WO2020184635A1 - 1,1,2-トリフルオロエタンを含む組成物 - Google Patents
1,1,2-トリフルオロエタンを含む組成物 Download PDFInfo
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- WO2020184635A1 WO2020184635A1 PCT/JP2020/010656 JP2020010656W WO2020184635A1 WO 2020184635 A1 WO2020184635 A1 WO 2020184635A1 JP 2020010656 W JP2020010656 W JP 2020010656W WO 2020184635 A1 WO2020184635 A1 WO 2020184635A1
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- 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
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
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- 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
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- 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
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
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- C—CHEMISTRY; METALLURGY
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- 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
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- 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
- the present disclosure relates to a composition containing 1,1,2-trifluoroethane (HFC-143).
- 1,1,2-Trifluoroethane is a foaming agent for polyolefins and polyurethanes, aerosol propellants, refrigerants, heat transfer media, dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particles. It is useful as a removing fluid, a transport fluid, a buffing polishing agent, and a replacement desiccant (Patent Document 1).
- the boiling point of HFC-143 is about 4 ° C.
- the subject of this disclosure is to provide a new composition containing HFC-143.
- HFC-143 and 1,1-difluoroethylene HFO-1132a), 1,1,2-trifluoroethylene (HFO-1123), 1,1,1-trifluoromethane (HFC-143a), 1,-chloro-1,2, 2-Trifluoroethylene (CTFE), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-152), trans-1-chloro -2-Fluoroethylene (HCFO-1131 (E)), cis-1-chloro-2-fluoroethylene (HCFO-1131 (Z)), 1,1,1,2-tetrafluoroethane (HFC-134a), Fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-2 , 2-
- a composition comprising at least one additional compound.
- Item 2. The composition according to Item 1, wherein the mixture of HFC-143 and the additional compound is azeotropic or azeotropic.
- Item 3. Item 2. The composition according to Item 1 or 2, wherein the additional compound is contained in an amount of more than 0% by mass and 30% by mass or less in total based on the total mixture of HFC-143 and the additional compound.
- Item 4. Use of the composition according to any one of Items 1 to 3 as a heat transfer medium composition.
- HFC-143 and 1,1-difluoroethylene HFO-1132a), 1,1,2-trifluoroethylene (HFO-1123), 1,1,1-trifluoromethane (HFC-143a), 1,-chloro-1,2, 2-Trifluoroethylene (CTFE), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-152), trans-1-chloro -2-Fluoroethylene (HCFO-1131 (E)), cis-1-chloro-2-fluoroethylene (HCFO-1131 (Z)), 1,1,1,2-tetrafluoroethane (HFC-134a), Fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-2 , 2-Diflu
- a method of separating HFC-143 from the additional compound By supplying the starting composition containing HFC-143 and the additional compound to the first distillation column: An azeotropic mixture composition containing HFC-143 and the additional compound is used as the first distillate; and a composition in which either HFC-143 or the additional compound is more concentrated than the starting composition is the first. With the process of extracting as a distillation column bottom composition; (2) If necessary, the first distillate or the bottom composition of the first distillation column is supplied to the second distillation column having different operating conditions from the first distillation column to be either HFC-143 or an additional compound. A method comprising the step of forming a composition richer in concentration than the starting composition.
- a new composition containing HFC-143 will be provided.
- refrigerant includes at least a compound having a refrigerant number (ASHRAE number) starting with R indicating the type of refrigerant defined by ISO817 (International Organization for Standardization), and further includes a refrigerant number. Even if it has not been attached yet, those having the same characteristics as a refrigerant are included.
- Refrigerants are roughly classified into “fluorocarbon-based compounds” and “non-fluorocarbon-based compounds” in terms of compound structure.
- “Fluorocarbon-based compounds” include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs). Examples of the “non-fluorocarbon compound” include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744) and ammonia (R717).
- composition containing a refrigerant further contains (1) a refrigerant itself (including a mixture of refrigerants) and (2) other components, and at least a refrigerator by mixing with refrigerating machine oil. At least a composition that can be used to obtain a working fluid and (3) a working fluid for a refrigerator containing refrigerating machine oil are included.
- the composition of (2) is referred to as a "refrigerant composition” to distinguish it from the refrigerant itself (including a mixture of refrigerants).
- the working fluid for a refrigerator in (3) is referred to as a "refrigerant oil-containing working fluid” to distinguish it from the "refrigerant composition”.
- azeotropic composition means a composition that can be treated substantially in the same manner as an azeotropic composition.
- azeotropic composition means a constant boiling point or a substantially constant boiling point mixture of two or more substances that behave as substantially a single substance.
- One of the characteristics of the azeotropic composition is that the composition of the vapor generated by evaporation or distillation of the liquid does not substantially change from the composition of the liquid. That is, in the present specification, when a mixture is boiled, distilled or refluxed without a substantial change in composition, the mixture is referred to as an azeotropic composition.
- the composition when the difference between the bubble point vapor pressure of the composition at a specific temperature and the dew point vapor pressure of the composition is 3% or less (based on the bubble point pressure), the composition. Is defined in the present disclosure as an azeotropic composition.
- the term "alternative” is used in the context of "substituting" a first refrigerant with a second refrigerant to, as the first type, to operate with the first refrigerant.
- a second refrigerant is used in the designed equipment with only minor changes (at least one of refrigerating machine oil, gaskets, packing, expansion valves, dryers and other parts) and equipment adjustments as needed. This means that it can be operated under optimum conditions. That is, this type refers to operating the same equipment by "substituting" the refrigerant.
- equipment designed to operate with a second refrigerant can also be used with a second refrigerant for the same use as the existing use of the first refrigerant. Included in the term "alternative”. This type refers to providing the same application as a "substitute" for the refrigerant.
- a refrigerator refers to a general device that keeps a temperature lower than the surrounding outside air by removing heat from an object or space and maintains this low temperature.
- a refrigerator is a conversion device that obtains energy from the outside to perform work and convert energy in order to transfer heat from the lower temperature side to the higher temperature side.
- GWP shall be calculated in accordance with the provisions of the IPCC Fifth Assessment Report (AR5).
- the refrigerants of the present disclosure further include HFO-1132a, HFO-1123, HFC-143a, CTFE, HCFO-1131a, HFC-152a, HFC-152, HCFO-. 1131 (E), HCFO-1131 (Z), HFC-134a, HFC-161, HCFC-141, HCFC-123, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, HFO-1141, HCFC- Includes at least one additional compound selected from the group consisting of 21, HCFC-22, HFC-23, ethylene and acetylene.
- the mixture of HFC-143 and the sum of the additional compounds is excellent in stability.
- this mixture can also be used as a refrigerant, and is very low compared to the conventionally used CFC refrigerant and HCFC refrigerant. It has ODP (ozone depletion potential).
- ODP ozone depletion potential
- the additional compound is from 0% by mass in total with respect to the entire mixture of HFC-143 and the additional compound. It is preferably contained in a large amount and 30% by mass or less, more preferably in an amount of more than 0% by mass and 20% by mass or less, further preferably more than 0% by mass and contained in an amount of 10% by mass or less, and 0. Even more preferably, it is contained in an amount of more than mass% and not more than 1% by mass.
- a mixture of HFC-143 and the sum of the additional compounds is preferably an azeotrope or azeotrope-like composition.
- These azeotropic or azeotropic compositions can be important compositions in the mixture of HFC-143 and additional ingredients when performing azeotropic distillation to separate the additional ingredients from HFC-143.
- Azeotrope distillation is a method of concentrating or separating an object by operating a distillation column under conditions such that an azeotropic or azeotropic composition is separated.
- azeotropic distillation occurs only when one or more of the components to be separated and another component forming an azeotropic mixture are added from the outside. In some cases. In a narrow sense, only the latter is called azeotropic distillation.
- an azeotropic or azeotropic composition containing HFC-143 and an additional component is extracted by azeotropic distillation from a composition containing at least HFC-143 and the additional component, thereby removing the additional component from HFC-.
- the mixture of HFC-143 and the sum of the additional compounds totals more than 0% by weight and 1 of the additional compounds relative to the total of the mixture. It is preferably contained in an amount of 0% by mass or less, more preferably more than 0% by mass and 0.5% by mass or less, further preferably more than 0% by mass and containing 0.1% by mass or less.
- Heat transfer medium composition The composition of the present disclosure can be used as a heat transfer medium composition.
- composition of the present disclosure used as a heat transfer medium composition may further contain at least one other component in addition to the additional compound.
- the compositions of the present disclosure can be used to obtain a working fluid for a refrigerator by further mixing with at least the refrigerating machine oil (the composition of the present disclosure in this case is referred to as "refrigerant composition of the present disclosure").
- the refrigerant composition of the present disclosure may contain at least one of the following other components, if necessary.
- Other components are not particularly limited, and specific examples thereof include water, tracers, ultraviolet fluorescent dyes, stabilizers, and polymerization inhibitors.
- the refrigerant composition of the present disclosure When the refrigerant composition of the present disclosure is used as a working fluid in a refrigerator, it is usually mixed with at least a refrigerator oil. Therefore, the refrigerant compositions of the present disclosure are preferably substantially free of refrigerating machine oil. Specifically, the refrigerant composition of the present disclosure has a refrigerating machine oil content of preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass, based on the entire composition.
- the refrigerant composition of the present disclosure may contain a trace amount of water.
- the water content in the refrigerant composition is preferably 0.1% by mass or less with respect to the entire refrigerant. Since the refrigerant composition contains a small amount of water, the intramolecular double bond of the unsaturated fluorocarbon compound that may be contained in the refrigerant is stabilized, and the unsaturated fluorocarbon compound is less likely to be oxidized. , The stability of the refrigerant composition is improved.
- the tracer is added to the refrigerant composition of the present disclosure at a detectable concentration so that if the refrigerant composition of the present disclosure is diluted, contaminated, or otherwise changed, the change can be tracked.
- the refrigerant composition of the present disclosure may contain one kind alone or two or more kinds as a tracer.
- the tracer is not particularly limited and can be appropriately selected from commonly used tracers.
- tracers examples include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodide compounds, alcohols, etc. Examples thereof include aldehydes, ketones, and nitrogen sulfite (N 2 O).
- hydrofluorocarbon, hydrochlorofluorocarbon, chlorofluorocarbon, hydrochlorocarbon, fluorocarbon and fluoroether are particularly preferable.
- FC-14 Tetrafluoromethane, CF 4
- HCC-40 Chloromethane, CH 3 Cl
- HFC-23 Trifluoromethane, CHF 3
- HFC-41 Fluoromethane, CH 3 Cl
- HFC-125 Pentafluoroethane, CF 3 CHF 2
- HFC-134a (1,1,1,2-tetrafluoroethane, CF 3 CH 2 F)
- HFC-134 (1,1,2,2-tetrafluoroethane, CHF 2 CHF 2 )
- HFC-143a 1,1,1-trifluoroethane, CF 3 CH 3
- HFC-152 (1,2-difluoroethane, CH 2 FCH 2 F) HFC-245fa (1,1,1,3,3-pentafluoropropane, CF 3 CH 2 CHF 2 )
- HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF 3 CH 2 CHF 2
- the refrigerant composition of the present disclosure may contain a total of about 10 parts per million (ppm) to about 1000 ppm of tracers with respect to the entire refrigerant composition.
- the refrigerant composition of the present disclosure may contain tracers in total, preferably from about 30 ppm to about 500 ppm, more preferably from about 50 ppm to about 300 ppm, with respect to the entire refrigerant composition.
- the refrigerant composition of the present disclosure may contain one kind alone or two or more kinds as an ultraviolet fluorescent dye.
- the ultraviolet fluorescent dye is not particularly limited, and can be appropriately selected from commonly used ultraviolet fluorescent dyes.
- the ultraviolet fluorescent dye examples include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene and fluorescein, and derivatives thereof.
- the ultraviolet fluorescent dye either or both of naphthalimide and coumarin are particularly preferable.
- the refrigerant composition of the present disclosure may contain one kind alone or two or more kinds as a stabilizer.
- the stabilizer is not particularly limited, and can be appropriately selected from commonly used stabilizers.
- stabilizers include nitro compounds, ethers and amines.
- nitro compound examples include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.
- ethers examples include 1,4-dioxane and the like.
- amines examples include 2,2,3,3,3-pentafluoropropylamine, diphenylamine and the like.
- the content ratio of the stabilizer is not particularly limited, and is usually preferably 0.01 to 5% by mass, preferably 0.05 to 2% by mass, based on the total mixture of HFC-143 and the total of the additional compounds. It is more preferable to do so.
- the refrigerant composition of the present disclosure may contain one kind alone or two or more kinds as a polymerization inhibitor.
- the polymerization inhibitor is not particularly limited, and can be appropriately selected from commonly used polymerization inhibitors.
- polymerization inhibitor examples include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, benzotriazole and the like.
- the content ratio of the polymerization inhibitor is not particularly limited, and is usually preferably 0.01 to 5% by mass, preferably 0.05 to 2% by mass, based on the total mixture of HFC-143 and the total of the additional compounds. Is more preferable.
- the composition of the present disclosure can also be used as a working fluid for a refrigerator containing refrigerating machine oil (this composition is referred to as "working fluid containing refrigerating machine oil of the present disclosure").
- the refrigerating machine oil-containing working fluid of the present disclosure contains at least the refrigerant composition of the present disclosure and refrigerating machine oil, and is used as a working fluid in a refrigerator.
- the refrigerating machine oil-containing working fluid of the present disclosure is a mixture of the refrigerating machine oil used in the compressor of the refrigerator and a mixture of HFC-143 and the total of the additional compounds or a refrigerant composition.
- Obtained by Refrigerating machine oil-containing working fluid generally contains 10 to 50% by mass of refrigerating machine oil.
- the refrigerating machine oil-containing working fluid of the present disclosure may contain one kind alone or two or more kinds as the refrigerating machine oil.
- the refrigerating machine oil is not particularly limited, and can be appropriately selected from commonly used refrigerating machine oils. In that case, if necessary, a refrigerating machine oil that is more excellent in terms of compatibility with the mixture, an action of improving the stability of the mixture, and the like can be appropriately selected.
- the base oil of the refrigerating machine oil for example, at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE) and polyvinyl ether (PVE) is preferable.
- PAG polyalkylene glycol
- POE polyol ester
- PVE polyvinyl ether
- the refrigerating machine oil may further contain additives in addition to the base oil.
- the additive may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper inactivating agents, rust inhibitors, oily agents and defoaming agents. ..
- the refrigerating machine oil one having a kinematic viscosity at 40 ° C. of 5 to 400 cSt is preferable in terms of lubrication.
- the refrigerating machine oil-containing working fluid of the present disclosure may further contain at least one kind of additive, if necessary.
- the additive include the following compatibilizers and the like.
- the refrigerating machine oil-containing working fluid of the present disclosure may contain one kind alone or two or more kinds as a compatibilizer.
- the compatibilizer is not particularly limited, and can be appropriately selected from commonly used compatibilizers.
- compatibilizer examples include polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoroether and 1,1,1-trifluoroalkane.
- polyoxyalkylene glycol ether is particularly preferable.
- the present disclosure also discloses a method for separating these components using the above composition.
- an azeotropic or azeotropic composition containing HFC-143 and an additional component is extracted by azeotropic distillation from a composition containing at least HFC-143 and the additional component, thereby removing the additional component from HFC-.
- the separation method of the present disclosure In a mixture containing HFC-143 and at least one additional compound A method of separating HFC-143 from the additional compound.
- An azeotropic mixture composition containing HFC-143 and the additional compound is used as the first distillate; and a composition in which either HFC-143 or the additional compound is more concentrated than the starting composition is the first.
- the first distillate or the bottom composition of the first distillation column is supplied to the second distillation column having different operating conditions from the first distillation column to be either HFC-143 or an additional compound.
- the method may include a step of forming a composition having a higher concentration than the starting composition.
- examples of the additional compound include 1,1-difluoroethylene (HFO-1132a), 1,1,2-trifluoroethylene (HFO-1123), and 1,1,1-trifluoromethane (HFC-).
- CTFE 1,-chloro-1,2,2-trifluoroethylene
- HCFO-1131a 1,1-difluoroethane
- HFC-152a 1,2- Difluoroethane
- trans-1-chloro-2-fluoroethylene HCFO-1131 (E)
- Example 1 shows the results of the refrigeration cycle calculation of the composition containing HFC-143 and each additional compound. The calculation conditions are as follows. Evaporation temperature 10 °C, condensation temperature 45 °C, superheat degree 5 °C, supercooling degree 5 °C, compression efficiency 70% Peng-Robinson was used as a physical property model.
- Example 2 Manufacturing method of HFC-143
- One 50A reaction tube was prepared, and the reaction tube was filled with 670 g of catalyst.
- the catalyst was formed using activated carbon as a carrier and a noble metal as palladium.
- CTFE chlorotrifluoroethylene
- HFC-143 One 50A reaction tube was prepared, and the reaction tube was filled with 670 g of catalyst.
- the catalyst was formed using activated carbon as a carrier and a noble metal as palladium.
- CTFE chlorotrifluoroethylene
- hydrogen was supplied at a flow rate of 1800 Nml / min from the raw material supply port of the reaction tube filled with the catalyst, and the catalyst was passed through the upstream portion and the downstream portion in this order. ..
- the temperature of the upstream portion was 320 ° C.
- the temperature of the downstream portion was 230 ° C.
- the charge amount of the catalyst in the reaction tube is W (g)
- the total flow rate of the fluoroethylene and hydrogen gas flowing into the reaction tube is Fo
- the contact time represented by W / Fo is 17.5 g ⁇ sec. It was set to / cc. The results are shown in Table 2.
- the target product, HFC-143 can be obtained in high yield.
- Example 3 Using the distillation column shown in FIG. 1, a composition containing HFC-143 and HFO-1123, ethylene, HFC-161, HFC-152, HCFC-133, HCFC-123, and HCFC-21 as additional components was distilled. The results are shown in Table 3.
- high-purity HFC-143 could be obtained by separating by distillation using an azeotropic composition consisting of HFC-143, HFO-1123, ethylene, and HFC-161.
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Abstract
Description
HFC-143と、
1,1-ジフルオロエチレン(HFO-1132a)、1,1,2-トリフルオロエチレン(HFO-1123)、1,1,1-トリフルオロメタン(HFC-143a)、1,-クロロ-1,2,2-トリフルオロエチレン(CTFE)、1-クロロ-1-フルオロエチレン(HCFO-1131a)、1,1-ジフルオロエタン(HFC-152a)、1,2-ジフルオロエタン(HFC-152)、トランス-1-クロロ-2-フルオロエチレン(HCFO-1131(E))、シス-1-クロロ-2-フルオロエチレン(HCFO-1131(Z))、1,1,1,2-テトラフルオロエタン(HFC-134a)、フルオロエタン(HFC-161)、1,2-ジクロロ-1-フルオロエタン(HCFC-141)、1,1-ジクロロ-2,2,2-トリフルオロエタン(HCFC-123)、1-クロロ-2,2-ジフルオロエタン(HCFC-142)、1-クロロ-1,2-ジフルオロエタン(HCFC-142a)、1-クロロ-2,2-ジフルオロエチレン(HCFO-1122)、1-クロロ-1,2-ジフルオロエチレン(HCFO-1122a)、フルオロエチレン(HFO-1141)、ジクロロフルオロメタン(HCFC-21)、クロロジフルオロメタン(HCFC-22)、トリフルオロメタン(HFC-23)、エチレン及びアセチレンからなる群より選択される少なくとも一種の追加的化合物と
を含む、組成物。
項2.
HFC-143と前記追加的化合物との混合物が、共沸又は共沸様である、項1に記載の組成物。
項3.
前記追加的化合物を、HFC-143と前記追加的化合物との混合物の全体に対して合計で0質量%より多く、かつ30質量%以下含む、項1又は2に記載の組成物。
項4.
項1~3のいずれか一項に記載の組成物の、熱移動媒体組成物としての使用。
項5.
HFC-143と、
1,1-ジフルオロエチレン(HFO-1132a)、1,1,2-トリフルオロエチレン(HFO-1123)、1,1,1-トリフルオロメタン(HFC-143a)、1,-クロロ-1,2,2-トリフルオロエチレン(CTFE)、1-クロロ-1-フルオロエチレン(HCFO-1131a)、1,1-ジフルオロエタン(HFC-152a)、1,2-ジフルオロエタン(HFC-152)、トランス-1-クロロ-2-フルオロエチレン(HCFO-1131(E))、シス-1-クロロ-2-フルオロエチレン(HCFO-1131(Z))、1,1,1,2-テトラフルオロエタン(HFC-134a)、フルオロエタン(HFC-161)、 1,2-ジクロロ-1-フルオロエタン(HCFC-141)、1,1-ジクロロ-2,2,2-トリフルオロエタン(HCFC-123)、1-クロロ-2,2-ジフルオロエタン(HCFC-142)、1-クロロ-1,2-ジフルオロエタン(HCFC-142a)、1-クロロ-2,2-ジフルオロエチレン(HCFO-1122)、1-クロロ-1,2-ジフルオロエチレン(HCFO-1122a)、フルオロエチレン(HFO-1141)、ジクロロフルオロメタン(HCFC-21)、クロロジフルオロメタン(HCFC-22)、トリフルオロメタン(HFC-23)、エチレン及びアセチレンからなる群より選択される少なくとも一種の追加的化合物とを含む混合物において、
HFC-143と前記追加的化合物とを分離する方法であって、
(1)HFC-143及び前記追加的化合物を含む出発組成物を第1蒸留塔に供給することにより:
HFC-143及び前記追加的化合物を含む共沸混合物組成物を第1留出物として;かつ
HFC-143又は前記追加的化合物のいずれかに前記出発組成物より濃度的に富む組成物を第1蒸留塔ボトム組成物として抜き出す工程と;
(2)必要に応じて、前記第1留出物又は第1蒸留塔ボトム組成物を第1蒸留塔と運転条件の異なる第2蒸留塔に供給してHFC-143又は追加的化合物のいずれかに前記出発組成物より濃度的に富む組成物を形成する工程と
を含む方法。
本明細書において用語「冷媒」には、ISO817(国際標準化機構)で定められた、冷媒の種類を表すRで始まる冷媒番号(ASHRAE番号)が付された化合物が少なくとも含まれ、さらに冷媒番号が未だ付されていないとしても、それらと同等の冷媒としての特性を有するものが含まれる。冷媒は、化合物の構造の面で、「フルオロカーボン系化合物」と「非フルオロカーボン系化合物」とに大別される。「フルオロカーボン系化合物」には、クロロフルオロカーボン(CFC)、ハイドロクロロフルオロカーボン(HCFC)及びハイドロフルオロカーボン(HFC)が含まれる。「非フルオロカーボン系化合物」としては、プロパン(R290)、プロピレン(R1270)、ブタン(R600)、イソブタン(R600a)、二酸化炭素(R744)及びアンモニア(R717)等が挙げられる。
1.1 追加的化合物
本開示の冷媒は、HFC-143に加えてさらに、HFO-1132a、HFO-1123、HFC-143a、CTFE、HCFO-1131a、HFC-152a、HFC-152、HCFO-1131(E)、HCFO-1131(Z)、HFC-134a、HFC-161、HCFC-141、HCFC-123、HCFC-142、HCFC-142a、HCFO-1122、HCFO-1122a、HFO-1141、HCFC-21、HCFC-22、HFC-23、エチレン及びアセチレンからなる群より選択される少なくとも一種の追加的化合物を含む。
HFC-143と、前記追加的化合物の合計との混合物は、好ましくは共沸又は共沸様組成物である。これらの共沸又は共沸様組成物は、HFC-143と追加的成分との混合物において、追加的成分をHFC-143から分離する共沸蒸留を行う際に重要な組成物となりうる。
本開示の組成物は、熱移動媒体組成物として用いることができる。
FC-14(テトラフルオロメタン、CF4)
HCC-40(クロロメタン、CH3Cl)
HFC-23(トリフルオロメタン、CHF3)
HFC-41(フルオロメタン、CH3Cl)
HFC-125(ペンタフルオロエタン、CF3CHF2)
HFC-134a(1,1,1,2-テトラフルオロエタン、CF3CH2F)
HFC-134(1,1,2,2-テトラフルオロエタン、CHF2CHF2)
HFC-143a(1,1,1-トリフルオロエタン、CF3CH3)
HFC-152(1,2-ジフルオロエタン、CH2FCH2F)
HFC-245fa(1,1,1,3,3-ペンタフルオロプロパン、CF3CH2CHF2)HFC-236fa(1,1,1,3,3,3-ヘキサフルオロプロパン、CF3CH2CF3)HFC-236ea(1,1,1,2,3,3-ヘキサフルオロプロパン、CF3CHFCHF2)HFC-227ea(1,1,1,2,3,3,3-ヘプタフルオロプロパン、CF3CHFCF3)HCFC-22(クロロジフルオロメタン、CHClF2)
HCFC-31(クロロフルオロメタン、CH2ClF)
CFC-1113(クロロトリフルオロエチレン、CF2=CClF)
HFE-125(トリフルオロメチル-ジフルオロメチルエーテル、CF3OCHF2)HFE-134a(トリフルオロメチル-フルオロメチルエーテル、CF3OCH2F)HFE-143a(トリフルオロメチル-メチルエーテル、CF3OCH3)
HFE-227ea(トリフルオロメチル-テトラフルオロエチルエーテル、CF3OCHFCF3)HFE-236fa(トリフルオロメチル-トリフルオロエチルエーテル、CF3OCH2CF3)
また、本開示では、上記の組成物を利用したこれらの成分の分離方法も開示される。
HFC-143と、少なくとも一種の追加的化合物とを含む混合物において、
HFC-143と前記追加的化合物とを分離する方法であって、
(1)HFC-143及び前記追加的化合物を含む出発組成物を第1蒸留塔に供給することにより:
HFC-143及び前記追加的化合物を含む共沸混合物組成物を第1留出物として;かつ
HFC-143又は前記追加的化合物のいずれかに前記出発組成物より濃度的に富む組成物を第1蒸留塔ボトム組成物として抜き出す工程と;
(2)必要に応じて、前記第1留出物又は第1蒸留塔ボトム組成物を第1蒸留塔と運転条件の異なる第2蒸留塔に供給してHFC-143又は追加的化合物のいずれかに前記出発組成物より濃度的に富む組成物を形成する工程と
を含む方法であってもよい。
HFC-143と、各追加化合物を含む組成物の冷凍サイクル計算の結果を表1に示す。計算条件は以下の通りである。
蒸発温度 10℃、凝縮温度 45℃、過熱度 5℃、過冷却度 5℃、圧縮効率70%物性モデルとしてPeng-Robinsonを用いた。
(HFC-143の製造方法)
50A反応管を1個準備し、この反応管に670gの触媒を充填した。触媒は、活性炭を担体とし、貴金属をパラジウムとして形成した。触媒を充填した反応管の原料供給口から、CTFE(クロロトリフルオロエチレン)を500Nml/minの流量で、水素を1800Nml/minの流量で供給し、上流部及び下流部の順に触媒を通過させた。このとき、上流部の温度は320℃、下流部の温度は230℃とした。以上の反応では、反応管内の触媒の充填量をW(g)、反応管に流入させるフルオロエチレン及び水素ガスの全流量をFoとして、W/Foで表される接触時間を17.5g・sec/ccとした。結果は表2の通りとなった。
図1に示す蒸留塔を用いてHFC-143と追加的成分としてHFO-1123、エチレン、HFC-161、HFC-152、HCFC-133、HCFC-123、HCFC-21を含む組成物を蒸留した。結果を表3に示す。
Claims (5)
1,1-ジフルオロエチレン(HFO-1132a)、1,1,2-トリフルオロエチレン(HFO-1123)、1,1,1-トリフルオロメタン(HFC-143a)、1,-クロロ-1,2,2-トリフルオロエチレン(CTFE)、1-クロロ-1-フルオロエチレン(HCFO-1131a)、1,1-ジフルオロエタン(HFC-152a)、1,2-ジフルオロエタン(HFC-152)、トランス-1-クロロ-2-フルオロエチレン(HCFO-1131(E))、シス-1-クロロ-2-フルオロエチレン(HCFO-1131(Z))、1,1,1,2-テトラフルオロエタン(HFC-134a)、フルオロエタン(HFC-161)、1,2-ジクロロ-1-フルオロエタン(HCFC-141)、1,1-ジクロロ-2,2,2-トリフルオロエタン(HCFC-123)、1-クロロ-2,2-ジフルオロエタン(HCFC-142)、1-クロロ-1,2-ジフルオロエタン(HCFC-142a)、1-クロロ-2,2-ジフルオロエチレン(HCFO-1122)、1-クロロ-1,2-ジフルオロエチレン(HCFO-1122a)、フルオロエチレン(HFO-1141)、ジクロロフルオロメタン(HCFC-21)、クロロジフルオロメタン(HCFC-22)、トリフルオロメタン(HFC-23)、エチレン及びアセチレンからなる群より選択される少なくとも一種の追加的化合物と
を含む、組成物。
1,1-ジフルオロエチレン(HFO-1132a)、1,1,2-トリフルオロエチレン(HFO-1123)、1,1,1-トリフルオロメタン(HFC-143a)、1,-クロロ-1,2,2-トリフルオロエチレン(CTFE)、1-クロロ-1-フルオロエチレン(HCFO-1131a)、1,1-ジフルオロエタン(HFC-152a)、1,2-ジフルオロエタン(HFC-152)、トランス-1-クロロ-2-フルオロエチレン(HCFO-1131(E))、シス-1-クロロ-2-フルオロエチレン(HCFO-1131(Z))、1,1,1,2-テトラフルオロエタン(HFC-134a)、フルオロエタン(HFC-161)、 1,2-ジクロロ-1-フルオロエタン(HCFC-141)、1,1-ジクロロ-2,2,2-トリフルオロエタン(HCFC-123)、1-クロロ-2,2-ジフルオロエタン(HCFC-142)、1-クロロ-1,2-ジフルオロエタン(HCFC-142a)、1-クロロ-2,2-ジフルオロエチレン(HCFO-1122)、1-クロロ-1,2-ジフルオロエチレン(HCFO-1122a)、フルオロエチレン(HFO-1141)、ジクロロフルオロメタン(HCFC-21)、クロロジフルオロメタン(HCFC-22)、トリフルオロメタン(HFC-23)、エチレン及びアセチレンからなる群より選択される少なくとも一種の追加的化合物とを含む混合物において、
HFC-143と前記追加的化合物とを分離する方法であって、
(1)HFC-143及び前記追加的化合物を含む出発組成物を第1蒸留塔に供給することにより:
HFC-143及び前記追加的化合物を含む共沸又は共沸様混合物組成物を第1留出物として;かつ
HFC-143又は前記追加的化合物のいずれかに前記出発組成物より濃度的に富む組成物を第1蒸留塔ボトム組成物として抜き出す工程と;
(2)必要に応じて、前記第1留出物又は第1蒸留塔ボトム組成物を第1蒸留塔と運転条件の異なる第2蒸留塔に供給してHFC-143又は追加的化合物のいずれかに前記出発組成物より濃度的に富む組成物を形成する工程と
を含む方法。
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| WO2022102681A1 (ja) * | 2020-11-10 | 2022-05-19 | ダイキン工業株式会社 | 冷媒を含む組成物、その使用、並びにそれを有する冷凍機及びその冷凍機の運転方法 |
| JP2022076886A (ja) * | 2020-11-10 | 2022-05-20 | ダイキン工業株式会社 | 冷媒を含む組成物、その使用、並びにそれを有する冷凍機及びその冷凍機の運転方法 |
| JP7116336B2 (ja) | 2020-11-10 | 2022-08-10 | ダイキン工業株式会社 | 冷媒を含む組成物、その使用、並びにそれを有する冷凍機及びその冷凍機の運転方法 |
| FR3123650A1 (fr) * | 2021-06-07 | 2022-12-09 | Arkema France | Composition azéotropique ou quasi-azéotropique comprenant chlorotrifluoroéthylène et/ou 1,1,2-trifluoroéthane |
| WO2022258915A1 (fr) * | 2021-06-07 | 2022-12-15 | Arkema France | Composition azéotropique ou quasi-azéotropique comprenant chlorotrifluoroéthylène et/ou 1,1,2-trifluoroéthane |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102760414B1 (ko) | 2025-02-03 |
| CN113631534A (zh) | 2021-11-09 |
| KR20210137152A (ko) | 2021-11-17 |
| JP2021088579A (ja) | 2021-06-10 |
| EP3939955A4 (en) | 2022-11-30 |
| JP7225151B2 (ja) | 2023-02-20 |
| JP2020147754A (ja) | 2020-09-17 |
| EP3939955A1 (en) | 2022-01-19 |
| US20210403778A1 (en) | 2021-12-30 |
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