法国专利FR3033791A1 STABILIZATION OF 1-CHLORO-3,3,3-TRIFLUOROPROPENE

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专利摘要:
The invention relates to the use of a C3-C6 alkene compound having a single double bond to limit or prevent the isomerization of trans-1-chloro-3,3,3-trifluoropropene to cis-1-chloro -3,3,3-trifluoropropene. The invention also provides a composition comprising 1-chloro-3,3,3-trifluoropropene and a C3-C6 alkene compound having a single double bond; as well as various uses of this composition.
公开号:FR3033791A1
申请号:FR1552222
申请日:2015-03-18
公开日:2016-09-23
发明作者:Wissam Rached；Sophie Guerin；Pascale KINDLER
申请人:Arkema France SA；
IPC主号:

专利说明:

[0001] FIELD OF THE INVENTION The present invention relates to compounds for stabilizing 1-chloro-3,3,3-trifluoropropene and more specifically to limiting or preventing isomerization. from the trans form to cis form. The invention also relates to the use of such stabilizers in heat transfer applications.
[0002] TECHNICAL BACKGROUND Trans-1-chloro-3,3,3-trifluoropropene (HCF0-1233zdE) is a product with low global warming potential (GWP). It has very favorable thermodynamic and thermophysical properties for use as a heat transfer fluid in cooling, air conditioning, power generation (including organic Rankine ring) and high heat pump applications. temperature. HCF0-1233zdE exhibits instability that manifests itself especially at relatively high temperatures. This instability is an isomerization of a fraction of the initial charge resulting in the formation of cis-1-chloro-3,3,3-trifluoropropene (HCF0-1233zdZ). However, HCF0-1233zdZ is a less volatile product than HCF0-1233zdE. The boiling temperature is of the order of 40 ° C for the Z isomer, and of the order of 18.3 ° C for the E isomer. This difference involves a change in the thermodynamic and thermophysical properties of the product. in facilities, and a loss of performance, when isomerization occurs. WO 20091003165 describes the risks of degradation of hydrofluoroolefins and hydrochlorofluoroolefins, as well as stabilizers for combating this degradation. These stabilizers include free radical scavenging compounds, acid scavenging compounds, oxygen scavenging compounds, and polymerization inhibitors. Particularly mentioned are: 1,2-epoxybutane, glycidyl methyl ether, d-1-limonene oxide, 1,2-epoxymethylpropane, nitromethane, alpha methylstyrene, isoprene, phenol, hydroquinones and hydrazine. US 7,795,480 discloses a process for making 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). A phenomenon of polymerization of the compound is mentioned (but not an isomerization phenomenon). Proposed stabilizers are p-tap (4-tert-amylphenol), methoxyhydroquinone, 4-methoxyphenol, triethylamine, di-isopropylamine, butylated hydroxyanisole and thymol. Document US Pat. No. 8,217,208 describes the phenomenon of isomerization of HF0-1233zdE under the effect of temperature, but it does not teach stabilizers making it possible to limit this isomerization. Document US 2012/0226081 describes the risks of degradation of hydrochloroolefins and hydrochloroalkanes, and proposes a set of possible stabilizers: alpha-methylstyrene, alpha-pinenoxide, beta-pinenoxide, 1,2-epoxybutane, 1,2-hexadecene oxide and oxygen scavenging compounds such as diethylhydroxylamine, hydroquinone, methylethylketooxime and p-methoxyphenol. Document US 2015/0034523 describes the risks of degradation of hydrochloroolefins and proposes two families of stabilizers, namely morpholines or trialkyl phosphates. Almost all the stabilizers proposed in the state of the art are solid products, or liquid products having a high boiling point. For example, the boiling point of alphamethylstyrene is 165 ° C, the boiling point of limonene oxide is above 200 ° C, and so on. Isoprene, mentioned in WO 2009/003165, is itself an unstable product in itself, which must generally be combined with a compound such as 4-tert-butylpyrocatechol to prevent its polymerization. The features described above render the stabilizers unsuitable for certain applications in which HCF0-1233zdE is likely to be employed. This is particularly the case for applications using flooded evaporators (especially with compressors without lubricating oil). In such applications, high boiling point state of the art stabilizers are ineffective because they concentrate in the evaporator and do not migrate with the heat transfer fluid to the condenser.
[0003] There is therefore a need to provide stabilizers for limiting or preventing the isomerization of HCF0-1233zdE to HCF0-1233zdZ, especially in vapor compression systems such as air-conditioning, refrigeration, air-conditioning and refrigeration systems. Rankine organic heat and cycle pump, and particularly the systems comprising a flooded evaporator. SUMMARY OF THE INVENTION The invention primarily relates to the use of a C3-C6 alkene compound having a single double bond to limit or prevent the isomerization of trans-1-chloro-3,3. 3-trifluoropropene to cis-1-chloro-3,3,3-trifluoropropene. According to one embodiment, the alkene compound is butene or pentene.
[0004] According to one embodiment, the alkene compound has: a boiling temperature of less than or equal to 100 ° C., preferably less than or equal to 75 ° C., and more particularly preferably less than or equal to 50 ° C .; and / or - a solidification temperature of less than or equal to 0 ° C, preferably less than or equal to -25 ° C, and more preferably less than or equal to -50 ° C. According to one embodiment, the alkene compound is 2-methyl-but-2-ene. According to one embodiment, the alkene compound is 3-methyl-1-butene. The invention also relates to a composition comprising 1-chloro-3,3,3-trifluoropropene and a C3-C6 alkene compound having a single double bond. In one embodiment, the alkene compound is butene or pentene. According to one embodiment, the alkene compound has: a boiling temperature of less than or equal to 100 ° C., preferably less than or equal to 75 ° C., and more particularly preferably less than or equal to 50 ° C .; and / or a solidification temperature of less than or equal to 0 ° C, preferably less than or equal to -25 ° C, and more preferably less than or equal to -50 ° C.
[0005] According to one embodiment, the alkene compound is 2-methyl-but-2-ene. According to one embodiment, the alkene compound is 3-methyl-1-butene.
[0006] According to one embodiment, the composition comprises from 0.01 to 5%, preferably from 0.1 to 2% and more particularly from 0.2 to 1%, by weight, of alkene compound. According to one embodiment, the 1-chloro-3,3,3-trifluoropropene is in trans form in a mass proportion of greater than or equal to 90%, preferably greater than or equal to 95%, more preferably greater than or equal to equal to 98%, even more preferably greater than or equal to 99%, and ideally greater than or equal to 99.5% or even greater than 99.9%. According to one embodiment, the composition further comprises one or more different heat transfer compounds of 1-chloro-3,3,3-trifluoropropene and / or one or more additives selected from different stabilizers of the alkene compound, lubricants, surfactants, tracers, fluorescers, odorants, solubilizers and mixtures thereof.
[0007] The invention also relates to the use of the above composition as a heat transfer fluid in a vapor compression system. According to one embodiment, the vapor compression system is: an air conditioning system; or - a refrigeration system; or - a freezing system; or - a heat pump system. According to one embodiment, the above use is a use as a heat transfer fluid in a heat engine. According to one embodiment, the heat transfer fluid is at a temperature greater than or equal to 100 ° C, preferably greater than or equal to 140 ° C, more preferably greater than or equal to 180 ° C, for at least a fraction of its useful life.
[0008] According to one embodiment, the heat transfer fluid is evaporated in an embedded evaporator.
[0009] The invention also relates to a heat transfer plant comprising a circuit containing the above composition as a heat transfer fluid. According to one embodiment, the plant is chosen from mobile or stationary heat pump heating, air conditioning, refrigeration, freezing and thermal engines. According to one embodiment, the installation comprises a flooded evaporator. The invention also relates to a method of heating or cooling a fluid or a body by means of a vapor compression system containing a heat transfer fluid, said method comprising successively the evaporation of the heat transfer fluid, compression of the heat transfer fluid, condensation of the heat medium and expansion of the heat transfer fluid, wherein the heat transfer fluid is the composition 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, the expansion of the heat transfer fluid in a turbine to generate electricity, condensing the heat medium and compressing the heat transfer fluid, wherein the heat transfer fluid is the composition described above. The present invention overcomes the disadvantages of the state of the art. More particularly, it provides stabilizers for limiting or preventing the isomerization of HCF0-1233zdE to HCF0-1233zdZ, especially in vapor compression systems such as air-conditioning, refrigeration, heat pump, and air-conditioning systems. thermal engine, and especially the systems comprising a flooded evaporator.
[0010] DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows. Unless stated otherwise, throughout the application the proportions of compounds indicated are given in percentages by weight. The invention is based on the discovery that C3-C6 alkenes having a single double bond make it possible to stabilize HCF0-1233zdE, that is to say to limit or prevent its isomerization to HCF0-1233zdZ, especially at high temperatures. The stabilizing compounds of the invention are therefore propene, butenes, pentenes and hexenes. Butenes and pentenes are preferred. Pentenes are even more particularly preferred. The stabilizing compounds of the invention may be straight-chain or branched and preferably branched. Preferably, they have a boiling point less than or equal to 100 ° C, more preferably less than or equal to 75 ° C, and more preferably less than or equal to 50 ° C. "Boiling temperature" means the boiling point at a pressure of 101.325 kPa, as determined according to standard NF EN 378-1 of April 2008. Preferably, they also have a lower solidification temperature. or equal to 0 ° C, preferably less than or equal to -25 ° C, and more preferably less than or equal to -50 ° C. The solidification temperature is determined according to Test No. 102: Melting Point / Melting Range (OECD Guidelines for the Testing of Chemicals, Section 1, OECD Publishing, Paris, 1995, 20 available at address http: // dx., 0, 10.1787 / 97892640695344r). Stabilizing compounds of the invention include: - but-1-ene; cis-but-2-ene; trans-but-2-ene; 2-methylprop-1-ene; pent-1-ene; cis-pent-2-ene; trans-pent-2-ene; 2-methylbut-1-ene; 2-methylbut-2-ene; and - 3-methylbut-1-ene. Among the preferred compounds, there is especially 2-methyl-but-2-ene, of formula (CH 3) 2 C = CH-CH 3 (boiling temperature of about 39 ° C); and 3-methyl-but-1-ene, of formula CH3-CH (CH3) -CH = CH2 (boiling temperature of about 25 ° C). Two or more of the above compounds may also be used in combination.
[0011] The stabilizing compounds according to the invention are thus advantageously used in combination with HCF0-1233zd, and more particularly with HCF0-1233zdE, in heat transfer applications. Thus, the invention provides a composition, particularly useful for heat transfer applications, comprising at least HCF0-1233zd and a stabilizing compound described above. The weight ratio of the above stabilizing compounds in the composition may especially be: from 0.01 to 0.05%; or from 0.05 to 0.1%; or 0.1 to 0.2%, or 0.2 to 0.3%; or from 0.3 to 0.4%; or from 0.4 to 0.5%; or from 0.5 to 0.6%; or from 0.6 to 0.7%; or from 0.7 to 0.8%; or from 0.8 to 0.9%; or from 0.9 to 1%; or from 1 to 1.2%; or 1.2 to 1.5%, or 1.5 to 2%; or 2 to 3%; or 3-4%; or 4 to 5%. The composition may comprise HCF0-1233zdE and optionally HCF0-1233zdZ. Advantageously, the proportion of HCF0-1233zdE, relative to the total of HCF0-1233zd, is greater than or equal to 90%, or 91%, or 92%, or 93%, or 94%, or 95%. %, or 96%, or 97%, or 98%, or 99%, or 99.1%, or 99.2%, or 99.3%, or 99.4%, or 99.5%, or 99.6%, or 99.7%, or 99.8%, or 99.9%, or 99.91%, or 99.92%, or to 99.93%, or 99.94%, or 99.95%, or 99.96%, or 99.97%, or 99.98%, or 99.99%. The presence of the stabilizing compound makes it possible to limit or prevent an increase in the proportion of HCF0-1233zdZ in the composition over time and / or when relatively high temperatures are applied.
[0012] The composition of the invention may also comprise various additives. In the case where it is a heat transfer composition, the additives may especially be chosen from lubricants, nanoparticles, stabilizers (different from the stabilizing compounds of the invention), surfactants, tracer agents, fluorescers, odorants and solubilizers. The stabilizer (s), when present, preferably represent at most 5% by weight in the heat transfer composition. Among the stabilizers, there may be mentioned in particular nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenol compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated or alkenyl or aromatic alkyl) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether , phosphites, phosphonates, thiols and lactones. Lubricants which may be used include oils of mineral origin, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, polyalphaolefins, polyalkene glycols, polyols and the like. esters and / or polyvinyl ethers. According to an advantageous embodiment of the invention, the composition of the invention is, however, devoid of lubricant.
[0013] As nanoparticles, it is possible to use, in particular, nanoparticles of carbon, metal oxides (copper, aluminum), TiO 2, Al 2 O 3, MoO 2, etc. Tracer agents that may be detected include deuterated hydrofluorocarbons. or not, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof. The tracer agent is different from the one or more heat transfer compounds composing the heat transfer fluid. As solubilizing agents, mention may be made of hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and the like. 1,1-trifluoroalcanes. The solubilizing agent is different from the one or more heat transfer compounds composing the heat transfer fluid. As fluorescent agents include naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanhthenes, fluoresceins and derivatives and combinations thereof. As odorants, mention may be made of alkyl acrylates, allyl acrylates, acrylic acids, acrylresters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allylisothiocyanates, and the like. alkanoids, amines, norbornenes, norbornene derivatives, cyclohexene, heterocyclic aromatic compounds, ascaridole, o-methoxy (methyl) phenol and combinations thereof. The composition according to the invention may also comprise at least one other heat transfer compound, in addition to HCF0-1233zd. Such other optional heat transfer compound may be especially a hydrocarbon compound, ether, hydrofluoroether, hydrofluorocarbon, hydrochlorofluorocarbon, hydrofluoroolefin, hydrochloroolefin or hydrochlorofluoroolefin. By way of example, the said other heat transfer compound may be chosen from 1,1,1,4,4,4-hexafluorobut-2-ene (HF0-1336mmz, E or Z isomer), 3, 3,4,4,4-pentafluorobut-1-ene (HFO-1345fz), 2,4,4,4-tetrafluorobut-1-ene (HF0-1354mfy), 1,1,1,3,3- pentafluoropropane (HFC-245fa), 2,3,3,3-tetrafluoropropene (HF0-1234yf), 1,3,3,3-tetrafluoropropene (HF0-1234ze), difluoromethane (HFC-32), 1, 1,1,2-tetrafluoroethane (HFC134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1-difluoroethane (HFC-152a), pentafluoroethane (HFC-125), 1 , 1,1,3,3-pentafluorobutane (HFC-365mfc), methoxynonafluorobutane (HFE7100), butane (HC-600), 2-methylbutane (HC-601a), pentane (HC-601), ethyl ether, methyl acetate and combinations thereof. In the composition of the invention, the HCF0-1233zd 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 60% of the composition. 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 than 99.9% of the composition. The content of HCF0-1233zd may also vary in several of the above ranges: for example from 50 to 55% and 55 to 60%, ie from 50 to 60%, etc. The composition of the invention can be used in a heat transfer process. The heat transfer method according to the invention is based on the use of an installation comprising a vapor compression system which contains the composition of the invention as a heat transfer fluid. The heat transfer process may be a method of heating or cooling a fluid or a body.
[0014] The composition of the invention can also be used in a method of producing mechanical work or electricity, in particular according to a Rankine cycle. For heating and cooling applications, the vapor compression system comprises at least one evaporator, a compressor, a condenser and a pressure reducer, as well as heat transfer fluid transport lines between these elements. The evaporator and the condenser comprise a heat exchanger allowing a heat exchange between the heat transfer fluid and another fluid or body.
[0015] As a compressor, it is possible to use in particular a centrifugal compressor with one or more stages or a centrifugal mini-compressor. Rotary, scroll, piston or screw compressors can also be used. The compressor may be driven by an electric motor or by a gas turbine (eg powered by vehicle exhaust, for mobile applications) or by gearing. The vapor compression system then operates in a conventional vapor compression cycle. The cycle comprises changing the state of the heat transfer fluid from a liquid phase (or two-phase liquid / vapor) to a vapor phase at a relatively low pressure, and then compressing the fluid in the vapor phase to a pressure relatively high, the change of state (condensation) of the heat transfer fluid from the vapor phase to the liquid phase at a relatively high pressure, and the reduction of pressure to restart the cycle. The installation may also optionally include at least one heat transfer fluid circuit used to transmit heat (with or without a change of state) between the heat transfer fluid circuit and the fluid or body to be heated or cooled. The plant may also optionally include two or more vapor compression systems containing identical or different heat transfer fluids. For example, steam compression systems can be coupled together. The cooling methods and installations according to the invention comprise air conditioning methods and installations (with mobile installations, for example in vehicles, or stationary), refrigeration (with mobile installations for example in containers, or stationary). and freezing or cryogenics.
[0016] The heating installations according to the invention comprise heat pumps. For mechanical work or electrical production applications, the plant is a heat engine, which comprises at least one evaporator, a turbine, a condenser and a pump, as well as heat transfer fluid transport lines. between these elements. The installation can then operate according to a Rankine cycle. It is possible to use any type of heat exchanger for the implementation of the heat transfer fluids according to the invention, and in particular co-current heat exchangers or, preferably, heat exchangers. against the current. In particular, the evaporator used in the context of the invention may be an overheated evaporator or an embedded evaporator. In an overheated evaporator, all of the heat transfer fluid is evaporated at the evaporator outlet, and the vapor phase is superheated. In a flooded evaporator, the heat transfer fluid in liquid form does not evaporate completely. A flooded evaporator has a liquid phase and vapor phase separator. The invention is particularly useful when such an evaporator is used.
[0017] Indeed, the stabilizers of the state of the art with high boiling point are inefficient when such an evaporator is used, because they concentrate in the evaporator and do not migrate with the heat transfer fluid to the condenser . The invention is also particularly useful where a high temperature exists at at least one point in the fluid circuit, and more particularly at a temperature of 100 ° C or higher, or at 110 ° C, or at 120 ° C, or at 130 ° C, or at 140 ° C, or at 150 ° C, or at 160 ° C, or at 170 ° C, or at 180 ° C, or at 190 ° C, or at 200 ° C. Indeed, it is under these conditions that HCF0-1233zdE is most likely to convert to HCF0-1233zdZ.
[0018] In particular, in air conditioning apparatus, the general operating temperature is below 100 ° C; but hot spots at the outlet of the compressor can reach temperatures above 100 ° C, affecting the heat transfer fluid on a small proportion of its full circulation time (for example less than 1%).
[0019] In heat pumps, the condensation temperature can reach about 140 ° C. In this case, the heat transfer fluid may be at a temperature of about 140 ° C over a substantial proportion of its full circulation time (e.g., about 50%). In addition, hot spots between 150 and 200 ° C can also be seen at the outlet of the compressor. The impact of a long residence time at temperatures above 100 ° C and the existence of points at temperatures that may be close to 200 ° C therefore require a stabilizer. Also preferably, in the plant according to the invention, the temperature of the composition used as a heat transfer fluid remains greater than the solidification temperature of the stabilizing compound, in order to avoid any deposit of solid material in the circuit. .
[0020] The composition according to the invention may also be useful as an expanding agent, propellant (eg for an aerosol), cleaning agent or solvent, dielectric gas, in addition to its use as a heat. As a propellant, the composition according to the invention may be used alone or in combination with known propellants. The propellant comprises, preferably consists of, a composition according to the invention. The active substance to be sprayed can be mixed with the propellant and inert compounds, solvents or other additives to form a sprayable composition. Preferably, the composition to be sprayed is an aerosol. As the blowing agent, the composition according to the invention can be included in an expansion composition, which preferably comprises one or more other compounds capable of reacting and forming a foam or cell structure under appropriate conditions, as is known to those skilled in the art. In particular, the invention provides a process for preparing an expanded thermoplastic product comprising first the preparation of a polymeric expansion composition. Typically, the polymeric expansion composition is prepared by plasticizing a polymer resin and blending the compounds of a blowing agent composition at an initial pressure. The plasticization of the polymer resin can be carried out under the effect of heat by heating the polymer resin to soften it sufficiently to mix a blowing agent composition. Generally, the plasticization temperature is close to the glass transition temperature or the melting temperature for the crystalline polymers. Other uses of the composition according to the invention include uses as a solvent, cleaning agent or the like. Examples include steam degreasing, precision cleaning, electronic circuit cleaning, dry cleaning, abrasive cleaning, solvents for the deposition of lubricants and release agents, and the like. other solvent or surface treatments.
[0021] EXAMPLES The following examples illustrate the invention without limiting it. Example 1 (Comparative) - Instability of HCF0-1233zdE in the Absence of Stabilizer The thermal stability tests of HCF0-1233zdE are carried out according to the ASHRAE 97-2007 standard entitled "Sealed glass tube method for testing the chemical stability of materials". use within refrigerant systems ". The compositions are determined by gas chromatograph on a CP-siI8-CB column. A first series of tests is carried out at 150 ° C for periods of between 10 minutes and 14 days. The results show a slight formation of the HF0-1233zdZ isomer, up to a content of 0.14% at 14 days.
[0022] A second series of tests is carried out at 200 ° C. for a duration of 24 hours. The results show a slight formation of the HCF0-1233zdZ isomer up to about 1%. Finally, a third series of tests is carried out at 250 ° C. for a duration of 24 hours also. The results show a formation of the HCF0-1233zdZ isomer of between 6 and 9%. Example 2 (Invention) - Stabilization of HCF0-1233zdE Thermal stability tests similar to those of Example 1 were carried out, adding 0.5% stabilizer to HCF0-1233zdE (mass content relative to the sum of the stabilizer and HCF0-1233zdE). The stabilizers tested are 2-methyl-but-2-ene (2m2b) and 3-methyl-but-1-ene (3m1b). A first series of tests is carried out at 150 ° C for a period of 14 days. Tests with 3m1b show a formation of the HCF0-1233zdZ isomer of the order of 0.08% at the end of the period. In tests with 2m2b, no formation of HF0-1233zd-Z was measured. A second series of tests is carried out at 200 ° C. for a duration of 24 hours. Tests with 3m1b show a slight formation of the isomer 3033791 14 HF0-1233zdZ of the order of 0.3%, and those with 2m2b show a formation of HCF0-1233zdZ of the order of 0.07% to the end of this period. The following table summarizes the stabilization effect observed: HCF0-1233zdE HCF0-1233zdE HCFP-1233zdE alone + 3m1b + 2m2b 14 days at 0.14% of 0.08% of HCF0-1233zdZ 150 ° C HCF0-1233zdZ HCF0-1233zdZ undetectable 24 hours at 1% of HCF0- 0.3% of HCF0- 0.07% of 200 ° C 1233zdZ 1233zdZ HCF0-1233zdZ 5 10

权利要求:
Claims (8)
[0001]
REVENDICATIONS1. Use of a C3-C6 alkene compound having a single double bond to limit or prevent the isomerization of trans-1-chloro-3,3,3-trifluoropropene to cis-1-chloro-3,3 3-trifluoropropene.
[0002]
2. Use according to claim 1, wherein the alkene compound is butene or pentene.
[0003]
3. Use according to claim 1 or 2, wherein the alkene compound has: a boiling temperature less than or equal to 100 ° C, preferably less than or equal to 75 ° C, and more preferably less than or equal to at 50 ° C; and / or - a solidification temperature of less than or equal to 0 ° C, preferably less than or equal to -25 ° C, and more preferably less than or equal to -50 ° C.
[0004]
4. Use according to claim 1, wherein the alkene compound is 2-methyl-but-2-ene.
[0005]
Use according to claim 1, wherein the alkene compound is 3-methyl-but-1-ene.
[0006]
6. A composition comprising 1-chloro-3,3,3-trifluoropropene and a C3-C6 alkene compound having a single double bond.
[0007]
The composition of claim 6 wherein the alkene compound is butene or pentene.
[0008]
8. Composition according to Claim 6 or 7, in which the alkene compound has: a boiling temperature of less than or equal to 100 ° C., preferably less than or equal to 75 ° C., and more particularly preferably less than or equal to at 50 ° C; and / or a solidification temperature of less than or equal to 0 ° C, preferably less than or equal to -25 ° C, and more preferably less than or equal to -50 ° C. The composition of claim 6, wherein the alkene compound is 2-methyl-but-2-ene. The composition of claim 6 wherein the alkene compound is 3-methyl-1-butene. Composition according to one of Claims 6 to 10, comprising from 0.01 to 5%, preferably from 0.1 to 2% and more particularly from 0.2 to 1%, by weight, of alkene compound. Composition according to one of Claims 6 to 11, in which the 1-chloro-3,3,3-trifluoropropene is in trans form in a mass proportion of greater than or equal to 90%, preferably greater than or equal to 95%, of more particularly preferably greater than or equal to 98%, even more preferably greater than or equal to 99%, and ideally greater than or equal to 99.5% or even greater than 99.9%. Composition according to one of claims 6 to 12, further comprising one or more different heat transfer compounds of 1-chloro-3,3,3-trifluoropropene and / or one or more additives selected from stabilizers different from the alkene compound lubricants, surfactants, tracers, fluorescers, odorants, solubilizers, and mixtures thereof. Use of a composition according to one of claims 6 to 13 as a heat transfer fluid in a vapor compression system. Use according to claim 14, wherein the vapor compression system is: - an air conditioning system; or 3033791 17 - a refrigeration system; or - a freezing system; or - a heat pump system. 16. Use of a composition according to one of claims 6 to 13 as a heat transfer fluid in a heat engine. 17. Use according to one of claims 14 to 16, wherein the heat transfer fluid is at a temperature greater than or equal to 100 ° C, preferably greater than or equal to 140 ° C, more preferably greater than or at 180 ° C, for at least a fraction of its useful life. 18. Use according to one of claims 14 to 17, wherein the heat transfer fluid is evaporated in an embedded evaporator. 19. Heat transfer plant comprising a circuit 20 containing a composition according to one of claims 6 to 13 as a heat transfer fluid. 20. Installation according to claim 19, selected from mobile or stationary heat pump heating, air conditioning, refrigeration, freezing and thermal engines. 21. Installation according to claim 19 or 20, comprising a flooded evaporator. 22. A method of heating or cooling a fluid or a body by means of a vapor compression system containing a heat transfer fluid, said method comprising successively evaporation of the heat transfer fluid the compression of the heat transfer fluid, the condensation of the heat medium and the expansion of the heat transfer fluid, wherein the heat transfer fluid is a composition according to one of claims 6 to 13. 3033791 18 23 A method of producing electricity by means of a heat engine, said method comprising successively evaporation of the heat transfer fluid, expansion of the heat transfer fluid in a turbine for generating electricity, the condensing the heat fluid and compressing the heat transfer fluid, wherein the heat transfer fluid is a composition according to one of claims 6 to 13. 10

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FR3008419A1|2015-01-16|2,3,3,3-TETRAFLUOROPROPENE-BASED COMPOSITIONS HAVING IMPROVED MISCIBILITY

EP2726570B1|2017-12-06|Compositions of 2,4,4,4-tetrafluorobut-1-ene and cis-1,1,1,4,4,4-hexafluorobut-2-ene

EP3516007B1|2022-01-05|Composition comprising 1-chloro-3,3,3-trifluoropropene

EP2569386A2|2013-03-20|Heat-transfer fluids and use thereof in countercurrent heat exchangers

CA2844478C|2019-01-08|Tetrafluoropropene-based supercritical heat-transfer fluids

EP3630909A1|2020-04-08|Trifluoroethylene-based compositions and uses thereof

EP2547745B1|2018-11-14|Refrigerant for high-temperature heat transfer

EP2694612B1|2017-04-19|Compositions comprising 3,3,3-trifluoropropene and ammonia

WO2020002789A1|2020-01-02|Trifluoroiodomethane stabilization

FR3082517A1|2019-12-20|STABILIZATION OF 1,1,1,1,4,4,4-HEXAFLUOROBUT-2-ENE

同族专利:

公开号 | 公开日

ES2794550T3|2020-11-18|

CA2979946A1|2016-09-22|

US20180148395A1|2018-05-31|

US20160272561A1|2016-09-22|

CN107567432B|2021-03-09|

WO2016146940A1|2016-09-22|

PT3271316T|2020-06-02|

EP3271316A1|2018-01-24|

FR3033791B1|2017-04-14|

CN107567432A|2018-01-09|

US10618861B2|2020-04-14|

US20190337874A1|2019-11-07|

PL3271316T3|2020-07-13|

EP3271316B1|2020-04-22|

US10399918B2|2019-09-03|

JP2018514508A|2018-06-07|

JP6727227B2|2020-07-22|

MX2017011974A|2018-04-24|

DK3271316T3|2020-06-02|

US9908828B2|2018-03-06|

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