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    • 专利摘要:
    The invention relates to a method of heat transfer by means of a heat transfer device containing a heat transfer composition, the heat transfer composition comprising: - a refrigerant, which comprises 2,3,3, 3-tetrafluoropropene, and - a lubricant; wherein the lubricant comprises a polyol ester, the solubility of 2,3,3,3-tetrafluoropropene in the lubricant at 0 ° C and at an absolute pressure of 2.2 bar being lower than the solubility of 1,1,1 2-tetrafluoroethane in the lubricant at 0 ° C and at an absolute pressure of 2.0 bar; the method comprising the successive steps of: - evaporation of a refrigerant; overheating of the refrigerant; - Compressing the refrigerant.
    公开号:FR3077822A1
    申请号:FR1851280
    申请日:2018-02-15
    公开日:2019-08-16
    发明作者:Wissam Rached
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    REPLACEMENT HEAT TRANSFER COMPOSITIONS FOR R-134A
    FIELD OF THE INVENTION
    The present invention relates to the use of heat transfer compositions comprising 2,3,3,3-tetrafluoropropene as well as a polyol ester lubricant, in particular in the context of the replacement of heat transfer compositions based on 1, 1,1,2-tetrafluoroethane.
    TECHNICAL BACKGROUND
    The problems posed by substances that deplete the atmospheric ozone layer were dealt with in Montreal where the protocol imposing a reduction in the production and use of chlorofluorocarbons (CFCs) was signed. This protocol has been the subject of amendments which have forced the abandonment of CFCs and extended the regulation to other products, including hydrochlorofluorocarbons (HCFCs).
    The refrigeration and air conditioning industry has invested a lot in the substitution of CFC and HCFC refrigerants, and this is how hydrofluorocarbons (HFCs), little or not harmful to the ozone layer, have been marketed.
    In particular, 1,1,1,2-tetrafluoroethane (HFC-134a) is an example of HFC which has known a very wide use, for example in automobile air conditioning.
    However, a large number of HFC fluids, including HFC-134a, can contribute adversely to the greenhouse effect. This contribution is quantified by a numerical parameter, the GWP (Global Warming Potential).
    Hydrofluoroolefins (HFO) such as 2,3,3,3-tetrafluoropropene (HFO1234yf) or 1,3,3,3-tetrafluoropropene (HFO-1234ze) are low GWP fluids that are likely to be used in heat transfer applications.
    In most applications, heat transfer fluids are used in vapor compression circuits. The fluid thus undergoes evaporation, followed by compression, condensation and expansion to complete the cycle.
    The use of a lubricant (or lubricating oil) is generally necessary to ensure the proper functioning of the moving mechanical parts in the circuit, and in particular to ensure the lubrication of the bearings of the compressor.
    Polyol esters (POE) have in particular been proposed as possible lubricants for HFOs.
    WO 2009/124128 describes a method of selecting a heat transfer fluid and a lubricant for a vapor compression system.
    WO 2010/083100 describes heat transfer compositions comprising carbon dioxide and a POE-based lubricant.
    The article Analysis of LGWP Alternatives for Small Refrigeration (Plugin) Applications, by Yana Motta et al., In International Refrigeration and Air Conditioning Conference at Purdue (2010) compares the effectiveness of HFO-1234yf and HFO-1234ze in systems small refrigeration.
    Document US 2012/024007 describes a compressor for refrigeration or air conditioning loaded with a heat transfer fluid which can be, inter alia, HFO-1234yf, and a lubricant comprising POE.
    The document WO 2012/001255 describes compositions comprising a POE-based lubricant and a heat transfer fluid containing at least 99.8% by weight of HFO-1234yf.
    Document US 8,685,271 describes a group of POEs and their use with various possible heat transfer fluids.
    The article Lubricant Development To Meet Lower GWP Refrigerant Challenges, by JA Karnaz, in 15 th International Refrigeration and Air Conditioning Conference at Purdue (2014) focuses on the evaluation of lubricants for next-generation heat transfer fluids , including HFO-1234ze.
    The article Convection-driven Absorption of R-1234yf in Lubricating OU, from Neto et al. in International Journal of Refrigeration 44: 151-160 (2014) describes the determination of the absorption rate of HFO-1234yf through the surface of a layer of POE ISO VG 10 lubricant in a closed system.
    Document EP 2947136 describes a lubricating oil comprising a base oil, a sulfur compound and a gallate. The base oil can in particular be POE. This lubricating oil can be used, among other things, with HFO-1234yf.
    The article Evaluating Lubricants for Lower GWP Refrigerant Compressor Operation, by JA Karnaz, in 16 th International Refrigeration and Air Conditioning Conference at Purdue (2015) focuses on the evaluation of lubricants for a set of heat transfer fluids, including in particular mixtures containing HFOs.
    Document US 2016/053153 describes heat transfer compositions comprising a tetrafluoropropene and a lubricant based on POE.
    WO 2016/209560 describes heat transfer compositions comprising a fluorinated olefin and a POE-based lubricant having a kinematic viscosity at 40 ° C from 150 to 360 cSt.
    There is still a need to provide efficient heat transfer methods, in particular in the context of an effective substitution of heat transfer compositions based on HFC-134a by low GWP heat transfer compositions.
    SUMMARY OF THE INVENTION
    The invention relates first of all to a method of heat transfer by means of a heat transfer installation containing a heat transfer composition, the heat transfer composition comprising:
    - a refrigerant, which comprises 2,3,3,3-tetrafluoropropene, and
    - a lubricant;
    wherein the lubricant comprises a polyol ester, the solubility of 2,3,3,3tetrafluoropropene in the lubricant at 0 ° C and at an absolute pressure of 2.2 bar being less than the solubility of 1,1,1,2 -tetrafluoroethane in the lubricant at 0 ° C and at an absolute pressure of 2.0 bar;
    the process comprising the successive stages:
    - evaporation of a refrigerant;
    - overheating of the refrigerant;
    - compression of the refrigerant.
    In certain embodiments, the overheating of the refrigerant is from 1 to 20 ° C, preferably from 2 to 10 ° C, more preferably from 3 to 5 ° C.
    In some embodiments, the lubricant includes a dipentaerythritol ester.
    In certain embodiments, the lubricant has a kinematic viscosity at 40 ° C of 10 to 200 cSt, preferably of 20 to 100 cSt, and more preferably of 30 to 80 cSt.
    In some embodiments, the method is a method of mobile or stationary air conditioning and / or heating, refrigeration, freezing or deep freezing.
    In certain embodiments, the refrigerant is evaporated at an average temperature less than or equal to 10 ° C, preferably less than or equal to 0 ° C, more preferably less than or equal to -10 ° C.
    In certain embodiments, the compression of the refrigerant is carried out in a screw compressor.
    In certain embodiments, the heat transfer installation is an installation intended to operate with an initial heat transfer composition comprising:
    - an initial refrigerant, and
    - An initial lubricant, the initial heat transfer composition being different from the heat transfer composition used in the process.
    In certain embodiments, said heat transfer composition is a replacement heat transfer composition, which is used to replace an initial heat transfer composition comprising:
    - an initial refrigerant, and
    - an initial lubricant.
    In some embodiments, the superheat with the replacement heat transfer composition is less than or equal to the superheat when the same process is carried out with the initial heat transfer composition; and preferably the overheating with the replacement heat transfer composition is at least 2 ° C, preferably at least 5 ° C, more preferably at least 10 ° C, relative to the overheating when the same process is carried out with the initial heat transfer composition.
    In some embodiments, the lubricant of the replacement heat transfer composition is identical to the original lubricant.
    In some embodiments, the lubricant of the replacement heat transfer composition is different from the original lubricant.
    In some embodiments, the lubricant of the replacement heat transfer composition has a kinematic viscosity at 40 ° C less than or equal to the kinematic viscosity at 40 ° C of the initial lubricant, the difference between the kinematic viscosity at 40 ° C of the initial lubricant and the kinematic viscosity at 40 ° C. of the lubricant of the replacement heat transfer composition being preferably greater than or equal to 5 cSt, more preferably still greater than or equal to 10 cSt.
    In some embodiments, the initial lubricant comprises a polyol ester, and preferably comprises a dipentaerythritol ester.
    In some embodiments, the initial refrigerant comprises 1,1,1,2-tetrafluoroethane or consists essentially of 1,1,1,2tetrafluoroethane.
    The present invention makes it possible to meet the need expressed above. It more particularly provides efficient heat transfer methods, in particular in the context of an effective substitution of heat transfer compositions based on HFC-134a by low GWP heat transfer compositions.
    The invention is based on the observation that HFO-1234yf is relatively poorly soluble in certain POE oils (and in particular in POE oils of the same type as POE ISO 55 oil), that is to say less soluble than HFO-1234ze and that the reference fluid HFC-134a.
    The use of such oils in combination with HFO-1234yf makes it possible to replace heat transfer compositions comprising HFC-134a in a particularly effective manner, in heat transfer processes involving overheating after evaporation.
    For example, in the context of replacing a composition containing HFC-134a with a composition containing HFO-1234yf, it is possible to obtain the following benefits:
    - a reduction in evaporative overheating during replacement; or
    - a reduction in the viscosity of the lubricant during replacement;
    It is of course possible to combine these two aspects.
    In a heat transfer installation, the lubricant is mainly present in the compressor, for the lubrication of the moving parts. A fraction of the lubricant can however be entrained out of the compressor and thus circulate in the entire circuit containing the refrigerant.
    A first benefit of the invention relates to the reduction of overheating when changing the heat transfer composition.
    The overheating of the refrigerant after evaporation allows:
    - limit the presence of refrigerant in liquid form in the compressor (liquid compression being a major cause of compressor failure);
    - to decrease the solubility of the refrigerant in the oil in the compressor and thus to avoid foaming and therefore again the compression of liquid especially at start-up;
    - limit the loss of viscosity of the oil when it is in contact with the refrigerant, this loss of viscosity being harmful for the lubrication of bearings and moving parts in the compressor; and
    - to facilitate the separation of the refrigerant and the lubricant at the outlet of the compressor.
    On the other hand, the presence of overheating has the effect of reducing system performance.
    By choosing a POE type lubricant in which the HFO-1234yf is sparingly soluble (compared to the reference fluid HFC-134a), the viscosity of the lubricant is relatively little affected in the presence of HFO-1234yf in the compressor. This reduces overheating, and thus increases performance, without having negative consequences on the prevention of foaming, on lubrication or on the separation of the lubricant and the refrigerant.
    Reducing overheating is particularly beneficial when the process is implemented for air conditioning.
    A second benefit of the invention relates to the use of an oil of lower viscosity, in order to reduce the frictional forces on the bearings of the compressor compared to a reference oil, especially in areas where the oil is not not mixed with refrigerants. However, the power consumed per lubrication level is proportional to the viscosity of the lubricant.
    The reduction in the viscosity of the oil also makes it possible to improve lubrication at the start of the installation (which can make it possible to limit the energy consumption linked to heating the compressor during this start-up); and limit the pressure drops in the circuit and therefore reduce the energy consumption linked to pumping.
    Thus, an object of the invention is the use, as a replacement heat transfer composition, of a composition comprising:
    - a replacement refrigerant comprising 2,3,3,3tetrafluoropropene, and
    - a replacement lubricant comprising a polyol ester;
    in place of an initial heat transfer composition comprising:
    - an initial refrigerant comprising 1,1,1,2-tetrafluoroethane, and
    - an initial lubricant;
    in a heat transfer process comprising the successive stages of evaporation of a refrigerant;
    - overheating of the refrigerant;
    - compression of the refrigerant;
    wherein the superheat when the process is carried out with the replacement heat transfer composition is less than the superheat when the process is carried out with the initial heat transfer composition.
    Another object of the invention is the use, as a replacement heat transfer composition, of a composition comprising:
    - a replacement refrigerant comprising 2,3,3,3tetrafluoropropene and
    - a replacement lubricant comprising a polyol ester;
    in place of an initial heat transfer composition comprising:
    - an initial refrigerant comprising 1,1,1,2-tetrafluoroethane and
    - an initial lubricant;
    in a heat transfer process;
    the replacement lubricant having a kinematic viscosity at 40 ° C lower than the kinematic viscosity at 40 ° C of the initial lubricant.
    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1 represents the pressure at the inlet of the compressor (in bar, on the ordinate) as a function of the temperature at the inlet of the compressor (in ° C, on the abscissa), for three refrigerant / lubricant mixtures A, B and C as described in more detail in the examples section.
    FIG. 2 represents the pressure at the inlet of the compressor (in bar, on the ordinate) as a function of the temperature at the inlet of the compressor (in ° C, on the abscissa), for three refrigerant / lubricant mixtures D, E and F as described in more detail in the examples section.
    FIG. 3 represents the kinematic viscosity (in cSt, on the ordinate) as a function of the temperature at the inlet of the compressor (in ° C, on the abscissa), for three refrigerant / lubricant mixtures A, B and C as described more in detail in the examples section.
    DESCRIPTION OF EMBODIMENTS OF THE INVENTION
    The invention is now described in more detail and without limitation in the description which follows. Unless otherwise stated, throughout the application, the proportions of compounds indicated are given in percentages by mass.
    The invention relates to a heat transfer method implemented by means of a heat transfer installation. The installation contains a heat transfer composition.
    In certain embodiments, the heat transfer installation was originally designed to operate with another heat transfer composition, called the so-called initial heat transfer composition (and in particular with another refrigerant, known as the refrigerant initial).
    In certain embodiments, the heat transfer composition used in the process of the invention is a so-called replacement heat transfer composition, that is to say that the same heat transfer installation was previously used for implementing a heat transfer process with another heat transfer composition, called the so-called initial heat transfer composition.
    The two preceding paragraphs correspond to the hypothesis of a replacement.
    In this case, the initial heat transfer composition consists of a so-called initial refrigerant, a so-called initial lubricant, and optional additives.
    The replacement heat transfer composition consists of a so-called replacement refrigerant, a so-called replacement lubricant, and optional additives.
    By “refrigerant” or “heat transfer fluid”, is meant a fluid capable of absorbing heat by evaporating at low temperature and low pressure and rejecting heat by condensing at high temperature and high pressure , in a vapor compression circuit, depending on the application considered. In general, a refrigerant can consist essentially of a single compound or be a mixture of several compounds.
    The replacement refrigerant is different from the original refrigerant.
    In some embodiments, the replacement lubricant is identical to the original lubricant.
    In other embodiments, the replacement lubricant is different from the original lubricant.
    The term "lubricant" is used synonymously with "lubricating oil" or "oil".
    In certain embodiments, the method of the invention successively comprises:
    - implementation with the initial heat transfer composition;
    - replacing the initial heat transfer composition with the replacement heat transfer composition; and
    - implementation with the replacement heat transfer composition.
    In other embodiments, the installation is directly implemented with the replacement heat transfer composition, without being implemented with the initial heat transfer composition - and this, although it is, by its original design, adapted to work with the initial heat transfer composition.
    This assumption is, by extension, also considered a case of "replacement" within the meaning of the invention.
    General presentation of the heat transfer process
    The heat transfer method of the invention is implemented in a heat transfer installation. The heat transfer system includes a vapor compression system. The system contains a heat transfer composition, which provides heat transfer.
    In some embodiments, the installation contains:
    - initially, the initial heat transfer composition;
    - Then, after replacement, the replacement heat transfer composition.
    The heat transfer process can be a process of heating or cooling a fluid or a body.
    In some embodiments, the vapor compression system is:
    - an air conditioning system; or
    - a refrigeration system; or
    - a freezing system; or
    - a heat pump system.
    The installation can be mobile or stationary.
    Thus, the heat transfer method can be a stationary air conditioning method (in residential premises or in industrial or commercial premises), or mobile air conditioning, in particular automobile air conditioning, a stationary refrigeration method, or mobile refrigeration ( eg refrigerated transport), or a stationary freezing or deep freezing process, or mobile freezing or deep freezing (eg refrigerated transport), or a stationary heating process, or mobile heating (eg automobile).
    The heat transfer process advantageously comprises the following steps, implemented cyclically:
    - the evaporation of the refrigerant in an evaporator;
    - compression of the refrigerant in a compressor;
    - condensation of the refrigerant in a condenser; and
    - expansion of the refrigerant in an expansion module.
    The refrigerant can be evaporated from a liquid phase or from a two-phase liquid / vapor phase.
    The compressor can be hermetic, semi-hermetic or open. Hermetic compressors include a motor part and a compression part which are confined in a non-removable hermetic enclosure. Semi-hermetic compressors include a motor part and a compression part which are directly assembled one against the other. The coupling between the engine part and the compression part is accessible by dissociating the two parts by disassembly. The open compressors include a motor part and a compression part which are separate. They can operate by belt drive or by direct coupling.
    As a compressor, it is possible in particular to use a dynamic compressor, or a positive displacement compressor.
    Dynamic compressors include axial compressors and centrifugal compressors, which can be one or more stages. Centrifugal mini-compressors can also be used.
    Positive displacement compressors include rotary compressors and reciprocating compressors.
    Reciprocating compressors include diaphragm compressors and piston compressors.
    Rotary compressors include screw compressors, lobe compressors, scroll (or scroll) compressors, liquid ring compressors, and vane compressors. The screw compressors can preferably be twin-screw or single-screw.
    The implementation of the invention is particularly advantageous when a screw compressor is used, since the oil in mixture with the refrigerant generally circulates in relatively large quantity in such a compressor.
    In the installation which is used, the compressor can be driven by an electric motor or by a gas turbine (for example supplied by the exhaust gases of a vehicle, for mobile applications) or by gear.
    The evaporator and the condenser are heat exchangers. It is possible to use any type of heat exchanger in the invention, and in particular co-current heat exchangers or, preferably, counter-current heat exchangers.
    By “counter-current heat exchanger” is meant 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, counter-current heat exchangers include devices in which the flow of the first fluid and the flow of the second fluid are in opposite directions, or almost opposite. Exchangers operating in cross-current mode with counter-current tendency are also included among the counter-current heat exchangers.
    The installation can also optionally include at least one heat transfer fluid circuit used to transport the heat (with or without change of state) between the circuit of the heat transfer composition and the fluid or body to be heated or cooled.
    The installation can also optionally include two (or more) vapor compression circuits, containing identical or distinct heat transfer compositions. For example, the vapor compression circuits can be coupled together.
    According to the invention, the refrigerant is overheated between evaporation and compression, that is to say it is brought to a temperature higher than the end of evaporation temperature, between evaporation and compression .
    "Evaporation start temperature" means the temperature of the refrigerant entering the evaporator.
    By "end of evaporation temperature" is meant the temperature of the refrigerant during the evaporation of the last drop of refrigerant in liquid form (saturated vapor temperature or dew temperature).
    When the refrigerant is a pure substance or an azeotropic mixture, the temperature at the start of evaporation is equal to the temperature at the end of evaporation.
    "Average evaporation temperature" means the arithmetic mean between the temperature at the start of evaporation and the temperature at the end of evaporation.
    The term “superheat” (here equivalent to “evaporator overheating”) designates the temperature differential between the maximum temperature reached by the refrigerant before compression (ie the maximum temperature reached by the refrigerant at the end of the superheating step) and the end of evaporation temperature. This maximum temperature is generally the temperature of the refrigerant entering the compressor. It can correspond to the temperature of the refrigerant at the outlet of the evaporator. Alternatively, the refrigerant may be at least partially overheated between the evaporator and the compressor (for example by means of an internal exchanger). The overheating can be adjusted by an adequate adjustment of the installation parameters, and in particular by an adjustment of the expansion module. In the process of the invention, the overheating is strictly greater than 0 ° C.
    The expansion module can be a thermostatic valve called a thermostatic or electronic regulator with one or more ports, or a pressure regulator that regulates the pressure. It can also be a capillary tube in which the expansion of the fluid is obtained by the pressure drop in the tube. The expansion module can also be a turbine to produce mechanical work (which can be converted into electricity), or a turbine coupled directly or indirectly to the compressor.
    In some embodiments, the invention provides for the replacement of an initial heat transfer composition with a replacement heat transfer composition, in the heat transfer process.
    In certain embodiments, this replacement can be carried out by emptying, preferably entirely or essentially entirely, the initial refrigerant of the installation, and by introducing the replacement refrigerant in place of the latter, in the installation - without emptying (or completely emptying) the initial lubricant. In this case, the replacement lubricant may be the original lubricant itself.
    In certain embodiments, this replacement can be carried out by emptying, preferably wholly or essentially entirely, the initial heat transfer composition of the installation, and by introducing the replacement heat transfer composition in place of this one, in the installation. In this case, preferably the replacement lubricant is different from the initial lubricant.
    It is considered that the "same" process is implemented, with the initial heat transfer composition on the one hand, and with the replacement heat transfer composition on the other hand.
    Preferably, before and after replacement, the process works as follows:
    - with the same average evaporation temperature; and
    - with the same average condensation temperature.
    Neither the compressor, the heat exchangers, nor the expansion module is replaced during the replacement.
    The setting of these elements can be optionally changed during replacement, to ensure that the average evaporation and condensation temperatures remain the same.
    In some embodiments, only the setting of the expansion module is changed.
    In other embodiments, no setting is changed.
    The average condensation temperature is defined as the arithmetic mean between the temperature at the start of condensation (temperature of the refrigerant in the condenser when the first liquid drop of refrigerant appears, called vapor saturation temperature or dew temperature ) and the temperature at the end of the condensation (temperature of the refrigerant during the condensation of the last bubble of refrigerant in gaseous form, called liquid saturation temperature or bubble temperature).
    The term “sub-cooling” designates the possible temperature differential (in absolute value) between the minimum temperature reached by the refrigerant before expansion and the temperature at the end of condensation. Generally this minimum temperature corresponds to the temperature of the refrigerant at the inlet of the expansion module. It can correspond to the temperature of the refrigerant at the outlet of the condenser. Alternatively, the refrigerant can be at least partially sub-cooled between the condenser and the expansion module (for example by means of an internal exchanger).
    Preferably, in the process of the invention, sub-cooling (strictly greater than 0 ° C) is applied, preferably sub-cooling of 1 to 15 ° C, more preferably 2 to 12 ° C and more preferably from 5 to 10 ° C.
    The invention is particularly useful when the average evaporation temperature is less than or equal to 10 ° C; or less than or equal to 5 ° C; or less than or equal to 0 ° C; or less than or equal to -5 ° C; or less than or equal to 10 ° C.
    Thus, the invention is particularly useful for the implementation of a refrigeration process at low temperature, or cooling at moderate temperature, or heating at moderate temperature.
    In “low temperature refrigeration” processes, the average evaporation temperature is preferably from -45 ° C to -15 ° C, in particular from -40 ° C to -20 ° C, more particularly from - 35 ° C to -25 ° C and for example about -30 ° C; and the average condensation temperature is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly preferably from 35 ° C to 55 ° C and for example around 40 ° C . These methods include in particular the freezing and deep-freezing methods.
    In “moderate temperature cooling” processes, the average evaporation temperature is preferably from -20 ° C to 10 ° C, in particular from -15 ° C to 5 ° C, more particularly from -10 ° C at 0 ° C and for example around -5 ° C; and the average condensation temperature is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly preferably from 35 ° C to 55 ° C and for example around 50 ° C . These methods can be in particular refrigeration or air conditioning methods.
    In “moderate temperature heating” processes, the average evaporation temperature is preferably from -20 ° C to 10 ° C, especially from -15 ° C to 5 ° C, more particularly from -10 ° C at 0 ° C and for example around -5 ° C; and the average condensation temperature is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly preferably from 35 ° C to 55 ° C and for example around 50 ° C .
    Friqoriqene fluids
    When the invention is applied to the replacement of an initial heat transfer composition, the initial refrigerant can be any refrigerant, for example a refrigerant comprising a CFC, or an HCFC, or an HFC. The initial refrigerant may in particular have a GWP greater than or equal to 150, or greater than or equal to 500, or greater than or equal to 1000.
    In some embodiments, the initial refrigerant includes HFC-134a.
    In certain embodiments, the initial refrigerant comprises at least 10% of HFC-134a, or at least 20% of HFC-134a, or at least 30% of HFC-134a, or at least 40% of HFC-134a, or at least 50% of HFC-134a, or at least 60% of HFC-134a, or at least 70% of HFC-134a, or at least 80% of HFC-134a, or at least 90% of HFC-134a, or at least 95% HFC-134a, based on the total mass of the initial refrigerant.
    In certain embodiments, the initial refrigerant essentially consists, or consists of HFC-134a (apart from impurities).
    In other embodiments, the initial refrigerant comprises HFC-134a in admixture with one or more heat transfer compounds, and preferably one or more hydrofluorocarbons and / or hydrocarbons.
    By "hydrofluorocarbons" is meant in the context of the present application saturated hydrofluorocarbons, which are not hydrofluoroolefins.
    Among the hydrofluorocarbons, mention may in particular be made of difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1-difluoroethane (HFC-152a) ), fluoroethane (HFC-161), 1,1,1,2,3,3,3heptafluoropropane (HFC-227ea), 1,1,1-trifluoropropane (HFC-263fb), and their mixtures.
    Preferably, the initial refrigerant is devoid of hydrofluoroolefins and hydrochlorofluoroolefins.
    In some embodiments, the initial refrigerant is a binary (consisting of two compounds) or ternary (consisting of three compounds) or quaternary (consisting of four compounds) or quinquenary (consisting of five compounds) composition.
    Examples of mixtures which can constitute the initial refrigerant are R-407A, R-407B, R-407C, R-407D, R-407E, R-407F, R-421A, R-421B , R-422A, R-422B, R-422C, R-422D, R-424A, R-425A, R426A and R-427A.
    Impurities may or may not be present in such refrigerants. When present, they can represent less than 1%, preferably less than 0.5%, preferably less than 0.1%, preferably less than 0.05% and preferably less than 0.01% ( by mass) of said fluid.
    The refrigerant used to implement the process of the invention, which is the replacement refrigerant if a replacement is made, includes HFO-1234yf.
    In certain embodiments, this refrigerant comprises at least 10% of HFO-1234yf, or at least 20% of HFO-1234yf, or at least 30% of HFO-1234yf, or at least 40% of HFO-1234yf, or at least 50% of HFO-1234yf, or at least 60% of HFO-1234yf, or at least 70% of HFO-1234yf, or at least 80% of HFO-1234yf, or at least 90% of HFO-1234yf, or at least 95% HFO-1234yf, based on the total mass of the replacement refrigerant.
    In certain embodiments, this refrigerant essentially consists, or consists of HFO-1234yf (apart from impurities).
    In other embodiments, this refrigerant comprises HFO1234yf in admixture with one or more hydrofluorocarbons and / or hydrofluoroolefins and / or hydrocarbons and / or hydrochlorofluoroolefins and / or CO 2 .
    Mention may in particular be made, among hydrofluoroolefins, of HFO-1234ze, in cis and / or trans form, and preferably in trans form; and trifluoroethylene (HFO-1123).
    Among the hydrochlorofluoroolefins, mention may in particular be made of 1-chloro3,3,3-trifluoropropene (HCFO-1233zd), in cis and / or trans form, and preferably in trans form.
    Among the hydrofluorocarbons, mention may in particular be made of difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1 , 1.1 trifluoropropane (HFC-263fb) and mixtures thereof.
    In certain embodiments, this refrigerant is a binary (consisting of two compounds) or ternary (consisting of three compounds) or quaternary (consisting of four compounds) or quinquenary (consisting of five compounds) composition.
    Impurities may or may not be present in such refrigerants. When present, they can represent less than 1%, preferably less than 0.5%, preferably less than 0.1%, preferably less than 0.05% and preferably less than 0.01% ( by mass) of said fluid.
    In addition to HFO-1234yf alone (apart from impurities), refrigerants capable of being used for the process of the invention (and therefore where appropriate as replacement refrigerants) are those consisting of (apart from impurities) :
    - HFO-1234yf and HFC-32;
    - HFO-1234yf and HFC-152a;
    - HFO-1234yf and HFC-134a;
    - HFO-1234yf and HFC-134;
    - HFO-1234yf and HFO-1123;
    - HFO-1234yf and HFC-125;
    - HFO-1234yf and CO 2 ;
    - HFO-1234yf, HFC-32 and CO 2 ;
    - HFO-1234yf, HFC-32 and HFO-1123;
    - HFO-1234yf, HFC-125 and HFO-1123;
    - HFO-1234yf, HFC-134a and HFO-1123;
    - HFO-1234yf, HFC-134 and HFO-1123;
    - HFO-1234yf, HFC-32 and HFC-125;
    - HFO-1234yf, HFC-152a and HFC-125;
    - HFO-1234yf, HFC-152a and HFC-32;
    - HFO-1234yf, HFC-134a and HFC-152a;
    - HFO-1234yf, HFC-134a and HFC-32;
    - HFO-1234yf, HFC-134a and HFC-125;
    - HFO-1234yf, HFO-1234ze and HFC-134a;
    - HFO-1234yf, HFO-1234ze and HFC-152a;
    - HFO-1234yf, HFO-1234ze and HFC-134;
    - HFO-1234yf, HFO-1234ze and HFC-32;
    - HFO-1234yf, HFO-1234ze and HFC-125;
    - HFO-1234yf, HFC-134a, HFC-125 and HFC-32;
    - HFO-1234yf, HFO-1234ze, HFC-125 and HFC-32;
    - HFO-1234yf, HFC-152a, HFC-125 and HFC-32;
    - HFO-1234yf, CO 2 , HFC-125 and HFC-32;
    - HFO-1234yf, HFC-134, HFC-125 and HFC-32;
    - HFO-1234yf, HFC-227ea, HFC-125 and HFC-32;
    - HFO-1234yf, HFC-134a, HFC-152a and HFC-32;
    - HFO-1234yf, HFC-134a, HFC-152a and HFC-125;
    - HFO-1234yf, HFO-1234ze, HFC-152a and HFC-32;
    - HFO-1234yf, HFO-1234ze, HFC-134a and HFC-32;
    - HFO-1234yf, HFO-1234ze, HFC-134a and HFC-152a;
    - HFO-1234yf, HFO-1234ze, HFC-134a and HFC-125;
    - HFO-1234yf, HFC-134a, HFC-152a, HFC-125 and HFC-32;
    - HFO-1234yf, HFC-134a, HFO-1234ze, HFC-125 and HFC-32;
    - HFO-1234yf, HFC-134a, HFC-227ea, HFC-125 and HFC-32;
    - HFO-1234yf, HFC-134a, CO2, HFC-125 and HFC-32;
    - HFO-1234yf, HFC-134a, HFC-134, HFC-125 and HFC-32.
    Preferred refrigerants are in particular those consisting of (apart from impurities):
    - HFO-1234yf and HFC-32 in respective mass proportions of 60 to 85% and 15 to 40%; or preferably from 63 to 79% and from 21 to 37%; or more preferably from 64 to 79% and from 21 to 36%;
    - HFO-1234yf and HFC-152a in mass proportions of 10 to 95% and 5 to 90%, respectively; or preferably from 50 to 95% and from 5 to 50%; or more preferably from 80 to 95% and from 5 to 20%;
    - HFO-1234yf and HFC-134a in respective mass proportions of 10 to 95% and 5 to 90%; or preferably 40 to 60% and 40 to 60%; or more preferably from 50 to 60% and from 40 to 50%;
    - HFO-1234yf and HFC-125 in respective mass proportions of 10 to 95% and 5 to 90%; or preferably from 50 to 95% and from 5 to 50%; or more preferably from 80 to 95% and from 5 to 20%;
    - HFO-1234yf, HFC-134a and HFC-152a in respective weight proportions of 1 to 98%, 1 to 98% and 1 to 98%; or preferably from 50 to 98%, from 1 to 49% and from 1 to 49%; or more preferably from 56 to 80%, from 5 to 22% and from 5 to 22%.
    - HFO-1234yf, HFC-125 and HFC-32 in respective weight proportions of 1 to 98%, 1 to 98% and 1 to 98%; or preferably from 1 to 49%, from 1 to 49% and from 50 to 98%; or more preferably from 20 to 30%, from 1 to 10% and from 60 to 75%.
    - HFO-1234yf, CO2 and HFC-32 in respective mass proportions of 1 to 98%, 1 to 98% and 1 to 98%; or preferably from 50 to 98%, from 1 to 49% and from 1 to 49%; or more preferably from 70 to 80%, from 1 to 10% and from 5 to 22%.
    In certain embodiments, the refrigerant of the invention (if applicable, replacement refrigerant) consists of (apart from impurities): from 74 to 81.5% (preferably from 75.5 to 79.5% ) of HFO-1234yf, from 12 to 16% of HFC-152a, and from 6.5 to 10.5% of HFC-134a (by mass). Such a refrigerant has the advantage of being azeotropic.
    In certain embodiments, the refrigerant of the invention (if applicable, replacement refrigerant) consists of (apart from impurities) approximately 77.5% of HFO-1234yf, approximately 14% of HFC-152a and approximately 8 , 5% of HFC-134a (by mass). Such a refrigerant has the advantage of being azeotropic.
    In certain embodiments, the refrigerant of the invention (if applicable, replacement refrigerant) consists of (apart from impurities) approximately 77.5% of HFO-1234yf, approximately 16% of HFC-152a and approximately 6 , 5% of HFC-134a (by mass). Such a refrigerant has the advantage of being azeotropic.
    In certain embodiments, the refrigerant of the invention (if applicable, replacement refrigerant) consists of (apart from impurities) approximately 81.5% of HFO-1234yf, approximately 12% of HFC-152a and approximately 6 , 5% of HFC-134a (by mass). Such a refrigerant has the advantage of being azeotropic.
    In certain embodiments, the refrigerant of the invention (where appropriate, replacement refrigerant) consists of (apart from impurities) approximately 75.5% of HFO-1234yf, approximately 14.5% of HFC-152a and about 10% HFC-134a (by mass). Such a refrigerant has the advantage of being azeotropic.
    In certain embodiments, the refrigerant of the invention (if applicable, replacement refrigerant) consists of (apart from impurities) approximately 77.5% of HFO-1234yf, approximately 12% of HFC-152a and approximately 10 , 5% of HFC-134a (by mass). Such a refrigerant has the advantage of being azeotropic.
    The GWP of the refrigerant used in the process of the invention (which if applicable is the replacement refrigerant) is preferably less than 1000, more preferably still less than 500, or 150, or 100, or 50 , or at 25.
    When a replacement is made, preferably, the GWP of the replacement refrigerant is lower than the GWP of the original refrigerant.
    The GWP is defined in relation to carbon dioxide and in relation 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".
    When a replacement is made, in some embodiments, the HFC-134a (only) is replaced by the HFO-1234yf (only).
    When a replacement is made, in certain embodiments, an initial refrigerant comprising HFC-134a in mixture with one or more other compounds is replaced by a replacement refrigerant comprising HFO-1234yf in mixture with the same or the same other compounds.
    Preferably, if HFC-134a is present in the replacement refrigerant, the mass proportion of HFC-134a in the replacement refrigerant is less than the mass proportion of HFC-134a in the initial refrigerant.
    Preferably, if one or more hydrofluorocarbons are present in the replacement refrigerant, the mass proportion of all the hydrofluorocarbons in the replacement refrigerant is less than the mass proportion of all the hydrofluorocarbons in the initial refrigerant.
    Lubricant
    The heat transfer composition used for the implementation of the process comprises a lubricant (so-called replacement lubricant, when a replacement is made).
    This lubricant includes a POE. Preferably, the lubricant is a POE. Alternatively, it can be envisaged that it is a mixture of POE and another product such as for example a PAG.
    In the above, by "a POE" is meant either a single POE, or preferably a mixture of several POEs.
    A POE can be obtained by reacting at least one polyol (that is to say a compound containing at least two OH groups) with at least one carboxylic acid.
    The POEs which can be used in the present invention include POEs of types A, B, C and D described in more detail below.
    Type A POEs correspond to the following formula (I):
    (I) R 1 [OC (O) R 2 ] n in which:
    - R 1 is a linear or branched hydrocarbon radical, optionally substituted by at least one hydroxyl group and / or comprising at least one heteroatom chosen from the group consisting of O, N, and S;
    each R 2 is, independently, chosen from the group consisting of: i) H; ii) an aliphatic hydrocarbon radical; iii) a branched hydrocarbon radical; iv) a mixture of a radical ii) and / or iii) with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms; and
    - n is an integer of at least 2.
    In the context of the invention, the term "hydrocarbon radical" means a radical composed of carbon and hydrogen atoms.
    In certain embodiments, the polyols used to obtain type A POEs correspond to the following formula (II):
    (II) R 1 (OH) n in which:
    - R 1 is a hydrocarbon radical, linear or branched, optionally substituted by at least one hydroxyl group, preferably by two hydroxyl groups, and / or comprising at least one heteroatom chosen from the group consisting of O, N, and S; and
    - n is an integer of at least 2.
    In certain embodiments, R 1 is a linear or branched hydrocarbon radical comprising from 4 to 40 carbon atoms, preferably from 4 to 20 carbon atoms.
    In certain embodiments, R 1 is a hydrocarbon radical, linear or branched, comprising at least one oxygen atom.
    In certain embodiments, R 1 is a branched hydrocarbon radical comprising from 4 to 10 carbon atoms, preferably 5 carbon atoms, substituted by two hydroxyl groups.
    In certain embodiments, the polyols comprise from 2 to 10 hydroxyl groups, preferably from 2 to 6 hydroxyl groups.
    The polyols can comprise one or more oxyalkylene groups, in this particular case it is polyether polyols.
    Polyols can also include one or more nitrogen atoms. For example, the polyols can be alkanol amines containing 3 to 6 hydroxyl groups. In certain embodiments, the polyols are alkanol amines containing at least two hydroxyl groups, and preferably at least three.
    In certain embodiments, the polyols are chosen from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentylglycol, 1,2butanediol, 1, 4-butanediol, 1,3-butanediol, pentaerythritol, dipentaerythritol, tripentaerythritol, triglycerol, trimethylolpropane, sorbitol, hexaglycerol, and mixtures thereof.
    In certain embodiments, the carboxylic acids used for obtaining POE type A correspond to the following formula (III):
    (III) R 2 COOH in which:
    - R 2 is chosen from the group consisting of: i) H; ii) an aliphatic hydrocarbon radical; iii) a branched hydrocarbon radical; iv) a mixture of a radical ii) and / or iii) with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms.
    In certain embodiments, R 2 is an aliphatic hydrocarbon radical comprising from 1 to 10, preferably from 1 to 7 carbon atoms, and in particular from 1 to 6 carbon atoms.
    In certain embodiments, R 2 is a branched hydrocarbon radical comprising from 4 to 20 carbon atoms, in particular from 5 to 14 carbon atoms, and preferably from 6 to 8 carbon atoms.
    In certain embodiments, a branched hydrocarbon radical as mentioned above corresponds to the following formula (IV):
    (IV) -C (R 3 ) (R 4 ) (R 5 ) in which R 3 , R 4 and R 5 are, independently of each other, an alkyl group, and at least one of the alkyl groups contains at least two carbon atoms. Such branched alkyl groups, once linked to the carboxyl group, are known under the name "neo group", and the corresponding acid as "neo acid". Preferably, R 3 and R 4 are methyl groups and R 5 is an alkyl group comprising at least two carbon atoms.
    The radical R 2 may comprise one or more carboxy groups, or ester groups such as -COOR 6 , with R 6 representing an alkyl, hydroxyalkyl radical or a hydroxyalkyloxy alkyl group.
    In certain embodiments, the R 2 COOH acid of formula (III) is a monocarboxylic acid.
    Examples of carboxylic acids in which the hydrocarbon radical is aliphatic are in particular: formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid and heptanoic acid .
    Examples of carboxylic acids in which the hydrocarbon radical is branched are in particular: 2-ethyl-n-butyric acid, 2-hexyldecanoic acid, isostearic acid, 2-methyl-hexanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3,5,5-trimethyl-hexanoic acid, 2ethylhexanoic acid, neoheptanoic acid, and neodecanoic acid.
    Other carboxylic acids which can be used in the preparation of type A POEs are carboxylic acids comprising an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms. We can for example cite: decanoic acid, dodecanoic acid, lauric acid, stearic acid, myristic acid, behenic acid ... Among the dicarboxylic acids, we can cite maleic acid , succinic acid, adipic acid, sebacic acid ...
    In certain embodiments, the carboxylic acids used to prepare type A POEs comprise a mixture of monocarboxylic and dicarboxylic acids, the proportion of monocarboxylic acids being in the majority. The presence of dicarboxylic acids results in particular in the formation of POEs of high viscosity.
    In particular, the reaction for the formation of type A POEs by reaction between the carboxylic acid and the polyols is an reaction catalyzed by an acid. These include a reversible reaction, which can be completed by the use of a large amount of acid or by removing the water formed during the reaction. The esterification reaction can be carried out in the presence of organic or inorganic acids, such as sulfuric acid, phosphoric acid, etc.
    In some embodiments, the reaction is carried out in the absence of a catalyst.
    The amount of carboxylic acid and polyol can vary in the mixture depending on the desired results. In the particular case where all the hydroxyl groups are esterified, a sufficient quantity of carboxylic acid must be added to react with all the hydroxyls.
    In some embodiments, when using mixtures of carboxylic acids, these may react sequentially with the polyols.
    In certain embodiments, when using a mixture of carboxylic acids, a polyol reacts first with a carboxylic acid, typically the highest molecular weight carboxylic acid, followed by the reaction with the carboxylic acid. having an aliphatic hydrocarbon chain.
    In certain embodiments, the esters can be formed by reaction between the carboxylic acids (or their anhydride derivatives or esters) with the polyols, in the presence of acids at high temperature, while removing the water formed during the reaction. . Typically, the reaction can be carried out at a temperature of from 75 to 200 ° C.
    In certain embodiments, the POEs formed can comprise hydroxyl groups which have not all reacted, in this case these are partially esterified POEs.
    In certain embodiments, the POEs are obtained from pentaerythritol alcohol, and from a mixture of carboxylic acids: isononanoic acid, at least one acid having an aliphatic hydrocarbon radical comprising from 8 to 10 carbon atoms , and heptanoic acid. The preferred polyol esters are obtained from pentaerythritol, and from a mixture of 70% isononanoic acid, 15% of at least one carboxylic acid having an aliphatic hydrocarbon radical comprising from 8 to 10 carbon atoms, and 15% heptanoic acid. We can for example quote the oil Solest 68 marketed by CPI Engineering Services Inc.
    Type B POEs comprise at least one ester of one or more branched carboxylic acids comprising at most 8 carbon atoms. The ester is obtained in particular by reacting said branched carboxylic acid with one or more polyols.
    Preferably, the branched carboxylic acid comprises at least 5 carbon atoms. In particular, the branched carboxylic acid contains from 5 to 8 carbon atoms, and preferably it contains 5 carbon atoms.
    Preferably, the above-mentioned branched carboxylic acid does not contain 9 carbon atoms. In particular, said carboxylic acid is not 3,5,5-trimethylhexanoic acid.
    In certain embodiments, the branched carboxylic acid is chosen from 2-methylbutanoic acid, 3-methylbutanoic acid and their mixtures.
    In certain embodiments, the polyol is chosen from the group consisting of neopentylglycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and their mixtures.
    In certain embodiments, the POEs are obtained from:
    i) a carboxylic acid chosen from 2-methylbutanoic acid, 3methylbutanoic acid, and mixtures thereof; and ii) a polyol chosen from the group consisting of neopentylglycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.
    In certain embodiments, the POE is that obtained from:
    - 2-methylbutanoic acid and pentaerythritol;
    - 2-methylbutanoic acid and dipentaerythritol;
    - 3-methylbutanoic acid and pentaerythritol;
    - 3-methylbutanoic acid and dipentaerythritol; or
    - 2-methylbutanoic acid and neopentylglycol.
    POE type C are poly (neopentylpolyol) esters obtained by:
    i) reaction of a neopentylpolyol having the following formula (V):
    H
    P (V) in which:
    - Each R independently represents CH3, C2H5 or CH2OH;
    - p is an integer ranging from 1 to 4;
    with at least one monocarboxylic acid having 2 to 15 carbon atoms, and in the presence of an acid catalyst, the molar ratio between the carboxyl groups and the hydroxyl groups being less than 1: 1, to form a poly (neopentyl ) partially esterified polyol; and ii) reaction of the partially esterified poly (neopentyl) polyol composition obtained at the end of step i), with another carboxylic acid having from 2 to 15 carbon atoms, to form the final ester composition ( s) of poly (neopentylpolyol).
    Preferably, reaction i) is carried out with a molar ratio ranging from 1: 4 to 1: 2.
    Preferably, the neopentylpolyol has the following formula (VI):
    R — CR pu f rr (V |) v. ^ Il2vJxl in which each R represents, independently of each other, CH 3 , C2H5 OR CH2OH.
    Preferred neopentyl polyols are those selected from pentaerythritol, dipentaerythritol, tripentaerythritol, tetraerythritol, trimethylolpropane, trimethylolethane, and neopentyl glycol. In particular, neopentylpolyol is dipentaerythritol.
    Preferably, a single neopentylpolyol is used to produce the lubricant. In some cases, two or more neopentylpolyols are used. This is especially the case when a commercial pentaerythritol product includes small amounts of dipentaerythritol, tripentaerythritol, and tetraerythritol.
    In certain embodiments, the above-mentioned monocarboxylic acid comprises from 5 to 11 carbon atoms, preferably from 6 to 10 carbon atoms.
    The monocarboxylic acids have in particular the following general formula (VII):
    (VII) R’C (O) OH in which R ’is a linear or branched C1-C12 alkyl radical, a C6-C12 aryl radical, a C6-C30 aralkyl radical. Preferably, R ’is a C4-C10, and preferably C5-C9, alkyl radical.
    In particular, the monocarboxylic acid can be chosen from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, n-octanoic acid, acid n-nonanoic, ndecanoic acid, 3-methylbutanoic acid, 2-methylbutanoic acid, 2,4-dimethylpentanoic acid, 2-ethylhexanoic acid, 3 acid, 3,5 trimethylhexanoic acid, benzoic acid, and mixtures thereof.
    In certain embodiments, the monocarboxylic acid is nheptanoic acid, or a mixture of n-heptanoic acid with another linear monocarboxylic acid, in particular n-octanoic acid and / or ndecanoic acid.
    Such a mixture of monocarboxylic acid can in particular comprise between 15 and 100 mol% of heptanoic acid and between 0 and 85 mol% of other monocarboxylic acid (s). In particular, the mixture can comprise between 75 and 100 mol% of heptanoic acid, and between 0 and 25 mol% of a mixture of octanoic acid and decanoic acid in a 3: 2 molar ratio.
    In certain embodiments, the POEs include:
    i) from 45 to 55% by mass of a monopentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms;
    ii) less than 13% by mass of a dipentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms;
    iii) less than 10% by mass of a tripentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms; and iv) at least 25% by mass of an ester of tetraerythritol and of other pentaerythritol oligomers, with at least one monocarboxylic acid having from 2 to 15 carbon atoms
    In certain embodiments, the POEs comprise, by mass, from 0 to 5%, or from 5 to 10%, or from 10 to 15%, or from 15 to 20%, or from 20 to 25%, or from 25 30%, or 30-35%, or 35-40%, or 40-45%, or 45-50%, or 50-55%, or 55-60%, or 60- 65%, or 65 to 70%, or 70 to 75%, or 75 to 80%, or 80 to 85%, or 85 to 90%, or 90 to 95%, or 95 to 100 %, of a monopentaerythritol ester with at least one monocarboxylic acid containing from 2 to 15 carbon atoms.
    Type D POEs correspond to the following formula (VIII):
    The J L )J X
    in which :
    - R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are, independently of each other, H or CH3;
    - a, b, c, y, x and z, are, independently of each other, an integer;
    - a + x, b + y, and c + z are, independently of each other, integers ranging from 1 to 20;
    - R 13 , R 14 and R 15 are, independently of each other, chosen from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls of cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryl and cycloalkylarylalkyls, R 13 , R 14 and R 15 having 1 to 17 carbon atoms, and possibly being substituted.
    In certain embodiments, each of R 13 , R 14 and R 15 represents, independently of each other, a linear or branched alkyl group, an alkenyl group, a cycloalkyl group, said alkyl, alkenyl or cycloalkyl groups which may comprise at least a heteroatom chosen from N, O, Si, F or S. Preferably, each of R 13 , R 14 and R 15 has, independently of each other, from 3 to 8 carbon atoms, preferably from 5 to 7 atoms of carbon.
    Preferably, a + x, b + y, and c + z are, independently of each other, integers ranging from 1 to 10, preferably from 2 to 8, and even more preferably from 2 to 4.
    Preferably, R 7 , R 8 , R 9 , R 10 , R 11 and R 12 represent H.
    The POEs of formula (VIII) above can typically be prepared as described in paragraphs [0027] to [0030] of the international application WO 2012/177742.
    In particular, the POEs of formula (VIII) can be obtained by esterification of glycerol alkoxylates (as described in paragraph [0027] of WO 2012/177742) with one or more monocarboxylic acids having from 2 to 18 carbon atoms.
    In certain embodiments, the monocarboxylic acids have one of the following formulas: R 13 COOH, R 14 COOH and R 15 COOH, in which R 13 , R 14 and R 15 are as defined above. Derivatives of carboxylic acids can also be used, such as anhydrides, esters and acyl halides.
    The esterification can be carried out with one or more monocarboxylic acids. Preferred monocarboxylic acids are those chosen from the group consisting of acetic acid, propanoic acid, butyric acid, isobutanoic acid, pivalic acid, pentanoic acid, isopentanoic acid, acid hexanoic acid, heptanoic acid, octanoic acid, 2ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, palmitoleic acid, lemonellic acid, undecenoic acid, lauric acid, undecylenic acid, linolenic acid, arachidic acid, behenic acid, tetrahydrobenzoic acid, abietic acid, hydrogenated or not, 2ethylhexanoic acid, furoi acid that, benzoic acid, 4-acetylbenzoic acid, pyruvic acid, 4-tert-butyl-benzoic acid, naphthenic acid, 2methyl benzoic acid, salicylic acid, their isomers, their methyl esters, and mixtures thereof.
    In certain embodiments, the esterification is carried out with one or more monocarboxylic acids chosen from the group consisting of pentanoic acid, 2-methylbutanoic acid, n-hexanoic acid, nheptanoic acid, 3, 3,5-trimethylhexanoic, 2-ethylhexanoic acid, n octanoic acid, n-nonanoic acid and isononanoic acid.
    Preferably, the esterification is carried out with one or more monocarboxylic acids chosen from the group consisting of butyric acid, isobutyric acid, n-pentanoic acid, 2-methylbutanoic acid, 3methylbutanoic acid, l n-hexanoic avid, n-heptanoic avid, noctanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, nnonanoic acid, decanoic acid, acid undecanoic, undecelenic acid, lauric acid, stearic acid, isostearic acid, and mixtures thereof.
    In certain embodiments, the POEs have the following formula (IX):
    λ ( / , m
    in which :
    - each of R 17 and R 18 , is, independently of one another, H or CH3;
    - each of m and n, is, independently of one another, an integer, with m + n being an integer ranging from 1 to 10;
    - R 16 and R 19 are, independently of one another, chosen from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls of cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyles, arylcycloalkylalkyls, arylalkylcycloalkyles, cycloalkylalkylaryls and cycloalkylarylalkyls, R 16 and R 19 having from 1 to 17 carbon atoms, and possibly being substituted.
    In certain embodiments, each of R 16 and R 19 represents, independently of one another, a linear or branched alkyl group, an alkenyl group, a cycloalkyl group, said alkyl, alkenyl or cycloalkyl groups which may comprise at least a heteroatom chosen from N, O, Si, F or S. Preferably, each of R 16 and R 19 has, independently of one another, from 3 to 8 carbon atoms, preferably from 5 to 7 atoms of carbon.
    In certain embodiments, each of R 17 and R 18 represents H, and / or m + n is an integer ranging from 2 to 8, from 4 to 10, from 2 to 5, or from 3 to 5. In particular, m + n is 2, 3 or 4.
    In certain embodiments, the POEs of formula (IX) above are diethylesters of triethylene glycol, diesters of tetraethylene glycol, in particular with one or two monocarboxylic acids having from 4 to 9 carbon atoms.
    The POEs of formula (IX) above can be prepared by esterifications of an ethylene glycol, of a propylene glycol, or of an oligo- or polyalkylene glycol, (which can be an oligo- or polyethylene glycol, oligo- or polypropylene glycol, or an ethylene glycol-propylene glycol block copolymer), with one or two monocarboxylic acids having from 2 to 18 carbon atoms. The esterification can be carried out in an identical manner to the esterification reaction used to prepare the POEs of formula (VIII) above.
    In particular, monocarboxylic acids identical to those used to prepare the POEs of formula (VIII) above, can be used to form the POEs of formula (IX).
    In certain embodiments, the lubricant comprises from 20 to 80%, preferably from 30 to 70%, and preferably from 40 to 60% by mass of at least one POE of formula (VIII), and from 80 to 20% , preferably from 70 to 30%, and preferably from 60 to 40% by mass of at least one POE of formula (IX).
    In general, certain alcohol functions may not be esterified during the esterification reaction, however their proportion remains low. Thus, the POEs can comprise between 0 and 5% molar relative of CH2OH units with respect to the -CH2-O-C (= O) - units.
    The lubricant used in the process of the invention is such that the solubility of HFO-1234yf in this lubricant is lower than the solubility of HFC-134a in the lubricant
    The term “solubility” of a compound A in the lubricant means the maximum mass proportion of compound A in the gaseous state which can be absorbed by the lubricant in the liquid phase (that is to say the maximum relative mass proportion of compound A in the lubricant in the liquid phase, when the lubricant is brought into contact with compound A in the gaseous state). Solubility can be measured as described below in Example 1.
    The above solubility condition is verified at a temperature of 0 ° C, and at a pressure which is:
    - 2.2 bar abs for the HFO-1234yf; and
    - 2.0 bar abs for HFC-134a.
    These pressure values correspond to the vapor saturation pressure of HFO-1234yf and HFC-134a respectively at a temperature of -10 ° C.
    When a replacement is made, the replacement lubricant may be the same as or different from the original lubricant.
    The initial lubricant can be of any type. It can in particular be chosen from mineral oils, silicone oils, natural or synthetic paraffins, naphthenes, alkylbenzenes, poly-alpha olefins, polyalkene glycols (PAG), polyol esters (POE), polyvinyl ethers and mixtures thereof.
    Preferably, the initial lubricant comprises a POE or is a POE.
    The detailed description of the possible types of POE given above also applies to the initial lubricant, when this comprises a POE or is a POE.
    additives
    The additives which may be present in the heat transfer composition of the invention can in particular be chosen from nanoparticles, stabilizers, surfactants, tracer agents, fluorescent agents, odorants and solubilizers.
    Preferably, the additives are not lubricants.
    The stabilizer or stabilizers, when they are present, preferably represent at most 5% by mass in the heat transfer composition. Among the stabilizers, mention may in particular be made of nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6di-ter-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated or alkenyl or aromatic alkyl) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphonates , thiols and lactones.
    As nanoparticles, it is possible in particular to use carbon nanoparticles, metal oxides (copper, aluminum), T1O2, AI2O3, M0S2 ...
    As tracer agents (capable of being detected), mention may be made of deuterated or non-deuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodized compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof. The tracer is different from the compounds that make up the refrigerant.
    As solubilizers, mention may be made of hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1.1 , 1trifluoroalcanes. The solubilizer is different from the heat transfer compound (s) making up the refrigerant.
    As fluorescent agents, there may be mentioned naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanhtenes, fluoresceins and derivatives and combinations thereof.
    As odorants, mention may be made of alkylacrylates, allylacrylates, acrylic acids, acrylesters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allylisothiocyanates, alkanoic acids , amines, norbornenes, norbornene derivatives, cyclohexene, heterocyclic aromatics, ascaridole, methoxy (methyl) phenol and combinations thereof.
    When a replacement is made, the additives described above may be present in the initial heat transfer composition and / or in the replacement heat transfer composition. Preferably, the same additives are present in the initial heat transfer composition and in the replacement heat transfer composition.
    Formulation of heat transfer compositions
    In each heat transfer composition described here (if necessary initial heat transfer composition on the one hand, and replacement heat transfer composition on the other hand), the mass proportion of refrigerant can represent in particular from 1 to 5% of the composition; or from 5 to 10% of the composition; or from 10 to 15% of the composition; or from 15 to 20% of the composition; or from 20 to 25% of the composition; or from 25 to 30% of the composition; or from 30 to 35% of the composition; or from 35 to 40% of the composition; or from 40 to 45% of the composition; or from 45 to 50% of the composition; or from 50 to 55% of the composition; or from 55 to 60% of the composition; or from 60 to 65% of the composition; or from 65 to 70% of the composition; or from 70 to 75% of the composition; or from 75 to 80% of the composition; or from 80 to 85% of the composition; or from 85 to 90% of the composition; or from 90 to 95% of the composition; or from 95 to 99% of the composition.
    In the present description, when several possible ranges are envisaged, the ranges resulting from the combination of these are also covered: for example, the proportion by mass of refrigerant in the heat transfer composition may be from 50 to 55%, and from 55 to 60%, i.e. from 50 to 60%, etc.
    Preferably, the heat transfer composition of the invention (which if appropriate is a replacement heat transfer composition) comprises at least 50% by mass of refrigerant, and in particular from 50% to 95% by mass .
    Where appropriate, the initial heat transfer composition preferably comprises at least 50% by mass of refrigerant, and in particular from 50% to 95% by mass.
    In each heat transfer composition described here (if necessary initial heat transfer composition on the one hand, and replacement heat transfer composition on the other hand), the mass proportion of lubricant can represent in particular from 1 to 5 % of the composition; or from 5 to 10% of the composition; or from 10 to 15% of the composition; or from 15 to 20% of the composition; or from 20 to 25% of the composition; or from 25 to 30% of the composition; or from 30 to 35% of the composition; or from 35 to 40% of the composition; or from 40 to 45% of the composition; or from 45 to 50% of the composition; or from 50 to 55% of the composition; or from 55 to 60% of the composition; or from 60 to 65% of the composition; or from 65 to 70% of the composition; or from 70 to 75% of the composition; or from 75 to 80% of the composition; or from 80 to 85% of the composition; or from 85 to 90% of the composition; or from 90 to 95% of the composition; or from 95 to 99% of the composition.
    The additives preferably represent from 0 to 30%, more preferably from 0 to 20%, more preferably from 0 to 10%, more preferably from 0 to 5%, and more preferably from 0 to 2% of each composition heat transfer, in mass proportions.
    Adaptation of overheating and / or viscosity
    The overheating in the heat transfer process of the invention (if necessary implemented with the replacement heat transfer composition, when a replacement is carried out) can be in particular from 1 to 2 ° C; or 2 to 3 ° C; or from 3 to 4 ° C; or from 4 to 5 ° C; or from 5 to 7 ° C; or from 7 to 10 ° C; or from 10 to 15 ° C; or from 15 to 20 ° C; or from 20 to 25 ° C; or from 25 to 30 ° C; or from 30 to 50 ° C.
    Examples of preferred ranges are overheating ranges from 1 to 20 ° C, 2 to 10 ° C and 3 to 5 ° C.
    When a replacement is made, the overheating in the same heat transfer process implemented with the initial heat transfer composition can be in particular from 1 to 2 ° C; or 2 to 3 ° C; or from 3 to 4 ° C; or from 4 to 5 ° C; or from 5 to 7 ° C; or from 7 to 10 ° C; or from 10 to 15 ° C; or from 15 to 20 ° C; or from 20 to 25 ° C; or from 25 to 30 ° C; or from 30 to 50 ° C.
    Examples of preferred ranges are overheating ranges from 1 to 20 ° C, 2 to 10 ° C and 3 to 5 ° C.
    In some embodiments, when a replacement is made, the overheating is set essentially to the same value, by an adequate adjustment of the installation parameters and in particular of the expansion module.
    In other embodiments, when a replacement is made, the overheating is reduced during the replacement of the heat transfer composition, by an adequate adjustment of the parameters of the installation and in particular of the expansion module.
    Thus, the difference between overheating when the process is carried out with the initial heat transfer composition and overheating when the process is carried out, according to the invention, with the replacement heat transfer composition may in particular be worth : 1 to 2 ° C; or 2 to 3 ° C; or from 3 to 4 ° C; or from 4 to 5 ° C; or from 5 to 6 ° C; or from 6 to 7 ° C; or from 7 to 8 ° C; or from 8 to 9 ° C; or from 9 to 10 ° C; or from 10 to 15 ° C; or more than 15 ° C.
    The lubricant used in the process of the invention (which if necessary is the replacement lubricant, when a replacement is carried out), preferably has a viscosity of 1 to 1000 centiStokes (cSt or mm 2 / s).
    All viscosity values relate to the kinematic viscosity, measured at a temperature of 40 ° C, according to DIN EN ISO 3104.
    This lubricant can thus have a viscosity of 1 to 5 cSt, or 5 to 10 cSt, or 10 to 20 cSt, or 20 to 30 cSt, or 30 to 40 cSt, or 40 to 50 cSt, or 50 to 60 cSt, or 60 to 70 cSt, or 70 to 80 cSt, or 80 to 90 cSt, or 90 to 100 cSt, or 100 to 150 cSt, or 150 to 200 cSt, or 200 at 250 cSt, or from 250 to 300 cSt, or from 300 to 400 cSt, or from 400 to 500 cSt, or from 500 to 600 cSt, or from 600 to 700 cSt, or from 700 to 800 cSt, or from 800 to 900 cSt, or from 900 to 1000 cSt.
    Examples of preferred ranges are 10 to 200 cSt, or 20 to 100 cSt, or 30 to 80 cSt.
    When a replacement is made, the initial lubricant may also have a viscosity of 1 to 5 cSt, or of 5 to 10 cSt, or of 10 to 20 cSt, or of 20 to 30 cSt, or of 30 to 40 cSt, or from 40 to 50 cSt, or from 50 to 60 cSt, or from 60 to 70 cSt, or from 70 to 80 cSt, or from 80 to 90 cSt, or from 90 to 100 cSt, or from 100 to 150 cSt, or from 150 to 200 cSt, or 200 to 250 cSt, or 250 to 300 cSt, or 300 to 400 cSt, or 400 to 500 cSt, or 500 to 600 cSt, or 600 to 700 cSt, or 700 at 800 cSt, or from 800 to 900 cSt, or from 900 to 1000 cSt.
    Examples of preferred ranges are 10 to 200 cSt, or 20 to 100 cSt, or 30 to 80 cSt.
    The viscosity of the lubricant is advantageously adapted as a function of the type of heat transfer process implemented and as a function of the compressor used.
    In some embodiments, the heat transfer method is a refrigeration method, implemented in a refrigerator; in such a case the viscosity of the lubricant is preferably from 2 to 60 cSt, more preferably from 5 to 50 cSt, and more preferably from 10 to 40 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant. When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In certain embodiments, the heat transfer method is implemented with a hermetic or semi-hermetic compressor; in such a case the viscosity of the lubricant is preferably from 5 to 100 cSt, more preferably from 10 to 80 cSt, and more preferably from 20 to 70 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant. When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In some embodiments, the heat transfer method is implemented with an open compressor; in such a case the viscosity of the lubricant is preferably from 10 to 200 cSt, more preferably from 20 to 150 cSt, and more preferably from 30 to 100 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant. When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In certain embodiments, the heat transfer method is implemented with a screw compressor; in such a case the viscosity of the lubricant is preferably from 50 to 500 cSt, more preferably from 80 to 400 cSt, and more preferably from 100 to 300 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant. When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In some embodiments, the heat transfer method is an automotive air conditioning method; in such a case the viscosity of the lubricant is preferably from 20 to 200 cSt, more preferably from 35 to 150 cSt, and more preferably from 50 to 100 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant. When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In certain embodiments, the heat transfer method is a stationary air conditioning method for the home, and the compressor used is an alternating compressor or a rotary compressor; in such a case the viscosity of the lubricant is preferably from 5 to 120 cSt, more preferably from 10 to 100 cSt, and more preferably from 20 to 70 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant. When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In certain embodiments, the heat transfer process is an air conditioning or refrigeration process for industrial or commercial premises, and the compressor used is an alternating compressor or a centrifugal compressor; in such a case the viscosity of the lubricant is preferably from 5 to 600 cSt, more preferably from 10 to 500 cSt, and more preferably from 20 to 400 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant. When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In certain embodiments, the heat transfer process is an air conditioning or refrigeration process for industrial or commercial premises, and the compressor used is a screw compressor; in such a case the viscosity of the lubricant is preferably from 20 to 600 cSt, more preferably from 30 to 500 cSt, and more preferably from 40 to 400 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant. When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In certain embodiments, the heat transfer method is an air conditioning or refrigeration process for industrial or commercial premises, and the compressor used is a scroll compressor; in such a case the viscosity of the lubricant is preferably from 5 to 250 cSt, more preferably from 10 to 200 cSt, and more preferably from 20 to 150 cSt. When a replacement is made, these ranges apply to the initial lubricant and / or to the replacement lubricant.
    When a replacement is made, preferably HFC-134a is used as the initial refrigerant.
    In certain embodiments of the invention, when a replacement is made, the replacement lubricant is different from the initial lubricant, and the viscosity of the replacement lubricant is lower than that of the initial lubricant. It is preferred that both the initial lubricant and the replacement lubricant be POE lubricants as described above.
    The viscosity of the replacement lubricant (in cSt) can thus be 1 to 2% lower; or from 2 to 3%; or from 3 to 4%, or from 4 to 5%; or from 5 to 10%; or from 10 to 15%; or from 15 to 20%; or from 20 to 25%; or from 25 to 30%; or from 30 to 40%; or from 40 to 50%; or more than 50%; relative to the viscosity of the initial lubricant (in cSt).
    The difference between the viscosity of the replacement lubricant and the viscosity of the initial lubricant can for example be between 1 and 2 cSt; or from 2 to 3 cSt; or from 3 to cSt; or from 4 to 5 cSt; or from 5 to 10 cSt; or from 10 to 15 cSt; or from 15 to 20 cSt;
    or from 20 to 25 cSt; or from 25 to 30 cSt; or from 30 to 40 cSt; or from 40 to 50 cSt; or from 50 to 60 cSt; or from 60 to 70 cSt; or from 70 to 80 cSt; or from 80 to 90 cSt; or from to 100 cSt; or from 100 to 150 cSt; or from 150 to 200 cSt; or from 200 to 250 cSt; or from 250 to 300 cSt; or more than 300 cSt.
    EXAMPLES
    The following examples illustrate the invention without limiting it.
    In these examples, we consider a refrigeration installation operating either with HFC-134a, or with HFO-1234yf, or with HFO-1234ze (in trans form). The lubricant used is an ISO 55 POE oil with a viscosity of 55 cSt at 40 ° C.
    Example 1 - measurement of solubility, viscosity and density.
    Solubility measurements are carried out according to the following protocol.
    The solubility measurement device consists of a metal cell with window with a camera to view the interior of the cell. The cell is also equipped with absolute pressure, high precision differential pressure, temperature and dynamic viscosity measurement sensors. The viscosity measurement sensor is immersed in the liquid phase of the mixture tested.
    All the sensors are calibrated before the tests in order to be able to measure the pressure, the temperature, the viscosity and the liquid volume in the cell. The density of the liquid phase is calculated from these measurements.
    The entire cell is kept at constant temperature thanks to a double jacket system supplied with a heat transfer fluid with adjustable temperature.
    A certain amount of oil is introduced into the cell. The first tests consist in measuring the viscosity of the oil at different temperatures. Certain quantities of gas are introduced gradually thereafter. After each addition of gas, the measurements are carried out over a determined temperature range.
    The quantity of gas in the vapor phase in the air above the cell is calculated thanks to the measurements of the liquid level and to prior knowledge of the behavior of pure gas as a function of temperature and pressure.
    The maximum amount of gas dissolved in the liquid is calculated based on the mass of the charged gas and the mass of the overhead gas.
    Example 2- determination of the solubility in a vapor compression system at the inlet of the compressor
    We consider a vapor compression installation operating with HFC-134a, HFO-1234yf or HFO-1234ze. The pressures at the compressor inlet for each fluid are 1.47 bar (HFO-1234ze), 2.0 bar (HFC-134a) and 2.2 bar (HFO-1234yf), respectively. They correspond to the vapor saturation pressure of each fluid at -10 ° C (the pressure drops being neglected). If we now consider an overheating of 10 ° C or 5 ° C in the installation, the temperature at the compressor inlet is 0 ° C or -5 ° C respectively.
    The solubility of the oil / refrigerant mixture at the inlet of the compressor is therefore a function of the operating pressure for each refrigerant and of the temperature at the inlet of the compressor.
    FIGS. 1 and 2 show the pressure curves as a function of temperature, at constant solubility, for HFO-1234yf, HFO-1234ze and HFC-134a.
    These curves were obtained by modeling from the measurement results of Example 1, using the following methodology: the viscosity, the pressure and the density are expressed in the form of equations, as a function of the temperature and of the solubility. . Each equation has a number of constants to be determined by regression based on the results of the above measurements. The viscosity equation is a modified form of the Walther equation, with nine constants. The pressure equation is also at nine constants. These two equations are described in the document Solubility, viscosity and density of refrigerant / lubricant mixtures by David R. Henderson (Spauschus Associates, Inc.
    300 Corporate Center Court Eagle's Landing Stockbridge, GA 30281, April 1994) on page 3. The density equation is a linear equation as a function of solubility (x) and temperature (t) with four constants to regress according to measurement results (density = a + bt + ex + dxt with a, b, c, d constant). Thus, to determine one of the parameters (temperature or pressure, density or viscosity or solubility), it suffices to solve a system of equations with several unknowns.
    The oil and refrigerant mixtures shown contain 22% HFC-134a (curve A), 15% HFO-1234yf (curve B), 23.8% HFO-1234ze (curve C), with overheating of 10 ° C in the installation; or 26% of HFC-134a (curve D), 18.5% of HFO-1234yf (curve E) and 27.6% of HFO-1234ze (curve F) with an overheating of 5 ° C in the installation.
    Thus, if the HFC-134a is replaced by HFO 1234yf, the solubility of the refrigerant is reduced, even by reducing the overheating from 10 ° C to 5 ° C. This is not the case with the HFO 1234ze.
    Example 3 - Determination of the viscosity in a vapor compression system at the inlet of the compressor
    With the measuring device described in example 1, dynamic viscosity measurements of different mixtures were carried out. Kinematic viscosity is calculated from measurements of dynamic viscosity and density.
    If we consider the same system of Example 2, The kinematic viscosity of the refrigerant / oil mixture at a temperature of 0 ° C and at the corresponding operating pressures (corresponding to an evaporation temperature of -10 ° C and 10 ° C for overheating) is 44 cSt with HFC-134a and 79 cSt with HFO-1234yf. It is 45.18 cSt with the HFO-1234ze
    The kinematic viscosity of the refrigerant / oil mixture at a temperature of -5 ° C and at the corresponding operating pressures (corresponding to an evaporation temperature of -10 ° C and 5 ° C of overheating) is 38.6 cSt with HFC-134a and 69 cSt with HFO-1234yf. It is 40.3 cSt with the HFO-1234ze.
    Thus, even by reducing overheating, the oil / HFO-1234yf mixture retains a high viscosity compared to the reference with HFC-134a.
    In FIG. 3, the kinematic viscosity is represented as a function of the temperature at constant pressure for each refrigerant under the pressure conditions of Example 2. The curve marked with a star (*) corresponds to the oil alone. These curves are results of the modeling of the measurement points discussed above.
    It is found that HFO-1234yf exhibits a viscosity behavior distinctly different from that of HFC-134a and that of HFO-1234ze when the temperature of the mixture is below 40 ° C.
    The table below summarizes the results obtained:
    Refrigerant HFC134a HFC134a HFO1234yf HFO1234yf HFO1234ze HFO1234ze Saturation pressure (bar) 2 2 2.2 2.2 1.47 1.47 Compressor inlet temperature 0 ° C -5 ° C 0 ° C -5 ° C 0 ° C -5 ° C Overheated 10 ° C 5 ° C 10 ° C 5 ° C 10 ° C 5 ° C Minimum oil temperature 0 ° C -5 ° C 0 ° C -5 ° C 0 ° C -5 ° C Solubility 22% 26% 15% 18.5% 23.8% 27.6% Viscosity (mm 2 / s) 44 38.6 79 69 45.2 40.3
    Example 4 - performance
    An analysis of the performance of an installation operating with a condensation temperature of 40 ° C, an evaporation temperature of -10 ° C in 10 evaporation, 7 ° C of sub-cooling and a variable overheating from 3 ° C to 10 ° C was carried out as follows. The thermodynamic properties were calculated using the Refprop software.
    The results are presented in the table below:
    P max(bar) P min(bar) ReportP max / P min OL.(° C) RI %CAP %COP HFC-134a 10.2 2.0 5.07 10.0 77 100 100 HFO-1234ze 7.7 1.5 5.20 10.0 77 73 99 HFO-1234yf 10.2 2.2 4.59 10.0 79 95 97 HFO-1234yf 10.2 2.2 4.59 9.0 79 96 98 HFO-1234yf 10.2 2.2 4.59 8.0 79 96 98 HFO-1234yf 10.2 2.2 4.59 7.0 79 97 99 HFO-1234yf 10.2 2.2 4.59 6.0 79 97 99 HFO-1234yf 10.2 2.2 4.59 5.0 79 98 100 HFO-1234yf 10.2 2.2 4.59 4.0 79 98 100
    P max(bar) P min(bar) ReportP max / P min OL.(° C) RI %CAP %COP HFO-1234yf 10.2 2.2 4.59 3.0 79 99 101
    In this table, Pmax and Pmin designate the maximum and minimum pressures in the system, Surch. designates overheating, RI designates isentropic efficiency, CAP designates volumetric capacity, COP designates the coefficient of performance.
    These results demonstrate that the coefficient of performance (COP) and the volumetric capacity increase with the decrease in overheating. Thus, the passage from an overheating of 10 ° C to 5 ° C increases the COP by 3% and the capacity by 2%.
    According to the invention, the drop in overheating at the compressor inlet is possible thanks to the low solubility of HFO-1234yf with POE oils compared to HFC-134a and HFO-1234ze.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. A method of heat transfer by means of a heat transfer installation containing a heat transfer composition, the heat transfer composition comprising:
    - a refrigerant, which comprises 2,3,3,3-tetrafluoropropene, and
    - a lubricant;
    in which the lubricant comprises a polyol ester, the solubility of 2,3,3,3-tetrafluoropropene in the lubricant at 0 ° C and at an absolute pressure of 2.2 bar being less than the solubility of 1.1.1 , 2tetrafluoroethane in the lubricant at 0 ° C and at an absolute pressure of 2.0 bar;
    the process comprising the successive stages:
    - evaporation of a refrigerant;
    - overheating of the refrigerant;
    - compression of the refrigerant.
    [2" id="c-fr-0002]
    2. Method according to claim 1, wherein the overheating of the refrigerant is from 1 to 20 ° C, preferably from 2 to 10 ° C, more preferably from 3 to 5 ° C.
    [3" id="c-fr-0003]
    3. Method according to one of claims 1 to 2, wherein the lubricant comprises a dipentaerythritol ester.
    [4" id="c-fr-0004]
    4. Method according to one of claims 1 to 3, wherein the lubricant has a kinematic viscosity at 40 ° C from 10 to 200 cSt, preferably from 20 to 100 cSt, and more preferably from 30 to 80 cSt.
    [5" id="c-fr-0005]
    5. Method according to one of claims 1 to 4, which is a method of mobile or stationary air conditioning and / or heating, refrigeration, freezing or deep-freezing.
    [6" id="c-fr-0006]
    6. Method according to one of claims 1 to 5, wherein the evaporation of the refrigerant is carried out at an average temperature less than or equal to 10 ° C, preferably less than or equal to 0 ° C, preferably still lower or equal to -10 ° C.
    [7" id="c-fr-0007]
    7. Method according to one of claims 1 to 6, wherein the compression of the refrigerant is carried out in a screw compressor.
    [8" id="c-fr-0008]
    8. Method according to one of claims 1 to 7, in which the heat transfer installation is an installation intended to operate with an initial heat transfer composition comprising:
    - an initial refrigerant, and
    - An initial lubricant, the initial heat transfer composition being different from the heat transfer composition used in the process.
    [9" id="c-fr-0009]
    9. Method according to one of claims 1 to 7, in which said heat transfer composition is a replacement heat transfer composition, which is used in replacement of an initial heat transfer composition comprising:
    - an initial refrigerant, and
    - an initial lubricant.
    [10" id="c-fr-0010]
    10. The method of claim 9, wherein the superheating with the replacement heat transfer composition is less than or equal to the superheating when the same process is carried out with the initial heat transfer composition; and preferably the overheating with the replacement heat transfer composition is at least 2 ° C, preferably at least 5 ° C, more preferably at least 10 ° C, relative to the overheating when the same process is carried out with the initial heat transfer composition.
    [11" id="c-fr-0011]
    11. The method of claim 9 or 10, wherein the lubricant of the replacement heat transfer composition is identical to the initial lubricant.
    [12" id="c-fr-0012]
    12. The method of claim 9 or 10, wherein the lubricant of the replacement heat transfer composition is different from the initial lubricant.
    [13" id="c-fr-0013]
    13. The method of claim 12, wherein the lubricant of the replacement heat transfer composition has a kinematic viscosity at 40 ° C less than or equal to the kinematic viscosity at 40 ° C of the initial lubricant, the difference between the kinematic viscosity at 40 ° C of the initial lubricant and the kinematic viscosity at 40 ° C of the lubricant of the replacement heat transfer composition being preferably greater than or equal to 5 cSt, more preferably still greater than or equal to 10 cSt.
    [14" id="c-fr-0014]
    14. Method according to one of claims 9 to 13, wherein the initial lubricant comprises a polyol ester, and preferably comprises a
    10 dipentaerythritol ester.
    [15" id="c-fr-0015]
    15. Method according to one of claims 8 to 14, wherein the initial refrigerant comprises 1,1,1,2-tetrafluoroethane or consists essentially of 1,1,1,2-tetrafluoroethane.
    类似技术:
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    同族专利:
    公开号 | 公开日
    WO2019158856A1|2019-08-22|
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    US9683158B2|2015-06-26|2017-06-20|Lanxess Solutions Us, Inc.|Working fluids comprising fluorinated olefins and polyol esters|FR2936806B1|2008-10-08|2012-08-31|Arkema France|REFRIGERANT FLUID|
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    FR3077572B1|2018-02-05|2021-10-08|Arkema France|TERNARY AZEOTROPIC OR QUASI-AZEOTROPIC COMPOSITION COMPRISING HF, 2,3,3,3-TETRAFLUOROPROPENE AND 1,1,1,2,2, -PENTAFLUOROPROPANE.|
    CN110845996B|2019-10-16|2021-02-09|珠海格力电器股份有限公司|Environment-friendly refrigerant and composition|
    法律状态:
    2019-01-11| PLFP| Fee payment|Year of fee payment: 2 |
    2019-08-16| PLSC| Publication of the preliminary search report|Effective date: 20190816 |
    2020-01-13| PLFP| Fee payment|Year of fee payment: 3 |
    2021-01-12| PLFP| Fee payment|Year of fee payment: 4 |
    2022-01-18| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1851280A|FR3077822B1|2018-02-15|2018-02-15|REPLACEMENT HEAT TRANSFER COMPOSITIONS FOR R-134A|
    FR1851280|2018-02-15|FR1851280A| FR3077822B1|2018-02-15|2018-02-15|REPLACEMENT HEAT TRANSFER COMPOSITIONS FOR R-134A|
    US16/962,143| US20200407613A1|2018-02-15|2019-02-13|Heat transfer compositions as replacement for r-134a|
    PCT/FR2019/050316| WO2019158856A1|2018-02-15|2019-02-13|Heat transfer compositions as replacement for r-134a|
    EP19711645.2A| EP3752573A1|2018-02-15|2019-02-13|Heat transfer compositions as replacement for r-134a|
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