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    • 专利摘要:
    The present invention relates to a composition comprising from 74% to 80% by weight of 2,3,3,3-tetrafluoropropene, from 19% to 25% by weight of difluoromethane, and from 1 to 1.9% by weight of propane, relative to the total weight of the composition. The present invention also relates to various uses of said composition, in particular in the field of refrigeration, air conditioning or heat pump.
    公开号:FR3061906A1
    申请号:FR1750415
    申请日:2017-01-19
    公开日:2018-07-20
    发明作者:Wissam Rached
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    Holder (s):
    Agent (s):
    ARKEMA FRANCE Public limited company.
    ARKEMA FRANCE Public limited company.
    ® COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE.
    (® The present invention relates to a composition comprising from 74% to 80% by weight of 2,3,3,3-tetrafluoropropene, from 19% to 25% by weight of difluoromethane, and from 1 to 1.9% by weight of propane, relative to the total weight of the composition The present invention also relates to various uses of said composition, in particular in the field of refrigeration, air conditioning or heat pump.
    FR 3,061,906 - A1
    COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE
    FIELD OF THE INVENTION
    The present invention relates to a composition comprising 2,3,3,3tetrafluoropropene, and their uses as heat transfer fluid, in particular in refrigeration, air conditioning and heat pump.
    Fluids based on fluorocarbon compounds are widely used in many industrial devices, including air conditioning, heat pump or refrigeration. These devices have in common that they are based on a thermodynamic cycle comprising the vaporization of the fluid at low pressure (in which the fluid absorbs heat); compression of the vaporized fluid to a high pressure; condensation of the vaporized fluid into high pressure liquid (in which the fluid rejects heat); and expansion of the fluid to complete the cycle.
    The choice of a heat transfer fluid (which can be a pure compound or a mixture of compounds) is dictated on the one hand by the thermodynamic properties of the fluid, and on the other hand by additional constraints.
    In particular, depending on the flammability of the fluid, more or less restrictive safety measures must be taken for the use of this fluid in certain applications, or else the use of this fluid may even be prohibited in other applications.
    Another important criterion is that of the impact of the fluid under consideration on the environment. This is how chlorine compounds (chlorofluorocarbons and hydrochlorofluorocarbons) have the disadvantage of damaging the ozone layer. Therefore, they are now generally preferred non-chlorinated compounds such as hydrofluorocarbons, fluoroethers and more recently fluoroolefins (or fluoroalkenes). Fluoroolefins also generally have a short lifespan, and therefore a lower global warming potential (GWP) than the other compounds.
    In this regard, documents WO 2004/037913 and WO 2005/105947 teach the use of compositions comprising at least one fluoroalkene having three or four carbon atoms, in particular pentafluoropropene and tetrafluoropropene, as heat transfer fluids.
    WO 2007/053697 and WO 2007/126414 disclose mixtures of fluoroolefins and other heat transfer compounds as heat transfer fluids.
    However, olefinic compounds tend to be more flammable than saturated compounds.
    There is therefore a real need to obtain and use heat transfer fluids that are less flammable than those of the state of the art, while having a low GWP, preferably less than 150.
    DESCRIPTION OF THE INVENTION
    The subject of the present invention is a composition comprising (preferably constituted) from 74% to 80% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), from 19% to 25% by weight of difluoromethane (HFC -32), and from 1 to 1.9% by weight of propane, relative to the total weight of the composition.
    The composition according to the invention is such that the total sum of the weight contents of 2,3,3,3-tetrafluoropropene (HFO-1234yf), difluoromethane (HFC-32) and propane is equal to 100%.
    Preferably, the propane content by weight in the composition is for example between 1.1% and 1.9%, 1.2% and 1.9%, 1.3% and 1.9%, 1.4% and 1.9%, 1.5% and 1.9%, 1.6% and 1.9%, 1.7% and 1.9%, 1.8% and 1.9%, 1.1% and 1.8%, 1.1% and 1.7%, 1.1% and
    1.6%, 1.1% and 1.5%, 1.1% and 1.4%, 1.1% and 1.3%, 1.1% and 1.2%, 1.2% and 1.8%, 1.2% and
    1.7%, 1.2% and 1.6%, 1.2% and 1.5%, 1.2% and 1.4%, 1.2% and 1.3%, 1.3% and 1.8%, 1.3% and
    1.7%, 1.3% and 1.6%, 1.3% and 1.5%, 1.3% and 1.4%, 1.4% and 1.8%, 1.4% and 1.7%, 1.4% and
    1.6%, 1.4% and 1.5%, 1.5% and 1.8%, 1.5% and 1.7%, 1.5% and 1.6%, 1.6% and 1.8%, 1.6% and
    1.7%, or between 1.7% and 1.8%. Preferably, the weight content of propane in the composition is 1.7% or 1.8%.
    Preferably, the weight content of 2,3,3,3-tetrafluoropropene in the composition according to the invention is for example between 74% and 79%, 74% and 78%, 74.1% and 78%, 74, 2% and 78%, 74.3% and 80%, 74.5% and 78%, 74.6% and 78%, 74.7% and 78%, 74.8% and 78%, 74.9% and 78%, 75% and 78%, 75.1% and 78%, 75.2% and 78%, 75.3% and 78%, 75.4% and 78%, 75.5% and 78%, 75.6% and 78%, 75.7% and 78%, 75.8% and 78%, 75.9% and 78%, 76% and 78%, 74% and 77.5%, 74% and 77 %, 74% and 76.9%, 74% and 76.8%, 74 and 76.7%, 74% and 76.6%, 74% and 76.5%, 74% and 76.4%, 74 % and 76.3%, 74% and 76.2%, 74% and 76.1%, 74% and 76%, 74.5% and 77.5%, 74.5% and 77%, 75% and 77.5%, or between
    75% and 77%. Preferably, the weight content of 2,3,3,3-tetrafluoropropene in the composition according to the invention is between 76% and 78%.
    Preferably, the weight content of difluoromethane in the composition according to the invention is for example between 19% and 24%, 19.5% and 24%, 20% and 24%, 20.5% and 24%, 21% and 24%, 21.5% and 24%, 19% and 23.5%, 19.5% and 23.5%, 20% and 23.5%, 20.5% and 23.5%, 21% and 23.5%, 21.5% and 23.5%, 19% and 23%, 19.5% and 23%, 20% and 23%, 20.5% and 23%, 21% and 23%, 21.5% and 23%, 19% and 22.5%, 19.5% and 22.5%, 20% and 22.5%, 20.5% and 22.5%, 21% and 22.5 %, 21.5% and 22.5%, 19% and 22%, 19.5% and 22%, 20% and 22%, 20.5% and 22%, 21% and 22%, or between 21, 5% and 22%.
    According to one embodiment, the composition according to the invention comprises (preferably consists) of 74.1% to 79.1% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), of 19% to 24% by weight of difluoromethane (HFC-32), and from 1 to 1.9% by weight of propane, relative to the total weight of the composition.
    According to one embodiment, the composition according to the invention comprises (preferably consists) of 74% to 80% by weight of 2,3,3,3-tetrafluoropropene (HFO1234yf), from 19% to 25% by weight of difluoromethane (HFC-32), and propane in one of the following contents: 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6% , 1.7%, 1.8% or 1.9% relative to the total weight of the composition.
    According to one embodiment, the composition according to the invention comprises (preferably consists) of 74.1% to 79.1% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), of 19% at 24% by weight of difluoromethane (HFC-32), and propane in one of the following contents: 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5 %, 1.6%, 1.7%, 1.8% or 1.9% relative to the total weight of the composition.
    According to one embodiment, the composition according to the invention comprises (preferably consists) of 76% to 79% by weight of 2,3,3,3-tetrafluoropropene (HFO1234yf), from 20% to 23% by weight of difluoromethane (HFC-32), and from 1% to 1.9% by weight of propane, relative to the total weight of the composition.
    According to one embodiment, the composition according to the invention comprises (preferably consists) of 76.5% to 78.5% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), of 20% to 22% by weight of difluoromethane (HFC-32), and from 1% to 1.9% by weight of propane, relative to the total weight of the composition.
    According to one embodiment, the composition according to the invention comprises (preferably consists) of 76% to 79% by weight of 2,3,3,3-tetrafluoropropene (HFO1234yf), from 20% to 23% by weight of difluoromethane (HFC-32), and propane in one of the following contents: 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6% , 1.7%, 1.8% or 1.9% relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 76.7% (± 0.5%) by weight of 2,3,3,3-tetrafluoropropene, 21.5% (± 0.5%) by weight of difluoromethane , and 1.8% (± 0.1%) by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 76.7% by weight of
    2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.8% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 76.6% by weight of
    2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.9% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.3% (± 0.5%) by weight of 2,3,3,3-tetrafluoropropene, 21.5% (± 0.5%) by weight of difluoromethane , and 1.2% (± 0.2%) by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.5 by weight of
    2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.0% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.3% by weight of
    2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.2% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.1% by weight of
    2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.4% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.6% by weight of
    2,3,3,3-tetrafluoropropene, 21.0% by weight of difluoromethane, and 1.4% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.0% (± 0.5%) by weight of 2,3,3,3-tetrafluoropropene, 21.5% (± 0.5%) by weight of difluoromethane , and 1.5% (± 0.4%) by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.3% by weight of
    2,3,3,3-tetrafluoropropene, 21.0% by weight of difluoromethane, and 1.7% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 76.8% by weight of
    2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.7% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.2% by weight of
    2,3,3,3-tetrafluoropropene, 21.0% by weight of difluoromethane, and 1.8% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 76.7% by weight of
    2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.8% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 77.1% by weight of
    2,3,3,3-tetrafluoropropene, 21.0% by weight of difluoromethane, and 1.9% by weight of propane, relative to the total weight of the composition.
    A preferred composition according to the invention is as follows: 76.6% by weight of
    2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.9% by weight of propane, relative to the total weight of the composition.
    The compositions according to the invention are advantageously little or not flammable.
    The compositions according to the invention advantageously have a flame propagation speed of less than 10 cm / s, preferably less than or equal to 9.5 cm / s, preferably less than or equal to 9 cm / s, advantageously less than or equal to 8 , 5 cm / s, and in particular less than or equal to 8 cm / s.
    The compositions according to the invention advantageously lead to a “WCFF” composition (after leakage) having a flame propagation speed of less than 10 cm / s, preferably less than or equal to 9.5 cm / s, preferably less than or equal to 9 cm / s, advantageously less than or equal to 8.5 cm / s, and in particular less than or equal to 8 cm / s.
    A composition called "WCF" ("worst case of formulation forflammability") is defined in the ASHRAE standard 34-2013, as being a formulation composition with the highest flame propagation speed. This composition is very close to the nominal composition with a certain tolerance.
    A composition called WCFF (“worst case of fractionation for flammability”) is defined in the ASHRAE standard 34-2013, as being the composition with the highest flame propagation speed. This composition is determined according to a method well defined in the same standard.
    The compositions according to the invention advantageously exhibit a good compromise between good energy performance, low or zero flammability, and low G WP.
    The compositions according to the invention advantageously have a GWP of less than 150, preferably less than 148.
    Due to their low flammability, the compositions according to the invention are advantageously safer when they are used as heat transfer fluids in refrigeration, air conditioning and for heating.
    In the context of the present invention, the flammability and the speed of flame propagation are defined and determined according to the test appearing in standard ASHRAE 34-2013, which refers to standard ASTM E 681 with regard to the apparatus. used.
    The test method described in standard ASHRAE 34-2013 is that developed in the thesis of T. Jabbour, "Classification of the flammability of refrigerants based on the fundamental flame speed" under the supervision of Denis Clodic. Thesis, Paris, 2004.
    The experimental device uses in particular the vertical glass tube method (number of tubes 2, length 150 cm, diameter 40 cm). The use of two tubes makes it possible to make two tests with the same concentration at the same time. The tubes are notably equipped with tungsten electrodes, these are placed at the bottom of each tube, 6.35mm (1/4 inch) apart and are connected to a 15kV and 30mA generator.
    The various compositions tested are qualified as flammable or non-flammable as such, according to the criteria defined in standard ASHRAE 342013.
    The composition according to the invention is advantageously classified 2L according to the ASHRAE 34-2013 standard. According to this standard, the 2L classification requires a flame propagation speed of less than 10 cm / s.
    The composition according to the invention can be prepared by any known process, such as for example by simple mixing of the different compounds with each other.
    Heat transfer composition
    According to one embodiment, the composition according to the invention is a heat transfer fluid.
    The present invention also relates to a heat transfer composition comprising (preferably consisting of) the composition according to the above-mentioned invention, and at least one additive chosen in particular from nanoparticles, stabilizers, surfactants, tracer agents, fluorescent agents , odorants, lubricants and solubilizers. Preferably, the additive is chosen from lubricants, and in particular lubricants based on polyol esters.
    The additives can in particular be chosen from nanoparticles, stabilizers, surfactants, tracer agents, fluorescent agents, odorous agents, lubricants and solubilizing agents.
    By “heat transfer compound”, respectively “heat transfer fluid” or “refrigerant”, is meant a compound, respectively a fluid, capable of absorbing heat by evaporating at low temperature and low pressure and to reject heat by condensing at high temperature and high pressure, in a vapor compression circuit. Generally, a heat transfer fluid can comprise a single, two, three or more of three heat transfer compounds.
    By "heat transfer composition" is meant a composition comprising a heat transfer fluid and optionally one or more additives which are not heat transfer compounds for the intended application.
    The 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, 2,6-di-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 hydrofluorocarbons, deuterated or not, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof. The tracer is different from the heat transfer compound (s) making up the heat transfer fluid.
    As solubilizers, mention may be made of hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1.1 , 1trifluoroalkanes. The solubilizer is different from the heat transfer compound (s) making up the heat transfer fluid.
    Mention may be made, as fluorescent agents, of 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, o-methoxy (methyl) -phenol and combinations thereof.
    In the context of the invention, the terms "lubricant", "lubricating oil" and "lubricating oil" are used in an equivalent manner.
    As lubricants, it is possible in particular to use oils of mineral origin, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkene glycols, polyol esters. (polyol ester) and / or polyvinyl ethers.
    According to one embodiment, the lubricant is based on polyol esters. In particular, the lubricant comprises one or more polyol ester (s).
    According to one embodiment, the polyol esters are obtained by reaction of at least one polyol, with a carboxylic acid or with a mixture of carboxylic acids.
    In the context of the invention, the term "carboxylic acid" covers both a monocarboxylic and polycarboxylic acid, such as for example dicarboxylic.
    In the context of the invention, and unless otherwise stated, the term "polyol" means a compound containing at least two hydroxyl groups (-OH).
    Polyol esters A)
    According to one embodiment, the polyol esters according to the invention correspond to the following formula (I):
    R 1 [OC (O) R 2 ] n (I) in which:
    R 1 is a linear or branched hydrocarbon radical, optionally substituted with 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 of each other, chosen from the group consisting of:
    o i) H;
    o ii) an aliphatic hydrocarbon radical;
    o iii) a branched hydrocarbon radical;
    o 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” is understood to mean a radical composed of carbon and hydrogen atoms.
    According to one embodiment, the polyols have the following general formula (II):
    R 1 (OH) n (II) in which:
    R 1 is a linear or branched hydrocarbon radical, 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.
    Preferably, R 1 is a linear or branched hydrocarbon radical comprising from 4 to 40 carbon atoms, preferably from 4 to 20 carbon atoms.
    Preferably, R 1 is a linear or branched hydrocarbon radical comprising at least one oxygen atom.
    Preferably, R 1 is a branched hydrocarbon radical comprising from 4 to 10 carbon atoms, preferably 5 carbon atoms, substituted by two hydroxyl groups.
    According to a preferred embodiment, the polyols comprise from 2 to 10 hydroxyl groups, preferably from 2 to 6 hydroxyl groups.
    The polyols according to the invention may comprise one or more oxyalkylene groups, in this particular case it is polyether polyols.
    The polyols according to the invention can also comprise one or more nitrogen atoms. For example, the polyols can be alkanol amines containing from 6 to 6 OH groups. Preferably, the polyols are alkanol amines containing at least two OH groups, and preferably at least three.
    According to the present invention, the preferred polyols are chosen from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, 1,2-butanediol, 1,4-butanediol, 1,3-butanediol, pentaerythritol, dipentaerythritol, tripentaerythritol, triglycerol, trimethylolpropane, sorbitol, hexaglycerol, and mixtures thereof. Preferably, the polyol is pentaerythritol or dipentaerythritol.
    According to the invention, the carboxylic acids can correspond to the following general formula (III):
    R 2 COOH (III) in which:
    R 2 is chosen from the group consisting of:
    o i) H;
    o ii) an aliphatic hydrocarbon radical;
    o iii) a branched hydrocarbon radical;
    o iv) a mixture of a radical ii) and / or iii), with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms.
    Preferably, 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.
    Preferably, 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.
    According to a preferred embodiment, a branched hydrocarbon radical has the following formula (IV):
    -C (R 3 ) R 4 ) (R 5 ) (IV) 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 atoms of carbon. 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 10 is an alkyl group comprising at least two carbon atoms.
    According to the invention, the radical R 2 may comprising 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.
    Preferably, the acid R 2 COOH 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, 3methylbutanoic acid, 3,5,5-trimethyl-hexanoic acid, 2-ethylhexanoic acid, neoheptanoic acid, and neodecanoic acid.
    The third type of carboxylic acids which can be used in the preparation of polyol esters of formula (I) are carboxylic acids comprising an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms. Mention may, for example, be made of: decanoic acid, dodecanoic acid, lauric acid, stearic acid, myristic acid, behenic acid, etc. Among the dicarboxylic acids, mention may be made of maleic acid , succinic acid, adipic acid, sebacic acid ...
    According to a preferred embodiment, the carboxylic acids used to prepare the polyol esters of formula (I) 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 polyol esters of high viscosity.
    In particular, the reaction for forming the polyol esters of formula (I) by reaction between the carboxylic acid and the polyols is an acid-catalyzed reaction. 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.
    Preferably, 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.
    According to one embodiment, when using mixtures of carboxylic acids, these can react sequentially with the polyols.
    According to a preferred embodiment, 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 acid. carboxylic having an aliphatic hydrocarbon chain.
    According to one embodiment, 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.
    According to another embodiment, the polyol esters formed can comprise hydroxyl groups which have not all reacted, in this case these are partially esterified polyol esters.
    According to a preferred embodiment, the polyol esters 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.
    According to a preferred embodiment, the polyol esters are obtained from dipentaerythritol 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
    Preferably, the polyol esters of the invention have one of the following formulas (l-A) or (l-B):
    in which each R represents, independently of each other:
    an aliphatic hydrocarbon radical comprising from 1 to 10, preferably from 2 to 9, preferably from 4 to 9 carbon atoms, and in particular from 1 to 6 carbon atoms.
    a branched hydrocarbon radical comprising from 4 to 20 carbon atoms, in particular from 4 to 14 carbon atoms, and preferably from 4 to 9 carbon atoms.
    In particular, the polyol esters of formula (1-A) or of formula (1-B) comprise different radicals R.
    A preferred polyol ester is an ester of formula (1-A) in which R is chosen from:
    an aliphatic hydrocarbon radical comprising 4 carbon atoms; and / or an aliphatic hydrocarbon radical comprising 6 carbon atoms; and / or an aliphatic hydrocarbon radical comprising 7 carbon atoms; and / or an aliphatic hydrocarbon radical comprising 8 carbon atoms; and / or an aliphatic hydrocarbon radical comprising 9 carbon atoms; and / or a branched hydrocarbon radical comprising 4 carbon atoms; and / or a branched hydrocarbon radical comprising 5 carbon atoms; and / or a branched hydrocarbon radical comprising 7 carbon atoms; and / or a branched hydrocarbon radical comprising 8 carbon atoms; and / or a branched hydrocarbon radical comprising 9 carbon atoms.
    A preferred polyol ester is an ester of formula (I-B) in which R is chosen from:
    an aliphatic hydrocarbon radical comprising 4 carbon atoms; and / or an aliphatic hydrocarbon radical comprising 6 carbon atoms; and / or an aliphatic hydrocarbon radical comprising 7 carbon atoms; and / or an aliphatic hydrocarbon radical comprising 8 carbon atoms; and / or an aliphatic hydrocarbon radical comprising 9 carbon atoms; and / or a branched hydrocarbon radical comprising 4 carbon atoms; and / or a branched hydrocarbon radical comprising 5 carbon atoms; and / or a branched hydrocarbon radical comprising 7 carbon atoms; and / or a branched hydrocarbon radical comprising 8 carbon atoms; and / or a branched hydrocarbon radical comprising 9 carbon atoms.
    Polyol esters B)
    According to another embodiment, the polyol esters of the invention 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.
    According to a preferred embodiment, the branched carboxylic acid is chosen from 2-methylbutanoic acid, 3-methylbutanoic acid, and their mixtures.
    According to a preferred embodiment, the polyol is chosen from the group consisting of neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and their mixtures.
    According to a preferred embodiment, the polyol esters 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 neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, tripentaerythritol, and mixtures thereof.
    dipentaerythritol,
    Preferably, the methylbutanoic polyol ester and pentaerythritol.
    Preferably, the methylbutanoic polyol ester and dipentaerythritol.
    Preferably, the methylbutanoic polyol ester and pentaerythritol.
    Preferably, the methylbutanoic polyol ester and dipentaerythritol.
    Preferably, the polyol ester is is is is is the one that the one obtained obtained obtained obtained obtained starting from starting from from from from acid acid acid acid acid
    22332methylbutanoic and neopentyl glycol.
    Polyol esters C)
    According to another embodiment, the polyol esters according to the invention are poly (neopentylpolyol) esters obtained by:
    i) reaction of a neopentylpolyol having the following formula (V):
    HO — CH2-C-CH2-O (V) in which:
    each R represents, independently of each other, 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):
    ch 2 oh
    R — C — R ™ (VI) wherein each R represents, independently of each other, CH3, C2H5 or CH2OH.
    Preferred neopentylpolyols are those chosen from pentaerythritol, dipentaerythritol, tripentaerythritol, tetraerythritol, trimethylolpropane, trimethylolethane, and neopentyl glycol. In particular, neopentylpolyol is pentaerythritol.
    Preferably, a single neopentylpolyol is used to produce the POE-based 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.
    According to a preferred embodiment, the abovementioned 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):
    R’C (O) OH (VII) 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 is chosen from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, n-octanoic acid, n acid -nonanoic, n-decanoic 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.
    According to a preferred embodiment, 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 comprise between 15 and 100 mol% of heptanoic acid and between 85 and 0 mol% of other monocarboxylic acid (s). In particular, the mixture comprises between 75 and 100 mol% of heptanoic acid, and between 25 and 0 mol% of a mixture of octanoic acid and decanoic acid in a 3: 2 molar ratio.
    According to a preferred embodiment, the polyol esters comprise:
    i) from 45% to 55% by weight of a monopentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms;
    ii) less than 13% by weight of a dipentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms;
    iii) less than 10% by weight of a tripentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms; and iv) at least 25% by weight of an ester of tetraerythritol and other pentaerythritol oligomers, with at least one monocarboxylic acid having 2 to 15 carbon atoms.
    Polyol esters D)
    According to another embodiment, the polyol esters according to the invention have the following formula (VIII):
    H (VIII) 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 cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyle, arylcycloalkylalkyle, arylalkylcycloalkyle, cycloalkylalkylaryl and cycloalkylarylalkyle,
    R 13 , R 14 and R 15 , having from 1 to 17 carbon atoms, and which may be optionally substituted.
    According to a preferred embodiment, 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 at least one 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 carbon atoms.
    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 polyol esters of formula (VIII) above can typically be prepared as described in paragraphs [0027] to [0030] of international application WO2012 / 177742.
    In particular, the polyol esters of formula (VIII) are obtained by esterification of glycerol alkoxylates (as described in paragraph [0027] of WO2012 / 177742) with one or more monocarboxylic acids having from 2 to 18 carbon atoms.
    According to a preferred embodiment, 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, heptanoic acid, octanoic acid, 2-ethylhexanoic 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, 2-ethylhexanoic acid, furo acid ic, benzoic acid, 4acetylbenzoic acid, pyruvic acid, 4-tert-butyl-benzoic acid, naphthenic acid, 2-methyl benzoic acid, salicylic acid, their isomers, their methyl esters, and mixtures thereof.
    Preferably, the esterification is carried out with one or more monocarboxylic acids chosen from the group consisting of pentanoic acid, 2methylbutanoic acid, n-hexanoic acid, n-heptanoic acid, 3,3,5-trimethylhexanoic , 2-ethylhexanoic acid, n-octanoic acid, nnonanoic 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 greedy, n-heptanoic greedy, n-octanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, n-nonanoic acid, decanoic acid, undecanoic acid, undecelenic acid, lauric acid, stearic acid, isostearic acid, and mixtures thereof.
    According to another embodiment, the polyol esters according to the invention have the following formula (IX):
    in which :
    each of R 17 and R 18 , is, independently of each other, 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 cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyle, arylcycloalkylalkyle, arylalkylcycloalkyle, cycloalkylalkylaryl and cycloalkylarylalkyle,
    R 16 and R 19 , having from 1 to 17 carbon atoms, and which may be optionally substituted.
    According to a preferred embodiment, 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 at least one 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 carbon atoms.
    According to a preferred embodiment, 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.
    According to a preferred embodiment, the polyol esters of formula (IX) above are diesters of triethylene glycol, diesters of tetraethylene glycol, in particular with one or two monocarboxylic acids having from 4 to 9 carbon atoms.
    The polyol esters 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 the same way as the esterification reaction used to prepare the polyol esters of formula (VIII) above.
    In particular, monocarboxylic acids identical to those used to prepare the polyol esters of formula (VIII) above, can be used to form the polyol esters of formula (IX).
    According to one embodiment, the lubricant based on polyol esters according to the invention comprises from 20 to 80%, preferably from 30 to 70%, and preferably from 40 to 60% by weight of at least one ester of polyol of formula (VIII), and from 80 to 20%, preferably from 70 to 30%, and preferably from 60 to 40% by weight of at least one polyol ester 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 mol% relative of CH2OH units with respect to the -CH 2 -OC (= O) - units.
    The preferred POE lubricants according to the invention are those having a viscosity of 1 to 1000 centiStokes (cSt) at 40 ° C, preferably from 10 to 200 cSt, even more preferably from 20 to 100 cSt, and advantageously from 30 to 80 cSt .
    The international classification of oils is given in particular by standard ISO3448-1992 (NF T60-141) and according to which oils are designated by their class of average viscosity measured at a temperature of 40 ° C.
    Uses
    The composition according to the present invention is very particularly suitable as a heat transfer fluid in refrigeration, air conditioning and for heating.
    The composition according to the present invention can be used in various applications for the replacement of current refrigerants such as R455A (mixture of R32 / R1234yf / CO2: 21.5 / 75.5 / 3% by mass) or else R454C (mixture of R1234yf / R32: 78.5 / 21.5% by mass).
    The present invention relates to the use of the composition according to the invention for reducing the risks of ignition and / or explosion in the event of a refrigerant leak.
    The low flammability of the composition advantageously allows its use in larger quantities in heat transfer installations.
    The use of refrigerants according to the flammability classes is described in particular in ISO standard 5149-1 (version 2014).
    The present invention also relates to the use of a composition according to the invention or of a heat transfer composition according to the invention, in a heat transfer system containing a vapor compression circuit.
    According to one embodiment, the heat transfer system is:
    - an air conditioning system; or
    - a refrigeration system; or
    - a freezing system; or
    - a heat pump system.
    The present invention also relates to a heat transfer method based on the use of a heat transfer installation containing a vapor compression circuit which comprises the composition according to the invention or the heat transfer composition according to the invention . The heat transfer process can be a process of heating or cooling a fluid or a body.
    The composition according to the invention or the heat transfer composition can also be used in a process for producing mechanical work or electricity, in particular in accordance with a Rankine cycle.
    The invention also relates to a heat transfer installation comprising a vapor compression circuit containing the composition according to the invention or the heat transfer composition according to the invention.
    According to one embodiment, this installation is chosen from mobile or stationary refrigeration, heating (heat pump), air conditioning and freezing installations, and heat engines.
    It can notably be a heat pump installation, in which case the fluid or body that is heated (generally air and possibly one or more products, objects or organisms) is located in a room or a vehicle interior (for mobile installation). According to a preferred embodiment, it is an air conditioning installation, in which case the fluid or body which is cooled (generally air and possibly one or more products, objects or organisms) is located in a room or vehicle interior (for mobile installation). It can be a refrigeration installation or a freezing installation (or cryogenic installation), in which case the fluid or body that is cooled generally comprises air and one or more products, objects or organisms , located in a room or container.
    The invention also relates to a method of heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid or a heat transfer composition, said method successively comprising evaporation of the fluid or heat transfer composition, compression of the fluid or heat transfer composition, condensation of the fluid or heat transfer composition, and expansion of the fluid or the heat transfer composition, in which the heat transfer fluid is the composition according to the invention, or the heat transfer composition is that described above.
    The invention also relates to a method of producing electricity by means of a heat engine, said method successively comprising the evaporation of the heat transfer fluid or of a heat transfer composition, the expansion of the fluid or of the heat transfer composition in a turbine for generating electricity, the condensation of the fluid or the heat transfer composition and the compression of the fluid or the heat transfer composition, wherein the transfer fluid is the composition according to the invention and the heat transfer composition is that described above.
    The vapor compression circuit, containing a fluid or a heat transfer composition according to the invention, comprises at least one evaporator, preferably a screw compressor, a condenser and an expansion valve, as well as lines for transporting the fluid or of the heat transfer composition between these elements. The evaporator and the condenser include a heat exchanger allowing heat exchange between the fluid or the heat transfer composition and another fluid or body.
    The evaporator used in the context of the invention can be an overheated evaporator or a flooded evaporator. In an overheated evaporator, all of the aforementioned fluid or heat transfer composition is evaporated at the outlet of the evaporator, and the vapor phase is superheated.
    In a flooded evaporator, the fluid / heat transfer composition in liquid form does not completely evaporate. A flooded evaporator has a liquid phase and vapor phase separator.
    As a compressor, it is possible in particular to use a centrifugal compressor with one or more stages or a centrifugal mini-compressor. Rotary, piston or screw compressors can also be used.
    According to one embodiment, the vapor compression circuit comprises a centrifugal compressor, and preferably a centrifugal compressor and a flooded evaporator.
    According to another embodiment, the vapor compression circuit comprises a screw compressor, preferably twin-screw or single-screw. In particular, the vapor compression circuit includes a twin-screw compressor, capable of implementing a substantial flow of oil, for example up to 6.3 L / s.
    A centrifugal compressor is characterized in that it uses rotating elements to radially accelerate the fluid or the heat transfer composition; it typically comprises at least one rotor and one diffuser housed in an enclosure. The heat transfer fluid or the heat transfer composition is introduced into the center of the rotor and flows to the periphery of the rotor under acceleration. Thus, on the one hand the static pressure increases in the rotor, and especially on the other hand at the level of the diffuser, the speed is converted into an increase in the static pressure. Each rotor / diffuser assembly constitutes a stage of the compressor. Centrifugal compressors can have from 1 to 12 stages, depending on the desired final pressure and the volume of fluid to be treated.
    The compression ratio is defined as the ratio of the absolute pressure of the fluid / composition of heat transfer at the outlet to the absolute pressure of said fluid or of said composition at the inlet.
    The speed of rotation for large centrifugal compressors ranges from 3000 to 7000 rpm. Small centrifugal compressors (or mini centrifugal compressors) generally operate at a rotational speed ranging from 40,000 to 70,000 revolutions per minute and have a small rotor (generally less than 0.15 m).
    A multistage rotor can be used to improve compressor efficiency and limit energy costs (compared to a single stage rotor). For a two-stage system, the output of the first stage of the rotor feeds the inlet of the second rotor. The two rotors can be mounted on a single axis. Each stage can provide a fluid compression ratio of approximately 4 to 1, that is, the absolute outlet pressure can be approximately four times the absolute suction pressure. Examples of two-stage centrifugal compressors, in particular for automotive applications, are described in documents US 5,065,990 and US 5,363,674.
    The centrifugal compressor can be driven by an electric motor or by a gas turbine (for example powered by vehicle exhaust gases, for mobile applications) or by gear.
    The installation may include a coupling of the regulator with a turbine to generate electricity (Rankine cycle).
    The installation can also optionally comprise at least one heat transfer fluid circuit used to transmit heat (with or without change of state) between the circuit of the heat transfer fluid or 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 fluids / heat transfer compositions. For example, the vapor compression circuits can be coupled together.
    The vapor compression circuit operates according to a conventional vapor compression cycle. The cycle includes changing the state of the fluid / heat transfer composition from a liquid phase (or two-phase liquid / vapor) to a vapor phase at a relatively low pressure, then compressing the fluid / composition into vapor phase to a relatively high pressure, the change of state (condensation) of the fluid / heat transfer composition from the vapor phase to the liquid phase at a relatively high pressure, and reducing the pressure to start again the cycle.
    In the case of a cooling process, heat from the fluid or from the body which is cooled (directly or indirectly, via a heat transfer fluid) is absorbed by the fluid / the heat transfer composition, during the 'evaporation of the latter, and at a relatively low temperature compared to the environment. The cooling methods include the methods of air conditioning (with mobile installations, for example in vehicles, or stationary), refrigeration and freezing or cryogenics. In the field of air conditioning, mention may be made of domestic, commercial or industrial air conditioning, where the equipment used is either chillers or direct expansion equipment. In the field of refrigeration, we can cite domestic, commercial refrigeration, cold rooms, the food industry, refrigerated transport (trucks, boats).
    In the case of a heating process, heat is transferred (directly or indirectly, via a heat transfer fluid) from the fluid / heat transfer composition, during the condensation thereof / this, to fluid or the body that is heated, and at a relatively high temperature compared to the environment. The installation for implementing the heat transfer is called in this case "heat pump". These may include medium and high temperature heat pumps.
    It is possible to use any type of heat exchanger for the implementation of the compositions according to the invention or heat transfer composition according to the invention, and in particular co-current heat exchangers or, preferably, counter-current heat exchangers.
    However, according to a preferred embodiment, the invention provides that the cooling and heating methods, and the corresponding installations, include a counter-current heat exchanger, either in the condenser or in the evaporator. In fact, the compositions according to the invention or the heat transfer composition defined above are particularly effective with countercurrent heat exchangers. Preferably, both the evaporator and the condenser include a counter-current heat exchanger.
    According to the invention, by "counter-current heat exchanger" means 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 within the meaning of the present application.
    In “low temperature refrigeration” processes, the inlet temperature of the composition according to the invention or heat transfer composition, to the evaporator is preferably from -45 ° C to -15 ° C, in particular from -40 ° C to -20 ° C, more particularly preferably from -35 ° C to -25 ° C and for example around -30 ° C or -20 ° C; and the temperature at the start of the condensation of the composition according to the invention or heat transfer compositions, to the condenser is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly preferred from 35 ° C to 55 ° C and for example about 40 ° C.
    In “moderate temperature cooling” processes, the inlet temperature of the composition according to the invention or heat transfer composition, to the evaporator is preferably from -20 ° C. to 10 ° C., in particular from - 15 ° C to 5 ° C, more particularly preferably from -10 ° C to 0 ° C and for example approximately
    5 ° C; and the temperature at the start of the condensation of the composition according to the invention or heat transfer composition, in the condenser is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly preferred from 35 ° C to 55 ° C and for example about 50 ° C. These methods can be refrigeration or air conditioning methods.
    In “moderate temperature heating” processes, the inlet temperature of the composition according to the invention or heat transfer composition, to the evaporator is preferably from -20 ° C. to 10 ° C., in particular from - 15 ° C to 5 ° C, more particularly preferably from -10 ° C to 0 ° C and for example around -5 ° C; and the temperature at the start of the condensation of the composition according to the invention or heat transfer composition, in the condenser is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly preferred from 35 ° C to 55 ° C and for example about 50 ° C.
    All of the embodiments described above can be combined with each other.
    In the context of the invention, by "between x and y", or "from x to y", is meant an interval in which the limits x and y are included. For example, the range "between 1 and 1.9%" notably includes the values 1 and 1.9%.
    The following examples illustrate the invention without, however, limiting it.
    EXPERIMENTAL PART
    Example 1:
    The following mixtures A to F were prepared from R32, R1234yf and propane, with a constant composition of 21.5% by mass of R32. The composition of propane was varied from 1.8 to 30% by mass relative to the total mass of the composition.
    Mixed R1234yf (mass%) R32(% by mass) R290 (propane) (mass%) Flame propagation speed (cm / s)AT 76.7 21.5 1.8 <10 Invention B 76.6 21.5 1.9 <10 Invention VS 70.5 21.5 8 > 10 Comparative D 68.5 21.5 10 > 10 Comparative E 58.5 21.5 20 > 10 Comparative F 48.5 21.5 30 > 10 Comparative
    Table 1
    The flame propagation speeds are measured as indicated in the ASHRAE 34-2013 standard.
    The experimental device for measuring the flame propagation speed uses the vertical glass tube method (number of tubes 2, length 150 cm, diameter 40 cm). The use of two tubes makes it possible to make two tests with the same concentration at the same time. The tubes are notably equipped with tungsten electrodes, these are placed at the bottom of each tube, 6.35mm (1/4 inch) apart and are connected to a 15kV and 30mA generator.
    Following the fractionation analysis in application of the ASHRAE 34-2013 standard, the most critical composition of these mixtures (WCFF) is for a leak test at boiling temperature + 10 ° C and for filling the cylinder. 90% in liquid phase at a temperature of 54.4 ° C (ASHRAE STANDARD 34-2013 appendix B, paragraph B2).
    The calculations were performed with Refprop version 9 software.
    The compositions and the rates of flame propagation after leakage (WCFF) are as follows:
    Corn WCFF positionsMixed R1234yf R32 propane Flame propagation speed (cm / s) AT 49.4 44.9 5.7 <10 B 47.1 46.4 6.5 <10 VS 36.21 45 18.8 > 10 D 33.26 44.8 22 > 10 E 24.4 45.3 30.3 > 10 F 19.94 47.4 32.6 > 10
    Table 2
    The compositions after leakage of mixtures A and B were also validated by measurements.
    Example 2:
    Or a low temperature refrigeration installation which operates between an average evaporation temperature at -35 ° C, an average condensation temperature at 45 ° C, an overheating of 10 ° C and a sub-cooling at 5 ° C.
    The isentropic efficiency of the compressor is 55%.
    % Mass P (bar) Temperature (° C) Condenser evaporator evaporator inlet evaporative vapor saturation compressor output saturated condenser steam liquid saturated condenser evaporator temperature slip pressure ratio % CAP % COP R454C 18.0 1.3 -37.0 -32.8 118 48.4 41.9 4.2 14.2 100 100 CXI CO (T R1234yf propane 21.5 77.5 1.0 18.2 1.3 -37.2 -32.8 119 48.4 41.5 4.4 14.1 101 100 21.5 77.3 1.2 18.3 1.3 -37.3 -32.8 119 48.4 41.5 4.5 14.1 102 100 21.0 77.6 1.4 18.2 1.3 -37.3 -32.8 118 48.4 41.3 4.5 14.1 101 100 21.5 77.1 1.4 18.3 1.3 -37.3 -32.8 119 48.4 41.4 4.5 14.1 102 100 21.0 77.3 1.7 18.2 1.3 -37.4 -32.8 118 48.4 41.2 4.5 14.1 101 100 21.5 76.8 1.7 18.4 1.3 -37.4 -32.8 119 48.4 41.3 4.6 14.1 102 100 21.0 77.2 1.8 18.3 1.3 -37.4 -32.8 118 48.4 41.2 4.6 14.1 102 100 21.5 76.7 1.8 18.4 1.3 -37.4 -32.8 119 48.4 41.3 4.6 14.1 102 100 21.0 77.1 1.9 18.4 1.3 -37.2 -32.7 118 48.6 41.4 4.6 14.1 102 100 21.5 76.6 1.9 18.5 1.3 -37.3 -32.7 119 48.6 41.4 4.6 14.1 103 100
    Table 3
    The compositions advantageously have a volumetric capacity greater than that of the R454C mixture.
    权利要求:
    Claims (12)
    [1" id="c-fr-0001]
    1. Composition comprising from 74% to 80% by weight of 2,3,3,3tetrafluoropropene, from 19% to 25% by weight of difluoromethane, and from 1 to 1.9% by weight of propane, relative to the total weight of the composition.
    [2" id="c-fr-0002]
    2. Composition according to claim 1, in which the weight content of propane is chosen from one of the following ranges: between 1.1% and 1.9%, between 1.2% and 1.9%, between 1, 3% and 1.9%, between 1.4% and 1.9%, between 1.5% and 1.9%, between 1.6% and 1.9%, between 1.7% and 1.9 %, between 1.8% and 1.9%, between 1.1% and 1.8%, between 1.1% and 1.7%, between 1.1% and 1.6%, between 1.1 % and 1.5%, between 1.1% and 1.4%, between 1.1% and 1.3%, between 1.1% and 1.2%, between 1.2% and 1.8% , between 1.2% and 1.7%, between 1.2% and 1.6%, between 1.2% and 1.5%, between 1.2% and 1.4%, between 1.2% and 1.3%, between 1.3% and 1.8%, between 1.3% and 1.7%, between 1.3% and 1.6%, between 1.3% and 1.5%, between 1.3% and 1.4%, between 1.4% and 1.8%, between 1.4% and 1.7%, between 1.4% and 1.6%, between 1.4% and 1.5%, between 1.5% and 1.8%, between 1.5% and 1.7%, between 1.5% and 1.6%, between 1.6% and 1.8%, between 1.6% and 1.7%, or between 1.7% and 1.8%.
    [3" id="c-fr-0003]
    3. Composition according to any one of claims 1 or 2, in which the weight content of 2,3,3,3-tetrafluoropropene chosen from one of the following ranges: between 74% and 79%, 74% and 78% , 74.1% and 78%, 74.2% and 78%, 74.3% and 80%, 74.5% and 78%, 74.6% and 78%, 74.7% and 78%, 74 , 8% and 78%, 74.9% and 78%, 75% and 78%, 75.1% and 78%, 75.2% and 78%, 75.3% and 78%, 75.4% and 78%, 75.5% and 78%, 75.6% and 78%, 75.7% and 78%, 75.8% and 78%, 75.9% and 78%, 76% and 78%, 74 % and 77.5%, 74% and 77%, 74% and 76.9%, 74% and 76.8%, 74 and 76.7%, 74% and 76.6%, 74% and 76.5 %, 74% and 76.4%, 74% and 76.3%, 74% and 76.2%, 74% and 76.1%, 74% and 76%, 74.5% and 77.5%, 74.5% and 77%, 75% and 77.5%, or between 75% and 77%, preferably between 76% and 78%.
    [4" id="c-fr-0004]
    4. Composition according to any one of claims 1 to 3, comprising from 74.1% to 79.1% by weight of 2,3,3,3-tetrafluoropropene, from 19% to 24% by weight of difluoromethane, and from 1 to 1.9% by weight of propane, relative to the total weight of the composition, said composition preferably comprising 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1 , 5%, 1.6%, 1.7%, 1.8% or 1.9% by weight of propane relative to the total weight of the composition.
    [5" id="c-fr-0005]
    5. Composition according to any one of claims 1 to 3, comprising from 76% to 79% by weight of 2,3,3,3-tetrafluoropropene, from 20% to 23% by weight of difluoromethane, and from 1% to 1.9% by weight of propane, relative to the total weight of the composition, said composition preferably comprising 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5% , 1.6%, 1.7%, 1.8% or 1.9% by weight of propane relative to the total weight of the composition.
    [6" id="c-fr-0006]
    6. Composition according to any one of claims 1 to 5, chosen from one of the following compositions:
    - 76.7% (± 0.5%) by weight of 2,3,3,3-tetrafluoropropene, 21.5% (± 0.5%) by weight of difluoromethane, and 1.8% (± 0, 1%) by weight of propane, relative to the total weight of the composition;
    - 76.7% by weight of 2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.8% by weight of propane, relative to the total weight of the composition;
    - 76.6% by weight of 2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.9% by weight of propane, relative to the total weight of the composition;
    - 77.3% (± 0.5%) by weight of 2,3,3,3-tetrafluoropropene, 21.5% (± 0.5%) by weight of difluoromethane, and 1.2% (± 0, 2%) by weight of propane, relative to the total weight of the composition;
    - 77.5 by weight of 2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.0% by weight of propane, relative to the total weight of the composition;
    - 77.3% by weight of 2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.2% by weight of propane, relative to the total weight of the composition;
    - 77.1% by weight of 2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.4% by weight of propane, relative to the total weight of the composition;
    - 77.6% by weight of 2,3,3,3-tetrafluoropropene, 21.0% by weight of difluoromethane, and 1.4% by weight of propane, relative to the total weight of the composition;
    - 77.0% (± 0.5%) by weight of 2,3,3,3-tetrafluoropropene, 21.5% (± 0.5%) by weight of difluoromethane, and 1.5% (± 0, 4%) by weight of propane, relative to the total weight of the composition;
    - 77.3% by weight of 2,3,3,3-tetrafluoropropene, 21.0% by weight of difluoromethane, and 1.7% by weight of propane, relative to the total weight of the composition;
    - 76.8% by weight of 2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.7% by weight of propane, relative to the total weight of the composition;
    - 77.2% by weight of 2,3,3,3-tetrafluoropropene, 21.0% by weight of difluoromethane, and 1.8% by weight of propane, relative to the total weight of the composition;
    - 76.7% by weight of 2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.8% by weight of propane, relative to the total weight of the composition;
    - 77.1% by weight of 2,3,3,3-tetrafluoropropene, 21.0% by weight of difluoromethane, and 1.9% by weight of propane, relative to the total weight of the composition;
    - 76.6% by weight of 2,3,3,3-tetrafluoropropene, 21.5% by weight of difluoromethane, and 1.9% by weight of propane, relative to the total weight of the composition.
    [7" id="c-fr-0007]
    7. Use of the composition according to any one of claims 1 to 6 as a heat transfer fluid.
    [8" id="c-fr-0008]
    8. Use of the composition according to any one of claims 1 to 6 to replace R455A or R454C.
    [9" id="c-fr-0009]
    9. A heat transfer composition comprising the composition according to any one of claims 1 to 6, and at least one additive chosen in particular from nanoparticles, stabilizers, surfactants, tracer agents, fluorescent agents, odorous agents, lubricants, preferably based on polyol esters, and solubilizers.
    [10" id="c-fr-0010]
    10. Use of a composition according to any one of claims 1 to 6, or a heat transfer composition according to claim 9, in a heat transfer system containing a vapor compression circuit.
    [11" id="c-fr-0011]
    11. Heat transfer installation comprising a vapor compression circuit containing the composition according to any one of claims 1 to 6 or the heat transfer composition according to claim 9, in particular chosen from mobile or stationary heating installations by heat pump, air conditioning, refrigeration, freezing and heat engines.
    [12" id="c-fr-0012]
    12. A method of heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid or a heat transfer composition, said method successively comprising the evaporation of the fluid or heat transfer composition, compression of the fluid or heat transfer composition, condensation of the fluid or heat transfer composition, and expansion of the fluid or heat transfer composition, wherein the heat transfer fluid is the composition according to any of claims 1 to 6, and the heat transfer composition is that according to claim 9.
    类似技术:
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    同族专利:
    公开号 | 公开日
    US20190367789A1|2019-12-05|
    FR3061906B1|2019-03-15|
    JP2020514481A|2020-05-21|
    EP3571259A1|2019-11-27|
    CN110234727A|2019-09-13|
    WO2018134528A1|2018-07-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2938550A1|2008-11-20|2010-05-21|Arkema France|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE|
    US20150041704A1|2012-03-27|2015-02-12|Jx Nippon Oil & Energy Corporation|Working fluid composition for refrigerator|
    WO2015036677A1|2013-09-11|2015-03-19|Arkema France|Heat transfer fluids comprising difluoromethane, pentafluoroethane, tetrafluoropropene and optionally propane|
    US5065990A|1986-12-15|1991-11-19|Susan M. Durfee|Vise jaw accessory system for attaching and releasing vise accessories while maintaining positional accuracy of the accessories|
    US5363674A|1993-05-04|1994-11-15|Ecoair Corp.|Zero superheat refrigeration compression system|
    US7279451B2|2002-10-25|2007-10-09|Honeywell International Inc.|Compositions containing fluorine substituted olefins|
    TR201908011T4|2002-10-25|2019-06-21|Honeywell Int Inc|Compositions containing fluorine-substituted olefins.|
    EP3216840B1|2005-11-01|2020-09-02|The Chemours Company FC, LLC|Compositions comprising 1,1,1,4,4,4-hexafluoro-2-butene and uses thereof|
    US7569170B2|2005-03-04|2009-08-04|E.I. Du Pont De Nemours And Company|Compositions comprising a fluoroolefin|
    CN110003858A|2005-03-04|2019-07-12|科慕埃弗西有限公司|Composition comprising fluoroolefin|
    US9187682B2|2011-06-24|2015-11-17|Emerson Climate Technologies, Inc.|Refrigeration compressor lubricant|FR2936806B1|2008-10-08|2012-08-31|Arkema France|REFRIGERANT FLUID|
    FR2937328B1|2008-10-16|2010-11-12|Arkema France|HEAT TRANSFER METHOD|
    US20170080773A1|2008-11-03|2017-03-23|Arkema France|Vehicle Heating and/or Air Conditioning Method|
    FR2950065B1|2009-09-11|2012-02-03|Arkema France|BINARY REFRIGERANT FLUID|
    FR2962442B1|2010-07-09|2016-02-26|Arkema France|STABLE 2,3,3,3-TETRAFLUOROPROPENE COMPOSITION|
    FR3033791B1|2015-03-18|2017-04-14|Arkema France|STABILIZATION OF 1-CHLORO-3,3,3-TRIFLUOROPROPENE|
    FR3055014B1|2016-08-10|2020-03-13|Arkema France|AZEOTROPE OR QUASI-AZEOTROPE COMPOSITION COMPRISING 1,1,1,2,2-PENTAFLUOROPROPANE AND TRANS-1,3,3,3-TETRAFLUOROPROPENE|
    FR3057271B1|2016-10-10|2020-01-17|Arkema France|USE OF TETRAFLUOROPROPENE COMPOSITIONS|
    FR3070982B1|2017-09-12|2019-08-30|Arkema France|COMPOSITION BASED ON HYDROCHLOROFLUOROOLEFIN AND MINERAL OIL|
    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.|
    法律状态:
    2017-12-11| PLFP| Fee payment|Year of fee payment: 2 |
    2018-07-20| PLSC| Search report ready|Effective date: 20180720 |
    2019-12-16| PLFP| Fee payment|Year of fee payment: 4 |
    2020-12-10| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1750415A|FR3061906B1|2017-01-19|2017-01-19|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE|
    FR1750415|2017-01-19|FR1750415A| FR3061906B1|2017-01-19|2017-01-19|COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE|
    US16/477,318| US20190367789A1|2017-01-19|2018-01-18|Composition comprising 2,3,3,3-tetrafluoropropene|
    CN201880007702.9A| CN110234727A|2017-01-19|2018-01-18|Composition comprising 2,3,3,3- tetrafluoropropene|
    JP2019538336A| JP2020514481A|2017-01-19|2018-01-18|Composition containing 2,3,3,3-tetrafluoropropene|
    PCT/FR2018/050125| WO2018134528A1|2017-01-19|2018-01-18|Composition comprising 2,3,3,3-tetrafluoropropene|
    EP18703066.3A| EP3571259A1|2017-01-19|2018-01-18|Composition comprising 2,3,3,3-tetrafluoropropene|
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