EP2569387A2

EP2569387A2 - Ternary heat-transfer fluids comprising difluoromethane, pentafluoroethane and tetrafluoropropene

Info

Publication number: EP2569387A2
Application number: EP11731420A
Authority: EP
Inventors: Wissam Rached
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2010-05-11
Filing date: 2011-04-18
Publication date: 2013-03-20
Also published as: WO2011141655A3; US9488398B2; JP2016186073A; JP5936605B2; US9057010B2; US20150184052A1; JP2013527283A; JP6449966B2; JP2018070885A; FR2959998B1; CN102884151B; US20130055738A1; CN102884151A; FR2959998A1; US20160252283A1; US9359540B2; WO2011141655A2

Abstract

The invention relates to a ternary composition comprising: - from 5 to 50% of difluoromethane; - from 2 to 20% of pentafluoroethane; and - from 30 to 90% of tetrafluoropropene. The tetrafluoropropene may be 1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene. This composition can be used as a heat-transfer fluid in a vapour compression circuit.

Description

TERNARY HEAT TRANSFER FLUIDS COMPRISING

DIFLUOROMETHANE, PENTAFLUOROETHANE AND

tetrafluoropropene

FIELD OF THE INVENTION

The present invention relates to transfer fluids based on difluoromethane, pentafluoroethane and tetrafluoropropene, which exhibit high performance and low GWP, and are therefore suitable for replacing conventional refrigerants.

TECHNICAL BACKGROUND

Fluorocarbon-based fluids are widely used in vapor compression heat transfer systems, including air conditioning, heat pump, refrigeration or freezing devices. These devices have in common to rely on a thermodynamic cycle comprising the vaporization of the fluid at low pressure (in which the fluid absorbs heat); compressing the vaporized fluid to a high pressure; condensing the vaporized fluid into a high pressure liquid (in which the fluid emits heat); and the expansion of the fluid to complete the cycle.

The choice of a heat transfer fluid (which may be a pure compound or a mixture of compounds) is dictated on the one hand by the thermodynamic properties of the fluid, and on the other hand by additional constraints. Thus, a particularly important criterion is that of the impact of the fluid considered on the environment. In particular, chlorinated compounds (chlorofluorocarbons and hydrochlorofluorocarbons) have the disadvantage of damaging the ozone layer. Thus, non-chlorinated compounds such as hydrofluorocarbons, fluoroethers and fluoroolefins are now generally preferred.

Currently used heat transfer fluids are HFC-134a, R404a (ternary mixture of 52% HFC-143a, 44% HFC- 125 and 4% HFC-134a) and R407c (ternary mixture of 52% HFC-134a, 25% HFC-125 and 23% HFC-32).

However, it is necessary to develop other heat transfer fluids having a global warming potential (GWP) lower than that of the above fluids, and having equivalent performance and preferably improved.

US 2009/0250650 discloses various fluoroolefin compositions and their use as heat transfer fluids. In particular, the document describes the mixture consisting of HFC-32, HFC-125 and HFO-1234ze as well as the mixture consisting of HFC-32, HFC-125 and HFO-1234yf. The compositions indicated as being preferred are the following:

23% HFC-32, 25% HFC-125 and 52% HFO-1234ze;

- 30% HFC-32, 50% HFC-125 and 20% HFO-1234ze;

40% HFC-32, 50% HFC-125 and 10% HFO-1234yf;

23% HFC-32, 25% HFC-125 and 52% HFO-1234yf;

- 15% HFC-32, 45% HFC-125 and 40% HFO-1234yf; and

- 10% HFC-32, 60% HFC-125 and 30% HFO-1234yf.

WO 2010/002014 discloses a non-flammable refrigerant based on HFC-32, HFC-125 and HFO-1234yf. Several compositions are disclosed, in particular that comprising 15% HFC-32, 25% HFC-125 and 60% HFO-1234yf.

However, there is still a need to develop other heat transfer fluids having a relatively low GWP, and having better energy performance than the heat transfer fluids of the state of the art.

SUMMARY OF THE INVENTION

The invention relates firstly to a ternary composition comprising:

from 5 to 50% of difluoromethane;

from 2 to 20% of pentafluoroethane; and

from 30 to 90% of tetrafluoropropene.

According to one embodiment, the tetrafluoropropene is 1, 3,3,3-tetrafluoropropene.

In another embodiment, the tetrafluoropropene is 2,3,3,3-tetrafluoropropene.

According to one embodiment, the composition comprises: from 15 to 35% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 45 to 80% of 2,3,3,3-tetrafluoropropene;

and, preferably:

from 18 to 25% of difluoromethane;

from 8 to 20% of pentafluoroethane; and

from 55 to 74% of 2,3,3,3-tetrafluoropropene;

According to one embodiment, the composition comprises:

from 15 to 50% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 30 to 80% of 1, 3,3,3-tetrafluoropropene;

and, preferably:

from 30 to 40% of difluoromethane;

from 8 to 20% of pentafluoroethane; and

from 40 to 62% of 1, 3,3,3-tetrafluoropropene.

According to one embodiment, the composition comprises:

from 5 to 30% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 50 to 90% of 1, 3,3,3-tetrafluoropropene;

and, preferably:

from 5 to 20% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 60 to 90% of 1, 3,3,3-tetrafluoropropene.

According to one embodiment, the composition comprises:

from 20 to 40% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 40 to 75% of 1, 3,3,3-tetrafluoropropene;

and, preferably:

25 to 40% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 40 to 70% of 1, 3,3,3-tetrafluoropropene.

The invention also relates to the use of the aforementioned ternary composition as a heat transfer fluid in a vapor compression circuit.

The invention also relates to a heat transfer composition comprising the aforementioned ternary composition as a heat transfer fluid, and one or more additives selected from lubricants, stabilizers, surfactants, tracer agents, agents and the like. fluorescents, odorants, solubilizers and mixtures thereof.

The invention also relates to a heat transfer installation comprising a vapor compression circuit containing the aforementioned ternary composition as a heat transfer fluid, or containing a heat transfer composition as mentioned above.

According to one embodiment, this installation is chosen from mobile or stationary installations for heat pump heating, air conditioning, refrigeration and freezing.

The invention also relates to a method for heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid, said method comprising successively the evaporation of the transfer fluid. heat, compressing the heat transfer fluid, condensing the heat fluid and expanding the heat transfer fluid, and the heat transfer fluid being the aforementioned ternary composition.

According to one embodiment of the heating or cooling method, this method is a method of cooling a fluid or a body, wherein the temperature of the cooled fluid or body is -40 ° C to -10 ° C, and preferably from -35 ° C to -25 ° C, more preferably from -30 ° C to -20 ° C, and wherein the heat transfer fluid comprises:

from 15 to 35% of difluoromethane, from 5 to 20% of pentafluoroethane and from 45 to 80% of 2,3,3,3-tetrafluoropropene, preferably from 18 to 25% of difluoromethane, from 8 to 20% of pentafluoroethane; and 55 to 74% 2,3,3,3-tetrafluoropropene; or

from 15 to 50% of difluoromethane, from 5 to 20% of pentafluoroethane and from 30 to 80% of 1, 3,3,3-tetrafluoropropene, preferably from 30 to 40% of difluoromethane, from 8 to 20% of pentafluoroethane; and from 40 to 62% 1,3,3,3-tetrafluoropropene. According to another embodiment of the heating or cooling process, this method is a method of cooling a fluid or a body, wherein the temperature of the fluid or cooled body is -15 ° C to 15 ° C, and preferably from -10 ° C to 10 ° C, more preferably from -5 ° C to 5 ° C, and wherein the heat transfer fluid comprises: from 15 to 35% of difluoromethane, from 5 to 20% of pentafluoroethane and from 45 to 80% of 2,3,3,3-tetrafluoropropene, preferably from 18 to 25% of difluoromethane, from 8 to 20% of pentafluoroethane; and 55 to 74% 2,3,3,3-tetrafluoropropene; or

from 5 to 30% of difluoromethane, from 5 to 20% of pentafluoroethane and from 50 to 90% of 1, 3,3,3-tetrafluoropropene, preferably from 5 to 20% of difluoromethane, from 5 to 20% of pentafluoroethane; and 60 to 90% 1,3,3,3-tetrafluoropropene; or

from 20 to 40% of difluoromethane, from 5 to 20% of pentafluoroethane and from 40 to 75% of 1, 3,3,3-tetrafluoropropene, preferably from 25 to 40% of difluoromethane, from 5 to 20% of pentafluoroethane; and from 40 to 70% 1,3,3,3-tetrafluoropropene. According to another embodiment of the heating or cooling process, this method is a method of heating a fluid or a body, wherein the temperature of the fluid or heated body is 30 ° C to 80 ° C and preferably from 35 ° C to 55 ° C, more preferably from 40 ° C to 50 ° C, and wherein the heat transfer fluid comprises:

from 20 to 40% of difluoromethane, from 5 to 20% of pentafluoroethane and from 40 to 75% of 1, 3,3,3-tetrafluoropropene, preferably from 25 to 40% of difluoromethane, from 5 to 20% of pentafluoroethane; and from 40 to 70% 1,3,3,3-tetrafluoropropene. The invention also relates to a method for reducing the environmental impact of a heat transfer installation comprising a vapor compression circuit containing an initial heat transfer fluid, said method comprising a step of replacing the heat transfer fluid. initial heat in the vapor compression circuit by a final transfer fluid, the final transfer fluid having a lower GWP to the initial heat transfer fluid, wherein the final heat transfer fluid is the aforementioned ternary composition.

According to one embodiment of this method of reducing the environmental impact, the initial heat transfer fluid is a ternary mixture of 52% of 1,1,1-trifluoroethane, 44% of pentafluoroethane and 4% of 1 , 1, 1, 2-tetrafluoroethane or a ternary mixture of 52% 1,1,1,2-tetrafluoroethane, 25% pentafluoroethane and 23% difluoromethane, and the final heat transfer fluid comprises:

from 15 to 50% of difluoromethane, from 5 to 20% of pentafluoroethane and from 30 to 80% of 1, 3,3,3-tetrafluoropropene, preferably from 30 to 40% of difluoromethane, from 8 to 20% of pentafluoroethane; and from 40 to 62% 1,3,3,3-tetrafluoropropene; or

from 20 to 40% of difluoromethane, from 5 to 20% of pentafluoroethane and from 40 to 75% of 1, 3,3,3-tetrafluoropropene, preferably from 25 to 40% of difluoromethane, from 5 to 20% of pentafluoroethane; and from 40 to 70% 1,3,3,3-tetrafluoropropene.

According to another embodiment of this method of reducing the environmental impact, the initial heat transfer fluid is 1,1,1,2-tetrafluoroethane, and the final heat transfer fluid comprises:

from 5 to 30% of difluoromethane, from 5 to 20% of pentafluoroethane and from 50 to 90% of 1, 3,3,3-tetrafluoropropene, preferably from 5 to 20% of difluoromethane, from 5 to 20% of pentafluoroethane; and from 60 to 90% 1,3,3,3-tetrafluoropropene.

The present invention overcomes the disadvantages of the state of the art. It provides more particularly heat transfer fluids having a relatively low GWP, and having better energy performance than known heat transfer fluids.

This is accomplished through ternary mixtures comprising HFC-32, HFC-125 and tetrafluoropropene in the proportions indicated above. According to some particular embodiments, the invention also has one or preferably more of the advantageous features listed below.

- The heat transfer fluids of the invention have a coefficient of performance higher than reference refrigerants

R404a, R407c and / or HFC-134, in the same type of applications.

- The capacity of the heat transfer fluids of the invention is greater than or equal to that of reference refrigerants, same type of applications. Correlatively, the invention makes it possible to reduce the GWP of existing systems comprising one of the reference refrigerants above, and this to a large extent improving the performance of these systems, by replacing reference refrigerants with transfer fluids. of heat of the invention.

- The heat transfer fluids of the invention have a higher coefficient of performance than the ternary mixtures of HFC-32, HFC-125 and HFO-1234ze or HFO-1 234yf which are described in documents US 2009/0250650 and WO 2010/002014.

Some heat transfer fluids according to the invention make it possible to obtain a temperature at the outlet of the compressor that is lower than that obtained with the heat transfer fluids of the state of the art.

According to the invention, the global warming potential (GWP) is defined with respect to carbon dioxide and with respect to a duration of 100 years, according to the method indicated in "The scientific assessment of ozone depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention is now described in more detail and without limitation in the description which follows.

By "heat transfer compound" or "heat transfer fluid" (or refrigerant), is meant a compound, respectively a fluid, capable of absorbing heat by evaporating at low temperature and low pressure and to reject heat by condensing at high temperature and high pressure, in a vapor compression circuit. In general, a transfer fluid of Heat may comprise a single, two, three or more than three heat transfer compounds.

By "heat transfer composition" is meant a composition comprising a heat transfer fluid and optionally one or more additives which are not heat transfer compounds for the intended application.

The heat transfer method according to the invention is based on the use of an installation comprising a vapor compression circuit which contains a heat transfer fluid. The heat transfer process may be a method of heating or cooling a fluid or a body.

The vapor compression circuit containing a heat transfer fluid comprises at least one evaporator, a compressor, a condenser and an expander, as well as heat transfer fluid transport lines between these elements. The evaporator and the condenser comprise a heat exchanger allowing a heat exchange between the heat transfer fluid and another fluid or body.

As a compressor, it is possible to use in particular a centrifugal compressor with one or more stages or a mini centrifugal compressor. Rotary, piston or screw compressors can also be used. The compressor may be driven by an electric motor or by a gas turbine (eg powered by vehicle exhaust, for mobile applications) or by gearing.

The facility may include a turbine to generate electricity (Rankine cycle).

The installation may also optionally include at least one coolant circuit used to transmit the heat (with or without change of state) between the heat transfer fluid circuit and the fluid or body to be heated or cooled.

The installation may also optionally include two or more vapor compression circuits containing identical or different heat transfer fluids. For example, the vapor compression circuits may be coupled together.

The vapor compression circuit operates in a conventional vapor compression cycle. The cycle comprises changing the state of the heat transfer fluid from a liquid phase (or two-phase liquid / vapor) to a vapor phase at a relatively low pressure, and then compressing the fluid in the vapor phase to a pressure relatively high, the change of state (condensation) of the heat transfer fluid from the vapor phase to the liquid phase at a relatively high pressure, and the reduction of pressure to restart the cycle.

In the case of a cooling process, heat from the fluid or the body that is cooled (directly or indirectly, via a coolant) is absorbed by the heat transfer fluid, during the evaporation of the latter, and this at a relatively low temperature compared to the environment. Cooling processes include air conditioning processes (with mobile installations, for example in vehicles, or stationary), refrigeration and freezing or cryogenics.

In the case of a heating process, heat is transferred (directly or indirectly via a heat transfer fluid) from the heat transfer fluid, during the condensation thereof, to the fluid or to the body that is heating, and this at a relatively high temperature compared to the environment. The installation for implementing the heat transfer is called in this case "heat pump".

It is possible to use any type of heat exchanger for the implementation of heat transfer fluids according to the invention, including co-current heat exchangers.

However, according to a preferred embodiment, the invention provides that the cooling and heating processes, and the corresponding facilities, comprise a countercurrent heat exchanger, either the condenser or the evaporator. Indeed, the heat transfer fluids according to the invention are particularly effective with countercurrent heat exchangers. Preferably, both the evaporator and the condenser comprise a countercurrent heat exchanger.

According to the invention, the term "countercurrent heat exchanger" is understood to mean a heat exchanger in which heat is exchanged between a first fluid and a second fluid, the first fluid at the inlet of the exchanger exchanging heat with the second fluid at the outlet of the exchanger, and the first fluid at the outlet of the exchanger exchanging heat with the second fluid at the inlet of the exchanger.

For example, countercurrent heat exchangers include devices in which the flow of the first fluid and the flow of the second fluid are in opposite or almost opposite directions. The exchangers operating in cross current mode tend to countercurrent are also included among the countercurrent heat exchangers within the meaning of the present application.

The meaning of the various abbreviations used to designate the different chemical compounds mentioned in the application is as follows:

HFC-134a: 1, 1, 1, 2-tetrafluoroethane;

HFC-125: pentafluoroethane;

- HFC-32: difluoromethane;

HFO-1234ze: 1, 3,3,3-tetrafluoropropene;

HFO-1234yf: 2,3,3,3-tetrafluoropropene.

The heat transfer fluids used in the invention are the following ternary mixtures:

1) HFC-32, HFC-125 and HFO-1234ze; and

2) HFC-32, HFC-125 and HFO-1234yf.

By "ternary mixture" is meant a composition consisting essentially of the three compounds mentioned, that is to say in which the three compounds mentioned represent at least 99% (preferably at least 99.5% or even at least 99.9%). %) of the composition.

Unless otherwise stated, in the whole of the application the proportions of compounds indicated are given in percentages by mass.

HFO-1234ze can be in cis or trans form (preferably trans) or be a mixture of both forms.

In the above compositions, HFC-32 is present in an amount of 5 to 50%, HFC-125 is present in an amount of 2 to 20% and HFO-1234yf or HFO-1234ze is present in an amount of 30%. at 90%.

For use in low temperature refrigeration processes, i.e. those in which the temperature of the cooled fluid or body is -40 ° C to -10 ° C, and preferably -35 ° C at -25 ° C, more preferably from -30 ° C to -20 ° C (ideally about -25 ° C), it has been found that the most effective compositions replacing R404a are as follows:

for the composition 1): from 15 to 50% of HFC-32, from 5 to 20% of HFC-125 and from 30 to 80% of HFO-1234ze, and preferably from 30 to 40% of HFC-32, from 8 to 20% HFC-125 and from 40 to 62% HFO-1234ze;

for the composition 2): from 15 to 35% of HFC-32, from 5 to 20% of HFC-125 and from 45 to 80% of HFO-1234yf, and preferably from 18 to 25% HFC-32, 8 to 20% HFC-125 and 55 to 74% HFO-1234yf.

For use in:

processes for cooling at a moderate temperature, that is to say those in which the temperature of the fluid or of the cooled body is from -15 ° C. to 15 ° C., preferably from -10 ° C. to 10 ° C., more preferably from -5 ° C to 5 ° C (ideally about 0 ° C), as well as

processes for heating at a moderate temperature, that is to say those in which the temperature of the fluid or of the heated body is from 30 ° C. to 80 ° C., and preferably from 35 ° C. to 55 ° C., more particularly preferably from 40 ° C to 50 ° C (ideally about 45 ° C),

it has been found that the most effective compositions replacing HFC-134a are the following:

for the composition 1): from 5 to 30% of HFC-32, from 5 to 20% of HFC-125 and from 50 to 90% of HFO-1234ze, and preferably from 5 to 20% of HFC-32, 5 to 20% HFC-125 and 60 to 90% HFO-1234ze.

For use in:

it has been found that the most effective compositions replacing R404a or R407c are as follows:

for the composition 1): from 20 to 40% of HFC-32, from 5 to 20% of HFC-125 and from 40 to 75% of HFO-1234ze, and preferably from 25 to 40% of HFC-32, 5 to 20% of HFC-125 and 40 to 70% of

HFO-1234ze;

In the "low temperature refrigeration" processes mentioned above, the inlet temperature of the heat transfer fluid to the evaporator is preferably from -45 ° C. to -15 ° C., especially from -40 ° C. at -20 ° C, more preferably -35 ° C to -25 ° C and for example about -30 ° C; and the temperature of the onset of condensation of the heat transfer fluid at the condenser is preferably 25 ° C to 80 ° C, especially 30 ° C to 60 ° C, more preferably 35 ° C to 55 ° C C and for example about 40 ° C.

In the "moderate temperature cooling" processes mentioned above, the inlet temperature of the heat transfer fluid to the evaporator is preferably from -20 ° C to 10 ° C, especially from -15 ° C to 5 ° C, more preferably from -10 ° C to 0 ° C and for example about -5 ° C; and the temperature of the onset of condensation of the heat transfer fluid at the condenser is preferably 25 ° C to 80 ° C, especially 30 ° C to 60 ° C, more preferably 35 ° C to 55 ° C C and for example about 50 ° C. These processes can be refrigeration or air conditioning processes.

In the "moderate temperature heating" processes mentioned above, the inlet temperature of the heat transfer fluid to the evaporator is preferably from -20 ° C to 10 ° C, especially from -15 ° C to 5 ° C, more preferably from -10 ° C to 0 ° C and for example about -5 ° C; and the temperature of the onset of condensation of the heat transfer fluid at the condenser is preferably 25 ° C to 80 ° C, especially 30 ° C to 60 ° C, more preferably 35 ° C to 55 ° C C and for example about 50 ° C.

The heat transfer fluids mentioned above are not quasi-azeotropic and are very effective when properly coupled to a countercurrent heat exchanger (with a temperature difference with the second approximately constant fluid in the water). exchanger).

Each above heat transfer fluid may be mixed with one or more additives to provide the heat transfer composition effectively flowing in the vapor compression circuit. The additives may especially be chosen from lubricants, stabilizers, surfactants, tracer agents, fluorescent agents, odorants, solubilizing agents and mixtures thereof. The stabilizer (s), when present, preferably represent at most 5% by weight in the heat transfer composition. Among the stabilizers, there may be mentioned in particular nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenol compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphonates, thiols and lactones.

Lubricants that may be used include oils of mineral origin, silicone oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkene glycols, polyol esters and / or polyvinyl ethers. .

As tracer agents (which can be detected) mention may be made of hydrofluorocarbons, deuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes and ketones. nitrous oxide and combinations thereof. The tracer agent is different from the one or more heat transfer compounds composing the heat transfer fluid.

As solubilizing agents, mention may be made of hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and magnesium compounds. 1-trifluoroalkanes. The solubilizing agent is different from the one or more heat transfer compounds composing the heat transfer fluid.

As fluorescent agents, mention may be made of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanhthenes, fluoresceins and derivatives and combinations thereof.

As odorants, mention may be made of alkyl acrylates, allyl acrylates, acrylic acids, acrylresters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allyl isothiocyanates and alkanoic acids. amines, norbornenes, norbornene derivatives, cyclohexene, heterocyclic aroma compounds, ascaridol, o-methoxy (methyl) phenol and combinations thereof. The compositions according to the invention may also be useful as an expansion agent, aerosol or solvent.

EXAMPLES

The following examples illustrate the invention without limiting it.

Example 1 - Method for calculating the properties of heat transfer fluids in the various configurations envisaged

The RK-Soave equation is used to calculate densities, enthalpies, entropies and vapor-liquid equilibrium data of mixtures.

The use of this equation requires knowledge of the properties of the pure bodies used in the mixtures in question and also the interaction coefficients for each binary.

The necessary data for each pure body are the boiling temperature, the critical temperature and the critical pressure, the pressure versus temperature curve from the boiling point to the critical point, the densities of saturated liquid and saturated steam as a function of temperature.

The HFC data are published in the ASHRAE Handbook 2005 Chapter 20 and are also available under Refrop (Software developed by NIST for calculating the properties of refrigerants).

The temperature-pressure curve data of the HFOs are measured by the static method. The critical temperature and the critical pressure are measured by a C80 calorimeter marketed by Setaram. The saturation densities as a function of temperature are measured by the vibrating tube densimeter technology developed by the laboratories of the Ecole des Mines de Paris.

The RK-Soave equation uses binary interaction coefficients to represent the behavior of products in mixtures. The coefficients are calculated based on the experimental vapor equilibrium data.

The technique used for liquid vapor equilibrium measurements is the analytical static cell method. The balance cell includes a sapphire tube and is equipped with two electromagnetic ROLSITM samplers. It is immersed in a cryothermostat bath (HUBER HS40). Variable speed rotary field driving magnetic stirring is used to accelerate equilibrium attainment.

The analysis of the samples is carried out by chromatography (HP5890 seriesll) in the gas phase using a katharometer (TCD). The liquid vapor equilibrium measurements on the HFC-32 / HFO-1234ze binary are carried out for the following isotherm: 15 ° C.

The liquid vapor equilibrium measurements on the HFC-32 / HFO-1234yf binary are carried out for the following isotherms: 70 ° C., 30 ° C., -10 ° C.

The vapor liquid equilibrium data for the HFC-32 / HFC-binary

125 are available under Refprop. Three isotherms (-30 ° C, 0 ° C and 30 ° C) are used to calculate the interaction coefficients for this binary.

The liquid vapor equilibrium measurements on the HFC-125 / HFO-1234yf binary are carried out for the following isotherms: -15 ° C., 0 ° C.

The liquid vapor equilibrium measurements on the HFC-125 / HFO-binary

1234ze are produced for the following isotherms: 25 ° C, 0 ° C.

We consider a compression system equipped with an evaporator and countercurrent condenser, a screw compressor and a pressure reducer.

The system operates with 15 ° C overheating and 5 ° C subcooling. The minimum temperature difference between the secondary fluid and the refrigerant is considered to be of the order of 5 ° C.

The isentropic efficiency of the compressors is a function of the compression ratio. This yield is calculated according to the following equation:

For a screw compressor, the constants a, b, c, d and e of equation (1) of the isentropic efficiency are calculated according to the standard data published in the "Handbook of air conditioning and refrigeration", page 1 1 .52 .

The coefficient of performance (COP) is defined as the useful power provided by the system on the power supplied or consumed by the system.

The Lorenz coefficient of performance (COPLorenz) is a benchmark coefficient of performance. It is temperature dependent and is used to compare the COPs of different fluids.

The coefficient of performance of Lorenz is defined as follows (the temperatures T are in K):

rj condenser J- condenser J- condenser

(2) average inlet outlet evaporator evaporator evaporator

average exit entrance The Lorenz COP in the case of air conditioning and refrigeration is:

(4) COPlorenz-

The Lorenz COP in the case of heating is:

For each composition, the performance coefficient of the Lorenz cycle is calculated according to the corresponding temperatures.

In low temperature refrigeration mode, the compression system operates between a refrigerant inlet temperature at the evaporator of -30 ° C and a condenser refrigerant inlet temperature of 40 ° C. The system supplied cold at -25 ° C.

In moderate heat mode, the compression system operates between a refrigerant inlet temperature at the evaporator of -5 ° C and a condensing temperature of the condenser refrigerant at 50 ° C. The system provides heat at 45 ° C.

In moderate cooling mode, the compression system operates between an evaporator refrigerant inlet temperature of -5 ° C and a start temperature of condenser refrigerant condensation at 50 ° C. The system supplied cold at 0 ° C.

In the following tables, "evap outlet temperature" designates the fluid temperature at the outlet of the evaporator, "comp outlet temperature" designates the temperature of the fluid at the outlet of the compressor, "T output cond" designates the fluid temperature at the outlet of the condenser, "evap P" designates the pressure of the fluid in the evaporator, "cond P" refers to the pressure of the fluid in the condenser, "Rate (w / w)" refers to the compression ratio, "Glide" refers to temperature slip, "comp efficiency" refers to the compressor efficiency, "% CAP" refers to the volumetric capacity of the fluid relative to the reference fluid indicated in the first line and "% COP / COPLorenz" refers to the ratio of the system COP relative to the COP of the corresponding Lorenz cycle. Example 2 - Results for low temperature refrigeration, comparison with R404a

Mixture HFC-32 / HFC-125 / HFO-1234ze

In the preceding table, as in the following tables, the shaded lines correspond to the compositions disclosed in the documents US 2009/0250650 or WO 2010/002014 and the following lines correspond to the compositions according to the invention.

Mixture HFC-32 / HFC-125 / HFO-1234yf

Example 3 - Results for Cooling at Moderate Temperature, Comparison with HFC-134a Mixture HFC-32 / HFC-125 / HFO-1234ze

Example 4 - Results for heating at moderate temperature, comparison with HFC-134a

Example 5 - Results for cooling at moderate temperature, comparison with R404a and R407c

Example 6 - Results for cooling at moderate temperature, comparison with R404a

Example 7 - Results for heating at moderate temperature, comparison with R404a

Claims

Ternary composition comprising:

from 5 to 50% of difluoromethane;

from 2 to 20% of pentafluoroethane; and

from 30 to 90% of tetrafluoropropene.

The composition of claim 1 wherein the tetrafluoropropene is 1, 3,3,3-tetrafluoropropene.

The composition of claim 1 wherein the tetrafluoropropene is 2,3,3,3-tetrafluoropropene.

The composition of claim 1 comprising:

from 15 to 35% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 45 to 80% of 2,3,3,3-tetrafluoropropene;

and, preferably:

from 18 to 25% of difluoromethane;

from 8 to 20% of pentafluoroethane; and

from 55 to 74% of 2,3,3,3-tetrafluoropropene;

The composition of claim 1 comprising:

from 15 to 50% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 30 to 80% of 1, 3,3,3-tetrafluoropropene;

and, preferably:

from 30 to 40% of difluoromethane;

from 8 to 20% of pentafluoroethane; and

from 40 to 62% of 1, 3,3,3-tetrafluoropropene.

The composition of claim 1 comprising:

from 5 to 30% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 50 to 90% of 1, 3,3,3-tetrafluoropropene;

and, preferably:

from 5 to 20% of difluoromethane; from 5 to 20% of pentafluoroethane; and

from 60 to 90% of 1, 3,3,3-tetrafluoropropene.

The composition of claim 1 comprising:

from 20 to 40% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 40 to 75% of 1, 3,3,3-tetrafluoropropene;

and, preferably:

25 to 40% of difluoromethane;

from 5 to 20% of pentafluoroethane; and

from 40 to 70% of 1, 3,3,3-tetrafluoropropene.

Use of a composition according to one of claims 1 to 7 as a heat transfer fluid in a vapor compression circuit.

A heat transfer composition comprising the composition according to one of claims 1 to 7 as a heat transfer fluid, and one or more additives selected from lubricants, stabilizers, surfactants, tracer agents, fluorescent agents, odorants, solubilizers and mixtures thereof.

A heat transfer apparatus comprising a vapor compression circuit containing a composition according to one of claims 1 to 7 as a heat transfer fluid or containing a heat transfer composition according to claim 9.

Installation according to claim 10, selected from mobile or stationary heat pump heating, air conditioning, refrigeration and freezing.

A method of heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid, said method comprising successively evaporation of the heat transfer fluid, compression of the heat transfer fluid, the condensing the heat fluid and expanding the heat transfer fluid, wherein the heat transfer fluid is a composition according to one of claims 1 to 7.

A process according to claim 12, which is a method of cooling a fluid or a body, wherein the temperature of the cooled fluid or body is -40 ° C to -10 ° C, and preferably -35 ° C At -25 ° C, more preferably -30 ° C to -20 ° C, and wherein the heat transfer fluid comprises:

from 15 to 50% of difluoromethane, from 5 to 20% of pentafluoroethane and from 30 to 80% of 1, 3,3,3-tetrafluoropropene, preferably from 30 to 40% of difluoromethane, from 8 to 20% of pentafluoroethane; and from 40 to 62% 1,3,3,3-tetrafluoropropene.

A process according to claim 12, which is a method of cooling a fluid or a body, wherein the temperature of the cooled fluid or body is -15 ° C to 15 ° C, and preferably -10 ° C At 10 ° C, more preferably from -5 ° C to 5 ° C, and wherein the heat transfer fluid comprises:

from 5 to 30% of difluoromethane, from 5 to 20% of pentafluoroethane and from 50 to 90% of 1, 3,3,3-tetrafluoropropene, preferably from 5 to 20% of difluoromethane, from 5 to 20% of pentafluoroethane; and 60 to 90% 1,3,3,3-tetrafluoropropene; or from 20 to 40% of difluoromethane, from 5 to 20% of pentafluoroethane and from 40 to 75% of 1, 3,3,3-tetrafluoropropene, preferably from 25 to 40% of difluoromethane, from 5 to 20% of pentafluoroethane; and from 40 to 70% 1,3,3,3-tetrafluoropropene.

A process according to claim 12, which is a method of heating a fluid or a body, wherein the temperature of the fluid or heated body is from 30 ° C to 80 ° C, and preferably from 35 ° C to 55 ° C, more preferably from 40 ° C to 50 ° C, and wherein the heat transfer fluid comprises:

A method of reducing the environmental impact of a heat transfer facility comprising a vapor compression circuit containing an initial heat transfer fluid, said method comprising a step of replacing the initial heat transfer fluid in the heat transfer circuit. vapor compression by a final transfer fluid, the final transfer fluid having a GWP lower than the initial heat transfer fluid, wherein the final heat transfer fluid is a composition according to one of claims 1 to 7. The process according to claim 16, wherein the initial heat transfer fluid is a ternary mixture of 52% 1,1,1-trifluoroethane, 44% pentafluoroethane and 4% 1,1,1,2-tetrafluoroethane. or a ternary mixture of 52% 1,1,1,2-tetrafluoroethane, 25% pentafluoroethane and 23% difluoromethane, and wherein the final heat transfer fluid comprises:

The method of claim 16, wherein the initial heat transfer fluid is 1,1,1,2-tetrafluoroethane, and wherein the final heat transfer fluid comprises: