WO2017184975A1 - Compositions de réfrigérant et mélanges à faible potentiel de réchauffement climatique - Google Patents

Compositions de réfrigérant et mélanges à faible potentiel de réchauffement climatique Download PDF

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WO2017184975A1
WO2017184975A1 PCT/US2017/028833 US2017028833W WO2017184975A1 WO 2017184975 A1 WO2017184975 A1 WO 2017184975A1 US 2017028833 W US2017028833 W US 2017028833W WO 2017184975 A1 WO2017184975 A1 WO 2017184975A1
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refrigerant
blend
chemical blend
cis
nonflammable
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William L. Kopko
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Johnson Controls Technology Company
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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
    • 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
    • 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
    • C09K2205/104—Carboxylic acid esters
    • 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
    • C09K2205/11—Ethers
    • C09K2205/112—Halogenated ethers
    • 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
    • C09K2205/122—Halogenated 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
    • C09K2205/10—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
    • C09K2205/10—Components
    • C09K2205/132—Components containing nitrogen
    • 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
    • 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
    • C09K2205/40—Replacement mixtures

Definitions

  • the present disclosure is generally directed to chemical blends with low global warming potential and to refrigerant compositions, and specifically to refrigerant compositions for use in chillers and to substantially-azeotropic fluorinated refrigerant mixtures.
  • CFCs chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • FCs fluorocarbons
  • Many of these gases have been associated with global warming.
  • These gases have been assigned a global warming potential (GWP) that provides an indication of their possible contribution to global warming - the higher the GWP of a gas, the greater its expected contribution to global warming.
  • GWP global warming potential
  • Many of the common refrigerants used in HVAC applications have high GWPs, and there is an industry-wide effort to identify environmentally friendlier replacements for these refrigerants.
  • f-tax a tax implemented on their usage, referred to as an f-tax.
  • an f-tax is to be fully implemented in 2016, based on the GWP of the gas.
  • the GWP of a gas is expressed as a factor relative to carbon dioxide, whose GWP is standardized to a value of one.
  • GWP is based on a number of factors. Currently, these factors include the radiative efficiency of each gas relative to that of carbon dioxide and the decay rate of each gas relative to that of carbon dioxide, as well as other possible factors.
  • the Intergovernmental Panel on climate Change is responsible for generating the generally-accepted values for GWP, which may be updated from time to time.
  • IPCC Intergovernmental Panel on climate Change
  • a GWP value of 150 or less is desirable, since this value is the upper limit for use in mobile air conditioning (such as automotive air conditioning), home refrigerators, and chillers (both centrifugal and positive displacement chillers) in accordance with the current European f-gas laws.
  • This value is also the upper limit for f-gas taxes established by those laws in some European countries and may be used as an upper GWP limit for other applications in future regulations.
  • the GWP value for gases that triggers the f-tax is subject to change, so lower values are desirable.
  • a goal is to replace current refrigerants, which have a high GWP, with effective refrigerants having lower, acceptable GWPs.
  • an acceptable GWP is but one factor in determining whether a refrigerant is effective.
  • the effective refrigerants desirably have a GWP of no greater than 150.
  • Low-pressure chillers normally use non-code vessels, since the working pressures are normally below 15 psig (0.103 MPa), which exempts them from American Society of Mechanical Engineers (ASME) requirements.
  • CFC-1 1 CFC-1 1
  • CC F CFC-1 1
  • HFC-134a hydrofluorocarbon-134a
  • R-1233zd(E) has a significantly higher vapor pressure that requires the use of an ASME pressure vessel and is not suitable for retrofit.
  • HFO-1336mzz(Z) also known as HFO-1336mzz(Z)
  • R-1336mzz(Z) has a significant capacity and efficiency penalty compared to HCFC-123.
  • R-1336mzz(Z) has a lower vapor pressure and a lower speed of sound, which reduces chiller capacity.
  • the lower speed of sound also changes the Mach number for the same compressor revolutions per minute (rpm), which may cause efficiency penalties in retrofit situations.
  • rpm revolutions per minute
  • compression of saturated vapor goes well inside the vapor dome, which may result in reduced efficiency.
  • the other HFO may be R-1336mzz(E).
  • the mixture of cis-1 ,3,3,3-tetrafluoropropene and trans-1 , 1 , 1 ,4,4,4-hexafluoro-2- butene is an azeotropic or substantially-azeotropic mixture across substantially the entire composition range and may be used as a refrigerant across this range.
  • a substantially-azeotropic composition with an acceptable GWP that also has little or no flammability consists essentially of 1 -67 mole percent cis-1 ,3,3,3- tetrafluoropropene, the balance being an effective amount of trans-1 , 1 , 1 , 4,4,4- hexafluoro-2-butene.
  • a composition is a refrigerant replacement in equipment designed for a predetermined refrigerant.
  • the replacement refrigerant is a mixture of R-1336mzz(Z) and hydrofluoroether (HFE)-263fb2.
  • HFE-263fb2 is CF3CH2OCH3 or 2,2,2-trifluoro methyl ether.
  • the refrigerant replacement may functionally replace the predetermined refrigerant as a retrofit in the equipment.
  • a chemical blend in another embodiment, includes 1 , 1 , 1 ,4,4,4- hexafluorobutene and at least one balancing solvent.
  • the balancing solvent is at least one hydrofluoro-olefin, ethylene chloride, methylene chloride, ammonia, at least one ester, at least one hydrocarbon, at least one fluoroether, or a combination thereof.
  • the chemical blend is a substantially-azeotropic blend with a low global warming potential.
  • a method retrofits equipment designed to run with a predetermined refrigerant having a refrigerant molecular weight.
  • the method includes combining cis-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene with at least one balancing solvent to form a replacement refrigerant blend having a blend average molecular weight within 3% of the refrigerant molecular weight.
  • the method also includes placing the replacement refrigerant blend in the equipment in place of the predetermined refrigerant.
  • a chemical blend in another embodiment, includes cis-1 , 3,3,3- tetrafluoropropene and a nonflammable hydrofluoro-olefin.
  • the blend is a substantially-azeotropic mixture.
  • a method of preparing a nonflammable refrigerant blend includes selecting a flammable refrigerant, selecting a nonflammable hydrofluoro-olefin, and combining the nonflammable hydrofluoro- olefin with the flammable refrigerant to form the nonflammable refrigerant.
  • the nonflammable refrigerant is a substantially-azeotropic mixture.
  • R- 1234ze(Z)/R-1336mzz(E) mixture may provide improved cycle efficiencies and heat transfer properties relative to other refrigerant substitutes or refrigerant mixtures.
  • R-1234ze(Z)/R-1336mzz(E) mixture is not only an effective substitute for refrigerants now, but it also may be a future substitute for refrigerants.
  • the IPCC is responsible for determining the GWP of gases including refrigerants, which determination may be updated from time to time.
  • the R-1234ze(Z)/R-1336mzz(E) mixture has a GWP that may be adjusted based on the composition of the mixture.
  • flammability test results or changes in flammability requirements may be accommodated with changes in the amount of R-1234ze(Z) in the mixture without a major penalty in performance.
  • the R-1234ze(Z)/R-1336mzz(E) mixture may provide a desirable combination of high compressor capacity, inflammability, and low-GWP, which is expected to make it an effective refrigerant substitute in most centrifugal and positive displacement compressor applications.
  • FIG. 1 shows the calculated vapor pressure of cis-1 , 3, 3, 3- tetrafluoropropene with trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene as a mole fraction of cis-1 ,3,3,3-tetrafluoropropene versus vapor pressure at three different values of a, the mixing parameter constant;
  • FIG. 2 shows the relation for cis-1 ,3,3, 3-tetrafluoropropene between mass (weight) fraction and mole fraction in mixtures with trans-1 , 1 ,1 ,4,4,4-hexafluoro- 2-butene;
  • FIG. 3 shows the temperature glide of the mixture as a function of cis- 1 ,3,3, 3-tetrafluoropropene and trans-1 , 1 , 1 , 4,4, 4-hexafluoro-2-butene at three different values of a;
  • FIG. 4 shows the GWP of the mixture as a function of the concentration of cis-1 ,3, 3, 3-tetrafluoropropene and trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene;
  • FIG.5 shows the estimated cooling capacity of a mixture in a centrifugal chiller as a function of the concentration of cis-1 ,3,3,3-tetrafluoropropene and trans-1 ,1 , 1 ,4,4,4-hexafluoro-2-butene at three different values of a;
  • FIG. 6 shows the estimated vapor pressure versus composition for R- 1336mzz(Z) with methylene chloride, HFE-263fb2, methyl formate, n-hexane, and cyclopentane;
  • FIG. 7 shows the estimated vapor pressure of R-1336mzz(E) with cyclopentane, methylene chloride, and ethyl chloride;
  • FIG. 8 shows the estimated vapor pressure of ammonia and R1336- mzz(E) based on published data for R-1234yf and ammonia mixtures.
  • low-GWP blends provide replacements of existing refrigerants, which may be desirable from the perspective of compliance with certain environmental procedures or other similar concerns in many HVAC applications.
  • the blends may also function in heat pumps, especially high temperature heat pumps.
  • Low-GWP blends may also be cost-effective chemicals for foam blowing applications, providing a desirable combination of low vapor density and low cost per unit of mass.
  • Low-GWP blends may also serve as desirable replacement chemicals for cleaning metal, as an aerosol propellant, or other applications in which HFCs, HCFCs, CFCs, and hydrofluoro-olefins (HFOs) have been used in the past.
  • blends of certain gases, such as refrigerants may be especially desirable.
  • An HFO is a compound with a double bond between two carbon atoms that also contains at least one hydrogen atom, at least one fluorine atom, and may optionally include one or more chlorine atoms and additional carbon atoms beyond the two connected with a double bond.
  • the number of carbon atoms generally ranges between 2 and 5 to get compounds with suitable boiling points, but other numbers of carbon atoms may be used in certain situations. It is believed that the fluorine and optional chlorine act to reduce or eliminate flammability of the compound, while the presence of the double bond gives a shorter atmospheric lifetime and low global warming potentials.
  • a low global-warming-potential blend includes a substantially-azeotropic mixture of two hydrofluoro-olefins (HFOs).
  • the first HFO is R-1234ze(Z).
  • the second HFO may be R-1336mzz(E).
  • the mixture of cis-1 ,3,3,3- tetrafluoropropene and trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene is an azeotropic or a substantially-azeotropic mixture consisting essentially of about 1 to 67 mole percent R-1234ze(Z), alternatively 10 to 57 mole percent R-1234ze(Z), alternatively 20 to 47 mole percent R-1234ze(Z), alternatively 30 to 37 mole percent R-1234ze(Z), or any range or sub-range therebetween, the balance being an effective amount of R-1336mzz(E), producing a nonflammable or nearly nonflammable azeotropic or substantially-azeotropic mixture.
  • the mole percentage ranges are selected to provide a blend having a low temperature glide in combination with no flammability.
  • the temperature glide is a minimum temperature glide. In other embodiments, the temperature glide is less than a predetermined value.
  • the composition may include other ingredients, which in character and/or amount do not affect the advantageous aspects of the mixture as a refrigerant.
  • the ingredients commonly added to refrigerants, which in character and/or amount should not affect their performance as refrigerants, may include lubricants, stabilizers, surfactants, tracers, fluorescent agents, and solubilizing agents. Such ingredients are well-known to those skilled in the HVAC art.
  • the mixture of R-1234ze(Z) and R-1336mzz(E) is substantially azeotropic with a normal boiling point of about 10 °C (50 °F).
  • a substantially-azeotropic mixture of R-1234ze(Z) and R-1336mzz(E) having at least about 50% by weight R-1336mzz(E) has a calculated GWP of 32 or less.
  • This substantially-azeotropic mixture of R-1234ze(Z) with an effective amount of R-1336mzz(E) to make it low in toxicity and nonflammable is expected to be an effective refrigerant.
  • R-1234ze(Z) has a lower molecular weight than R-1336mzz(E)
  • the substantially- azeotropic mixture of R-1234ze(Z)/R-1336mzz(E) has a lower average molecular weight compared to R-1336mzz(E) alone, which increases the speed of sound within the R-1234ze(Z)/R-1336mzz(E) mixture.
  • the increased speed of sound is particularly effective in providing increased capacity and rotational speed for a centrifugal compressor running at a constant Mach number.
  • the replacement refrigerant mixture when providing a refrigerant mixture as a replacement refrigerant, it is important that the replacement refrigerant mixture be as close as possible to an azeotrope so as to avoid problems associated with fractional distillation of the mixtures.
  • the composition of the components of the replacement refrigerant mixture must be approximately the same in the vapor state as in the liquid state so as to avoid problems associated with such fractional distillation.
  • Substantially azeotropic refers to a mixture having a temperature glide of less than about 0.5 °C at 1 atm. Such a mixture generally exhibits no more than a slight amount of fractional distillation that does not affect the characteristics of the mixture as a refrigerant.
  • the mixture also has a low vapor pressure, making it suitable for operation with very high condensing temperatures, such as those required for high temperature heat pump applications, while remaining within component pressure limits.
  • the mixture has a sufficiently high condensing temperature at its vapor pressure so that it operates efficiently as a refrigerant in these high temperature heat pumps.
  • the vapor pressure of a blend of R-1234ze(Z) and a selected HFO, R- 1336mzz(E) is provided in FIG. 1 for three different values of a as a function of composition, where a is a mixing parameter constant.
  • the vapor pressure may be calculated assuming a regular solution.
  • a regular solution may alternatively be described by Raoult's law modified with a Margules function with only one parameter, a, where
  • Values of a between 0 and 0.3 provide a good fit with vapor pressure curves for mixtures, here of 1336mzz isomers with other HFOs and HFCs.
  • a value of 0 corresponds to an ideal solution, which means that vapor pressure versus mole fraction of the components is a straight line function.
  • a value of 0.3 results in a moderate increase in vapor pressure above this straight line.
  • a surprising result of this sensitivity analysis is that the temperature glide and other properties of the mixture do not vary much for a range of likely values for a, so it is not necessary to know the exact value of a to show that the mixtures have desirable properties as refrigerants.
  • a true azeotrope develops for cases where there is a maximum vapor pressure.
  • the calculated azeotrope is very near 0.35 mole fraction of R-1234ze(Z).
  • the temperature glide is very small up to about 0.5 mole fraction, which is the value shown in the example in Table 1 , below.
  • the temperature glides, discussed below are desirably very small, indicating that the mixture is still effectively functioning substantially as an azeotrope for a wide range of a.
  • a blend includes cis-1 ,3,3,3-tetrafluoropropene and a nonflammable HFO that produces a substantially-azeotropic mixture.
  • a useful mixture is nonflammable and may include cis-1 ,3,3,3-tetrafluoropropene and the balance a nonflammable HFO.
  • An example nonflammable HFO is trans- 1 , 1 , 1 ,4,4,4-hexafluoro-2-butene.
  • the weight percentage for inflammability is expected to be less than about 50% by weight of cis-1 ,3,3,3-tetrafluoropropene and the balance trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene.
  • FIG. 2 is provided for convenience and shows the relation between mass fraction (weight) and mole fraction for cis-1 ,3,3,3-tetrafluoropropene in a mixture with trans-1 , 1 ,1 ,4,4,4-hexafluoro-2-butene.
  • a blend comprising 50% by weight of cis-1 ,3,3,3-tetrafluoropropene and the balance trans-1 , 1 , 1 ,4,4,4-hexafluoro-2- butene is expected to have a GWP of about 20 or less.
  • Increasing the weight percentage of the trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene is an effective method for decreasing the GWP of the mixture.
  • the blend consists essentially of cis-1 ,3,3,3-tetrafluoropropene and trans-1 ,1 , 1 ,4,4,4, -hexafluoro-2-butene as an azeotropic or near azeotropic mixture consisting essentially of about 1 to 66.1 mole percent cis-1 , 3,3,3- tetrafluoropropene the balance an effective amount of 1 , 1 , 1 ,4,4, 4-hexafluoro-2- butene, producing a nonflammable substantially-azeotropic mixture and having a GWP of about 20 or less.
  • composition of the substantially-azeotropic blend of cis-1 ,3,3,3-tetrafluoropropene and trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene may include other ingredients, which in character and/or amount do not affect the advantageous aspects of the mixture as a refrigerant.
  • the ingredients commonly added to refrigerants which in character and/or amount do not affect the performance as refrigerants include lubricants, stabilizers, surfactants, tracers, fluorescent agents and solubilizing agents.
  • Stabilizer(s) when present, may include nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic 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, butylphenyl glycidyl ether, phosphites, phosphonates, thiols and lactones, hydrocarbons such as amylene or cyclohexene, and combinations thereof.
  • epoxides optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic
  • Lubricants when present, may include mineral oils, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha- olefins, polyalkene glycols, polyol esters and/or polyvinyl ethers, and combinations thereof.
  • Tracers when present, are capable of being detected and may include deuterated or nondeuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide, and combinations thereof.
  • Solubilizing agents when present, may include hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1 , 1 , 1 -trifluoroalkanes, and combinations thereof.
  • Fluorescent agents when present, may include naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins and derivatives, and combinations thereof.
  • Cis-1 ,3,3,3-tetrafluoropropene has normal boiling point of about 9.7 °C (about 49.5 °F). It is a relatively simple compound that is easily made using a variety of techniques developed for production of similar two-carbon HFOs, such as the refrigerants R-152a (CH3CHF2) and R-134a. According to The Fifth Assessment Report (AR5) of the Intergovernmental Panel on Climate Change (IPCC), R-1234ze(Z)'s GWP is less than one relative to carbon dioxide for a 100- year horizon, with an estimated atmospheric lifetime of only 10 days. By itself, R- 1234ze(Z) is moderately flammable.
  • Toxicity data is not available, but similar compounds generally have low toxicity, which gives it a likely A2L classification according to American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASHRAE) Standard 34, indicating a lower toxicity and a lower flammability with a maximum burning velocity of ⁇ 10 cm/s.
  • ASHRAE American Society of Heating, Refrigerating, and Air-Conditioning Engineers
  • Trans-1 , 1 , 1 , 4,4, 4-hexafluoro-2-butene is a nonflammable HFO with a normal boiling point of about 8 °C (about 46.5 °F).
  • the compound also has a cis- isomer with a slightly different boiling point.
  • the GWP of the trans- isomer is not defined in AR5 but is estimated at about 32 in U.S. Pat. App. Pub. No. U.S. 2012/0159976, hereby incorporated by reference herein.
  • cis-1 ,3,3,3-tetrafluoropropene and trans-1 , 1 , 1 , 4,4,4- hexafluoro-2-butene when mixed together, form a substantially-azeotropic mixture with a negligible temperature glide over a very wide range of compositions.
  • Temperature glide is the difference between the dew point and the bubble point of a mixture at a given pressure. Stated differently, the temperature glide corresponds to the temperature change between the start of the boiling process and the end of the boiling process at a constant pressure. The temperature glide is the result of the more volatile component evaporating first, which changes the composition and properties of the remaining liquid.
  • the azeotropic properties of a mixture decrease with increasing temperature glide.
  • An azeotropic mixture or substantially-azeotropic mixture of two or more components cannot be separated by fractional distillation, a desirable property for refrigerant mixtures.
  • a non-azeotropic mixture the composition of the liquid changes during the evaporation process, as the remaining liquid has an increasing concentration of the higher temperature evaporating components.
  • the replacement refrigerant desirably is substantially azeotropic. This is a particularly important consideration in systems that use shell-side condensers and/or evaporators.
  • a substantially-azeotropic mixture one having a temperature glide of 0.5 °C or less between or among the constituents, normally shows negligible effects of separation during phase changes.
  • the boiling points of the components of the mixture must not be disparate.
  • cis-1 ,3,3,3-tetrafluoropropene having a normal boiling point of about 9.7 °C (about 49.5 °F)
  • trans-1 , 1 , 1 , 4,4, 4-hexafluoro-2-butene an HFO
  • HFOs may also satisfy the requirements for the present blends; however should the boiling point deviate significantly from that of cis-1 ,3,3,3-tetrafluoropropene, temperature glide is expected to be adversely affected, as is the value of the blend as a refrigerant.
  • a graph representing the temperature glide of the mixture of cis-1 , 3,3,3- tetrafluoropropene and trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene is shown in FIG. 3 at three different values of a.
  • the temperature glide is less than 0.1 K for mole fractions up to about 64% R-1234ze(Z), with a maximum temperature glide of about 0.14 K at about 80% R-1234ze(Z).
  • Table 1 provides some calculated physical properties for a 50:50 mol% substantially-azeotropic mixture of cis-1 ,3,3,3-tetrafluoropropene and trans- 1 , 1 , 1 ,4,4,4-hexafluoro-2-butene.
  • the weigh percentages of the components of the mixture may be adjusted while maintaining the GWP at an acceptable level below 150 without adversely affecting the substantially azeotropic characteristics of the mixture, as indicated by the temperature glide.
  • Table 1 also shows the capacity ratio in a cooling system of the several different mixtures both in positive-displacement compressors and in centrifugal compressors.
  • the bottom curve in FIG. 1 shows the vapor pressure of the mixture as a function of the concentration of cis-1 ,3,3,3-tetrafluoropropene and trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene when the mixing parameter constant a is 0.
  • the vapor pressure of trans-1 , 1 , 1 ,4,4,4-hexafluoro-2- butene is the lower of the two components, as the mole fraction of cis-1 , 3,3,3- tetrafluoropropene is reduced, the vapor pressure of the substantially-azeotropic mixture also is reduced, and pressure reduction follows a straight line relationship, that is, the pressure change is constant with the change in mole fraction of the components.
  • the capacity ratio of the substantially-azeotropic mixture for a positive displacement compressor is estimated to be directly proportional to the vapor pressure.
  • R-1336mzz(E) has a vapor pressure of about 14.7 psia (0.101 MPa).
  • R-1234ze(Z) has other benefits.
  • a lower average molecular weight reduces vapor and liquid density, which reduces the required mass of refrigerant for a particular piece of equipment. Lower density also reduces refrigerant pressure drop, which improves system efficiency or allows smaller refrigerant piping.
  • the simple structure of R-1234ze(Z) is expected to give better cycle efficiency and a lower evaporator inlet vapor quality, which may further increase the cooling capacity of the mixture beyond the estimates above.
  • FIGS. 3, 4, and 5 show temperature glide, global warming potential (GWP), and cooling capacity, respectively, of R-1234ze(Z) in a mixture with R- 1336mzz(E).
  • GWP global warming potential
  • temperature glide and cooling capacity depend somewhat on the assumed value for alpha (a), so curves for three values of a are included to show the uncertainty.
  • the GWP of the mixture is simply the sum of the mass fraction of each component times the GWP of each component, so it is independent of the value of a.
  • the molecular weight of a refrigerant is an important factor in determining its performance in a centrifugal compressor.
  • the speed of sound for a refrigerant mixture is a function of its molecular weight, the speed of sound in a refrigerant mixture being inversely proportional to the square root of the molecular weight.
  • the capacity is expected to be proportional to the speed of sound.
  • Acoustic velocity is the speed of sound in a gas.
  • the impeller Mach number is the tip speed of the impeller divided by the acoustic velocity of the speed of sound in the gas within the refrigerant system, where the gas is the refrigerant.
  • a higher speed of sound means that the impeller runs faster at the same Mach number, which gives a proportional increase in available cooling capacity.
  • C P is the constant pressure specific heat (J/kg * K)
  • Cv is the constant volume specific heat (J/kg * K)
  • T is the temperature in K
  • W is the molecular weight of the refrigerant vapor.
  • the ratio of C P to Cv does not vary greatly between refrigerants, so the controlling factor in determining the speed of sound is the molecular weight of the refrigerant.
  • the lower molecular weight for the mixture of cis- 1 ,3,3,3-tetrafluoropropene and trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene yields a higher acoustic velocity and a corresponding cooling capacity increase.
  • the ratio of cis-1 ,3,3,3-tetrafluoropropene to trans-1 ,1 , 1 ,4,4,4- hexafluoro-2-butene may be tailored to provide a refrigerant that is nonflammable and has an acceptable GWP.
  • flammability test results or changes in flammability requirements may be accommodated with changes in the amount of R-1234ze(Z) in the mixture without a penalty in performance from excessive temperature glide.
  • the ratios may be varied to produce refrigerants that operate efficiently in centrifugal compressors or in positive displacement compressors, the ratios being different due to different operating conditions.
  • substantially azeotropic nature of the mixture of cis-1 , 3,3,3- tetrafluoropropene and trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene allows the ratios to be changed to lower GWP values as the IPCC modifies global warming potential standards.
  • some future tuning for GWP is possible.
  • the concentration of the R-1234ze(Z) (cis-1 ,3,3,3-tetrafluoropropene) may be increased within the constraints of acceptable flammability to lower the global warming potential of the mixture.
  • Mixtures of R-1234ze(Z) and R-1336mzz(E) may also have desirable non- refrigerant applications. As a two-carbon HFO, R-1234ze(Z) is relatively simple to make and may have significantly lower cost than R-1336mzz(E), which means that mixtures are also expected to be less expensive to produce.
  • the low molecular weight of R-1234ze(Z) provides a lower density in both liquid and vapor phase, which further reduces cost for many applications that required a given volume of fluid.
  • the combination of lower vapor density and lower cost per unit mass may give much lower cost, which is a major advantage.
  • Other applications may include, but are not limited to, metal cleaning, secondary refrigerants (brine), and aerosol propellants.
  • R-1345zfc has a reported normal boiling point of about 5 °C, so it is expected to form substantially-azeotropic mixtures with R-1234ze(Z) and is thus especially attractive in systems with shell-side evaporation and condensation. Other mixtures are expected to have relatively large temperature glide, making them more suitable for use in refrigeration systems with tube-side evaporation and condensation.
  • the addition of R- 1234ze(Z) is expected to lower the vapor pressure, which may allow operation in high temperature heat pumps or other applications with unusually high condensing temperatures while staying within the pressure limits of compressors and other components. Mixtures of more than two components may also be desirable in some cases.
  • a composition is a refrigerant replacement in equipment designed for a predetermined refrigerant.
  • the refrigerant replacement may be selected to have a GWP lower than the GWP of the predetermined refrigerant.
  • the refrigerant replacement may functionally replace the predetermined refrigerant as a retrofit. It may be desirable for the refrigerant replacement to be able to replace the predetermined refrigerant such that the equipment operates without any modification to its structure other than the replacement of the predetermined refrigerant by the refrigerant replacement.
  • the refrigerant replacement is a mixture of two or more compounds.
  • the refrigerant replacement includes an HFO and a balancing solvent.
  • the refrigerant replacement has an average molar molecular weight equal to the average molecular weight of the predetermined refrigerant, alternatively an average molar molecular weight within 1 % of the average molecular weight of the predetermined refrigerant, alternatively an average molar molecular weight within 2% of the average molecular weight of the predetermined refrigerant, alternatively an average molar molecular weight within 3% of the average molecular weight of the predetermined refrigerant, alternatively an average molar molecular weight within 5% of the average molecular weight of the predetermined refrigerant, alternatively an average molar molecular weight within 10% of the average molecular weight of the predetermined refrigerant, or any range or sub-range therebetween.
  • a composition for use as a refrigerant replacement in equipment designed for HCFC-123 is a blend of HFO- 1336mzz(Z) as the HFO and HFE-263fb2 as the balancing solvent, the blend having a molar average molecular weight near that of HFC-123, which is 152.93 g/mol.
  • the molar average molecular weight of the refrigerant replacement is in the range of about 145 to 160 g/mol.
  • an optimum blend depends on matching the speed of sound to provide an optimum compressor mach number for the head conditions for optimum compressor performance, while at the same time assuring that the blend remains nonflammable.
  • balancing solvents may include, but are not limited to, other fluorinated ethers, methylene chloride (R-30), hydrocarbons such as cyclopentane, and ammonia.
  • Ammonia and R-1336mzz(E) mixtures may be especially desirable in positive displacement systems, since the mixtures are expected to be nonflammable, but with capacity and vapor pressure near that of ammonia.
  • Table 2 summarizes the estimated performance of blends of R- 1336mzz(Z) with certain balancing solvents, with the blends having mixture molecular weights near that of R-123.
  • FIG. 6 shows the expected vapor pressures of blends of R-1336mzz(Z) with methylene chloride, HFE-263fb2, n- hexane, methyl formate, and cyclopentane as a function of mole fraction.
  • HFE-263fb2 as a balancing solvent is expected to have much better miscibility, since it contains less fluorine and it includes a methyl ester (-OCH3) group. HFEs with this group have good miscibility with hydrocarbons. For example, C3F7OCH3 (HFE-7000) is used as a solvent and is fully miscible with toluene.
  • HFE-263fb2 the solubility with hydrocarbons is expected to be even better, since it contains less fluorine. This improved solubility may allow the use of hydrocarbon lubricants and/or reduce the need for flushing mineral oil from existing systems. Alkylbenzene lubricants are especially attractive for retrofitting. HFE-263fb2 is expected to have excellent stability in blends with R- 1336mzz(Z).
  • R-1336mzz(Z) blends with HFE-263fb2 provide a replacement refrigerant with a low GWP for low-pressure applications.
  • HFE- 263fb2 is a flammable fluorinated ether with a measured normal boiling point of 31 .6 °C (88.9 °F) that was considered as a foam blowing agent in the 1990s.
  • AR5 lists its atmospheric life as 23 days with a 100-year GWP of 1 . It has not been considered as a refrigerant mainly because of its flammability. It is easily synthesized from trifluoroethanol, which is commercially available from multiple suppliers.
  • HFE-263fb2 may currently be used as a chemical intermediary for making fluorinated anesthetics.
  • the azeotrope with methylene chloride as the balancing solvent is expected to have properties close to that for CFC-1 1 , which has an average molecular weight of 137.37 g/mol, and may serve as a retrofit fluid in old chillers, especially those with open-drive motors, where compatibility with motor insulation is not an issue.
  • Blends with methylene chloride as the balancing solvent may also include one or more stabilizers.
  • Common stabilizers for methylene chloride include methanol, ethanol, t-butylamine and/or hydrocarbons such as cyclohexane, cyclohexene, or amylene at levels of 0.005 to 0.2%. Higher levels of stabilizers (up to roughly 1 or 2% by weight) may be added to nearly azeotropic mixtures without affecting the flammability classification, which may allow the use of aluminum impellers with the mixture.
  • the blend with n-hexane as the balancing solvent is essentially azeotropic but may become flammable at concentrations that match the molecular weight of R-123.
  • the blend with cyclopentane as the balancing solvent that matches the molecular weight of R-123 is expected give close to the same capacity in a centrifugal chiller and is an especially desirable replacement.
  • the amount of cyclopentane is likely to be near the amount to produce a flammable mixture, so it may be desirable to reduce the amount of cyclopentane to keep the mixture nonflammable.
  • Methyl formate may be a desirable balancing solvent that forms mixtures with very little temperature glide.
  • the low molecular weight of methyl formate means only a small amount in a blend is necessary to match the molecular weight of R-123.
  • the lower heat of combustion for methyl formate combined with the small amount of methyl formate required, means that the blend in Table 2 is expected to be nonflammable.
  • FIG. 7 shows the expected vapor pressures of blends of R-1336mzz(E) with ethyl chloride, cyclopentane, and methylene chloride as a function of mole fraction.
  • R-1336mzz(E) blends with ammonia provide a replacement refrigerant with a low GWP for high-pressure applications.
  • FIG. 8 shows the calculated vapor pressure of ammonia and R-1336mzz(E) based on published data for R-1234yf and ammonia mixtures.
  • FIG. 8 shows a very flat vapor pressure curve over a broad range compositions with low temperature glides.
  • a composition of about 10% ammonia by weight is especially desirable since it has a mixture molecular weight similar to that of halocarbon refrigerants such as R-22 and R-134a, which should limit compressor tip-speed requirements.
  • a blend with about 50% ammonia by weight as the balancing solvent is especially desirable since it has somewhat higher capacity and lower refrigerant cost. These mixtures are expected to have much lower discharge temperatures, little or no flammability, and lower toxicity than ammonia alone.

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Abstract

L'invention concerne un mélange chimique comprenant du 1,1,1,4,4,4-hexafluorobutène et au moins un solvant d'équilibrage. Le solvant d'équilibrage est au moins une hydrofluorooléfine, le chlorure d'éthylène, le chlorure de méthylène, l'ammoniac, au moins un ester, au moins un hydrocarbure, au moins un fluoroéther ou une combinaison correspondante. Le mélange chimique est un mélange sensiblement azéotropique présentant un faible potentiel de réchauffement climatique. L'invention concerne également un procédé de rétroadaptation d'un équipement conçu pour fonctionner avec un réfrigérant prédéterminé présentant un poids moléculaire de réfrigérant. Le procédé comprend la combinaison de cis-1,1,1,4,4,4-hexafluoro-2-butène avec au moins un solvant d'équilibrage pour former un mélange de réfrigérant de remplacement présentant un poids moléculaire moyen en mélange dans les 3 % du poids moléculaire de réfrigérant. Le procédé consiste également à placer le mélange de réfrigérant de remplacement dans l'équipement à la place du réfrigérant prédéterminé.
PCT/US2017/028833 2016-04-21 2017-04-21 Compositions de réfrigérant et mélanges à faible potentiel de réchauffement climatique WO2017184975A1 (fr)

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WO2018175367A1 (fr) * 2017-03-20 2018-09-27 The Chemours Company Fc, Llc Compositions et utilisations de trans-1,1,1,4,4,4-hexafluoro-2-butène
CN111378417A (zh) * 2018-12-28 2020-07-07 浙江省化工研究院有限公司 一种组合物及其应用
CN112760081A (zh) * 2021-02-09 2021-05-07 浙江大学 一种混合工质及其应用
CN113167509A (zh) * 2018-11-21 2021-07-23 霍尼韦尔国际公司 具有低gwp的不可燃制冷剂以及提供制冷的系统和方法
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Publication number Priority date Publication date Assignee Title
WO2018175367A1 (fr) * 2017-03-20 2018-09-27 The Chemours Company Fc, Llc Compositions et utilisations de trans-1,1,1,4,4,4-hexafluoro-2-butène
US11311761B2 (en) 2017-03-20 2022-04-26 The Chemours Company Fc, Llc Compositions and uses of trans-1,1,1,4,4,4-hexafluoro-2-butene
US11986692B2 (en) 2017-03-20 2024-05-21 The Chemours Company Fc, Llc Compositions and uses of trans-1,1,1,4,4,4-hexafluoro-2-butene
CN113167509A (zh) * 2018-11-21 2021-07-23 霍尼韦尔国际公司 具有低gwp的不可燃制冷剂以及提供制冷的系统和方法
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CN114072881A (zh) * 2019-06-21 2022-02-18 日立能源瑞士股份公司 介电绝缘或消弧流体
CN114072881B (zh) * 2019-06-21 2023-12-22 日立能源有限公司 介电绝缘或消弧流体
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CN112760081A (zh) * 2021-02-09 2021-05-07 浙江大学 一种混合工质及其应用
CN112760081B (zh) * 2021-02-09 2022-01-14 浙江大学 一种混合工质及其应用

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