Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/048—Boiling liquids as heat transfer materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
  • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
  • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
  • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
  • F25B13/00—Compression machines, plants or systems, with reversible cycle
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
  • C09K2205/126—Unsaturated fluorinated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/22—All components of a mixture being fluoro compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/32—The mixture being azeotropic

Definitions

• Azeotropic composition comprising 2,3,3,3-tetrafluoropropene and trans-1,,3,3,3-tetrafluoropropene
• the present invention relates to compositions comprising 2,3,3,3-tetrafluoropropene and trans-1,,3,3,3-tetrafluoropropene, useful in many fields of application.
• HFCs hydrofluorocarbons
• HFC-134a 1430
• GWP Global Warming Potential
• Carbon dioxide being non-toxic, non-flammable and having a very low GWP, has been proposed as refrigerant air conditioning systems replacing HFC-134a.
• the use of carbon dioxide has several disadvantages, particularly related to the very high pressure of its implementation as a refrigerant in existing devices and technologies.
• WO2004 / 037913 discloses the use of compositions comprising at least one fluoroalkene having three or four carbon atoms, especially pentafluoropropene and tetrafluoropropene, preferably having a GWP of at most 150, as heat transfer fluids.
• WO 2005/105947 teaches the addition to tetrafluoropropene, preferably 1, 3,3,3 tetrafluoropropene, of a co-blowing agent such as difluoromethane (HFC-32), pentafluoroethane (HFC-125 ), tetrafluoroethane, difluoroethane, heptafluoropropane, hexafluoropropane, pentafluoropropane, pentafluorobutane, water and carbon dioxide.
• a co-blowing agent such as difluoromethane (HFC-32), pentafluoroethane (HFC-125 ), tetrafluoroethane, difluoroethane, heptafluoropropane, hexafluoropropane, pentafluoropropane, pentafluorobutane, water and carbon dioxide.
• WO 2006/094303 discloses an azeotropic composition containing 70.4% by weight of 2,3,3,3-tetrafluoropropene (1234yf) and 29.6% by weight of 1,1,1,2-tetrafluoroethane (HFC-134a) .
• This document also discloses an azeotropic composition containing 91% by weight of 2,3,3,3-tetrafluoropropene and 9% by weight of difluoroethane (HFC-152a).
• US 2006/243944 discloses a nearly azeotropic composition consisting of 1 -99% HFO-1234yf and 99-1% trans-HFC-1234ze at -25 ° C.
• WO 2010/129920 discloses refrigerant compositions comprising R32, R125, R134a, 1234ze and 1234yf in different proportions.
• the present invention relates to a quasi-azeotropic composition
• a quasi-azeotropic composition comprising (preferably constituted) from 60 mol% to 98.9 mol% of 2,3,3,3-tetrafluoropropene, and from 1, 1 mol% to 40 mol% of trans-1, 3,3,3-tetrafluoropropene, relative to the total number of moles of the composition, preferably from 71 mol% to 98.9 mol% of 2,3,3,3-tetrafluoropropene, and from 1, 1 mol% to 29 mol% of trans-1, 3,3,3-tetrafluoropropene, and advantageously from 71 mol% to 98 mol% of 2,3,3,3-tetrafluoropropene, and from 2 mol% to 29 mol% of trans-1, 3,3 , 3-tetrafluoropropene, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C, at a
• HFO-1234yf refers to 2,3,3,3-tetrafluoropropene.
• trans-HFO-1234ze refers to the trans-
• between x and y" or “ranging from x to y” or “comprises from x to y” means an interval in which the terminals x and y are included.
• the range “between 0 and 0.5%” includes in particular the values 0 and 0.5%.
• compositions according to the invention may be prepared by any known method, such as for example by simple mixing of the various compounds with each other.
• the compositions of the invention advantageously have a zero ODP and a lower GWP than existing HFCs.
• these compositions advantageously have better energy performance than existing HFCs, and especially that of R134a.
• the quasi-azeotropic compositions according to the invention can advantageously be used to replace R134a, in particular in existing installations, for example in heat pumps.
• compositions advantageously have a very low flammability or are non-flammable at 23 ° C and will advantageously be classified as non-flammable for transport.
• flammability is defined by reference to ASHRAE 34-2007. Specifically, the flammability of a heat transfer fluid at 50% relative humidity is determined according to the test in ASHRAE 34-2007 (which refers to ASTM E681 for the equipment used).
• compositions according to the invention can advantageously be used at high condensation temperatures due to the low overheating at the outlet of the compressor.
• the quasi-azeotropic composition has a boiling point of between 50 ° C. and 75 ° C., preferably between 55 ° C. and 70 ° C., preferably between 55 ° C. and 65 ° C., and especially between 58 ° C and 62 ° C; in particular at a pressure of between 1 and 50 bar abs, preferably between 10 and 40 bar abs, preferably between 12 and 20 bar abs, preferably between 12 and 17 bar abs ( ⁇ 0.5%), preferentially between 15 and 17 bar abs ( ⁇ 0.5%).
• the quasi-azeotropic composition comprises (preferably consists of) 70 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene, and from 0.1 mol% to 30 mol% of trans-1, 3,3,3-tetrafluoropropene, based on the total number of moles of the composition, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C, at a pressure between 1 and 50 bar abs, preferably between 12 and 20 bar abs.
• the quasi-azeotropic composition comprises (preferably consists of) from 71 mol% to 98 mol% of 2,3,3,3-tetrafluoropropene, and from 2 mol% to 29 mol% of trans-1 , 3,3,3-tetrafluoropropene, relative to the total number of moles of the composition, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C, at a pressure of between 1 and 50 bar abs, preferably between 12 and 20 bar abs.
• the quasi-azeotropic composition comprises (preferably consists of) of 75 mol% to 98 mol% of 2,3,3,3-tetrafluoropropene, and 2 mol% to 25 mol% of trans-1 , 3,3,3-tetrafluoropropene, relative to the total number of moles of the composition, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C, at a pressure of between 1 and 50 bar abs, preferably between 12 and 20 bar abs.
• the quasi-azeotropic composition comprises (preferably consists of) from 80 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene, and from 0.1 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, based on the total number of moles of the composition, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C, at a pressure between 1 and 50 bar abs, preferably between 12 and 20 bar abs.
• the quasi-azeotropic composition comprises (preferably consists of) 80 mol% to 98 mol% of 2,3,3,3-tetrafluoropropene, and 2 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, relative to the total number of moles of the composition, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C at a pressure of between 1 and 50 bar abs, preferably between 12 and 20 bar abs.
• the quasi-azeotropic composition comprises (preferably consists of) 85 mol% to 95 mol% of 2,3,3,3-tetrafluoropropene, and 5 mol% to 15 mol% of trans-1 , 3,3,3-tetrafluoropropene, relative to the total number of moles of the composition, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C, at a pressure of between 1 and 50 bar abs, preferably between 12 and 20 bar abs.
• the quasi-azeotropic composition comprises (preferably consists of) from 88 mol% to 93 mol% of 2,3,3,3-tetrafluoropropene, and from 7 mol% to 12 mol% of trans-1 , 3,3,3-tetrafluoropropene, relative to the total number of moles of the composition, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C, at a pressure of between 1 and 50 bar abs, preferably between 12 and 20 bar abs.
• the quasi-azeotropic composition comprises (preferably consists of) from 60 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene, and from 0.1 mol% to 40 mol% of trans-1, 3,3,3-tetrafluoropropene, based on the total number of moles of the composition, said quasi-azeotropic composition having a boiling point between 45 ° C and 80 ° C, at a pressure between 1 and 50 bar abs, preferably between 12 and 20 bar abs.
• the quasi-azeotropic composition comprises from 60 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene and from 0.1 mol% to 40 mol% of trans-1,3 , 3,3-tetrafluoropropene, advantageously from 70 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene and from 0.1 mol% to 30 mol% of trans-1, 3,3,3- tetrafluoropropene, preferably from 80 mol% to 99 mol% of 2,3,3,3-tetrafluoropropene and from 1 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, more preferably of 80 mol% 98 mol% of 2,3,3,3-tetrafluoropropene and 2 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, even more preferably 85 mol%
• the quasi-azeotropic composition comprises from 60 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene and from 0.1 mol% to 40 mol% of trans-1,3 , 3,3-tetrafluoropropene, advantageously from 70 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene and from 0.1 mol% to 30 mol% of trans-1, 3,3,3- tetrafluoropropene, preferably from 80 mol% to 99 mol% of 2,3,3,3-tetrafluoropropene and from 1 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, more preferably of 80 mol% 98 mol% of 2,3,3,3-tetrafluoropropene and 2 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, even more preferably 85 mol%
• the quasi-azeotropic composition comprises from 60 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene and from 0.1 mol% to 40 mol% of trans-1,3 , 3,3-tetrafluoropropene, advantageously from 70 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene and from 0.1 mol% to 30 mol% of trans-1, 3,3,3- tetrafluoropropene, preferably from 80 mol% to 99 mol% of 2,3,3,3-tetrafluoropropene and from 1 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, more preferably of 80 mol% 98 mol% of 2,3,3,3-tetrafluoropropene and 2 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, even more preferably 85 mol%
• the quasi-azeotropic composition comprises from 60 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene and from 0.1 mol% to 40 mol% of trans-1,3 , 3,3-tetrafluoropropene, advantageously from 70 mol% to 99.9 mol% of 2,3,3,3-tetrafluoropropene and from 0.1 mol% to 30 mol% of trans-1, 3,3,3- tetrafluoropropene, preferably from 80 mol% to 99 mol% of 2,3,3,3-tetrafluoropropene and from 1 mol% to 20 mol% of trans-1, 3,3,3-tetrafluoropropene, more preferably from 80 mol% to 98 mol% of 2,3,3,3-tetrafluoropropene and from 2 mol% to 20 mol % trans-1, 3,3,3-tetrafluoropropene, more preferably 85 mol
• the quasi-azeotropic composition according to the invention comprises (preferably consists of) from 64 mol% to 95 mol% of 2,3,3,3-tetrafluoropropene and from 5 mol% to 36 mol % of trans-1, 3,3,3-tetrafluoropropene, said composition having a boiling temperature of 60 ° C ( ⁇ 0.1 ° C) at a pressure of between 15 and 17 bar abs ( ⁇ 0.5 ° C) %).
• the quasi-azeotropic composition according to the invention comprises (preferably consists of) of 64 mol% to 94 mol% of 2,3,3,3-tetrafluoropropene and 6 mol% to 36 mol % of trans-1, 3,3,3-tetrafluoropropene, said composition having a boiling temperature of 60 ° C ( ⁇ 0.1 ° C) at a pressure of between 15 and 17 bar abs ( ⁇ 0.5 ° C) %).
• the quasi-azeotropic composition according to the invention comprises (preferably consists of) of 65 mol% ( ⁇ 3%) of 2,3,3,3-tetrafluoropropene and 35 mol% ( ⁇ 3%) of trans-1, 3,3,3-tetrafluoropropene, said composition having a boiling temperature of 60 ° C ( ⁇ 0.1 ° C) at a pressure of between 15 and 17 bar abs ( ⁇ 0 ° C). , 5%).
• the quasi-azeotropic composition according to the invention comprises (preferably consists of) of 75 mol% ( ⁇ 3%) of 2,3,3,3-tetrafluoropropene and 25 mol% ( ⁇ 3%) of trans-1, 3,3,3-tetrafluoropropene, said composition having a boiling temperature of 60 ° C ( ⁇ 0.1 ° C) at a pressure of between 15 and 17 bar abs ( ⁇ 0 ° C). , 5%).
• the quasi-azeotropic composition according to the invention comprises (preferably consists of) of 80 mol% ( ⁇ 3%) of 2,3,3,3-tetrafluoropropene and 20 mol% ( ⁇ 3%) of trans-1, 3,3,3-tetrafluoropropene, said composition having a boiling temperature of 60 ° C ( ⁇ 0.1 ° C) at a pressure of between 15 and 17 bar abs ( ⁇ 0 ° C). , 5%).
• the quasi-azeotropic composition according to the invention comprises (preferably consists of) of 86 mol% ( ⁇ 3%) of 2,3,3,3-tetrafluoropropene and 14 mol% ( ⁇ 3%) of trans-1, 3,3,3-tetrafluoropropene, said composition having a boiling temperature of 60 ° C ( ⁇ 0.1 ° C) at a pressure of between 15 and 17 bar abs ( ⁇ 0 ° C). , 5%).
• the quasi-azeotropic composition according to the invention comprises (preferably consists of) 90 mol% ( ⁇ 3%) of 2,3,3,3-tetrafluoropropene and 10 mol% ( ⁇ 3%) of trans-1, 3,3,3-tetrafluoropropene, said composition having a boiling temperature of 60 ° C ( ⁇ 0.1 ° C) at a pressure of between 15 and 17 bar abs ( ⁇ 0 ° C). , 5%).
• the quasi-azeotropic composition according to the invention comprises (preferably consists of) of 92 mol% ( ⁇ 3%) of 2,3,3,3-tetrafluoropropene and 8 mol% ( ⁇ 3%) of trans-1, 3,3,3-tetrafluoropropene, said composition having a boiling temperature of 60 ° C ( ⁇ 0.1 ° C) at a pressure of between 15 and 17 bar abs ( ⁇ 0 ° C). , 5%).
• the azeotropic composition of the invention is a heat transfer fluid.
• the azeotropic composition according to the invention may comprise one or more additives (which are essentially not heat transfer compounds for the intended application).
• the additives may especially be chosen from nanoparticles, stabilizers, surfactants, tracer agents, fluorescent agents, odorants, lubricants and solubilizing agents.
• heat transfer compound means 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.
• a heat transfer fluid may comprise one, two, three or more than three heat transfer compounds.
• 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 present invention also relates to a heat transfer composition
• a heat transfer composition comprising (preferably consisting of) the azeotropic composition according to the invention mentioned above, and at least one additive especially chosen from nanoparticles, stabilizers, surfactants, tracer agents, agents fluorescent agents, odorants, lubricants and solubilizers.
• the additive is chosen from lubricants, and especially lubricants based on polyol esters.
• the stabilizer (s), when present, preferably represent at most 5% by weight in the heat transfer composition.
• the stabilizers there may be mentioned in particular nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenol compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphonates, thiols and lactones.
• nanoparticles it is possible to use, in particular, nanoparticles of carbon, metal oxides (copper, aluminum), ⁇ 2, Al2O3, M0S2, etc.
• tracer agents which can be detected
• the tracer agent is different from the one or more heat transfer compounds composing the heat transfer fluid.
• solubilizing agents mention may be made of hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and magnesium compounds. , 1 - trifluoroalkanes.
• the solubilizing agent is different from the one or more heat transfer compounds composing the heat transfer fluid.
• fluorescent agents mention may be made of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanhthenes, fluoresceins and derivatives and combinations thereof.
• alkyl acrylates As odorants, mention may be made of alkyl acrylates, allyl acrylates, acrylic acids, acrylresters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allyl isothiocyanates and alkanoic acids. , amines, norbornenes, norbornene derivatives, cyclohexene, heterocyclic aromatic compounds, ascaridole, o-methoxy (methyl) phenol and combinations thereof.
• lubricant In the context of the invention, the terms “lubricant”, “lubricating oil” and “lubricating oil” are used equivalently.
• Lubricants that may be used include oils of mineral origin, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkene glycols, polyol esters, and / or polyvinyl ethers.
• Polyvinyl ether oils are preferably copolymers of the two units
• Preferred PVE oils are those having 50 to 95% by weight of units 1.
• the lubricant is based on polyol esters.
• the lubricant comprises one or more polyol ester (s).
• the polyol esters are obtained by reaction of at least one polyol, with a carboxylic acid or with a mixture of carboxylic acids.
• polyol means a compound containing at least two hydroxyl groups (-OH).
• the polyol esters according to the invention have the following formula (I):
• R 1 is a linear or branched hydrocarbon radical, optionally substituted with at least one hydroxyl group and / or comprising at least one heteroatom selected from the group consisting of -O-, -N-, and -S-;
• each R 2 is, independently of one another, selected from the group consisting of:
• hydrocarbon radical means a radical composed of carbon atoms and hydrogen.
• the polyols have the following general formula (II):
• R 1 is a linear or branched hydrocarbon radical, optionally substituted with at least one hydroxyl group, preferably with 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.
• R 1 is a linear or branched hydrocarbon radical comprising from 4 to 40 carbon atoms, preferably from 4 to 20 carbon atoms.
• R 1 is a hydrocarbon radical, linear or branched, comprising at least one oxygen atom.
• 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, it being in this particular case polyether polyols.
• the polyols according to the invention may also comprise one or more nitrogen atoms.
• the polyols may be alkanol amines containing from 3 to 6 OH groups.
• the polyols are alkanol amines containing at least two OH groups, and preferably at least three.
• the preferred polyols are selected 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.
• the carboxylic acids can satisfy the following general formula (III):
• R 2 is selected from the group consisting of:
• 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.
• 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.
• a branched hydrocarbon radical has the following formula (IV):
• R 3 , R 4 and R 5 are, independently of one another, an alkyl group, and at least one of the alkyl groups contains at least two atoms of carbon.
• Such branched alkyl groups, once bound to the carboxyl group, are known as the "neo group", and the corresponding acid as "neo acid”.
• R 3 and R 4 are methyl groups and R 10 is an alkyl group comprising at least two carbon atoms.
• the radical R 2 can comprise one or more carboxyl groups, or ester groups such as -COOR 6 , with R 6 representing an alkyl radical, hydroxyalkyl radical or a hydroxyalkyloxy alkyl group.
• R 6 representing an alkyl radical, hydroxyalkyl radical or a hydroxyalkyloxy alkyl group.
• the R 2 COOH acid of formula (III) is a monocarboxylic acid.
• carboxylic acids in which the hydrocarbon radical is branched include: 2-ethyl-n-butyric acid, 2-hexyldecanoic acid, isostearic acid, 2-methyl-hexanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neoheptanoic acid, and neodecanoic acid.
• the third type of carboxylic acids which can be used in the preparation of the polyol esters of formula (I) are carboxylic acids comprising an aliphatic hydrocarbon radical containing from 8 to 14 carbon atoms.
• carboxylic acids comprising an aliphatic hydrocarbon radical containing from 8 to 14 carbon atoms.
• We can Examples include: decanoic acid, dodecanoic acid, lauric acid, stearic acid, myristic acid, behenic acid, etc.
• dicarboxylic acids mention may be made of maleic acid, succinic acid, adipic acid, sebacic acid ...
• 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 the majority.
• the presence of dicarboxylic acids results in particular in the formation of polyol esters of high viscosity.
• the formation reaction of the polyol esters of formula (I) by reaction between the carboxylic acid and the polyols is an acid catalyzed reaction.
• This is especially a reversible reaction, which can be complete by using 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.
• organic or inorganic acids such as sulfuric acid, phosphoric acid, etc.
• the reaction is carried out in the absence of a catalyst.
• the amount of carboxylic acid and polyol may vary in the mixture depending on the desired results. In the particular case where all the hydroxyl groups are esterified, a sufficient amount 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.
• the esters can be formed by reaction between the carboxylic acids (or their anhydride or ester derivatives) with the polyols in the presence of acids at elevated temperature, while removing the water formed during the reaction. .
• the reaction can be carried out at a temperature of 75 to 200 ° C.
• the polyol esters formed may comprise hydroxyl groups which are not all reactive, in this case they are esters of partially esterified polyols.
• 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 a mixture of 70% of 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.
• 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 especially obtained by reacting said branched carboxylic acid with one or more polyols.
• the branched carboxylic acid comprises at least 5 carbon atoms.
• the branched carboxylic acid comprises from 5 to 8 carbon atoms, and preferably it contains 5 carbon atoms.
• the polyol is selected from the group consisting of neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.
• the polyol esters are obtained from: i) a carboxylic acid selected from 2-methylbutanoic acid, 3-methylbutanoic acid, and mixtures thereof; and
• a polyol selected from the group consisting of neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.
• the polyol ester is that obtained from 2-methylbutanoic acid and pentaerythritol.
• the polyol ester is that obtained from 2-methylbutanoic acid and dipentaerythritol.
• the polyol ester is that obtained from 3-methylbutanoic acid and pentaerythritol.
• the polyol ester is that obtained from 3-methylbutanoic acid and dipentaerythritol.
• the polyol ester is that obtained from 2-methylbutanoic acid and neopentyl glycol.
• the polyol esters according to the invention are poly (neopentylpolyol) esters obtained by: i) reacting a neopentylpolyol having the following formula (V):
• each R is, independently of one another, CH3, C2H5 or p is an integer 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 composition of poly (neopentyl partially esterified polyol; and ii) reacting the partially esterified poly (neopentyl) polyol composition obtained at the end of step i) with another carboxylic acid having 2 to 15 carbon atoms to form the final ester composition ( s) poly (neopentyl polyol).
• the reaction i) is carried out with a molar ratio ranging from 1: 4 to 1: 2.
• the neopentyl polyol has the following formula (VI):
• each R is, independently of one another, Ch, C 2 H 5 or
• Preferred neopentyl polyols are those selected from pentaerythritol, dipentaerythritol, tripentaerythritol, tetraerythritol, trimethylolpropane, trimethylolethane, and neopentyl glycole.
• the neopentyl polyol is pentaerythritol.
• a single neopentyl polyol is used to produce the POE-based lubricant.
• two or more neopentyl polyols are used. This is particularly the case when a commercial product of pentaerythritol includes small amounts of dipentaerythritol, tripentaerythritol, and tetraerythritol.
• 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 C 1 -C 12 alkyl radical, a C 6 -C 12 aryl radical or a C 6 -C 30 aralkyl radical.
• R ' is a C4-C10 alkyl radical, and preferentially a C5-C9 alkyl radical.
• the monocarboxylic acid is selected from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, n-octanoic acid, n nonanoic acid, n-decanoic acid, 3-methylbutanoic acid, 2-methylbutanoic acid, 2,4-dimethylpentanoic acid, 2-ethylhexanoic acid, , 3,5-trimethylhexanoic acid, benzoic acid, and mixtures thereof.
• the monocarboxylic acid is n-heptanoic acid, or a mixture of n-heptanoic acid with another linear monocarboxylic acid, in particular n-octanoic acid and / or n-octanoic acid. - decanoic.
• a mixture of monocarboxylic acid may comprise between 15 and 100 mol% of heptanoic acid and between 85 and 0 mol% of other monocarboxylic acid (s).
• 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 molar ratio of 3: 2.
• the polyol esters comprise: i) from 45% to 55% by weight of a monopentaerythritol ester with at least one monocarboxylic acid having 2 to 15 carbon atoms;
• polyol esters according to the invention have the following formula (VIII):
• a + x, b + y, and c + z are, independently of one another, integers ranging from 1 to 20;
• R 13 , R 14 and R 15 are, independently of one another, selected from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls; cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryls and cycloalkylarylalkyls, R 13 , R 14 and R 15 , having from 1 to 17 carbon atoms, and which may be optionally substituted.
• 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 may comprise at least at least one heteroatom selected from N, O, Si, F or S.
• each of R 13 , R 14 and R 15 has, independently of one another, from 3 to 8 carbon atoms, preferably from 5 to 7 carbon atoms. carbon atoms.
• 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 preferentially from
• 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.
• 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.
• the monocarboxylic acids have one of the following formulas:
• R 15 COOH wherein R 13, R 14 and R 15 are as defined above.
• Derivatives of the carboxylic acids can also be used, such as anhydrides, esters and acyl halides. Esterification can be carried out with one or more monocarboxylic acids.
• Preferred monocarboxylic acids are those selected from the group consisting of acetic acid, propanoic acid, butyric acid, isobutanoic acid, pivalic acid, pentanoic acid, isopentanoic acid, hexanoic acid, 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, citronellic acid, undecenoic acid, lauric acid, undecylenic acid, linolenic acid, arachidic acid, behenic acid, tetrahydrobenzoic acid, hydrogen
• 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 and 3-methylbutanoic acid. , n-hexanoic acid, n-heptanoic acid, 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.
• monocarboxylic acids chosen from the group consisting of butyric acid, isobutyric acid, n-pentanoic acid, 2-methylbutanoic acid and 3-methylbutanoic acid.
• n-hexanoic acid n-heptanoic acid
• polyol esters according to the invention have the following formula (IX):
• each of R 17 and R 18 is, independently of one another, H or CH 3;
• 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, selected from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls; cycloalkylaryls, alkylcycloalkylaryls, alkylarylcycloalkyls, arylcycloalkylalkyls, arylalkylcycloalkyls, cycloalkylalkylaryls and cycloalkylarylalkyls,
• each of R 16 and R 19 represents, independently of one another, a linear or branched alkyl group, an alkenyl group or a cycloalkyl group, said alkyl, alkenyl or cycloalkyl groups possibly comprising at least one heteroatom chosen from N, O, Si, F or S.
• 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. carbon atoms.
• 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.
• the polyol esters of formula (IX) above are triethylene glycol diesters, tetraethylene glycol diesters, in particular with one or two monocarboxylic acids having from 4 to 9 carbon atoms.
• the polyol esters of formula (IX) above may be prepared by esterifications of an ethylene glycol, a propylene glycol, or an oligo- or polyalkylene glycol, (which may 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 2 to 18 carbon atoms.
• the esterification can be carried out identically to the esterification reaction used to prepare the polyol esters of formula (VIII) above.
• 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).
• 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.
• 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).
• Preferred POE lubricants according to the invention are those having a viscosity of from 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 in particular given by the standard
• the azeotropic composition content according to the invention in the heat transfer composition ranges from 1 to 5% by weight; or 5 to 10%; or 10 to 15%; or 15 to 20%; or from 20 to 25%; or 25 to 30%; or from 30 to 35%; or 35 to 40%; or 40 to 45%; or 45 to 50%; or 50 to 55%; or 55 to 60%; or from 60 to 65%; or from 65 to 70%; or 70 to 75%; or from 75 to 80%; or from 80 to 85%; or from 85 to 90%; or from 90 to 95%; or from 95 to 99%; or from 99 to 99.5%; or from 99.5 to 99.9%; or more than 99.9%, based on the total weight of the heat transfer composition.
• the content of azeotropic composition according to the invention may also vary in several of the above ranges: for example from 50 to 55%, and from 55
• the heat transfer composition comprises more than 50% by weight of azeotropic composition according to the invention, and in particular from 50% to 99% by weight, relative to the total weight of the transfer composition. heat.
• the mass proportion of lubricant, and in particular of polyol ester (POE) lubricant may 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; or from 99 to 99.5% of the composition; or from 99.5 to 99.9% of the composition; or more
• POE polyol ester
• the present invention relates to the use of a quasi-azeotropic composition as defined above, as a heat transfer fluid.
• the present invention also relates to the use of a quasi-azeotropic composition or a heat transfer composition according to the invention, in a heat transfer system containing a vapor compression circuit.
• the heat transfer system is:
• the present invention also relates to a heat transfer method based on the use of a heat transfer system containing a vapor compression circuit which comprises the quasi-azeotropic composition or the heat transfer composition according to the invention.
• the heat transfer process may be a method of heating or cooling a fluid or a body.
• the quasi-azeotropic composition or the heat transfer composition may also be used in a method of 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 quasi-azeotropic composition or the heat transfer composition according to the invention.
• this installation is selected from mobile or stationary refrigeration, heating (heat pump), air conditioning and freezing, and thermal engines.
• the heat transfer installation is a heat pump, or an air conditioning installation, for example a chiller.
• the invention also relates to a method for heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid 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 heat transfer composition.
• heat transfer composition wherein the heat transfer fluid is the azeotropic composition according to the invention, or the heat transfer composition is as described above.
• the invention also relates to a method for producing electricity by means of a heat engine, said method comprising successively the evaporation of the heat transfer fluid or a heat transfer composition, the expansion of the fluid or the heat transfer composition in a turbine for generating electricity, condensing the fluid or heat transfer composition and compressing the fluid or heat transfer composition, wherein the transfer fluid of heat is the almost azeotropic 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, a compressor preferably screw, a condenser and a pressure regulator, and lines for transporting the fluid or of the heat transfer composition between these elements.
• the evaporator and the condenser comprise a heat exchanger for heat exchange between the fluid or the heat transfer composition and another fluid or body.
• the evaporator used in the context of the invention may be an overheating evaporator or an embedded evaporator. In an overheated evaporator, all of the aforementioned fluid or heat transfer composition is evaporated at the evaporator outlet, and the vapor phase is superheated.
• a flooded evaporator In a flooded evaporator, the fluid / heat transfer composition in liquid form does not evaporate completely.
• a flooded evaporator has a liquid phase and vapor phase separator.
• As a compressor it is possible to use in particular a centrifugal compressor with one or more stages or a mini centrifugal compressor. Rotary, piston or screw compressors can also be used.
• the vapor compression circuit comprises a screw compressor, preferably twin-screw or single-screw.
• the vapor compression circuit comprises a twin-screw compressor, which can implement a substantial flow of oil, for example up to 6.3 Us.
• 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 a diffuser housed in an enclosure.
• the heat transfer fluid or heat transfer composition is introduced into the center of the rotor and flows towards the periphery of the rotor while undergoing acceleration.
• 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 of the static pressure.
• Each rotor / diffuser assembly constitutes a compressor stage.
• the centrifugal compressors may comprise 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 / output heat transfer composition to the absolute pressure of said fluid or composition at the inlet.
• the rotational speed for large centrifugal compressors ranges from 3000 to 7000 revolutions per minute.
• Small centrifugal compressors (or centrifugal mini-compressors) generally operate at a rotation speed that ranges from 40000 to 7000 revolutions per minute and comprise a small rotor (generally less than 0.15 m).
• a multi-stage rotor can be used to improve the efficiency of the compressor and to limit the energy cost (compared to a single-stage rotor).
• the output of the first stage of the rotor feeds the input of the second rotor.
• Both rotors can be mounted on a single axis.
• Each stage can provide a fluid compression ratio of about 4 to 1, i.e. the output absolute pressure can be about four times the absolute suction pressure.
• Examples of two-stage centrifugal compressors, particularly for automotive applications, are described in 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 the exhaust gas of a vehicle, for mobile applications) or by gearing.
• the installation may include a coupling of the expander with a turbine to generate electricity (Rankine cycle).
• the installation may also optionally comprise at least one heat transfer fluid circuit used for transmitting the heat (with or without a change of state) between the circuit of the heat transfer fluid or the heat transfer composition, and the fluid or body to be heated or cooled.
• the installation may also optionally include two or more vapor compression circuits containing identical or different heat transfer fluids / compositions. For example, the vapor compression circuits may be coupled together.
• the vapor compression circuit operates in a conventional vapor compression cycle.
• the cycle comprises changing the state of the fluid / heat transfer composition from a liquid phase (or diphasic liquid / vapor) to a vapor phase at a relatively low pressure, and then compressing the fluid / composition 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 the reduction of the pressure to start again the cycle.
• Cooling processes include air conditioning processes (with mobile installations, for example in vehicles, or stationary), refrigeration and freezing or cryogenics.
• air conditioning processes there may be mentioned domestic air conditioning, commercial or industrial, where the equipment used are either chillers or direct expansion equipment.
• domestic air conditioning commercial, cold rooms, the food industry, refrigerated transport (trucks, boats).
• heat is transferred (directly or indirectly, via a heat transfer fluid) from the fluid / heat transfer composition, during the condensation thereof / it, to fluid or body that is heated, and at a relatively high temperature relative to the environment.
• heat pump The installation for implementing the heat transfer is called in this case "heat pump”.
• These can include medium and high temperature heat pumps.
• thermodynamical it is possible to use any type of heat exchanger for the implementation of the compositions (azeotropic or heat transfer) according to the invention, and in particular co-current heat exchangers or, preferably, exchangers countercurrent heat.
• the invention provides that the cooling and heating processes, and the corresponding facilities, comprise a countercurrent heat exchanger, either the condenser or the evaporator.
• a countercurrent heat exchanger either the condenser or the evaporator.
• the compositions according to the invention quadsi-azeotropic composition or heat transfer composition defined above
• both the evaporator and the condenser comprise a countercurrent heat exchanger.
• countercurrent heat exchanger is understood to mean a heat exchanger in which heat is exchanged between a first fluid and a second fluid, the first fluid at the inlet of the exchanger exchanging heat with the second fluid at the outlet of the exchanger, and the first fluid at the outlet of the exchanger exchanging heat with the second fluid at the inlet of the exchanger.
• countercurrent heat exchangers include devices in which the flow of the first fluid and the flow of the second fluid are in opposite or almost opposite directions.
• the exchangers operating in cross current mode with countercurrent tendency are also included among the countercurrent heat exchangers within the meaning of the present application.
• the inlet temperature of the composition according to the invention (quasi-azeotropic or heat transfer composition) to the evaporator is preferably from -45 ° C. to -15 ° C. C, especially from -40 ° C to -20 ° C, more preferably from -35 ° C to -25 ° C, and for example about -30 ° C; and the temperature of the beginning of the condensation of the composition according to the invention (quasi-azeotropic or heat transfer composition) at the condenser is preferably from 25 ° C. to 80 ° C., in particular from 30 ° C. to 60 ° C., more preferably from 35 ° C to 55 ° C and for example from about 40 ° C.
• the inlet temperature of the composition according to the invention (quasi-azeotropic or heat transfer composition) to the evaporator is preferably from -20 ° C. to 10 ° C. in particular from -15 ° C to 5 ° C, more preferably from -10 ° C to 0 ° C and for example from about -5 ° C; and the temperature of the beginning of the condensation of the composition according to the invention (quasi-azeotropic or heat transfer composition) at the condenser is preferably from 25 ° C. to 80 ° C., in particular from 30 ° C. to 60 ° C., more preferably from 35 ° C to 55 ° C and for example from about 50 ° C.
• the inlet temperature of the composition according to the invention (quasi-azeotropic or heat transfer composition) to the evaporator is preferably from -20 ° C. to 10 ° C. in particular from -15 ° C to 5 ° C, more preferably from -10 ° C to 0 ° C and for example from about -5 ° C; and the temperature of the beginning of the condensation of the composition according to the invention (quasi-azeotropic or heat transfer composition) at the condenser is preferably from 25 ° C. to 80 ° C., in particular from 30 ° C. to 60 ° C., more preferably from 35 ° C to 55 ° C and for example from about 50 ° C.
• compositions according to the invention are particularly interesting in the refrigerated transport.
• Refrigerated transport can be carried out by truck, rail or boat, possibly using multi-platform containers that fit equally well on trucks, rails or boats.
• the temperature of refrigerated spaces is between -30 ° C and 16 ° C.
• the refrigerant charge in the transport by truck, rail or Multi-platform containers vary between 4 kg and 8 kg of refrigerant.
• the installations in the boats can contain between 100 and 500kg.
• the operating temperatures of the refrigerating plants depend on the refrigeration temperature requirements and the external climatic conditions.
• the same refrigeration system must be able to cover a wide temperature range of -30 ° C to 16 ° C and operate in both cold and hot climates.
• the most restrictive condition at evaporation temperature is -30 ° C.
• compositions according to the invention can be used to replace various heat transfer fluids in various heat transfer applications, such as 1,1,1,2-tetrafluoroethane (R134a).
• R134a 1,1,1,2-tetrafluoroethane
• the present invention also relates to the use of the quasi-azeotropic compositions according to the invention, replacing R134a in refrigeration and / or in heat pumps.
• Tsat evap designates the temperature of the saturated vapor fluid at the outlet of the evaporator
• Evap inlet designates the temperature of the fluid at the inlet of the evaporator
• T output comp designates the temperature of the fluid at the outlet of the compressor
• T sat liq cond designates the temperature of the liquid saturated fluid at the outlet of the condenser
• T sat vap cond designates the temperature of the saturated vapor fluid at the condenser
• Pévap designates the pressure fluid in the evaporator
• Pcond refers to the fluid pressure in the condenser
• evap slip refers to the temperature slip at the evaporator.
• COP coefficient of performance and is defined, in the case of a refrigeration system as being the useful cold power supplied by the system on the power supplied or consumed by the system.
• Isentropic efficiency of the compressor it is the ratio between the real energy transmitted to the fluid and the isentropic energy. This isentropic efficiency is a function of the compression ratio. It is determined according to a typical yield curve. According to the "Handbook of Air Conditioning and Refrigeration, Shan Wang,”
• compositions of the invention advantageously have a better coefficient of performance COP with respect to R134a.
• compositions of the invention advantageously have a compressor outlet temperature lower than that of R134a.
• the compositions according to the invention can be used to replace the R134a without modifying the compressor technology. This also advantageously makes it possible to limit the mechanical stresses on the compressors, and to limit their heating.

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