GB2440258A

GB2440258A - Heat transfer compositions

Info

Publication number: GB2440258A
Application number: GB0713800A
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: 2007-07-17
Publication date: 2008-01-23
Also published as: WO2008009922A3; WO2008009922A2; GB0614080D0; GB0713800D0

Abstract

A heat transfer composition comprising: (i) R-1225; (ii) R-1234; and (iii) at least one further refrigerant selected from carbon dioxide (R-744); fluoromethane (R-41); difluoromethane (R-32); fluorethane (R-161); 1,1-difluoroethane (R-152a); 1,1,1-trifluoroethane (R-143 a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoropropane (R-227ea); propane (R-290); propene (R-1270); isobutane (R-600a); n-butane (R-600); 3,3,3-trifluoropropene (R-1234zf); 1,3,3,3-tetrafluoropropene (R-1234ze, cis- or trans-isomers), 1,1 - difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, or ammonia, or mixtures thereof. Also shown is a heat transfer device, blowing agent, foamable composition, sprayable composition and method of cooling using the heat transfer composition.

Description

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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-507 and R- 404a, especially R-1 34a.

Mechanical refrigeration systems (and related heat transfer devices such as heat pumps and air-conditionrng 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 temperature 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.

Dichlorodifluoromethane (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 and use should be severely restricted and eventually phased out completely. The use of dichiorodifluoromethane was phased out in the 1990's.

I,1,1,2-tetrafluoroethane (refrigerant R-I 34a) was introduced as a replacement refrigerant for R-1 2. However, despite having a low ozone depletion potential, R-134a 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.

R-1225ye is a non-flammable refrigerant, and has a relatively low Greenhouse Warming Potential. Its boiling point, critical temperature, and other properties make it a potential alternative to higher GWP refrigerants such as R-I 34a.

R-1225ye (also known as F[FC-1225ye) is 1,2,3,3,3-pentafluoropropene (CF3CF=CHF). It can exist as two stereoisomers, which are known to have very similar boiling points. Our reference to R-1225ye encompasses both isomers, and also mixtures thereof. 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-1234 (tetrafluoropropene) encompasses a number of isomers. Our reference to R-1234 encompasses all these isomers, preferably but not exclusively those where a trifluoromethyl group (CF3-) is present in the molecule, particularly the isomers cis-R-I 234ze (cis-I,3,3,3-tetrafluoroprop-I -ene, trans-R-I 234ze (trans-1,3,3,3-tetrafluoroprop-I -ene) and R-123 4yf (2,3,3,3 -tetrafluoroprop-1- ene). Most preferably the R-1234 exists in the invention predominantly as R- 1234yf or as an azeotrope-like mixture of R-1234yf with other R-1234 isomers.

However, the properties of these fluids alone render them not suitable as a direct replacement for R-1 34a. In particular, their capacity is too low, by which is meant 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 e.g. 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 have a capacity and energy s efficiency (which may be conveniently expressed as the "Coefficient of Performance") ideally within 20% of the values, for example R-I 34a, and preferably with 10% of these values. 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. The composition should also ideally have reduced toxicity and flammability.

In accordance with one aspect of the invention, there is provided a heat transfer composition comprising: (i) R-1225 (pentafluoropropene); (ii) R-1234 (tetrafluoropropene); and (iii) a further refrigerant selected from one or more of carbon dioxide (R.-744; fluoromethane (R-41); difluoromethane (R-32); fluorethane (R-161); 1,1 -difluoroethane (R-1 52a); 1,1,1 -trifluoroethane (R-143 a); 1,1,1,2-tetrafluoroethane (R-134a); 1,1,2,2-tetrafluoroethane (R-134); dimethyl ether; heptafluoropropane (R-227ea); propane (R-290); propene (R-1270); isobutane (R-600a); n-butane (R-600); 3,3,3-trifluoropropene (R-1243zf); 1,3,3,3-tetrafluoropropene (R-1 234ze, cis-or trans-isomers), 1,1 -difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, or ammonia, or mixtures thereof.

In a highly preferred embodiment, the R-1225 is R-1225ye.

In a further highJy preferred embodiment, the R-1234 is R-1234yf.

In a still further preferred embodiment the mass ratio of R-1225 to R-1234 is sufficient to render the mixture of R-1225 and R-1234 non flammable; in certain preferred embodiments the preferred further refrigerant is R-32, and may optionally additionally include R-1 34a.

In certain embodiments, preferred compositions according to the invention may comprise (parts by weight, all parts totalling 100) 5-30 parts R-32, 50-75 parts R-1234yf, and 15-25 parts R-1225ye, optionally additionally including 0.1 to 10 parts of R-134a. Preferred specific compositions within this range comprise (parts by weight) 10 parts R- 32, 70 parts R-1234yf, and 20 parts R-1225ye; 15 parts R-32, 65 parts R1234yf and 20 parts R-1225ye; 20 parts R-32, 60 parts R-1234yf and parts R-1225ye; and 25 parts R-32, 55 parts R-1234yf and 20 parts R-1225ye.

Particularly in the context of the above specifically preferred compositions, but also in general, it is preferred that the R-1225ye component comprises at least 50% Z isomer, preferably at least 80% Z isomer, preferably at least 90%, 95% or 98% Z isomer.

It is reported that the refrigerant fluid R-1 225ye exhibits low acute toxicity. However, we have found in chronic 28 day toxicology testing that R-1225ye, although preferred in refrigerant blends because of the relatively high refrigeration performance exhibits toxicological activity at exposures of 10,000 ppm. This may result in reduced occupational exposure limits for compositions comprising R-1 225ye when compared to the fluids that they are intended to replace. Therefore in certain embodiments it is preferred thai the refrigerant composition comprises no more than 30% R-1225ye, preferably no more than 25% R-1225ye.

Preferred compositions according to the invention comprising R.-1234, s especially R-1234yf, and R-1225ye and comprise no more than 30% R- 1225ye, and preferably no more than 25% R-1225ye. They further additionally comprise R-32, and optionally further additionally comprise R-I 34a, and may have suitable flammability as well as reduced toxicity compared to compositions comprising more than 50% R-1225ye. The compositions may also have good performance characteristics as refrigerant blends.

Preferably, the further refrigerant is selected from R-134a, dimethyl ether R-161, R-32, R-152a, R-744, R-41, R-290, R-1270, ammonia, R- 600a, R-600, or R-1243zf.

Preferably, the resultant heat transfer composition has a GWP less than that of the fluid it is intended to replace, for example lower than that of R-134a.

Preferably also the resultant heat transfer composition has a capacity greater than that of R-1225 or R-1225ye alone. Preferably also the resultant heat transfer composition has a capacity greater than that of R-1225 (or R-1225ye) and R-1234 (or R-1234yf) combined.

Preferably, the nature and amount of the further refrigerant fluid is such that the resultant ternary (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 with test methodology as per Addendum 34.p dated 2004, the entire content of which is incorporated herein by reference.

In some applications it may not be necessary for the formulation to be classed as non-flammable by the ASHRAE 34 methodology: it is possible to develop fluids whose flammability limits will be sufficiently reduced in air to render them safe for use in the application, for example if it is physically not possible to make a flammable mixture by leaking the refrigeration equipment charge into the surrounds. We have found that the effect of adding R-11225ye to flammable refrigerants like R-1234yf is to modify their flammability in mixtures with air in this manner.

Compositions according to the invention typically have improved capacity compared to either R-1225ye or R-l234yf alone. In one facet, the incorporation of a relatively small proportion of further refrigerant(s) (component (iii) of the composition), which further refrigerant(s) may be flammable, have a higher GWP, or both, to provide a resultant heat transfer composition having both a low GWP and substantially no flammability characteristic, and relatively small temperature "glide", yet providing 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.

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

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 1 to about 6% by weight of the composition.

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

Preferably, the composition is azeotrope-like.

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.

All amounts mentioned in compositions herein, including in the claims, are by weight unless otherwise stated.

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 with mineral oils by the use of appropriate additives.

Preferably, the composition further comprises a lubricant.

Conveniently, the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkyl benzenes (PABs), poiyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (aipha-olefins) 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,

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(chloropropyl)phosphate. iri-(2,3 -dibromopropyl)-phosphate, tri-( 1,3 -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.

Preferably, the composition is a refrigerant composition.

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

Preferably, the heat transfer device is a refrigeration device.

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 centrifugal-type compressor.

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.

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Preferably, the one or more components capable of forming foam are selected from polvurethanes, 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.

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.

is According to a further aspect of the invention, there is provided a method for cooling an article which comprises condensing a composition of the invention 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.

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.

According to another aspect of the invention, there is provided a method of reirofltting 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

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acceptable for composition to have a higher GWP, for example a GVTP of up to 250, 500 or 750.

The GWP values of the candidate additional fluids dictate the maximum allowable percentages for each application. The 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 2900 R-125 2800 R-143a 3800 CO2 1 R-32 650 R-600a 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.

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.

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 preferred compositions of selected additional refrigerants having GWP higher than 150 are as follows: R-32 6% weight basis; R-134a 9% weight basis; R-227ea 4% weight basis; R-125 4% weight basis.

if the desired C1\VP 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.

For example a mixture of R-32 (10%); R-125 (10%) and R-1225ye (80%) will have a GWP of 351. Its refrigeration capacity is very similar to R-134a (estimated as typically 100-104% that of R-134a) and it has similar COP characteristic.

For example, the existing refrigerant fluid R-407C is a ternary mixture of R-32, R-125 and R-134a in the proportions of 23%/25%152% by weight and has a GWP of 1525. 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-1251R-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 wifl have a GWP that is substantially lowered compared to that of R-407C.

The above example teaches that the optimal matching of replacement properties may require the use of more than one additional fluid; so the replacements of the invention can encompass ternary or higher mixtures.

The refrigerant compositions may be altered by the skilled man to Suit the application requirements and flammability characteristics so desired.

In particular he may choose to add components such as CF3I, which are known to reduce or suppress flammability, to the refrigerant mixtures of the invention.

Examples

The data in Table I (see below provides illustration of the performance of exemplar blends, which are not limiting, for the replacement of R-134a. The thermodynamic properties used to calculate the performance have been derived as follows: Table 1: Compositions suitable for replacement of R-134a Calculations are based on these conditions Heat duty of cycle 10.00 Condenser mean temperature 45 Evaporator mean temperature S Subcool 0 Useful superheat 0 Suction temperature 25 Isentropic efficiency 65% Clearance ratio 4%

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CapacHy COP Suction Discharge Discharge relative to relative to pressure pressure temperature Evaporator Condenser Blend Components Weight GWP R134a R-134a bara tiara degC glide K glide K ________________________________ fractions R-134a 100% 1300 100% 100% 348 11.61 826 00 0 R-1225yefR-1234yf 79%/21% 7 80% 98% 2.92 960 731 1.5 1.7 R-1225ye/R-1234yf7R-32 75%/20%/5% 39 92% 99% 3.30 10.90 76.8 4.7 34 R-l225yefR-1234yt7C02 77%/20%13% 7 97% 96% 3.41 12.14 79.6 5.7 13 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 vaponsation and vapour equilibrium data for the mixtures of interest. The basic properties required by this equation (critical s 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 http://webbook.nist.gov. The critical properties of R-1234yf were determined by measurement using a static cell. The critical properties of R-1225ye were estimated using the boiling point for the isomeric mixture of -18 C and Joback's group contribution method. The acentric factor for R-1 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-32/R-125/R-134a were obtained from measurements published in M. Nagel, K. Bier, In!. J. Refrig. 18 (1995) 534-543. Binary data for R-1225ye with R-1234yf were taken from US Patent Application US2005/0233932A1. Binary data for R-32 with CO2 were taken from Rivollet et al. Fluid Phase Equilib 218 (2004), pp. 95- 101. Bmary data for R-32 with propane were taken from Fluid Phase Equilibria 199 (2002) 175-183. Binary data for R-1270 ropene) with R-I 34a and R-I 52a 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 interaction parameters for use with the equation of state.

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Example 2

The]ower and upper flammability limits quoted in Table 2 below are according to the ASTMIASHRAE test in a 12 litre flask at 100 C.

Table 2

Composition (parts Lower Upper GWP by weight) flammabi1y flammability _______________ limit (V/V%) Limit (V/V%) ____ R-1234yf 4.5 17.5 _____ R-32 14 II ____ R-32(1 0)/R-I 234yf (70)! R-l225yeZ(20) ___________ 1 ____ R-32( I 5)!R-1 234yf (65)! R-l225yeZ(20) ___________ _____________ ____ R-32 (20)/R-1234yf (60)! R-1225yeZ (20) ____________ L_4 fl R-32 (25)! R-1234yf(55)/ R-1225yeZJ20) ________________ 141 Note for the blends in Table 2 the flammability limits were estimated using the Le Chatelier rule.

The above compositions were assessed for refrigeration performance using a theoretical cycle typical of mobile air conditioning systems: Evaporator mean temperature + 5 C Condenser mean temperature + 55 C Subcoding 7K Superheat 5K Compressor suction temperature 15 C Compressor isentropric efficiency 70% The results are shown in Tables 3 and 4.

Table 3

R-32/R-1 234yf/R-1 225yeZ ternary compositions __________________________ R-134a 5/80/IS 10/75/IS 15/70/IS 20/65/15 5/75/20 10/70/20 15/65/20 20/60/20 25/55/20 5/70/25 (0/65/25 (5/60/25 20/55/25 25/50/25 Presure ratio 4.29 4.03 4.02 4.01 3.99 4.05 4.04 4.03 4.00 3.98 4.06 4.06 4.05 4.02 4.00 volumetric effic,cnc 88.2% 88.7% 88.9% 89.2% 89.5% 88.6% 88.8% 89.1% 89.4% 89.7% 88.5% 88.7% 89.0% 89.3% 89.6% Condenser glide K 0 2.63 4.21 5.17 5.71 2.78 4.42 5.42 5.97 6.19 2.93 4. 63 5.66 6.23 6.45 Evaporator glide K 0 1.70 2.92 3.85 4.53 1.82 3.08 4.06 4.78 5.23 (.92 3.24 4.26 5.00 -5.50 Evaporator inlet 5 4.2 3.6 3.1 2.7 4. 1 3.5 3.0 2.6 2.4 4.0 3.4 2.9 2.5 2.3 Temperature __________ __________ ___________ ___________ ___________ __________ ___________ ____________ ___________ ___________ ___________ -_________ Condenser outlet 48 46.7 45.9 45.4 45.1 46.6 45.8 45.3 45.0 44.9 46.5 45.7 45.2 44.9 44.8 t5mperature __________ __________ ____________ _____________ ____________ __________ ____________ _____________ ____________ ____________ __________ ____________ -_________ Condenserpressure bare 14.96 15.78 17.27 18.70 20.06 15.64 17.15 18.58 19.96 21.28 15.50 (7.02 (8.47 19.116 21.19 Evaporator pressure nra 3.48 3.92 4.29 4.66 5.03 3.87 4.24 4.61 4.98 5.35 3.81 4.19 4.57 4.94 5.30 Reirigeralioneffect kJ/kg 138.7 115.6 122.5 129. 0 135.2 115.4 (22.4 (29.0 135.2 141.2 115.3 (22.3 128.9 (35.1 141.1 COP 3. 02 2.93 2.93 2.93 2.93 2.93 2.94 2.94 2.93 2.93 2.93 2.94 2.94 2.94 2.93 Discharge (cmp C 81.7 79.1 82.5 85.8 88.8 78.6 82.1 85.3 88.4 91.3 78.2 81.7 84.9 87.9 90.9 Mass llowrate kg/hr 259.6 311.5 293.8 279.0 266.2 311.9 294.1 279.2 266.3 255.0 3(2.3 294.3 279.3 266.4 255.2 Volumetric flowrnle m3/hr 16.16 15.75 14.29 13.12 12.16 15.90 14.40 13.20 12.22 11. 42 16.06 14.52 I3.29 12.29 11.47 VolumtrIccapacity kJ/m' 2228 2286 2520 2745 2961 2264 2500 2727 2946 3153 2242 2480 2709 2929 _3139

Table 4 R-32/-1234yf/R-134aIR-1225yeZ quaternaries _______________________

R-134a 6/75/4/15 11/70/4/15 16/65/4/15 6/70/4/20 11/65/4/20 16/60/4/20 6/65/4/25 11/60/4/25 16/55/4/25 GWP _______ 93 120 147 93 120 147 92 119 146 Presure ratio 429 4 03 4 02 401 4 05 4 04 4 03 4 07 4 06 4 05 volumetric efficiency 882% 88 7% 889% 892% 88 6% 88 8% 89.1% 88 5% 88 7% 890% Condenser glide K 0 99 4.38 5.1 I 3.16 4.60 5.47 333 4 83 5 73 Evaporatorglude K 0 98 3 1 384 2 II 329 4 18 224 3.46 440 Evaporator unietlemperature "C 5 -0 3 -3 I 4.0 34 29 39 33 28 Conden5er outlet temperature "C 48 465 45 -454 46.4 45.7 453 lb 3 456 45 1 Condenserpressure bars 14.96 1622 17.69 1886 1607 1756 1898 1593 1743 IS 86 Evaporator pressure Bara 3.48 4.02 440 470 3.97 4.34 471 391 429 466 Refulgeratuoneffect kJ/Icg 1387 117.6 1244 1298 111.5 124.4 130.9 1174 1243 130.8 COP 3.02 2.93 2.93 293 2 93 2 94 2 94 2 94 2 94 2 94 Discharge temp "C 81 7 799 83 3 85 9 79 5 82.9 86 I 79.1 82 5 85.6 Mass flowrate kg/hr 2596 306.1 289 3 277 3 306.4 2894 275 I 306 6 289 5 275 I Volumetric flowrate i-1616 1530 1393 13.00 1545 14.04 12.91 15.59 1415 1300 Volumetnccapacity 2228 2353 2584 2769 2331 2564 2788 2309 2544 2770 Table 4 continued R-134a 3/75/7/15 6/72/7/15 8/70/7/15 3/70/7/20 6/67/7/20 8/65)7/20 3/65/7/25 6/62/7/25 8/60/7/25 GWP ________ 115 132 142 115 131 142 115 131 142 Presure ratio 429 4.03 403 4 03 405 405 4.05 4 07 4 07 4 07 volumetric efficiency 88.2% 88 6% 88 7% 88 8% 86 5% 88 6% 88.7% 88 4% 88 5% 88.6% Condenser glide K 0 1.81 297 3 59 I 94 3 15 -79 2 06 3 32 3 99 Evaporalorglkie K 0 120 I 99 246 130 212 62 I 39 225 2.77 Evaporatorunlettemperature "C 5 4.4 40 38 4.4 3.9 -7 43 3.9 3.6 Condenseroutlettemperature "C 48 41 I 465 462 470 46.4 461 47.0 46.3 460 Condenserpressure bars 1496 15.40 1631 1691 1524 1616 1676 1508 16.01 1662 Evaporator pressure bars 348 3.82 404 4 19 3 76 3 99 4 14 3.71 393 4.08 Relngeratuoneffect Id/kg 1387 113.8 1181 120.9 113.7 118.0 1208 1135 1180 1208 COP 3 02 2.92 2.93 2.93 2 93 2 93 2 94 2 93 2 94 2 94 Discharge temp "C 81.7 77.9 800 81 4 774 79.6 81 0 770 792 806 Mass flowuate kg/hr 259.6 316 5 304.8 297 8 316 8 305.0 2979 317 I 305.2 298 1 Volumetrkfiowrate 1616 16.18 1521 1464 1636 1536 1477 1654 1551 1490 Volumetriccapacuty 5 2228 2225 2367 2460 2201 2344 2438 2177 2321 2416

Claims

I

CLAIMS

1. A heat transfer composition comprising: (i) R-1225; (ii) R-1234;and (iii) at least one further refrigerant selected from carbon dioxide (R-744); fluoromethane (R-41); difluoromethane (R-3 2); fluorethane (R-161); 1,1 -difluoroethane (R-1 52a); 1,1,1 - trifluoroethane (R-1 43a); 1,1,1,2-tetrafluoroethane (R-1 34a); 1,1,2,2- tetrafluoroethaiie (R-134); dim ethyl ether; heptafluoropropane (R-227ea); propane (R-290); propene (R-1270); isobutane (R-600a); n-butane (R-600); 3,3,3-trifluoropropene (R-1 243zf); 1,3,3,3 - tetrafluoropropene (R-1234ze, cis-or trans-isomers), 1,1-difluorocyclopropane; 1,1,2-trifluorocyclopropane; 1,1,2,2-tetrafluorocyclopropane; pentafluorocyclopropane, or ammonia, or mixtures thereof
2. A composition according to Claim 1 wherein the R-1225 is R-1225ye.

3. A composition according to Claim 1 or 2 wherein the R-1234 is R-1234yf.

4. A composition according to any one of the preceding claims wherein the further refrigerant is selected from R-134a, dimethyl ether, R-161, R-32, R-152a, R-744, R-41, R-290, R-1270, ammonia, R-600a, R-600 or R-1243 zf.

S

5. A composition according to any one of the preceding claims wherein the further refrigerant is R-32.

6. A composition according to any one of the preceding claims wherein the composition comprises (parts by weight) 5 to 30 parts R-32, to 75 parts R-1234yf and 15 to 25 parts R-1225ye.

7. A composition according to any one of the preceding claims wherein the R-1225ye in the composition comprises at least 50% Z isomer.

8. A composition according to Claim 7 wherein the R-1225ye in the composition comprises at least 80% Z isomer.

9. A composition according to any one of the preceding claims wherein the further refrigerants are R-32 and R-1 34a.

10. A composition according to any one of the preceding c'aims wherein the composition has a Coefficient of Performance within 20% of that of the fluid it is intended to replace, for example R-134a.

11. A composition according to Claim 10 wherein the composition has a Coefficient of Performance within 10% of that of the fluid it is intended to replace, for example R-1 34a.

12. A composition according to any one of the preceding claims which is azeotrope-like.

13. A composition according to any one of the preceding claims which has a GWP of about 750 or less.

14. A composition according to any one of the preceding claims which has a GWP of about 500 or less.

15. A composition according to any one of the preceding claims which has a GWP of about 250 or less.

16. A composition according to any one of the preceding claims which has a OWP of about 150 or less.

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

18. A composition according to any one of the preceding claims is further comprising a lubricant.

19. A composition according to Claim 18 wherein the lubricant is selected from mineral oil, silicone oil, polyalkyl benzenes (PABs), polyoi esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (aipha-olefins) and combinations thereof.

20. A composition according to any one of the preceding claims further comprising a stabiliser.

21. A composition according to Claim 10 wherein the stabiliser is selected from diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.

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

23. A composition according to Claim 22 wherein the additional s flame retardant is selected from tri-(2-chloroethyl)-phosphate, (chioropropyl)phosphate, tri-(2,3 -dibromopropyl)-phosphate, tri-( 1,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated io bromocarbon, trifluoroiodomethane, perfluoroalkyl amines, bromo-fluoroallcyl amines and mixtures thereof.

24. A composition according to any one of the preceding claims wherein the composition is non-flammable.

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

26. A heat transfer device containing a composition as defined any one of Claims ito 23.

27. A heat transfer device according to Claim 26 which is a refrigeration device.

28. A heat transfer device according to Claim 27 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.

29. A heat transfer device according to Claim 27 or 28 which contains a compressor.

30. A blowing agent comprising a composition as defined in any one of Claims 1 to 24.

31. A foamable composition comprising one or more components capable of forming foam and a composition as defined in any one of Claims I to 24.

32. A foamable composition according to Claim 31 wherein the one or more components capable of forming foam are selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene, and epoxy resins, and mixtures thereof.

33. A foam obtainable from the foamable composition of Claim 31 or 32.

34. A foam according to Claim 33 comprising a composition as defined in any one of Claims 1 to 24.

35. A sprayable composition comprising a material to be sprayed and a propellant comprising a composition as defined in any one of Claims I to 24.

36. A method for cooling an article which comprises condensing a composition as defined in any one of Claims 1 to 24 and thereafter evaporating the composition in the vicinity of the article to be cooled.

37. A method for heating an article which comprises condensing a composition as defined in any one of Claims I to 24 in the vicinity of the article to be heated and thereafter evaporating the composition.

38. 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 24, and separating the substance from the solvent.

39. A method of cleaning an article comprising contacting the article with a solvent comprising a composition as defined in any one of Claims Ito 24.

40. 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 24, and separating the substance from the solvent.

41. A method for extracting a material from a particulate solid matrix comprising contacting the particulate solid matrix with a solvent compnsmg a composition as defined in any one of Claims 1 to 24, and separating the substance from the solvent.

42. A mechanical power generation device containing a composition as defined in any one of Claims 1 to 24.

43. A mechanical power generation device according to Claim 42 which is adapted to use a Rankine Cycle or modification thereof to generate work from heat.

I

44. A method of retrofitting a refrigeration device comprising the step of removing an existing heat transfer fluid, and introducing a composition as defined in any one of Claim 1 to 24.

s 45. A heat transfer composition substantially as hereinbefore described.