaporator Condenser Volumetric Relative Relative Fluid mass ratio CWP pressure pressure temperature flow glide glide capacity COP capacity COP bar(a) bar(a) C Ani3/hr K K kifm3 R134a 1300 3.48 11.61 82.6 16.8 0.0 0.0 2143 3.25 100.0% 100.0% 0/10/90 0.000 139 2.48 8.48 74.9 23.1 0.3 0.4 1558 3.27 72.7% 100.6% 0/4/96 0.000 62 2.41 8.26 74.3 23.8 0.1 0.2 1515 3.27 70.7% 100.6% 2/10/88 0.023 150 2.64 9.14 76.8 21.5 1.6 3.0 1677 3.27 78.3% 100.6% 3/4/93 0.032 78 2.66 9.25 77.2 21.2 2.1 4.0 1695 3.27 79.1% 100.7% 3/9/88 0.034 142 2.72 9.42 77.6 20.8 2.2 4.0 1729 3.27 80.7% 100.6% 4/8/88 0.045 135 2.76 9.7 78.4 20.2 2.8 5.0 1779 3.27 83.0% 100.6% 5/0/95 0.053 37 2.78 9.73 78.5 20.2 3.3 6. 0 1784 3.27 83.2% 100.7% 5/8/87 0.056 140 2.87 10.01 79.2 19.6 3.4 5.9 1838 3.28 85.8% 100.9% 6/8/86 0.057 146 2.96 10.31 79.9 19.0 3.9 6.6 1896 3.28 88.5% 100.9% 6/4/90 0.067 94 2.91 10.18 79.6 19.3 3.9 6.8 1869 3.28 87.2% l00.9% 7/7/86 0.069 138 3.04 10.57 80.6 18.5 4.4 74 1947 3.28 90.9% 100. 9% 6/7/87 0.070 133 2.95 10.28 79.8 19.1 3.9 6.7 1889 3.28 88.1% 100.9% 8/6/86 0.081 131 3.1! [0.83 81.2 18.0 5.0 8.0 1998 329 93.2% 101.2% 8/0/92 0.087 53 3.04 10.64 80.7 18.4 5.0 8.3 1959 3.29 91.4% 101.1% 8/7/85 0.093 144 3.12 10.87 81.3 18.0 4.9 8.0 2005 3.29 93.6% 101.2% 9/4/87 0103 1.10 3.18 11.06 81.7 17.6 5.5 8.7 2043 3.29 95.3% 101.2% 9/6/85 0.106 136 3.2 11.12 81.9 17.5 5.5 8.6 2056 3.29 95.9% 101.2% 10/6/84 0.119 141 3.29 11.41 82.5 17.1 5.9 9.1 2112 3.29 98.6% 101.2% * S * * S *S S* ** * * S * I * S SI * S * S S * S U I * I * S * * .. IS* *** S S Actual R32:R1225ye Evaporator Condenser Discharge volumetric Evaporator Condenser Vol unietric Relative Relali ye Fluid mass ratio CWP pressure pressure temperature flow glide glide capacity COP capacity COP 11/0/89 0.124 69 3.31 11.49 82.7 16.9 6.5 9.8 2131 3.30 99.5% 101.5% 11/5/84 0.131 134 3. 36 11.65 83.1 16.7 6.4 9.5 2162 3.30 100.9% 101.5% 12/4/84 0.143 126 3.44 11.90 83.6 16.3 6.8 10.0 2211 3.30 103.2% 101.5% 12/6/82 0.146 152 3.46 11.96 83.7 16.2 6.7 9.9 2223 3.30 103.7% 101.5% 13/6/81 0.161 158 3.55 12.23 84.3 15.8 7.! 10.2 2278 3.30 106.3% 101.6% 1510/85 0.176 91 3.66 12.58 85.1 15.3 8.0 11.1 2351 3.31 109.7% 101.8% *15/4/81 0.185 143 3.70 12.70 85.4 15.2 7.9 10.8 2374 3.31 110.8% 101.7% *15/6/79 0.190 168 3.73 12.76 85.5 15.1 7.8 10.7 2385 3.30 111.3% 101.7% *18/6/76 0.237 185 3.99 13.54 87.2 14.2 8.6 11.2 2540 3.31 118.5% 101.8% *18/4/78 0.237 159 3.97 13.48 87.0 14.2 8.7 11.3 2529 3.31 118.0% 101.8% *20/0/80 0.250 118 4.10 13.86 87.9 13.8 9.3 11.9 2609 3.31 121.8% 101.9% *21/4/75 0.280 175 4.22 14.23 88.7 13.4 9.3 11.6 2679 3.31 125.0% 101.8% *21/6/73 0.288 201 4.25 14.29 88.8 13.4 9.2 11.4 2689 3.30 125.5% 101.7% *24/4/72 0.333 191 4.48 14.95 90.2 12.8 9.7 11.6 2821 3.30 131.7% 101.6% 25/0/75 0.333 145 4.52 15.08 90.5 12.6 10.1 11.9 2848 3.30 132.9% 101.7% *24/6/70 0.343 217 4.50 15.01 90.4 12.7 9.6 11.4 2831 3.30 132.1% 101.5% t') *27/4/69 0.391 207 4.73 15.66 91.8 12.2 9.9 11.5 2957 3.29 138.0% 101.3% *27/6/67 0.403 233 4.75 15.72 91.9 12.1 9.8 11.3 2966 3.29 138.4% 101.2% *30/0/70 0.429 172 4.94 16.24 93.1 11.7 10.3 11.6 3070 3.29 143.3% 101.1% 30/4/66 0.455 224 4.98 16.35 93.4 11.7 10.0 11.2 3087 3.28 144.1% 101.0% 30/6/64 0.469 249 5.00 16.41 93.5 11.6 9.9 11.1 3096 3.28 144.5% 100.9% *35/0/65 0.538 199 5.34 17.36 95.7 11.0 10.2 10.9 3275 3.26 152.9% 100.4% *36/4/60 0.600 256 5.46 17.68 96.4 10.8 9.8 10.5 3334 3.25 155.6% 100.1% 36/6/58 0.621 282 5.48 17.74 96.5 10.8 9.6 10.3 3343 3.25 156.0% 100.1% *39/4/57 0.684 272 5.69 18.33 97.9 10.4 9.5 10.0 3449 3.24 161.0% 99.6% 39/6/55 0.709 298 5.71 18.38 98.0 10.4 9.4 9.8 3457 3.23 161.3% 99.5% A number of iniportant features are to be found from the compositions shown in Table 2. In particular, there is a range of compositions for which a COP is found which is higher than that of R-134a. As R-32 is added to the blend, the COP increases above that for R-1 34a, peaks and then declines. The effect has been S found to be not sensitive to the addition of R-I 34a to the system. To attain maximum COP, it is preferred that the mass ratio of R32 to R-l225yeE in a blend containing both of them (binary, ternary or quaternary) lies between 0.20 and 0.35, though the COP of the blend is higher than that of R-134a when the mass ratio of R-32:Rl225yeE is between 0 and 0.6.

Since an important objective is to reduce the emission greenhouse gases, increasing the energy efficiency of a R-134a replacement, especially in (but not limited to) a mobile air conditioning systems is desirable, as well as reducing the direct greenhouse warming potential of refrigerant. In the context of mobile air conditioning systems, this is because the running of an air conditioning system is powered by burning car fuel, and hence releasing CO2 into the atmosphere.

In addition, the fractionation analysis shows that blends having a mass ratio of R- 32:R-l225yeE of greater than about 0.16:1 generate flammable vapours at the - 20C fractionation analysis condition. Hence keeping the mass ratio of these two components below this threshold is beneficial.

Additionally, the evaporator temperature glide increases as R-32 is added to the mixture. Temperature glides of 5K or lower are attained when the mass ratio of R-32 to R-1225yeE is less than 0.081.

: *. Further, it has been advantageously found that the volumetric capacity of blends S...

containing R-32 and R-1225yeE is 90% or more of the capacity of R-134a when the mass ratio R-32:R-l225yeE is 0.056:1 or higher. * .

In relation to preferred compositions containing both R-32 and R-l225yeE, the mass fraction R-32 should be up to 0.6 of the mass fraction of R-I 225yeE in the I..

: composition to maximise the COP. Additionally, the mass fraction of R-32:R-S... r

1225yeE should be up to about 0.25 (i.e 0 to 0.25) to ensure maximised COP with a "non-flammable" classification. Also, the mass ratio of R-32:R-l225yeE should be up to about 0.081 to keep the glide of the composition as 5C or less.

Also, the mass ratio of R-32:R-1225yeE should be between 0.056 and 0.081 to keep the capacity of the composition within 10% of that of R-134a, with a glide less than 5CC.

A composition comprising a mass ratio of 5 to 7 parts R-32, 6 to 8 parts R-134a and 86 to 88 parts R-1225yeE (the sum of all parts being 100), preferably 6:7:87 R-32:R-134a:R-1225yeE, which has a mass ratio of R-32:Rl225yeE of 0.07 combines these beneficial attributes.

Example 3

Tables 3 to 7 show similar information to that shown in the context of Example 2 for different formulations.

In the ensuing tables lines marked * correspond to compositions where the worst case fractionated formulation at the low temperature 90% fill test case (as per ASHRAE p34) will have flammable vapour according to the specified ASHRAE p34 test protocol at I 00C. * .. * p * I... * * **** * p

S

**** *5 * S 5. * S* I. S S...

S S S.5 S. ** * 0 * * * S S S * ) 55 * -S. * . S S S * S S * S 50 *5* **S S S Actual Evaporator Condenser Discharge volumetric Evaporator Condenser Volumetric Relative Relative R125 R161 Rl225yeE GWP pressure pressure temperature flow glide glide capacity COP capacity COP bar(a) bar(a) C Am3/hr K K kJ/m3 2 0 98 78 2.42 8.29 74.0 23.73 0.3 0.6 1517 3.26 70.8% 100.4% 2 3 95 78 2.56 8.74 75.5 22.39 1.0 1.5 1608 3.28 75.0% 100.8% *2 4 94 78 2.60 8.88 75.9 21.99 1.2 1.7 1637 3.28 76.4% 100.9% *2 5 93 76 2.65 9.02 76.4 21.61 1.4 1.9 1666 3.28 77.7% 101.0% 6 92 78 2.69 9.15 76.8 21.25 1.5 2.1 1694 3.29 79.0% 101.1% *2 9 89 78 2.83 9.54 78.1 20.28 2.0 2.6 1775 3.30 82.8% 101.4% *2 12 86 78 2.95 9.91 79.2 19.44 2.3 2.9 1851 3.30 86.4% 101.7% 83 78 3.07 10.25 80.3 18.71 2.6 3.1 1924 3.31 89.8% 101.9% 18 80 78 3.19 10.58 81.3 18.06 2.8 3.3 1993 3.32 93.0% 102. 0% 21 77 78 3.30 10.88 82.3 17.49 2.9 3.3 2058 3.32 96.1% 102.1% 24 74 78 3.41 11.18 83.3 16.98 3.0 3.3 2120 3.32 98.9% 102.2% 2 27 71 78 3.51 11. 45 84.2 16.52 3.0 3.3 2179 3.33 101.7% 102.3% 2 30 68 78 3.61 11.72 85.0 16.11 3.0 3.3 2235 3.33 104.3% 102.4% 2 33 65 78 3.71 11.97 85.8 15.73 3. 0 3.2 2288 3.33 106.8% 102.4% 2 36 62 79 3.80 12.21 86.6 15.39 3.0 3.1 2339 3.33 109.2% 102.5% 2 39 59 79 3.89 12.44 87.4 15.08 2.9 3.0 2388 3.33 111.4% 102.5% *2 42 56 79 3.98 12.66 88.1 14.79 2.8 2.8 2434 3.33 113.6% 102.5% 3 0 97 112 2.44 8.39 74.1 23.49 0.5 0.9 1533 3.26 71.5% 100.3% 3 3 94 112 2.59 8.83 75.6 22.18 1.2 1.7 1623 3.27 75.8% 100.7% *3 4 93 112 2.63 8.97 76.0 21.78 1.3 1.9 1653 3.28 77.1% 100.8% *3 5 92 112 2.68 9.11 76.5 21.41 1.5 2.1 1681 3.28 78.5% 101.0% 3 6 91 112 2.72 9.24 76.9 21.06 1.7 2.3 1709 3.28 79.8% 101.1% *3 9 88 112 2.85 9.63 78.1 20.11 2.1 2.8 1790 3.29 83.5% 101.3% 3 12 85 112 2.98 10.00 79.3 19.28 2.4 3.1 1867 3. 30 87.1% 101.6% 82 112 3.10 10.34 80.3 18.56 2.7 3.3 1939 3.31 90.5% 101.8% 3 18 79 112 3.22 10.66 81.4 17.93 2.9 3.4 2008 3.31 93.7% 101.9% 3 21 76 112 3.33 10.97 82.3 17.37 3.0 3.4 2073 3.32 96.7% 102.1% *3 24 73 112 3.44 11.26 83.3 16.86 3.1 3.4 2135 3.32 99.6% 102.2% *3 27 70 112 3.54 11.54 84.2 16.41 3.1 3.4 2193 3.32 102.4% 102.2% 67 112 3.64 11.80 85.0 16.01 3.1 3.3 2249 3.32 105.0% 102.3% 3 33 64 112 3.74 12.06 85.9 15.64 3.1 3.3 2302 3.33 107.4% 102.3% :: TABLE 3 (CONT'I)) * : . . * * * * * S. **. **. S * *3 * 36 61 112 3.83 12.30 86.6 15.30 3.0 3.1 2353 3.33 109.8% 102.4% *3 39 58 112 3.92 12.52 87.4 14.99 2.9 3.0 2402 3.33 112.1% 102.4% *3 42 55 113 4.00 12.74 88.1 14.71 2.8 2.9 2448 3.33 114.2% 102.4% 4 0 96 146 2.47 8.48 74.2 23.25 0.7 1.2 1548 3.26 72.3% 100.3% 4 3 93 146 2.61 8.93 75.6 21.96 1.3 2.0 1639 3.27 76.5% 100.6% *4 4 92 146 2.66 9.07 76.1 21. 58 1.5 2.2 1668 3.27 77.9% 100.8% 91 146 2.70 9.20 76.5 21.22 1.7 2.4 1697 3.28 79.2% 100.9% 6 90 146 2.75 9.34 76.9 20.87 1.8 2.5 1725 3.28 80.5% 101.0% *4 9 87 146 2.88 9.72 78.2 19.94 2.2 2.9 1806 3.29 84.3% 101.3% *4 12 84 146 3.01 10.09 79.3 19.13 2.5 3.2 1882 3.30 87.8% 101.5% *4 15 81 146 3.13 10.43 80.4 18.42 2.8 3.4 1954 3.30 91.2% 101.7% 18 78 146 3.25 10.75 81.4 17.80 3.0 3.5 2023 3.3) 94.4% 101.8% 21 75 146 3.36 11.06 82.4 17.24 3.1 3.5 2088 3.31 97.4% 102.0% *4 24 72 146 3.47 11.35 83.3 16.75 3.1 3.5 2149 3.32 100.3% 102.1% *4 27 69 146 3.57 11.63 84.2 16.31 3.2 3. 5 2208 3.32 103.0% 102.1% 66 146 3.67 11.89 85.0 15.91 3.2 3.4 2263 3.32 105.6% 102.2% *4 33 63 146 3.77 12.14 85.9 15.54 3.1 3.3 2316 3.32 108.1% 102.2% 36 60 146 3.86 12.38 86.7 15.21 3.0 3.2 2367 3.32 110.5% 102.3% +4 39 57 146 3.95 12.61 87.4 14.91 3.0 3.1 2415 3.32 112.7% 102.3% 42 54 146 4.03 12.83 88.2 14.63 2.9 2.9 2462 3.32 114.9% 102.3% :: :: * s. *. *..

. . ...DTD: TABLE 4

Actual Evaporator Condenser Discharge volumetric Evaporator Condenser Volumetric Relative Relative R161 R134a RI22SyeE GWP pressure pressure temperature flow glide glide capacity CUP capacity COP bar(a) bar(a) C Am3/Itr K K kJ/m3 0 2 98 36 2.39 8.18 74.1 23.99 0.1 0.1 1501 3.27 70.0% 100.6% 3 2 95 36 2.53 8.62 75.5 22.63 0.7 1.0 1591 3.28 74.3% 101.0% 2 94 36 2.57 8.76 76.0 22.22 0.9 1.3 1620 3.29 75.6% 101.1% *5 2 93 36 2.62 8.90 76.4 21.84 1.1 1.5 1649 3.29 76.9% 101.2% 6 2 92 36 2.66 9. 04 76.9 21.47 1.3 1.7 1676 3.29 78.2% 101.3% *9 2 89 36 2.79 9.42 78.! 20.49 1.7 2.2 1757 3.30 82.0% 101.6% 12 2 86 36 2.92 9.79 79.3 19.63 2.1 2.5 1834 3.31 85.6% 101.8% *15 2 83 36 3.04 10.13 80.4 l8.89 2.3 2.8 1906 3. 32 89.0% 102.0% *18 2 80 36 3.15 10.46 81.4 18.23 2.6 3.0 1975 3.32 92.2% 102.2% 21 2 77 36 3.27 10.77 82.4 17.65 2.7 3.0 2040 3.32 95.2% 102.3% 24 2 74 36 3.37 11.06 83.3 17.13 2.8 3.1 2102 3.33 98.1% 102.4% 0 4 96 62 2.41 8.26 74.3 23.76 0.1 0.2 1515 3.27 70.7% 100.6% 3 4 93 62 2.55 8.70 75.7 22.43 0.8 1.1 1605 3.28 74.9% 101.0% *4 4 92 62 2.60 8.84 76.2 22.03 1.0 1.3 1634 3.29 76.2% 101.1% *5 4 91 62 2.64 8.97 76.6 21.66 1.1 1.5 1662 3.29 77.6% 101.2% 6 4 90 62 2.68 9.11 77.0 21.30 1.3 1.7 1690 3.29 78.9% 101.3% *9 4 87 62 2.81 9.49 78.3 20.34 1.7 2.2 1770 3.30 82.6% 101.6% l2 4 84 62 2.94 9.85 79.4 19.50 2.! 2.5 1846 3.3! 86.1% 101.8% 4 81 62 3.06 10.20 80.5 18.77 2.3 2.8 1918 3.31 89.5% 102.0% *18 4 78 62 3.17 10.52 81.6 18.13 2.5 2.9 1986 3.32 92.7% 102.2% 21 4 75 62 3.28 10.82 82. 5 17.55 2.7 3.0 2051 3.32 95.7% 102.3% 24 4 72 62 3.39 11.12 83.5 17.04 2.8 3.0 2112 3.33 98.6% 102.4% 0 6 94 87 2.43 8.33 74.5 23.54 0.2 0.3 1529 3.27 71.4% 100.7% 3 6 91 87 2.57 8.77 75.9 22.24 0,8 1.1 1619 3.28 75.5% 101.0% *4 6 90 87 2.62 8.91 76.4 21.85 1.0 1.3 1647 3.29 76.9% 101.1% *5 6 89 88 2.66 9.04 76.8 21.49 1.2 1.5 1675 3.29 78.2% 101.2% 6 88 88 2.71 9.18 77.2 21.14 1.3 1.7 1703 3.29 79.5% 101.3% 9 6 85 88 2.84 9.56 78.5 20.19 1.7 2.2 1783 3.30 83.2% 101.6% * . . . * **

:* TABLE4(CONT'D)

* S. *** 555 5 S 12 6 82 88 2.96 9.92 79.6 19.37 2.1 2.5 1858 3.31 86.7% 101.8% 6 79 88 3.08 10.26 80.7 18.66 2.3 2.7 1930 3.31 90.1% 102.0% *18 6 76 88 3.19 10.58 81.7 18.02 2.5 2.9 1997 3.32 93.2% 102.1% 21 6 73 88 3.30 10.88 82.7 17.46 2.6 3.0 2062 3.32 96.2% 102.2% 24 6 70 88 3.41 11.17 83.6 16.96 2.7 3.0 2123 3.33 99.1% 102.3% 0 8 92 113 2.46 8.41 74.7 23.32 0.2 0.3 1544 3.27 72.0% 100.7% 3 8 89 113 2.59 8.84 76.1 22.05 0.8 1.2 1633 3.28 76.2% l01.0>'o 8 88 113 2.64 8.98 76.5 21.67 1.0 1.4 1661 3.29 77.5% 101.1% *5 8 87 113 2.68 9.11 77.0 21.32 1.2 1.6 1689 3.29 78.8% 101.2% *6 8 86 113 2.73 9.24 77.4 20.98 1.3 1.7 1716 3.29 80.1% 101.3% *9 8 83 113 2.86 9.62 78.6 20.05 1.7 2.2 1795 3.30 83.8% 101.6% *12 8 80 113 2.98 9.98 79.8 19.25 2.1 2.5 1870 3.31 87.3% 101.8% *15 8 77 114 3.10 10.32 80.8 18.54 2.3 2.7 1941 3.31 90.6% 102.0% 18 8 74 114 3.21 10.64 81.8 17.92 2.5 2.8 2009 3.32 93.7% 102.1% 21 8 71 114 3.32 10.94 82.8 17.37 2.6 2.9 2073 3.32 96.7% 102.2% 24 8 68 114 3.43 11.23 83.7 16.88 2.7 2.9 2133 3.32 99.6% 102.3% 0 10 90 139 2.48 8.48 74.9 23.11 0.3 0.4 1558 3.27 72.7% 100.7% 3 10 87 139 2.62 8.91 76.3 21.87 0.9 1.2 1646 3.28 76.8% 101.0% 86 139 2.66 9.05 76.7 21.50 1.0 1.4 1675 3.29 78.1% 101.1% *5 10 85 139 2.71 9.18 77.2 21.15 1.2 1.6 1702 3.29 79.4% 101.2% 84 139 2.75 9.31 77.6 20.82 1.3 1.8 1729 3.29 80.7% 101.3% *9 10 81 139 2.88 9.69 78.8 19.91 1.7 2.2 1808 3.30 84.4% 101.6% 12 10 78 139 3.00 10.04 79.9 19.12 2.0 2.5 1883 3.31 87.9% 101.8% 10 75 139 3.12 10.38 81.0 18.43 2.3 2.7 1953 3.31 91.1% 101.9% *13 10 72 139 3.23 10.70 82.0 17.82 2.4 2. 8 2020 3.32 94.3% 102.1% 21 10 69 139 3.34 11.00 83.0 17.28 2.6 2.9 2083 3.32 97.2% 102.2% 24 10 66 139 3.45 11.28 83.9 16.79 2.6 2.9 2144 3.32 100.0% 102.3% S S S * ** . S S *S ** S * * : : .: : : S ** *eS.5. * Ternary blends comprising R-1611R-134a/R-1225ye TABLE 5 Actual Evaporator Condenser Discharge volumetric Evaporator Condenser Volumetric Relalive Relative R32 R125 R161 Rl225yeE GWP pressure pressure temperature flow glide glide capacity COP capacity COP bar(a) bar(a) C Aiu3/hr K K kJ/m 2 2 0 96 89 2.58 8.97 76.0 21.97 1.7 3.3 1639 3.26 76.5% 100.4% 2 2 2 94 89 2.68 9.25 76.9 21.21 2.1 3.7 1697 3.27 79.2% 100.7% 2 2 3 93 89 2.72 9.38 77.3 20.87 2.2 3.8 1725 3.28 80.5% 100.8% 2 2 4 92 89 2.77 9.51 77.7 20. 54 2.4 3.9 1753 3.28 81.8% 101.0% 2 5 91 89 2.81 9.64 78.1 20.22 2.5 4.0 1780 3.28 83.1% l0I.l h 2 6 90 89 2.86 9.76 78.5 19.92 2.7 4.1 1807 3.29 84.3% 101.2% *2 2 8 88 89 2.94 10.00 79.2 19.36 2.9 4.2 1859 3.30 86.8% 101.4% 2 10 86 89 3.03 10.24 80.0 18.86 3.1 4.3 1909 3.30 89.1% 101.6% *2 2 12 84 89 3.11 10.46 80.7 18.39 3.2 4.4 1957 3.31 91.3% 101.7% 3 3 0 94 128 2.70 9.40 77.0 21.01 2.5 4.7 1714 3.26 80.0% 100.3% 3 3 2 92 128 2.79 9.66 77. 8 20.33 2.8 4.9 1770 3.27 82.6% 100.6% 3 3 3 91 128 2.84 9.79 78.2 20.02 3. 0 5.0 1798 3.27 83.9% 100.7% 3 3 4 90 128 2.88 9.91 78.6 19.72 3.1 5.0 1825 3.28 85.2% 100.9% 3 3 5 89 128 2.93 10.03 78.9 19.42 3.2 5.! 1854 3.28 86.5% I0I.l h 43 3 6 88 128 2.97 10.15 79.3 19.15 3.3 5.1 1880 3.29 87.7% 101.2% *3 3 8 86 128 3.06 10.39 80.0 18.65 3.5 5.1 1930 3.29 90.1% 101.4% *3 3 10 84 128 3.14 10.61 80.7 18.19 3.7 5.2 1979 3.30 92.3% 101.5% *3 3 12 82 128 3.22 10.83 81.4 17.78 3.8 5.1 2025 3.30 94.5% I01.6% 4 4 0 92 167 2.81 9.82 77.9 20.11 3.3 5.9 1790 3.26 83.6% 100.4% 4 4. 2 90 167 2. 91 10.07 78.7 19.50 3.6 6.0 1846 3.27 86.1% 100.6% 4 4 3 89 167 2.95 10.19 79.0 19.23 3.7 6.0 1873 3.27 87.4% 100.7% 4 4 4 88 167 3.00 10.31 79.4 18.96 3.8 6.0 1899 3.28 88.6% 100.9% 4 4 5 87 167 3.04 10.43 79.8 18.71 3.9 6.0 1925 3.28 89.8% 101.0% 4 6 86 167 3.08 10.54 80.1 18.46 4.0 6.0 1950 3.28 91.0% 101.1% *4 4 8 84 167 3.17 10.77 80.8 18.01 4.1 6.0 1999 3.29 93.3% 101.2% *4 4 10 82 167 3.25 10.98 81.4 17.58 4.2 5.9 2048 3.30 95.6% 101.5% 44 4 12 80 167 3.33 11.19 82.1 17.20 4.3 5.8 2093 3.30 97.7% 101.6% S * S I SI : : : : : : : : :.

* : : : : . . TABLE6 1.5 ** *** I.. S S Actual, Evaporator Condenser Discharge voltinietric Evaporator Condenser Volumetric Relative Relalive R125 R152a Rl225yeE GWP pressure pressure temperature flow glide glide capacity CO capacily cor 2 0 98 78 2.42 8.29 74.0 23.73 0.3 0.6 1517 3.26 70.8% 100.4% 2 3 95 81 2.46 8.42 74.9 23.25 0.4 0.7 1548 3.28 72.3% 100.8% 2 6 92 84 2.50 8.54 75.8 22.82 0.5 0.8 1578 3.29 73.6% 101.1% 2 8 90 87 2.52 8.62 76.3 22.55 0.5 0.8 1597 3.29 74.5% 101.3% 2 9 89 88 2.54 8.65 76.6 22.42 0.5 0.8 1606 3.30 75.0% 101.4% 2 10 88 89 2.55 8.69 76.8 22.29 0.5 0.8 1615 3.30 75.4% 101.5% 2 11 87 90 2.56 8.73 77.1 22.16 0.6 0.8 1624 3.30 75.8% 101.6% *2 12 86 91 2.57 8.76 77.4 22.04 0.6 0.9 1633 3.30 76.2% 101.7% *2 13 85 92 2.58 8.80 77.6 21.93 0.6 0.9 1642 3.31 76. 6% 101.8% *2 14 84 93 2.60 8.83 77.9 21.81 0.6 0.9 1651 3.31 77.0% 101.9% *2 15 83 94 2.61 8.87 78.2 21.70 0.6 0.9 1659 3.31 77.4% 102.0% *2 18 80 98 2.64 8.96 78.9 21.38 0.6 0.9 1684 3.32 78.6% 102.2% *2 21 77 101 2.67 9. 06 79.7 21.08 0.6 0.9 1708 3.33 79.7% 102.4% *2 24 74 104 2.70 9.15 80.4 20.80 0.6 0.9 1731 3.34 80.8% 102.6% 27 71 108 2.73 9.23 81.1 20.54 0.7 0.9 1753 3.34 81.8% 102.9% 68 111 2.76 9.31 81.9 20.30 0.6 0.9 1774 3.35 82.8% 103.0% *2 33 65 114 2.79 9.39 82.5 20.07 0.6 0.9 1794 3.35 83.7% 103.2% 3 0 97 112 2.44 8.39 74.1 23.49 0.5 0.9 1533 3.26 71.5% 100.3% 3 3 94 115 2.49 8.51 75.0 23.02 0.6 1.0 1564 3.27 73.0% 100.7% 3 6 91 118 2. 52 8.63 75.8 22.60 0.6 1.0 1593 3.28 74.3% 101.0% 3 8 89 121 2.55 8.71 76.4 22.33 0.7 1.1 1612 3.29 75.2% 101.2% 3 9 88 122 2.56 8.75 76.7 22.21 0.7 1.1 1621 3.29 75.7% 101.3% 3 10 87 123 2.57 8.78 76.9 22.08 0.7 1.1 1630 3.30 76.1% 101.4% 3 II 86 124 2.59 8.82 77.2 21.96 0.7 1.1 1639 3.30 76. 5% 101.5% 3 12 85 125 2.60 8.85 77.5 21.84 0.7 LI 1648 3.30 76.9% 101.6% 13 84 126 2.61 8.89 77.7 21.73 0.7 1.1 1657 3.31 77.3% 101.7% 14 83 127 2.62 8.92 78.0 21.61 0.7 1.1 1666 3.31 77.7% 101.8% 82 128 2.63 8.95 78.2 21. 51 0.8 1.1 1674 3.31 78.1% 10I.9% *3 18 79 132 2.67 9.05 79.0 21.19 0.8 1.1 1699 3.32 79.3% l02.1% *3 21 76 135 2.70 9.14 79.7 20.90 0.8 1.1 1722 3. 33 80.4% 102.4% *3 24 73 138 2.73 9.23 80.5 20.63 0.8 1.1 1745 3.33 81.4% 102.6% *3 27 70 141 2.76 9.32 81.2 20.37 0.8 1.1 1767 3.34 82.5% 102.8% *3 30 67 145 2.78 9.40 81.9 20.13 0.8 1.1 1788 3.35 83.4% 103.0% *3 33 64 148 2.81 9.47 82.6 19.91 0.8 1.1 1808 3.35 84.4% 103.1% * , S S ** *. * S S ::.: : : Actual *5 **. **P S S Evaporator Condenser Discharge volumetric Evaporator Condenser Volumetric Relative ReIae R32 R125 R152a Rl225yeE GWP pressure pressure temperature flow glide glide capacity COP capacity COP bar(s) bar(e) C Am3lhr K K kJ/m3 2 2 0 96 89 2.58 8.97 76.0 21.97 1.7 3. 3 1639 3.26 76.5% 100.4% 2 2 3 93 92 2.62 9.07 76.8 21.61 1.7 3.3 1666 3.27 77.8% 100.8% 2 2 6 90 95 2.66 9.17 77.6 21.27 1.7 3.2 1693 3.29 79.0% 101.1% 2 2 8 88 97 2.68 9.24 78.1 21.05 1.7 3.1 1710 3.29 79.8% 101.3% 2 2 9 87 99 2.69 9.27 78.4 20.95 1.7 3.1 1718 3.30 80.2% 101.4% 2 2 10 86 100 2.70 9.30 78.6 20.85 1.7 3.0 1726 3.30 80.6% 101.5% 2 2 11 85 101 2.72 9.33 78.9 20.76 1.7 3.0 1734 3.30 80.9% 101.6% 2 2 12 84 102 2.73 9.36 79.1 20.66 1.7 3.0 1742 3.30 81.3% 101.7% 2 2 13 83 103 2.74 9.38 79.4 20.57 1.7 3.0 1750 3.31 81.7% 101.8% 2 2 14 82 104 2.75 9.41 79.6 20.48 1.7 2.9 1758 3.31 82.0% 101.8% 2 2 15 81 105 2.76 9.44 79.9 20.39 1.7 2.9 1766 3.31 82.4% 101.9% 2 2 18 78 108 2.79 9.52 80.6 20.14 1.7 2.8 1788 3.32 83.4% 102.2% *2 2 21 75 112 2.82 9.60 81.3 19.90 1.6 2.7 1809 3.33 84.4% 102.4% 2 24 72 115 2.84 9.67 82.0 19.67 1.6 2.6 1830 3.33 85.4% 102.6% 2 2 27 69 118 2.87 9.74 82.7 19.47 1.6 2.5 1849 3.34 86.3% 102.8% *2 2 30 66 122 2.go 9.81 83.4 19.27 1.5 2.4 1868 3.35 87.2% 103.0% 2 2 33 63 125 2.92 9.88 84.0 19.08 1.5 2.3 1887 3.35 88.0%103.2% 3 3 0 94 128 2.70 9.40 77.0 21.01 2.5 4.7 1714 3.26 80.0% 100.3% 3 3 3 91 131 2.73 9. 49 77.8 20.69 2.5 4.5 1740 3.27 81.2% 100.7% 3 3 6 88 135 2.77 9.57 78.5 20.38 2.5 4.4 1766 3.28 82.4% 101.1% 3 3 8 86 137 2.79 9.63 79.0 20.20 2. 5 4.3 1782 3.29 83.2% 101.3% 3 3 9 85 138 2.80 9.66 79.2 20.11 2.4 4.2 1790 3.29 83.5% 101.4% 3 3 10 84 139 2,81 9.68 79.5 20.03 2.4 4.2 1798 330 83.9% 101.5% 3 3 11 83 140 2.82 9.71 79.7 19.94 2.4 4.1 1805 3.30 84.2% 101.5% 3 3 12 82 141 2.83 9.74 80.0 19.86 2.4 4.1 1813 3.30 84.6% 101.6% *3 3 13 81 142 2.84 9.76 80.2 19.78 2.4 4.0 1820 3.31 84.9% 101.7% 3 3 14 80 143 2.85 9.79 80.5 19.70 2.4 4.0 1827 3.31 85.3% 101.8% 3 3 15 79 144 2.86 9.81 80.7 19.63 2.4 3.9 1834 3.31 85.6% 101.9% *3 3 18 76 148 2.89 9.88 81.4 19.41 2.3 3.8 1855 3.32 86.6% 102.1% *3 3 21 73 151 2.92 9.95 82.1 19.20 2.2 3.7 1875 3.33 87.5% 102.3% *3 3 24 70 154 2.94 10.02 82.8 19.01 2.2 3.5 1894 3.33 88.4% 102.5% *3 3 27 67 158 2.97 10.08 83.4 18.82 2.1 3.4 1913 3.34 89.3% 102.7% *3 3 30 64 161 2.99 10.14 84.1 18.65 2.1 3.3 1930 3.34 90.1% 102.9% *3 3 33 61 164 3.01 10.20 84.7 18.49 2.0 3.2 1947 3.35 90.9% 103.1% )

Claims

CLAIMS

1. A heat transfer composition comprising: (i) R-1225ye; (ii) at least one further refrigerant selected from carbon dioxide (R- 744); fluoromethane (R-41); difluoromethane (R-32); fluoroethane (R-161); 1,1,1-trifluoroethane (R-1 43a); 1,1,1,2-tetrafluoroethane (R-1 34a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoroproane (R-227ea); propane (R-290); propene (R-1270); isobutane (R-600a); nbutane (R600) 2,3,3,3- tetrafluoropropene (R-I 234yf); 1,1 -difluorocyclopropane; 1,1,2-io trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, or ammonia.
2. A heat transfer composition comprising: (i) R-1225yeE; (ii) R-32,R-l6lorR-152a;and (iii) at least one further refrigerant selected from carbon dioxide (R- 744); fluoromethane (R-4 1); fluoroethane (R-161); 1,1,1 -trifluoroethane (R-1 43a); 1,1,1,2-tetrafluoroethane (R-1 34a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoroproane (R-227ea); propane (R-290); propene (R-1270); isobutane (R-600a); nbutane (R-600) 2,3,3,3-tetrafluoropropene (R-1234yf); 1,1difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, pentafluororethane (R-125) or ammonia or mixtures thereof.

: *.
3. A heat transfer composition comprising: S...

(i) R-1225yeE; S...

(ii) R-32; *1***S * (iii) R-1234yf; and (iv) at least one further refrigerant selected from carbon dioxide (R- : 744); fluoromethane (R-41); fluoroethane (R-161); 1,1,1-trifluoroethane (R-143a); 1,1,1,2-tetrafluoroethane (R-I 34a); 1,1,2,2-tetrafluoroethane (R-1 34); dimethyl *..

ether; heptafluoroproane (R-22 7ea); propane (R-290); propene (R-1270); isobutane R-600a); n-butane (R-600); 1,1 -difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2 -tetrafluorocyclopropane; pentafluorocyclopropane, or ammonia or mixtures thereof
4. A heat transfer composition comprising: (i) R-1225yeE; (ii) R-32; (iii) R-125; and (iv) R-161 orR-152a.

5. A composition according to claim 2 or claim 3, wherein the further refrigerant is R-143a or R-125, preferably R-134a.

6. A composition according to claim 2, wherein the R-32 or R-161 is R-32.

7. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-I 225yeE, R-1 52a and R-125.

8. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-1225yeE, R-161 and R-134a 9. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-1225yeE, R-161 and R-125.

* 25 10. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-l225yeE, R-125 and R-32. *.* * * *.**

* 11. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-125 (1 to 3 parts), R-152a (1 to 12 parts) and R-1225yeE (85 to 98 parts). I.. * ** ** S S... * S S...

C

12. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-125 (1 to 4 parts), R-161 (1 to 3 parts) and R-1225yeE (93 to 98 parts).

13. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-161 (1 to 3 parts), R-134a (1 to 10 parts) and R-l225yeE (87 to 98 parts).

14. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-32 (1 to 3 parts), R- 125 (1 to 3 parts), R- 152a (Ito 12 parts) and R-l225yeE (82 to 97 parts).

15. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-132 (1 to 3 parts), R-125 (I to 3 parts), R- 161 (1 to 5 parts) and R-1225yeE (89 to 97 parts).

16. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-32 (1 to 9 parts), R-134a (4 to 8 parts), R- 1234yf(4 to 52 parts) and R-1225yeE (39 to 78 parts).

17. A composition according to any one of the preceding claims wherein the* heat transfer composition comprises R-32 (3 to 9 parts), R-134a (4 to 8 parts), R- 1234yf(4 to 28 parts), and R-1225ye (59 to 79 parts).

18. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-32 (3 to 7 parts), R-134a (4 to 6 parts), R- 1234yf(4 to 28 parts), and R-1225yeE (59 to 78 parts).

S.....

19. A composition according to any one of the preceding claims wherein the heat transfer composition comprises R-32 (1 to 3 parts), R-134a (4 to 6 parts), R- : 1234yf(4 to 52 parts) and R-1225yeZ (39 to 78 parts). I... * S )

20. A composition according to anyone of the preceding claims, wherein the composition has a Coefficient of Performance within 10% of the fluid it is intended to replace, for example R-134a.

21. A composition according to any one of the preceding claims, wherein the composition has a capacity greater than R-1225ye and/or R-1225yeE.

22. A composition according to any one of the preceding claims, wherein the composition is non-azeotropic.

23. A composition according to any one of the preceding claims, wherein the rn mass ratio of R-32 to R-1225yeE in the composition is between 0.20 and 0.35:1.

24. A composition according to any one of the preceding claims, wherein the mass ratio of R-32 to R-1 225yeE in the composition is below 0.16:1.

25. A composition according to any one of the preceding claims, wherein the mass ratio of R-32 to R-1225yeE is less than 0.081:1.

26. A composition according to any one of the preceding claims, wherein the mass ratio of R-32 to R-l225yeE is less than 0.6:1.

27. A composition according to any one of the preceding claims, wherein the mass ratio of R-32 to R-1225yeE is 0.056:1 or higher.

28. A composition according to any one of the preceding claims, wherein the : ** 20 mass ratio of R-32 to R-1225yeE is between 0.06 and 0.08.

29. A composition according to any one of the preceding claims, wherein the mass ratio of R-32 to R-1225yeE is 0.07:1. *

30. A composition according to any one of the preceding claims, wherein the composition comprises 6% R-32, 7% -R134a and 87% R-1225yeE.

::.: 25 31. A composition according to any one of the preceding claims, wherein the R-l 22SyeE component comprises at least 95% E isomer.

32. A composition according to claim 31, wherein the R-1225yeE component comprises at least 98% E isomer.

33. A composition according to any one of thc preceding claims which has a GWP of about 150 or less.

34. A composition according to any one of the preceding claims which has a GWP of about 100 or less.

35. A composition according to any one of the preceding claims comprising 5 to 7 parts R-32 or R-161, preferably R-32, 6 to 8 parts R-134a or R-125, preferably R-134a, and 86 to 88 parts R-1225 yeE, the sum of all parts being 100.

36. A composition according to any one of the preceding claims comprising 2 to 4 parts R-32, 2 to 4 parts R-125, 3 to 6 parts R-161 and 86 to 93 parts R-1225 yeF, the sum of all parts being 100.

37. A composition according to any one of the preceding claims comprising 2 to 4 parts R-32, 2 to 4 parts R-125, 10 to 13 parts R-152a, and 79 to 86 parts R- 1225 yeE, the sum of all parts being 100.

38. A composition according to any one of the preceding claims comprising 2 to 4 parts R-161, 2 to 4 parts R-125, and 92 to 96 parts R-1225 yeE, the sum of all parts being 100. * S

39. A composition according to any one of the preceding claims further comprising a lubricant. a.. * S S *. . S...

I **. Th

40. A composition according to Claim 39 wherein the lubricant is selected from mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (FOEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (aipha-olefins) and combinations thereof 41. A composition according to any one of the preceding claims further comprising a stabiliser.

42. A composition according to Claim 4139 wherein the stabiliser is selected from diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.

43. A composition according to any one of the preceding claims further comprising an additional flame retardant.

44. A composition according to Claim 43 wherein the additional flame retardant is selected from tri-(2-chloroethyl)-phosphate, (chloropropyl)phosphate, tri-(2,3-dibromopropyl)-phosphate, tri-( I,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoroiodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.

45. A composition according to any one of the preceding claims wherein the : 25 composition is non-flammable. as

46. A composition according to any one of the preceding claims which is a refrigerant composition. a

fSs454 * a 47. A heat transfer device containing a composition as defined any one of a..

* Claims 1 to 46. *... 4 5 )

48. A heat transfer device according to Claim 47 which is a refrigeration device.

49. A heat transfer device according to Claim 48 which is selected from automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, and heat pump systems.

50. A heat transfer device according to Claim 48 or 49 which contains a compressor.

51. A blowing agent comprising a composition as defined in any one of Claims I to 45.

52. A foamable composition comprising one or more components capable of forming foam and a composition as defined in any one of Claims 1 to 45.

53. A foamable composition according to Claim 52 wherein the one or more components capable of forming foam are selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene, and epoxy resins or mixtures thereof. * . *

54. A foam obtainable from the foamable composition of Claim 52 or 53.

*:" 55. A foam according to Claim 54 comprising a composition as defined in any oneof Claims Ito 45. ** * S *.**

S )

56. A sprayable composition comprising a material to be sprayed and a propellant comprising a composition as defined in any one of Claims I to 45.

57. A method for cooling an article which comprises condensing a composition as defined in any one of Claims 1 to 45 and thereafter evaporating said composition in the vicinity of the article to be cooled.

58. A method for heating an article which comprises condensing a composition as defined in any one of Claims ito 45 in the vicinity of the article to be heated and thereafter evaporating said composition.

59. A method for extracting a substance from biomass comprising contacting the biomass with a solvent comprising a composition as defined in any one of Claims I to 45, and separating the substance from the solvent.

60. A method of cleaning an article comprising contacting the article with a solvent comprising a composition as defined in any one of Claims 1 to 45.

61. A method for extracting a material from an aqueous solution comprising contacting the aqueous solution with a solvent comprising a composition as defined in any one of Claims I to 45, and separating the substance from the solvent.

62. A method for extracting a material from a particulate solid matrix comprising contacting the particulate solid matrix with a solvent comprising a :;:: composition as defined in any one of Claims 1 to 45, and separating the substance from the solvent.

S..... * S

63. A mechanical power generation device containing a composition as defined in any one of Claims I to 45. * S.

S J _.i. S..

64. A mechanical power generation device according to Claim 63 which is adapted to use a Rarikine Cycle or modification thereof to generate work from heat.

65. A method of retrofitting a refrigeration device comprising the step of removing aii existing heat transfer fluid, and introducing a composition as defined in any one of Claim I to 458.

66. A heat transfer composition substantially as hereinbefore described. * ** * * S *S.. **.S * S S... * * . S.... * S S.. * SI S. * IS.. * S

I... 40