US20120216551A1 - Cascade refrigeration system with fluoroolefin refrigerant - Google Patents

Cascade refrigeration system with fluoroolefin refrigerant Download PDF

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US20120216551A1
US20120216551A1 US13/505,538 US201013505538A US2012216551A1 US 20120216551 A1 US20120216551 A1 US 20120216551A1 US 201013505538 A US201013505538 A US 201013505538A US 2012216551 A1 US2012216551 A1 US 2012216551A1
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refrigerant
hfo
outlet
inlet
hfc
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Barbara Haviland Minor
Konstantinos Kontomaris
Thomas J. Leck
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Chemours Co FC LLC
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EI Du Pont de Nemours and Co
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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
    • F25B7/00—Compression machines, plants or systems, with cascade operation, i.e. with two or more circuits, the heat from the condenser of one circuit being absorbed by the evaporator of the next circuit
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • 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
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • 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
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • F25B9/006—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
    • 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
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • F25B9/008—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • 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
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • F25B2400/121—Inflammable refrigerants using R1234

Definitions

  • the present disclosure relates to a cascade refrigeration system which circulates a refrigerant comprising a fluoroolefin therethrough.
  • a cascade system includes a medium temperature loop and a low temperature loop, and a fluoroolefin refrigerant may be used in either loop, or both.
  • Cascade refrigeration systems are known in the art, see for example, ICR07-B2-358, “CO 2 -DX Systems for Medium-and Low-Temperature Refrigeration in Supermarket Applications”, T. Sienel, O. Finckh, International Congress of Refrigeration, 2007, Beijing.
  • Such a system typically uses a refrigerant such as 1,1,1,2-tetrafluoroethane (R134a) or blends thereof with HFC-125 and HFC-143a (i.e., R404A) in the medium temperature loop and carbon dioxide (CO 2 ) in the low temperature loop to provide cooling to display cases, for instance, in supermarkets.
  • a refrigerant such as 1,1,1,2-tetrafluoroethane (R134a) or blends thereof with HFC-125 and HFC-143a (i.e., R404A) in the medium temperature loop and carbon dioxide (CO 2 ) in the low temperature loop to provide cooling to display cases, for instance, in supermarkets.
  • HFC-134a Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or “natural” refrigerants such as CO 2 . Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. New replacements are also being proposed for HCFC-22, R404A, R407C and R410A, among others. As these replacements are found, new uses of such alternative refrigerants are being sought in order to take advantage of their low or zero ozone depletion potential and lower global warming potential.
  • the object of the present disclosure is to provide cascade refrigeration systems which use refrigerant compositions which have unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.
  • the cascade refrigeration systems of the present invention may have higher energy efficiency and capacity than currently used cascade refrigeration systems.
  • a cascade refrigeration system having at least two refrigeration loops, each circulating a refrigerant therethrough, comprising:
  • Either the first refrigerant or the second refrigerant, or both, may comprise a fluoroolefin.
  • the cascade heat exchanger system may include a first and a second cascade heat exchanger, and a secondary heat transfer loop which extends between the first and the second cascade heat exchanger.
  • the second refrigerant liquid indirectly absorbs the heat rejected by the first refrigerant vapor through a heat transfer fluid which circulates between the first cascade heat exchanger and the second cascade heat exchanger through the secondary heat transfer loop.
  • the first cascade heat exchanger has a first inlet and a first outlet, and a second inlet and a second outlet, wherein the first refrigerant vapor circulates from the first inlet to the first outlet and rejects heat and is condensed, and a secondary heat transfer fluid circulates from the second inlet to the second outlet and absorbs the heat rejected from the first refrigerant vapor and circulates to the second cascade heat exchanger.
  • the second cascade heat exchanger has a first inlet and a first outlet, and a second inlet and a second outlet, wherein the heat transfer fluid circulates from the second outlet of the first cascade heat exchanger to the first inlet of the second cascade heat exchanger and to the first outlet of the second cascade heat exchanger and rejects the heat absorbed from the first refrigerant.
  • the second refrigerant liquid circulates from the second inlet to the second outlet of the second cascade heat exchanger and absorbs the heat rejected by the heat transfer fluid and forms a second refrigerant vapor.
  • either the first and/or second refrigerant may be, but need not necessarily be, a fluoroolefin.
  • a method of exchanging heat between at least two refrigeration loops comprising:
  • FIG. 1 is a schematic diagram of a cascade refrigeration system according to one embodiment of the present invention.
  • FIG. 2 is a schematic diagram of another embodiment of the cascade refrigeration system of the present invention.
  • FIG. 3 is a schematic diagram of a further embodiment of the present invention which shows a cascade refrigeration system with a secondary heat transfer loop which transfers heat from a lower temperature loop to a higher temperature loop.
  • FIG. 4 is a schematic diagram of yet another embodiment of the cascade refrigeration system of the present invention which has multiple low temperature loops.
  • FIG. 5 is a graph of the cooling capacity and COP for a refrigerant composition comprising HFO-1234yf and HFC-134a versus the weight percent of HFO-1234yf in the composition.
  • Refrigeration capacity is a term to define the change in enthalpy of a refrigerant in an evaporator per unit mass of refrigerant circulated, or the heat removed by the refrigerant in the evaporator per unit volume of refrigerant vapor exiting the evaporator (volumetric capacity).
  • the refrigeration capacity is a measure of the ability of a refrigerant or heat transfer composition to produce cooling. Therefore, the higher the capacity, the greater the cooling that is produced for a given refrigerant circulation rate. Cooling rate refers to the heat removed by the refrigerant in the evaporator per unit time.
  • Coefficient of performance is the amount of heat removed from a body to be cooled divided by the required energy input to operate the cycle over a given time interval. The higher the COP, the higher is the energy efficiency. COP is directly related to the energy efficiency ratio (EER) that is the efficiency rating for refrigeration or air conditioning equipment at a specific set of internal and external temperatures.
  • EER energy efficiency ratio
  • Global warming potential is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide.
  • GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas.
  • the GWP for the 100 year time horizon is commonly the value referenced.
  • a mass-fraction weighted average can be calculated based on the individual GWPs for each component.
  • ODP Ozone depletion potential
  • CFC-11 fluorotrichloromethane
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • transitional phrase “consisting essentially of” is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do materially affect the basic and novel characteristic(s) of the claimed invention.
  • the term ‘consisting essentially of’ occupies a middle ground between “comprising” and ‘consisting of’.
  • a cascade refrigeration system having at least two refrigeration loops for circulating a refrigerant through each loop.
  • a cascade system is shown generally at 10 in FIG. 1 .
  • the cascade refrigeration system of the present invention has at least two refrigeration loops, including a first, or lower loop 12 as shown in FIG. 1 , which is a low temperature loop, and a second, or upper loop 14 as shown in FIG. 1 , which is a medium temperature loop 14 .
  • Each circulates a refrigerant therethrough.
  • the cascade refrigeration system of the present invention includes a first expansion device 16 .
  • the first expansion device has an inlet 16 a and an outlet 16 b.
  • the first expansion device reduces the pressure and temperature of a first refrigerant liquid which circulates through the first or low temperature loop.
  • the cascade refrigeration system of the present invention also includes an evaporator 18 as shown in FIG. 1 .
  • the evaporator has an inlet 18 a and an outlet 18 b.
  • the first refrigerant liquid from the first expansion device enters the evaporator through the evaporator inlet and is evaporated in the evaporator to form a first refrigerant vapor.
  • the first refrigerant vapor then circulates to the outlet of the evaporator.
  • the cascade refrigeration system of the present invention also includes a first compressor 20 .
  • the first compressor has an inlet 20 a and an outlet 20 b.
  • the first refrigerant vapor from the evaporator circulates to the inlet of the first compressor and is compressed, thereby increasing the pressure and the temperature of the first refrigerant vapor.
  • the compressed first refrigerant vapor then circulates to the outlet of the first compressor.
  • the cascade refrigeration system of the present invention also includes a cascade heat exchanger system 22 .
  • the heat exchanger has a first inlet 22 a and a first outlet 22 b.
  • the first refrigerant vapor from the first compressor enters the first inlet of the heat exchanger and is condensed in the heat exchanger to form a first refrigerant liquid, thereby rejecting heat.
  • the first refrigerant liquid then circulates to the first outlet of the heat exchanger.
  • the heat exchanger also includes a second inlet 22 c and a second outlet 22 d.
  • a second refrigerant liquid circulates from the second inlet to the second outlet of the heat exchanger and is evaporated to form a second refrigerant vapor, thereby absorbing the heat rejected by the first refrigerant (as it is condensed). This heat is rejected to ambient.
  • the second refrigerant vapor then circulates to the second outlet of the heat exchanger.
  • the heat rejected by the first refrigerant is directly absorbed by the second refrigerant, and this heat is rejected to ambient.
  • the cascade refrigeration system of the present invention also includes a second compressor 24 as shown in FIG. 1 .
  • the second compressor has an inlet 24 a and an outlet 24 b.
  • the second refrigerant vapor from the cascade heat exchanger is drawn into the compressor through the inlet and is compressed, thereby increasing the pressure and temperature of the second refrigerant vapor.
  • the second refrigerant vapor then circulates to the outlet of the second compressor.
  • the cascade refrigeration system of the present invention also includes a condenser 26 having an inlet 26 a and an outlet 26 b.
  • the second refrigerant from the second compressor circulates from the inlet and is condensed in the condenser to form a second refrigerant liquid.
  • the second refrigerant liquid exits the condenser through the outlet.
  • the cascade refrigeration system of the present invention also includes a second expansion device 28 having an inlet 28 a and an outlet 28 b.
  • the second refrigerant liquid passes through the second expansion device, which reduces the pressure and temperature of the second refrigerant liquid exiting the condenser. This liquid may be partially vaporized during this expansion.
  • the reduced pressure and temperature second refrigerant liquid circulates to the second inlet of the cascade heat exchanger system from the expansion device.
  • FIG. 1 various modifications to the embodiment as shown in FIG. 1 may be made without departing from the spirit or scope of the present invention.
  • a secondary heat transfer loop as shown in this diagram, which uses a secondary heat transfer fluids such as glycol, may be used with the system of the present invention to transfer heat from bodies to be cooled (e.g., supermarket food display cases) to either the high or low refrigeration loops or both.
  • the secondary heat transfer loop is used to transfer heat from a body to be cooled to the refrigeration loop, as opposed to a secondary heat transfer loop which is used to transfer heat between the refrigeration loops, as will be described below with respect to FIG. 3 .
  • either the first refrigerant or the second refrigerant in the cascade system of the embodiment of FIG. 1 may comprise a fluoroolefin.
  • at least the second refrigerant i.e., the refrigerant which circulates through the medium temperature loop, comprises a fluoroolefin.
  • the first refrigerant i.e., the refrigerant in the low temperature loop
  • both the first and the second refrigerants to comprise a fluoroolefin.
  • the first or the second refrigerant may be any of the fluoroolefins or mixtures of fluoroolefins or mixtures of fluoroolefins with additional refrigerants as described herein.
  • Such fluoroolefins may be selected from the group consisting of:
  • fluoroolefins are compounds, which comprise carbon atoms, fluorine atoms and optionally hydrogen or chlorine atoms.
  • the fluoroolefins used in the compositions of the present invention comprise compounds with 2 to 12 carbon atoms.
  • the fluoroolefins comprise compounds with 3 to 10 carbon atoms, and in yet another embodiment the fluoroolefins comprise compounds with 3 to 7 carbon atoms.
  • Representative fluoroolefins include but are not limited to all compounds as listed in Table 1, Table 2, and Table 3.
  • the first refrigerant is selected from fluoroolefins having the formula E- or Z—R 1 CH ⁇ CHR 2 (Formula (i)), wherein R 1 and R 2 are, independently, C 1 to C 6 perfluoroalkyl groups.
  • R 1 and R 2 groups include, but are not limited to, CF 3 , C 2 F 5 , CF 2 CF 2 CF 3 , CF(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , CF(CF 3 )CF 2 CF 3 , CF 2 CF(CF 3 ) 2 , C(CF 3 ) 3 , CF 2 CF 2 CF 2 CF 3 , CF 2 CF 2 CF(CF 3 ) 2 , C(CF 3 ) 2 C 2 F 5 , CF 2 CF 2 CF 2 CF 2 CF 3 , CF(CF 3 )CF 2 CF 2 C 2 F 5 , and C(CF 3 ) 2 CF 2 C 2 F 5 .
  • the fluoroolefins of Formula (i) have at least 4 carbon atoms in the molecule.
  • the first refrigerant is selected from fluoroolefins of Formula (i) having at least 5 carbon atoms in the molecule.
  • the first refrigerant is selected from fluoroolefins of Formula (i) having at least 6 carbon atoms in the molecule.
  • Exemplary, non-limiting Formula (i) compounds are presented in Table 1.
  • Compounds of Formula (i) may be prepared by contacting a perfluoroalkyl iodide of the formula R 1 I with a perfluoroalkyltrihydroolefin of the formula R 2 CH ⁇ CH 2 to form a trihydroiodoperfluoroalkane of the formula R 1 CH 2 CHIR 2 . This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R 1 CH ⁇ CHR 2 .
  • the olefin R 1 CH ⁇ CHR 2 may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R 1 CHICH 2 R 2 formed in turn by reacting a perfluoroalkyl iodide of the formula R 2 I with a perfluoroalkyltrihydroolefin of the formula R 1 CH ⁇ CH 2 .
  • the contacting of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may take place in batch mode by combining the reactants in a suitable reaction vessel capable of operating under the autogenous pressure of the reactants and products at reaction temperature.
  • suitable reaction vessels include fabricated from stainless steels, in particular of the austenitic type, and the well-known high nickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickel based alloys and Inconel® nickel-chromium alloys.
  • reaction may be conducted in semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant by means of a suitable addition apparatus such as a pump at the reaction temperature.
  • a suitable addition apparatus such as a pump at the reaction temperature.
  • the ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin should be between about 1:1 to about 4:1, preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct as reported by Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974).
  • Preferred temperatures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably within the range of about 150° C. to 300° C., preferably from about 170° C. to about 250° C., and most preferably from about 180° C. to about 230° C.
  • Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours.
  • the trihydroiodoperfluoroalkane prepared by reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be used directly in the dehydroiodination step or may preferably be recovered and purified by distillation prior to the dehydroiodination step.
  • the dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance.
  • Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime.
  • Preferred basic substances are sodium hydroxide and potassium hydroxide.
  • Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane.
  • solvent may depend on the boiling point product and the ease of separation of traces of the solvent from the product during purification.
  • ethanol or isopropylene glycol e.g., ethanol or isopropanol
  • isopropanol e.g., isopropanol
  • isobutanol e.g., isobutan
  • the dehydroiodination reaction may be carried out by addition of one of the reactants (either the basic substance or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel.
  • Said reaction may be fabricated from glass, ceramic, or metal and is preferably agitated with an impeller or stirring mechanism.
  • Temperatures suitable for the dehydroiodination reaction are from about 10° C. to about 100° C., preferably from about 20° C. to about 70° C.
  • the dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure.
  • dehydroiodination reactions in which the compound of Formula (i) is distilled out of the reaction vessel as it is formed.
  • the dehydroiodination reaction may be conducted by contacting an aqueous solution of said basic substance with a solution of the trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity such as an alkane (e.g., hexane, heptane, or octane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of a phase transfer catalyst.
  • an alkane e.g., hexane, heptane, or oc
  • Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), or cyclic polyether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).
  • quaternary ammonium halides e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylam
  • the dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substance.
  • Suitable reaction times for the dehydroiodination reactions are from about 15 minutes to about six hours or more depending on the solubility of the reactants. Typically the dehydroiodination reaction is rapid and requires about 30 minutes to about three hours for completion.
  • the compound of Formula (i) may be recovered from the dehydroiodination reaction mixture by phase separation after addition of water, by distillation, or by a combination thereof.
  • the first refrigerant is selected from fluoroolefins comprising cyclic fluoroolefins (cyclo-[CX ⁇ CY(CZW) n —] (Formula (ii)), wherein X, Y, Z, and W are independently selected from H and F, and n is an integer from 2 to 5).
  • the fluoroolefins of Formula (ii) have at least about 3 carbon atoms in the molecule.
  • the fluoroolefins of Formula (ii) have at least about 4 carbon atoms in the molecule.
  • the fluoroolefins of Formula (ii) have at least about 5 carbon atoms in the molecule. In yet another embodiment, the fluoroolefins of Formula (ii) have at least about 6 carbon atoms in the molecule. Representative cyclic fluoroolefins of Formula (ii) are listed in Table 2.
  • the first refrigerant of the present invention may comprise a single compound of Formula (i) or Formula (ii), for example, one of the compounds in Table 1 or Table 2, or may comprise a combination of compounds of Formula (i) or Formula (ii).
  • the first refrigerant is selected from fluoroolefins comprising those compounds listed in Table 3.
  • 1,1,1,4,4-pentafluoro-2-butene may be prepared from 1,1,1,2,4,4-hexafluorobutane (CHF 2 CH 2 CHFCF 3 ) by dehydrofluorination over solid KOH in the vapor phase at room temperature.
  • the synthesis of 1,1,1,2,4,4-hexafluorobutane is described in U.S. Pat. No. 6,066,768.
  • 1,1,1,4,4,4-hexafluoro-2-butene may be prepared from 1,1,1,4,4,4-hexafluoro-2-iodobutane (CF 3 CHICH 2 CF 3 ) by reaction with KOH using a phase transfer catalyst at about 60° C.
  • 1,1,1,4,4,4-hexafluoro-2-iodobutane may be carried out by reaction of perfluoromethyl iodide (CF 3 I) and 3,3,3-trifluoropropene (CF 3 CH ⁇ CH 2 ) at about 200° C. under autogenous pressure for about 8 hours.
  • CF 3 I perfluoromethyl iodide
  • CF 3 CH ⁇ CH 2 3,3,3-trifluoropropene
  • 3,4,4,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorination of 1,1,1,2,2,3,3-heptafluoropentane (CF 3 CF 2 CF 2 CH 2 CH 3 ) using solid KOH or over a carbon catalyst at 200-300° C.
  • 1,1,1,2,2,3,3-heptafluoropentane may be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF 3 CF 2 CF 2 CH ⁇ CH 2 ).
  • 1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,3,3,4-heptafluorobutane (CH 2 FCF 2 CHFCF 3 ) using solid KOH.
  • 1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,2,4,4-heptafluorobutane (CHF 2 CH 2 CF 2 CF 3 ) using solid KOH.
  • 1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehydrofluorination of 1,1,1,3,3,4,4-heptafluorobutane (CF 3 CH 2 CF 2 CHF 2 ) using solid KOH.
  • 1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,2,3-hexafluorobutane (CH 2 FCH 2 CF 2 CF 3 ) using solid KOH.
  • 1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,3,3,4-hexafluorobutane (CF 3 CH 2 CF 2 CH 2 F) using solid KOH.
  • 1,1,1,3-tetrafluoro-2-butene may be prepared by reacting 1,1,1,3,3-pentafluorobutane (CF 3 CH 2 CF 2 CH 3 ) with aqueous KOH at 120° C.
  • 1,1,1,4,4,5,5,5-octafluoro-2-pentene may be prepared from (CF 3 CHICH 2 CF 2 CF 3 ) by reaction with KOH using a phase transfer catalyst at about 60° C.
  • the synthesis of 4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out by reaction of perfluoroethyliodide (CF 3 CF 2 I) and 3,3,3-trifluoropropene at about 200° C. under autogenous pressure for about 8 hours.
  • 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF 3 CF 2 CHICH 2 CF 2 CF 3 ) by reaction with KOH using a phase transfer catalyst at about 60° C.
  • the synthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane may be carried out by reaction of perfluoroethyliodide (CF 3 CF 2 I) and 3,3,4,4,4-pentafluoro-1-butene (CF 3 CF 2 CH ⁇ CH 2 ) at about 200° C. under autogenous pressure for about 8 hours.
  • 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be prepared by the dehydrofluorination of 1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane (CF 3 CHICH 2 CF(CF 3 ) 2 ) with KOH in isopropanol.
  • CF 3 CHICH 2 CF(CF 3 ) 2 is made from reaction of (CF 3 ) 2 CFI with CF 3 CH ⁇ CH 2 at high temperature, such as about 200° C.
  • 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reaction of 1,1,1,4,4,4-hexafluoro-2-butene (CF 3 CH ⁇ CHCF 3 ) with tetrafluoroethylene (CF 2 ⁇ CF 2 ) and antimony pentafluoride (SbF 5 ).
  • 2,3,3,4,4-pentafluoro-1-butene may be prepared by dehydrofluorination of 1,1,2,2,3,3-hexafluorobutane over fluorided alumina at elevated temperature.
  • 2,3,3,4,4,5,5,5-ocatafluoro-1-pentene may be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solid KOH.
  • 1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over fluorided alumina at elevated temperature.
  • the first refrigerant may be any of the single fluoroolefins of Formula (i), Formula (ii), Table 1, Table 2 and Table 3, or may be any combination of the different fluoroolefins from Formula (i), Formula (ii), Table 1, Table 2 and Table 3.
  • the first refrigerant may be any combination of a single fluoroolefin or multiple fluoroolefins selected from Formula (i), Formula (ii), Table 1, Table 2 and Table 3 with at least one additional refrigerant selected from hydrofluorocarbons, fluoroethers, hydrocarbons, CF 3 I, ammonia (NH 3 ), carbon dioxide (CO 2 ), nitrous oxide (N 2 O), and mixtures thereof, meaning mixtures of any of the foregoing compounds.
  • the first refrigerant may contain hydrofluorocarbons comprising at least one saturated compound containing carbon, hydrogen, and fluorine.
  • hydrofluorocarbons having 1-7 carbon atoms and having a normal boiling point of from about ⁇ 90° C. to about 80° C.
  • Hydrofluorocarbons are commercial products available from a number of sources or may be prepared by methods known in the art.
  • hydrofluorocarbon compounds include but are not limited to fluoromethane (CH 3 F, HFC-41), difluoromethane (CH 2 F 2 , HFC-32), trifluoromethane (CHF 3 , HFC-23), pentafluoroethane (CF 3 CHF 2 , HFC-125), 1,1,2,2-tetrafluoroethane (CHF 2 CHF 2 , HFC-134), 1,1,1,2-tetrafluoroethane (CF 3 CH 2 F, HFC-134a), 1,1,1-trifluoroethane (CF 3 CH 3 , HFC-143a), 1,1-difluoroethane (CHF 2 CH 3 , HFC-152a), fluoroethane (CH 3 CH 2 F, HFC-161), 1,1,1,2,2,3,3-heptafluoropropane (CF 3 CF 2 CHF 2 , HFC-227ca), 1,1,1,2,3,3,3-heptafluoropropan
  • the first refrigerant may further comprise fluoroethers.
  • Fluoroethers comprise at least one compound having carbon, fluorine, oxygen and optionally hydrogen, chlorine, bromine or iodine. Fluoroethers are commercially available or may be produced by methods known in the art.
  • fluoroethers include but are not limited to nonafluoromethoxybutane (C 4 F 9 OCH 3 , any or all possible isomers or mixtures thereof); nonafluoroethoxybutane (C 4 F 9 OC 2 H 5 , any or all possible isomers or mixtures thereof); 2-difluoromethoxy-1,1,1,2-tetrafluoroethane (HFOC-236ea ⁇ , or CHF 2 OCHFCF 3 ); 1,1-difluoro-2-methoxyethane (HFOC-272fbE ⁇ ,CH 3 OCH 2 CHF 2 ); 1,1,1,3,3,3-hexafluoro-2-(fluoromethoxy)propane (HFOC-347mmzE ⁇ , or CH 2 FOCH(CF 3 ) 2 ); 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFOC-356mmzE ⁇ , or CH 3 OCH(CH 3 ) 2 ); 1,1,1,2,2-p
  • the first refrigerant may further comprise at least one hydrocarbon.
  • Hydrocarbons are compounds having only carbon and hydrogen. Of particular utility are compounds having 3-7 carbon atoms. Hydrocarbons are commercially available through numerous chemical suppliers. Representative hydrocarbons include but are not-limited to propane, n-butane, isobutane, cyclobutane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, cyclohexane, n-heptane, cycloheptane, and mixtures thereof.
  • the disclosed compositions may comprise hydrocarbons containing heteroatoms, such as dimethylether (DME, CH 3 OCH 3 ). DME is commercially available.
  • the first refrigerant may further comprise carbon dioxide (CO 2 ), which is commercially available from various sources or may be prepared by methods known in the art.
  • CO 2 carbon dioxide
  • the first refrigerant may further comprise ammonia (NH 3 ), which is commercially available from various sources or may be prepared by methods known in the art.
  • NH 3 ammonia
  • the first refrigerant may further comprise iodotrifluoromethane (CF 3 I), which is commercially available from various sources or may be prepared by methods known in the art.
  • CF 3 I iodotrifluoromethane
  • the first and the second refrigerants may be as shown in the Table 4 below.
  • the second refrigerant may consist essentially of HFO-1234yf. In other embodiments, the second refrigerant may comprise HFO-1234yf and R134a. In yet other embodiments, the second refrigerant may comprise HFO-1234yf and R32, or it may comprise trans HFO-1234ze and HFC-32, or trans HFO-1234ze and HFC-134a or trans HFO-1234ze and HFC-125.
  • the first refrigerant may comprise carbon dioxide (CO 2 ) or nitrous oxide (N 2 O).
  • the first refrigerant may comprise HFO-1234yf and HFC-32.
  • the first refrigerant may comprise trans HFO-1234ze and HFC-32.
  • the first refrigerant may comprise either carbon dioxide or nitrous oxide.
  • the first refrigerant may comprise HFO-1234yf and HFC-32.
  • the first refrigerant may comprise trans HFO-1234ze and HFC-32.
  • the second refrigerant may comprise 1-99% HFO-1234yf and 99-1% HFC-134a.
  • the second refrigerant comprises 1-53.1% HFO-1234yf and 46.9-99% HFC-134a.
  • the second refrigerant comprises 53% HFO-1234yf and 47% HFC-134a.
  • the second refrigerant comprises 1-59% HFO-1234yf and 41-99% HFC-134a.
  • the second refrigerant is non-flammable at 100° C. or 60° C. This composition is non-flammable and has maximum capacity in the range of 40-59% 1234yf and 41-60% 134a.
  • the second refrigerant may comprise 53% HFO-1234yf and 47% HFC-134a.
  • the ranges for these components may be 1-99% HFO-1234yf and 99-1% HFC-32.
  • the second refrigerant may comprise 20-99% HFO-1234yf and 80-99% HFC-32. More particularly, the second refrigerant may comprise 50-99% HFO-1234yf and 50-99% HFC-32, and even more particularly, the second refrigerant may comprise 63% HFO-1234yf and 37% HFC-32.
  • the second refrigerant may be used as a replacement for R404A.
  • the second refrigerant may comprise 27.5% HFO-1234yf and 72.5% HFC-32.
  • the second refrigerant may be used as a replacement for R410A.
  • the first refrigerant may comprise either CO 2 or N 2 O, a blend of HFO-1234yf/HFC-32, or a blend of trans HFO-1234ze/HFC-32.
  • the first refrigerant may comprise either carbon dioxide or nitrous oxide.
  • the first refrigerant may comprise HFO-1234yf and HFC-32.
  • the first refrigerant may comprise trans HFO-1234ze and HFC-32.
  • the second refrigerant comprises trans HFO-1234ze and HFC-32
  • the second refrigerant comprises 1-99% HFO-1234ze and 99-1% HFC-32.
  • the 1234ze may be either trans-1234ze or cis-1234ze.
  • the first refrigerant may comprise the first refrigerant may comprise either CO 2 or N 2 O, a blend of HFO-1234yf/HFC-32, or a blend of trans HFO-1234ze/HFC-32.
  • the first refrigerant may comprise either CO 2 or N 2 O.
  • the first refrigerant may comprise HFO-1234yf and HFC-32.
  • the first refrigerant may comprise trans HFO-1234ze and HFC-32.
  • the first refrigerant may comprise either carbon dioxide or nitrous oxide.
  • the first refrigerant may comprise HFC-32 and HFO-1234yf.
  • the first refrigerant may comprise trans HFO-1234ze and HFC-32.
  • FIG. 2 shows a cascade system according to the present invention, where elements which correspond to the elements shown in FIG. 1 are indicated with a like reference numeral and a prime (′).
  • the elements in FIG. 2 which correspond to the elements shown in FIG. 1 all operate as described above with respect to FIG. 1 .
  • the cascade system of FIG. 2 includes a secondary heat transfer loop, which includes a secondary fluid chiller 30 and a secondary fluid heat exchanger 32 .
  • the secondary fluid heat exchanger is located near a body to be cooled, such as food in a medium temperature display case.
  • the secondary chiller cools a secondary heat transfer fluid.
  • a secondary heat transfer loop in the embodiment of FIG. 2 is advantageous because it limits the amount of refrigerant that must be used and the length of piping through which refrigerant must circulate, while at the same time transferring heat between locations that have to be remote from each other (e.g., remote locations in a large supermarket). Minimization of the amount of refrigerant and length of refrigerant piping reduces refrigerant cost, leakage rates and mitigates risks associated with using refrigerants which are flammable and/or toxic.
  • a secondary loop could be used to transfer heat form low temp display cases to the LOW temp loop in a configuration similar to that shown in FIG. 2 for the high or mid temp loop.
  • the choice of secondary heat transfer fluids would be quit limited because the viscosity of liquids and associated pumping costs increase at low temperatures.
  • the cascade refrigeration system of FIG. 2 also includes a cascade heat exchanger system disposed between the low temperature refrigeration loop and the medium temperature refrigeration loop.
  • the cascade heat exchanger system has a first inlet 22 a ′ and a first outlet 22 b ′, wherein the first refrigerant vapor circulates from the first inlet to the first outlet and is condensed in the heat exchanger system to form a first refrigerant liquid, thereby rejecting heat.
  • the cascade heat exchanger system also includes a second inlet 22 c ′ and a second outlet 22 d ′, wherein a second refrigerant liquid circulates from the second inlet to the second outlet and absorbs the heat rejected by the first refrigerant and forms a second refrigerant vapor, as will be explained below.
  • a second refrigerant liquid circulates from the second inlet to the second outlet and absorbs the heat rejected by the first refrigerant and forms a second refrigerant vapor, as will be explained below.
  • the heat rejected by the first refrigerant is directly absorbed by the second refrigerant.
  • a secondary heat transfer fluid enters the secondary chiller at a first inlet 30 a and exits the secondary chiller at a first outlet 30 b.
  • the secondary heat transfer fluid may comprise ethylene glycol, propylene glycol, carbon dioxide, water brine or any of several other fluids or slurries known to the art.
  • the secondary heat transfer fluid may undergo a phase change.
  • the secondary chiller includes a second inlet 30 c and a second outlet 30 d. The second refrigerant enters the secondary fluid chiller through second inlet 30 c and evaporates, thus causing the heat transfer fluid in the chiller to be cooled.
  • the cooled heat transfer fluid exits the chiller 30 through first outlet 30 b and circulates to a secondary fluid heat exchanger 32 located near a body to be cooled.
  • This body to be cooled may be food items inside a refrigerated display case in a supermarket.
  • the heat transfer fluid is warmed by this body and returns to the secondary fluid chiller to be cooled again by the evaporation of the second refrigerant, which also circulates through the secondary fluid chiller.
  • a liquid pump (not shown) pumps the heat transfer fluid from the secondary fluid heat exchanger back to the secondary fluid chiller. This warmed heat transfer fluid causes the second refrigerant to evaporate in the secondary fluid chiller.
  • a separate expansion device may be disposed in the inlet line entering cascade heat exchanger 22 ′ and the inlet line entering secondary fluid chiller 30 in order to control the pressure and flow rate through the cascade heat exchanger and the secondary fluid chiller, respectively.
  • cascade heat exchanger 22 ′ and secondary fluid chiller 30 are shown connected in parallel, they may alternatively be connected in series without departing from the scope of the present invention.
  • cascade heat exchanger 22 ′ as in the first embodiment of FIG. 1 , the first refrigerant is condensed, and the second refrigerant evaporates and exits from the heat exchanger 22 ′ at outlet 22 d′ .
  • the second refrigerant which exits secondary fluid chiller 30 at second outlet 30 d merges with the second refrigerant from outlet 22 d′ of the cascade heat exchanger and circulates to second compressor 24 ′.
  • the cycle through medium temperature loop 14 ′ and low temperature loop 12 ′ are otherwise the same as discussed above with respect to FIG. 1 .
  • FIG. 3 Another embodiment of the cascade refrigeration system of the present invention is shown in FIG. 3 .
  • elements which correspond to the elements shown in FIG. 1 are indicated with a like reference numeral and a double prime (′′).
  • the elements in FIG. 3 which correspond to the elements shown in FIG. 1 all operate as described above with respect to FIG. 1 .
  • the system of FIG. 3 includes a secondary heat transfer loop, shown generally at 40 , which includes two cascade heat exchangers instead of one cascade heat exchanger as shown in the embodiments of FIGS. 1 and 2 .
  • the use of a secondary heat transfer loop in the embodiment of FIG. 3 is advantageous because it limits the amount of refrigerant that must be used and the length of piping through which refrigerant must circulate, while at the same time transferring heat between locations that have to be remote from each other.
  • the embodiment of FIG. 3 includes a cascade heat exchanger system which includes two cascade heat exchangers connected to each other through a secondary heat transfer loop.
  • the cascade heat exchanger system in FIG. 3 has a first inlet 42 a and a first outlet 42 b, wherein the first refrigerant vapor circulates from the first inlet to the first outlet and is condensed in the cascade heat exchanger system to form a first refrigerant liquid, thereby rejecting heat.
  • the cascade heat exchanger system also includes a second inlet 44 c and a second outlet 44 d, wherein a second refrigerant liquid circulates from the second inlet to the second outlet and indirectly absorbs the heat rejected by the first refrigerant and forms a second refrigerant vapor.
  • the second refrigerant liquid indirectly absorbs the heat rejected by the first refrigerant through the secondary heat transfer fluid, that is to say, the first refrigerant rejects heat to the heat transfer fluid, and the heat transfer fluid circulates to the second cascade heat exchanger 44 where it transfers the heat from the first refrigerant to the second refrigerant, as will be described below. This heat is rejected to ambient.
  • cascade refrigeration system 10 ′′ includes a first cascade heat exchanger 42 in low temperature loop 12 ′′, having a first inlet 42 a and a first outlet 42 b, and a second inlet 42 c and a second outlet 42 d.
  • the medium temperature loop 14 ′′ includes a second cascade heat exchanger 44 , having a first inlet 44 a and a first outlet 44 b, and a second inlet 44 c and a second outlet 44 d.
  • Compressed first refrigerant vapor circulates from the outlet of the first compressor 20 b ′′ as shown in FIG. 3 to the first inlet 42 a of the first heat exchanger 42 .
  • FIG. 3 Compressed first refrigerant vapor circulates from the outlet of the first compressor 20 b ′′ as shown in FIG. 3 to the first inlet 42 a of the first heat exchanger 42 .
  • this compressed refrigerant vapor is condensed in the first cascade heat exchanger to form a first refrigerant liquid, thereby rejecting heat.
  • the first refrigerant liquid then circulates to the first outlet 42 b of the first cascade heat exchanger.
  • a heat transfer fluid circulates in the secondary heat transfer loop between the first cascade heat exchanger and a second cascade heat exchanger 44 , which is also part of the medium temperature loop 14 ′′. Specifically, the heat transfer fluid enters first heat exchanger 42 through a second inlet 42 c and exits the first heat exchanger through a second outlet 42 d. This heat transfer fluid absorbs the heat rejected by the condensing first refrigerant that enters that heat exchanger through inlet 42 a, and is warmed.
  • the warmed heat transfer fluid exits the first heat exchanger through second outlet 42 d and circulates to second heat exchanger 44 .
  • the heat transfer fluid is cooled in the second heat exchanger by rejecting heat to the second refrigerant, which enters the second heat exchanger at a second inlet 44 c, and exits the second heat exchanger at a second outlet 44 d.
  • the second refrigerant evaporates in the second cascade heat exchanger since it is warmed by the heat transfer fluid, and forms a second refrigerant vapor. Cooled heat transfer fluid exits the first outlet 44 b of the second heat exchanger.
  • the cycle through the low temperature loop 12 ′′ and the medium temperature loop 14 ′′ are otherwise the same as discussed above with respect to FIG. 1 , except that in this embodiment, the first and/or second refrigerant may be, but need not necessarily be, a fluoroolefin.
  • FIG. 4 A further embodiment of the cascade refrigeration system of the present invention is shown in FIG. 4 .
  • elements which correspond to the elements shown in FIG. 1 are indicated with a like reference numeral and a triple prime (′′′).
  • the elements in FIG. 4 which correspond to the elements shown in FIG. 1 all operate as described above with respect to FIG. 1 .
  • the system of FIG. 4 includes two low temperature loops, Loop 12 A, which is similar to the low temperature loop 12 of FIG. 1 , and Loop 12 B.
  • One of the two low temperature loops, e.g., loop 12 B provides refrigeration at a temperature which is different from, for example, intermediate to, the temperature at which refrigeration is provided by the other low temperature loop and by the medium temperature loop.
  • the advantage of such a system is that the refrigerant in the low temperature loop can be used to cool two different bodies, such as two separate freezer display cases, at two different temperatures.
  • a cascade heat exchanger system is disposed between the two loops.
  • the cascade heat exchanger system has a first inlet 22 a ′′′ and a second inlet 22 b ′′′, and a first outlet 52 wherein the first refrigerant vapor circulates from the first and second inlets to the first outlet and is condensed in the heat exchanger system to form a first refrigerant liquid, thereby rejecting heat.
  • the cascade heat exchanger system also includes a third inlet 22 c ′′′ and a second outlet 22 d ′′′, wherein a second refrigerant liquid circulates from the third inlet to the second outlet and absorbs the heat rejected by the first refrigerant and forms a second refrigerant vapor.
  • a second refrigerant liquid circulates from the third inlet to the second outlet and absorbs the heat rejected by the first refrigerant and forms a second refrigerant vapor.
  • FIG. 4 encompasses all cascade heat exchanger systems that transfer heat in the above described manner.
  • the flow of the first refrigerant liquid is split as or after it exits the cascade heat exchanger 22 ′′′ at 52 .
  • One portion circulates through one low temperature loop 12 A, and another portion circulates through the other low temperature loop 12 B.
  • the portion of the first refrigerant that circulates through loop 12 B enters an additional expansion device 54 at inlet 54 a, and the pressure and temperature of this portion of the first refrigerant liquid is reduced.
  • This reduced pressure and temperature liquid refrigerant then circulates through outlet 54 b of the additional expansion device, and circulates to an additional evaporator 56 . It should be noted that this liquid may be partially vaporized during this expansion.
  • the additional evaporator 56 includes an inlet 56 a and an outlet 56 b.
  • the refrigerant liquid from the additional expansion device enters the evaporator through evaporator inlet 56 a and is evaporated in the evaporator to form a refrigerant vapor, thereby producing cooling, and circulates to outlet 56 b.
  • Low temperature loop 12 B also includes an additional compressor 58 having an inlet 58 a and an outlet 58 b.
  • low temperature loop 12 A also includes an evaporator 18 ′′′, which could be housed inside a freezer display case, and additional evaporator 56 could be housed inside a freezer display case. This system thereby could provide cooling to two separate freezer display cases.
  • a method of exchanging heat between at least two refrigeration loops comprising: (a) absorbing heat from a body to be cooled in a first refrigeration loop and rejecting this heat to a second refrigeration loop; and (b) absorbing the heat from the first refrigeration loop in the second refrigeration loop and rejecting this heat to ambient.
  • the refrigerant in either loop i.e., the loop in which heat is absorbed or the loop in which heat is rejected, or both, may comprise a fluoroolefin.
  • the heat from the first refrigeration loop may be absorbed directly in the second refrigeration loop, such as in the embodiments of FIGS. 1 , 2 and 4 , or it may be directly absorbed in the second refrigeration loop, such as in the embodiment of FIG. 3 .
  • Table 5 shows the performance of some exemplary compositions as compared to HFC-134a.
  • Evap Pres is evaporator pressure
  • Cond Pres is condenser pressure
  • Comp Disch T is compressor discharge temperature
  • COP coefficient of performance (analogous to energy efficiency)
  • CAP capacity
  • Avg. Temp. glide is the average of the temperature glide in the evaporator and condenser
  • GWP global warming potential. The data are based on the following conditions.
  • HFO-1234yf/HFC-134a 200.6 1016.5 81.4 2.231 2.742 0 1430 HFO-1234yf 220.5 1015.6 68.3 2.113 94.7 2.580 94.1 0 4 HFO-1234yf/HFC-134a 224.8 1097.0 78.1 2.371 106.3 2.685 97.9 0.05 1145 (20/80 wt %) HFO-1234yf/HFC-134a 245.3 1149.3 74.7 2.470 110.7 2.653 96.8 0.25 848 (40/60 wt %) HFO-1234yf/HFC-134a 252.1 1160.2 72.8 2.487 111.5 2.640 96.3 0.10 674 (53/47 wt %) HFO-1234yf/HFC-134a 252.7 1156.7 72.0 2.475 110.9 2.635 96.1 0.11 574 (60/40 wt %) HFO-1234yf/HFC-134a 243.4 1112.0 70.0 2.357 105.6 2.618 95.5 0.80
  • HFO-1234yf was published in Papadimitriou et al., Physical Chemistry Chemical Physics , 2007, vol. 9, pp. 1-13. Specifically, the 100 year time horizon GWP values are used. The GWP values for the compositions containing HFC-134a and HFO-1234yf are calculated as weighted averages of the individual component GWP values.
  • the data in Table 5 indicate that the 1234yf/134a compositions are a close match to 134a, in terms of COP, capacity, pressures and temperatures in the system, with lower GWP values. In addition, all the compositions have low temperature glide and a specific composition could be selected based on regulatory requirements for GWP, which have not at this time been determined.
  • the composition containing 53 wt % HFO-1234yf and 47 wt % HFC-134a has the particular benefit of providing a low GWP and a peak in the cooling capacity. This is shown graphically in FIG. 5 .
  • Flammable compositions may be identified by testing under ASTM (American Society of Testing and Materials) E681-2004, with an electronic ignition source. Such tests of flammability were conducted on compositions containing HFO-1234yf and HFC-134a at 101 kPa (14.7 psia), 50 percent relative humidity, and about 23° C. (room temperature), 60° C. and 100° C. at various concentrations in air in order to determine if flammable and if so, to find the lower flammability limit (LFL) and the upper flammability limit (UFL). The results are given in Table 6.
  • compositions with 66.25 weight percent or less HFO-1234yf in HFC-134a would be considered non-flammable.
  • compositions with 60.00 weight percent or less HFO-1234yf in HFC-134a would be considered non-flammable.
  • compositions containing 53.10 weight percent or less HFO-1234yf in HFC-134a would be considered non-flammable.
  • Table 7 shows the performance of certain compositions as compared to CO 2 , R404A (ASHRAE designation for a mixture containing HFC-125, HFC-134a, and HFC-143a), R410A (ASHRAE designation for a mixture containing HFC-32 and HFC-125) and HFC-32.
  • Evap Pres is evaporator pressure
  • Cond Pres is condenser pressure
  • Comp Disch T is compressor discharge temperature
  • COP coefficient of performance (analogous to energy efficiency)
  • CAP capacity
  • Avg. Temp. glide is the average of the temperature glide in the evaporator and condenser
  • GWP global warming potential. The data are based on the following conditions.
  • HFO-1234yf was published in Papadimitriou et al., Physical Chemistry Chemical Physics , 2007, vol. 9, pp. 1-13. Specifically, the 100 year time horizon GWP values are used. The GWP values for the compositions containing more than one component are calculated as weighted averages of the individual component GWP values.
  • composition containing 63 wt % HFO-1234yf and 37 wt % HFC-32 actually shows improved COP and capacity relative to R404A and also has significantly lower GWP.
  • the composition containing 27.5 wt % HFO-1234yf and 72.5 wt % HFC-32 matches the COP and capacity of R410A, has very low temperature glide indicating azeotrope-like behavior and also has significantly lower GWP.
  • compositions comprising mixtures of HFO-1234yf and HFC-32 have improved COP (energy efficiency) as compared to CO 2 .
  • the total equivalent warming impact is determined for systems as disclosed herein in comparison to conventional uncoupled supermarket refrigeration systems as well as conventional cascade systems.
  • the TEWI takes into consideration the effects of the energy efficiency of the system, the contribution due to the energy source used to provide the electrical power to the equipment, and the amount of refrigerant charged to the system as well as the rate of leakage to quantify a more complete environmental impact of use of different refrigerants.
  • This Example uses a conventional European direct expansion (DX) supermarket refrigeration system, traditionally using R404A in both medium temperature (MT) and low temperature (LT) refrigeration systems, as the base case for comparison. Certain assumptions were made based on a typical European supermarket system are shown in Table 8. Additionally, the expected equipment life was assumed to be 15 years and the CO 2 emitted from electricity generation was estimated to be 0.616 kg CO 2 /kw-hr.
  • DX European direct expansion
  • Table 9 provides the conditions for which the system performance (COP, or coefficient of performance, a measure of energy efficiency) was estimated.
  • COP system performance
  • temp is temperature
  • evap is evaporator
  • cond condenser
  • comp is compressor.
  • Table 10 lists several different embodiments of the present invention as compared to conventional uncoupled and cascade systems for which the determinations of TEWI are made, as well as the estimated COP values as calculated based on the conditions listed above in Table 9.
  • the TEWI value includes an indirect contribution, which incorporates energy source and usage, and a direct contribution due to the emissions of refrigerant with a given GWP from a system.
  • Table 11 lists the indirect and direct contributions and the TEWI value calculated for the different systems described above, in terms of equivalent CO 2 emissions over equipment life (in million kg) in order from greatest to least environmental impact.

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Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110232306A1 (en) * 2008-04-30 2011-09-29 Honeywell International Inc. Absorption refrigeration cycles using a lgwp refrigerant
US20130227979A1 (en) * 2010-11-04 2013-09-05 Junichiro Kasuka Heat Pump Type Air-Warming Device
US20130239603A1 (en) * 2012-03-15 2013-09-19 Luther D. Albertson Heat pump with independent subcooler circuit
US20140260357A1 (en) * 2013-03-15 2014-09-18 Energy Recovery Systems Inc. Energy exchange system and method
WO2014151344A1 (en) * 2013-03-15 2014-09-25 Honeywell International Inc. Low gwp heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene
JP2014529661A (ja) * 2011-08-30 2014-11-13 アルケマ フランス テトラフルオロプロペンをベースにした超臨界熱伝達流体
US8940180B2 (en) 2012-11-21 2015-01-27 Honeywell International Inc. Low GWP heat transfer compositions
WO2015054110A1 (en) * 2013-10-10 2015-04-16 E. I. Du Pont De Nemours And Company Compositions comprising difluoromethane, pentafluoroethane, tetrafluoroethane and tetrafluoropropene and uses thereof
US20150191639A1 (en) * 2012-08-01 2015-07-09 E I Du Pont De Nemours And Company Use of e-1,1,1,4,4,4-hexafluoro-2-butene in heat pumps
CN105004088A (zh) * 2015-07-31 2015-10-28 广东申菱空调设备有限公司 一种中温、低温两用的复叠式冷水机组
WO2016048613A1 (en) * 2014-09-23 2016-03-31 The Chemours Company Fc, Llc Use of (2e)-1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene in high temperature heat pumps
US20160138837A1 (en) * 2013-06-14 2016-05-19 Siemens Aktiengesellschaft Heat pump arrangement and method for operating heat pump arrangement
US20160178246A1 (en) * 2013-09-27 2016-06-23 Panasonic Healthcare Holdings Co., Ltd. Refrigeration apparatus
US20160178244A1 (en) * 2014-12-22 2016-06-23 Heatcraft Refrigeration Products Llc Carbon Dioxide Based Auxiliary Cooling System
US20160280387A1 (en) * 2015-03-25 2016-09-29 United Technologies Corporation Aircraft thermal management system
EP3037744A4 (en) * 2013-09-27 2016-11-02 Panasonic Healthcare Holdings Co Ltd REFRIGERATION DEVICE
EP3121240A1 (en) * 2015-07-20 2017-01-25 Ideas Hub, S.L. A refrigerant composition
WO2017099814A1 (en) * 2015-12-08 2017-06-15 Trane International Inc. Using heat recovered from heat source to obtain high temperature hot water
US20170167765A1 (en) * 2015-12-15 2017-06-15 WinWay Tech. Co., Ltd. Evaporator for a cascade refrigeration system
US20170205119A1 (en) * 2014-10-08 2017-07-20 Inertech Ip Llc Systems and methods for cooling electrical equipment
WO2017143018A1 (en) * 2016-02-16 2017-08-24 Honeywell International Inc. Multi-stage low gwp air conditioning system
US20170268805A1 (en) * 2014-12-04 2017-09-21 United Technologies Corporation Field-active heat pumping using liquid materials
WO2017165764A1 (en) * 2016-03-25 2017-09-28 Honeywell International Inc. Low gwp cascade refrigeration system
US9783721B2 (en) 2012-08-20 2017-10-10 Honeywell International Inc. Low GWP heat transfer compositions
US9982180B2 (en) 2013-02-13 2018-05-29 Honeywell International Inc. Heat transfer compositions and methods
US20180195773A1 (en) 2017-01-12 2018-07-12 Emerson Climate Technologies, Inc. Micro Booster Supermarket Refrigeration Architecture
US20180356130A1 (en) * 2013-03-15 2018-12-13 Trane International Inc. Cascading heat recovery using a cooling unit as a source
WO2018237208A1 (en) * 2017-06-21 2018-12-27 Honeywell International Inc. REFRIGERATION SYSTEMS AND METHODS
WO2018237175A1 (en) * 2017-06-21 2018-12-27 Honeywell International Inc. REFRIGERATION SYSTEMS AND METHODS
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
EP3417215A4 (en) * 2016-02-16 2019-10-02 Honeywell International Inc. LOW PRG MULTI-STAGE AIR CONDITIONING SYSTEM
WO2020014220A1 (en) * 2018-07-09 2020-01-16 Honeywell International Inc. Refrigeration systems and methods
CN114502898A (zh) * 2019-09-30 2022-05-13 大金工业株式会社 空调装置
FR3120992A1 (fr) * 2019-10-15 2022-09-23 Arkema France Procédé de régulation de la température d’une batterie d’un véhicule automobile
US20220325923A1 (en) * 2019-06-12 2022-10-13 Daikin Industries, Ltd. Refrigerant cycle system
WO2022266622A3 (en) * 2021-06-16 2023-01-26 Colorado State University Research Foundation Air source heat pump system and method of use for industrial steam generation
US11739243B2 (en) 2018-12-21 2023-08-29 Honeywell International Inc. Azeotrope or azeotrope-like compositions of 1,2,2-trifluoro-1-trifluoromethylcyclobutane (TFMCB) and applications thereof
US12006274B2 (en) 2022-11-03 2024-06-11 The Chemours Company Fc, Llc Compositions including olefin and hydrofluoroalkane

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8974688B2 (en) 2009-07-29 2015-03-10 Honeywell International Inc. Compositions and methods for refrigeration
US9845419B2 (en) * 2009-07-29 2017-12-19 Honeywell International Inc. Low GWP heat transfer compositions containing difluoromethane and 1,3,3,3-tetrafluoropropene
MX2012013314A (es) 2010-05-20 2013-02-01 Mexichem Amanco Holding Sa De Capital Variable Composiciones de transferencia de calor.
GB2480517B (en) * 2010-05-20 2013-03-06 Mexichem Amanco Holding Sa Heat transfer compositions
JP2013002737A (ja) * 2011-06-16 2013-01-07 Mitsubishi Electric Corp 冷凍サイクル装置
US9605887B2 (en) 2011-07-29 2017-03-28 Hdt Expeditionary Systems, Inc. Transportable packaged ice supply system for high temperature environments
EP2741028B1 (en) * 2011-08-04 2020-03-11 Mitsubishi Electric Corporation Refrigeration device
GB2493395B (en) * 2011-08-05 2014-07-23 Mexichem Amanco Holding Sa Heat transfer compositions
JP5717584B2 (ja) * 2011-08-10 2015-05-13 三菱電機株式会社 冷凍サイクル装置
ES2795775T3 (es) * 2011-12-01 2020-11-24 Daikin Ind Ltd Uso nuevo para composiciones que comprenden HFC-134a y HFO-1234yf
EP2794804A1 (en) * 2011-12-21 2014-10-29 E. I. Du Pont de Nemours and Company Use of e-1,1,1,4,4,5,5,5-octafluoro-2-pentene and optionally 1,1,1,2,3-pentafluoropropane in high temperature heat pumps
FR2986309B1 (fr) * 2012-01-26 2018-05-25 Arkema France Systeme de refrigeration en cascade
US20130301781A1 (en) * 2012-05-14 2013-11-14 Parviz Parvin Modified dry ice heat exchanger for heat removal of portable reactors
TW201411068A (zh) * 2012-08-01 2014-03-16 Du Pont 於級聯熱泵中在最終級聯階段使用包含ｚ－１，１，１，４，４，４－六氟－２－丁烯之工作流體製造加熱
TW201829721A (zh) 2013-06-04 2018-08-16 美商杜邦股份有限公司 烷基全氟烯醚及其混合物於高溫熱泵的應用
JPWO2014199445A1 (ja) * 2013-06-11 2017-02-23 三菱電機株式会社 冷凍装置
JP6519909B2 (ja) * 2014-07-18 2019-05-29 出光興産株式会社 冷凍機油組成物、及び冷凍装置
CN105526728B (zh) * 2014-09-28 2018-06-15 青岛海尔开利冷冻设备有限公司 一种超市冷链系统
US20170217592A1 (en) * 2016-02-01 2017-08-03 General Electric Company Aircraft Thermal Management System
EP3423541A1 (en) * 2016-02-29 2019-01-09 The Chemours Company FC, LLC Refrigerant mixtures comprising difluoromethane, pentafluoroethane, tetrafluoroethane, tetrafluoropropene, and carbon dioxide and uses thereof
CN114526561A (zh) * 2016-03-25 2022-05-24 霍尼韦尔国际公司 低gwp级联制冷系统
CN106750488B (zh) 2016-12-26 2019-05-17 浙江衢化氟化学有限公司 一种低碳环保型发泡剂组合物
CN115638555A (zh) * 2017-06-21 2023-01-24 霍尼韦尔国际公司 制冷系统和方法
TWI794296B (zh) 2017-10-12 2023-03-01 美商科慕Ｆｃ有限責任公司 含有二氟甲烷、四氟丙烯和二氧化碳的組合物及其用途
FR3080169B1 (fr) * 2018-04-13 2020-12-18 Arkema France Procede de refroidissement et/ou de chauffage d'un corps ou d'un fluide dans un vehicule automobile
CN108954905A (zh) * 2018-06-01 2018-12-07 北京清天精创节能设备有限公司 一种带喷射器的复叠压缩式制冷-溶液再生复合机组
CN110358503A (zh) * 2019-07-22 2019-10-22 珠海格力电器股份有限公司 一种制冷剂、应用其的压缩机和空调装置或热泵装置
KR20210017119A (ko) * 2019-08-07 2021-02-17 현대자동차주식회사 차량용 히트펌프 시스템
RU201645U1 (ru) * 2019-08-29 2020-12-24 Антон Юрьевич Дымов Двухконтурный чиллер с тремя компрессорами
FR3102010B1 (fr) * 2019-10-15 2022-06-03 Arkema France Procédé de régulation de la température d’une batterie comprenant un sel de lithium
EP4077580B1 (en) * 2019-12-16 2023-12-06 Angelantoni Test Technologies S.R.L., in short ATT S.R.L. Refrigerant
CN110849011A (zh) * 2019-12-19 2020-02-28 海信容声(广东)冷柜有限公司 一种冷柜及其运行方法
JP2023135138A (ja) * 2022-03-15 2023-09-28 株式会社デンソー 冷凍サイクル装置
US20230375230A1 (en) * 2022-05-21 2023-11-23 Honeywell International Inc. Nonflammable refrigerants having low gwp, and systems for and methods of providing refrigeration

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0734368B1 (en) 1993-12-14 2001-08-29 E.I. Du Pont De Nemours And Company Process for perhalofluorinated butanes
JPH08189714A (ja) * 1995-01-13 1996-07-23 Daikin Ind Ltd 二元冷凍装置
JPH09138046A (ja) * 1995-11-16 1997-05-27 Sanyo Electric Co Ltd 冷却装置
EP1578883A4 (en) * 2002-10-25 2006-06-21 Honeywell Int Inc COMPOSITIONS BASED ON PENTAFLUOROPROPENE
JP4043386B2 (ja) * 2002-11-08 2008-02-06 幸信 池本 ヒートポンプ
US7655610B2 (en) * 2004-04-29 2010-02-02 Honeywell International Inc. Blowing agent compositions comprising fluorinated olefins and carbon dioxide
EP1782001B1 (en) * 2004-08-09 2016-11-30 Carrier Corporation Flashgas removal from a receiver in a refrigeration circuit
JP2007071519A (ja) * 2005-09-09 2007-03-22 Sanden Corp 冷却システム
US7476771B2 (en) * 2005-11-01 2009-01-13 E.I. Du Pont De Nemours + Company Azeotrope compositions comprising 2,3,3,3-tetrafluoropropene and hydrogen fluoride and uses thereof
WO2007076060A2 (en) * 2005-12-21 2007-07-05 Seth Smith Monitoring system
JP2007278666A (ja) * 2006-04-11 2007-10-25 Daikin Ind Ltd 二元冷凍装置
JP2008002759A (ja) * 2006-06-23 2008-01-10 Matsushita Electric Ind Co Ltd 二元冷凍システムおよび保冷庫
US20080003127A1 (en) * 2006-07-03 2008-01-03 Honeywell International Inc. Non-Ferrous Metal Cover Gases
JP4815286B2 (ja) * 2006-07-10 2011-11-16 東芝キヤリア株式会社 ２元冷凍サイクル装置
CN101528887B (zh) * 2006-09-01 2014-07-16 纳幕尔杜邦公司 氟烯烃用的环氧化物和氟化环氧化物稳定剂
AR062864A1 (es) * 2006-09-15 2008-12-10 Du Pont Metodo para determinar los componentes de una composicion de fluoroolefina, metodo para recargar un sistema de fluido en respuesta a ello, y sensores que se utilizan con dicho fin
EP4160127B1 (en) * 2007-01-31 2024-02-28 The Chemours Company FC, LLC A vapor compression heat transfer system
JP5129491B2 (ja) * 2007-02-27 2013-01-30 Ｊｘ日鉱日石エネルギー株式会社 冷凍機油組成物および冷凍機用作動流体組成物
JP5572284B2 (ja) * 2007-02-27 2014-08-13 Ｊｘ日鉱日石エネルギー株式会社 冷凍機油および冷凍機用作動流体組成物
WO2008108365A1 (ja) * 2007-03-08 2008-09-12 Idemitsu Kosan Co., Ltd. 圧縮型冷凍機用潤滑油、及びそれを用いた冷凍装置
WO2009003165A1 (en) * 2007-06-27 2008-12-31 Arkema Inc. Stabilized hydrochlorofluoroolefins and hydrofluoroolefins
JP2009243768A (ja) * 2008-03-31 2009-10-22 Sanden Corp 冷却システム
US8322149B2 (en) * 2008-04-01 2012-12-04 Honeywell International Inc. Method for selecting lubricants for heat pumps

Cited By (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110232306A1 (en) * 2008-04-30 2011-09-29 Honeywell International Inc. Absorption refrigeration cycles using a lgwp refrigerant
US20130227979A1 (en) * 2010-11-04 2013-09-05 Junichiro Kasuka Heat Pump Type Air-Warming Device
US9157667B2 (en) * 2010-11-04 2015-10-13 Sanden Corporation Heat pump-type heating device
JP2014529661A (ja) * 2011-08-30 2014-11-13 アルケマ フランス テトラフルオロプロペンをベースにした超臨界熱伝達流体
US20130239603A1 (en) * 2012-03-15 2013-09-19 Luther D. Albertson Heat pump with independent subcooler circuit
US20150191639A1 (en) * 2012-08-01 2015-07-09 E I Du Pont De Nemours And Company Use of e-1,1,1,4,4,4-hexafluoro-2-butene in heat pumps
US9783721B2 (en) 2012-08-20 2017-10-10 Honeywell International Inc. Low GWP heat transfer compositions
US8940180B2 (en) 2012-11-21 2015-01-27 Honeywell International Inc. Low GWP heat transfer compositions
US9982180B2 (en) 2013-02-13 2018-05-29 Honeywell International Inc. Heat transfer compositions and methods
US9016074B2 (en) * 2013-03-15 2015-04-28 Energy Recovery Systems Inc. Energy exchange system and method
WO2014151344A1 (en) * 2013-03-15 2014-09-25 Honeywell International Inc. Low gwp heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene
US20180356130A1 (en) * 2013-03-15 2018-12-13 Trane International Inc. Cascading heat recovery using a cooling unit as a source
US20140260357A1 (en) * 2013-03-15 2014-09-18 Energy Recovery Systems Inc. Energy exchange system and method
US10767908B2 (en) * 2013-03-15 2020-09-08 Trane International Inc. Cascading heat recovery using a cooling unit as a source
US20160138837A1 (en) * 2013-06-14 2016-05-19 Siemens Aktiengesellschaft Heat pump arrangement and method for operating heat pump arrangement
US10598415B2 (en) 2013-09-27 2020-03-24 Phc Holdings Corporation Refrigeration apparatus with dry ice occurrence suppression structure
US20160178246A1 (en) * 2013-09-27 2016-06-23 Panasonic Healthcare Holdings Co., Ltd. Refrigeration apparatus
EP3037744A4 (en) * 2013-09-27 2016-11-02 Panasonic Healthcare Holdings Co Ltd REFRIGERATION DEVICE
WO2015054110A1 (en) * 2013-10-10 2015-04-16 E. I. Du Pont De Nemours And Company Compositions comprising difluoromethane, pentafluoroethane, tetrafluoroethane and tetrafluoropropene and uses thereof
US9902888B2 (en) 2013-10-10 2018-02-27 The Chemours Company Fc, Llc Compositions comprising difluoromethane, pentafluoroethane, tetrafluoropropene, and tetrafluoroethane and uses thereof
TWI621603B (zh) * 2013-10-10 2018-04-21 杜邦股份有限公司 含二氟甲烷、五氟乙烷、四氟乙烷及四氟丙烯的組合物及其應用
US10703948B2 (en) 2014-09-23 2020-07-07 The Chemours Company Fc, Llc Use of (2E)-1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl) pent-2-ene in high temperature heat pumps
US10385247B2 (en) 2014-09-23 2019-08-20 The Chemours Company Fc, Llc Use of (2E)-1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene in high temperature heat pumps
WO2016048613A1 (en) * 2014-09-23 2016-03-31 The Chemours Company Fc, Llc Use of (2e)-1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene in high temperature heat pumps
US10739042B2 (en) * 2014-10-08 2020-08-11 Inertech Ip Llc Systems and methods for cooling electrical equipment
US20170205119A1 (en) * 2014-10-08 2017-07-20 Inertech Ip Llc Systems and methods for cooling electrical equipment
US11555635B2 (en) * 2014-10-08 2023-01-17 Inertech Ip Llc Systems and methods for cooling electrical equipment
US20170268805A1 (en) * 2014-12-04 2017-09-21 United Technologies Corporation Field-active heat pumping using liquid materials
US20160178244A1 (en) * 2014-12-22 2016-06-23 Heatcraft Refrigeration Products Llc Carbon Dioxide Based Auxiliary Cooling System
US20160280387A1 (en) * 2015-03-25 2016-09-29 United Technologies Corporation Aircraft thermal management system
US10082078B2 (en) * 2015-03-25 2018-09-25 United Technologies Corporation Aircraft thermal management system
US11156161B2 (en) 2015-03-25 2021-10-26 Raytheon Technologies Corporation Aircraft thermal management system
US11572326B2 (en) 2015-05-21 2023-02-07 The Chemours Company Fc, Llc Method for preparing 1,1,1,2,2-pentafluoropropane
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
US11008267B2 (en) 2015-05-21 2021-05-18 The Chemours Company Fc, Llc Hydrofluoroalkane composition
US10988422B2 (en) 2015-05-21 2021-04-27 The Chemours Company Fc, Llc Hydrofluoroalkane composition
WO2017013100A1 (en) * 2015-07-20 2017-01-26 Ideas Hub, S.L. A refrigerant composition
EP3121240A1 (en) * 2015-07-20 2017-01-25 Ideas Hub, S.L. A refrigerant composition
CN105004088A (zh) * 2015-07-31 2015-10-28 广东申菱空调设备有限公司 一种中温、低温两用的复叠式冷水机组
US11231205B2 (en) 2015-12-08 2022-01-25 Trane International Inc. Using heat recovered from heat source to obtain high temperature hot water
WO2017099814A1 (en) * 2015-12-08 2017-06-15 Trane International Inc. Using heat recovered from heat source to obtain high temperature hot water
US20170167765A1 (en) * 2015-12-15 2017-06-15 WinWay Tech. Co., Ltd. Evaporator for a cascade refrigeration system
US9845979B2 (en) * 2015-12-15 2017-12-19 WinWay Tech. Co., Ltd. Evaporator for a cascade refrigeration system
US20180017292A1 (en) * 2016-01-06 2018-01-18 Honeywell International Inc. Low gwp cascade refrigeration system
JP2019504985A (ja) * 2016-02-16 2019-02-21 ハネウェル・インターナショナル・インコーポレーテッドＨｏｎｅｙｗｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｉｎｃ． 多段低ｇｗｐ空調システム
EP3417215A4 (en) * 2016-02-16 2019-10-02 Honeywell International Inc. LOW PRG MULTI-STAGE AIR CONDITIONING SYSTEM
WO2017143018A1 (en) * 2016-02-16 2017-08-24 Honeywell International Inc. Multi-stage low gwp air conditioning system
JP7476398B2 (ja) 2016-03-25 2024-04-30 ハネウェル・インターナショナル・インコーポレーテッド 低ｇｗｐカスケード冷却システム
WO2017165764A1 (en) * 2016-03-25 2017-09-28 Honeywell International Inc. Low gwp cascade refrigeration system
WO2018132726A1 (en) * 2017-01-12 2018-07-19 Emerson Climate Technologies, Inc. Control, diagnostics, and architecture for micro booster supermarket refrigeration architecture
US10969165B2 (en) 2017-01-12 2021-04-06 Emerson Climate Technologies, Inc. Micro booster supermarket refrigeration architecture
US10634424B2 (en) 2017-01-12 2020-04-28 Emerson Climate Technologies, Inc. Oil management for micro booster supermarket refrigeration system
US20180195773A1 (en) 2017-01-12 2018-07-12 Emerson Climate Technologies, Inc. Micro Booster Supermarket Refrigeration Architecture
WO2018237175A1 (en) * 2017-06-21 2018-12-27 Honeywell International Inc. REFRIGERATION SYSTEMS AND METHODS
WO2018237208A1 (en) * 2017-06-21 2018-12-27 Honeywell International Inc. REFRIGERATION SYSTEMS AND METHODS
US20190137147A1 (en) * 2017-06-21 2019-05-09 Honeywell Interntional Inc. Refrigeration systems and methods
EP3821180A4 (en) * 2018-07-09 2022-03-23 Honeywell International Inc. REFRIGERATION SYSTEMS AND PROCESSES
WO2020014220A1 (en) * 2018-07-09 2020-01-16 Honeywell International Inc. Refrigeration systems and methods
US11739243B2 (en) 2018-12-21 2023-08-29 Honeywell International Inc. Azeotrope or azeotrope-like compositions of 1,2,2-trifluoro-1-trifluoromethylcyclobutane (TFMCB) and applications thereof
US20220325923A1 (en) * 2019-06-12 2022-10-13 Daikin Industries, Ltd. Refrigerant cycle system
CN114502898A (zh) * 2019-09-30 2022-05-13 大金工业株式会社 空调装置
FR3120992A1 (fr) * 2019-10-15 2022-09-23 Arkema France Procédé de régulation de la température d’une batterie d’un véhicule automobile
WO2022266622A3 (en) * 2021-06-16 2023-01-26 Colorado State University Research Foundation Air source heat pump system and method of use for industrial steam generation
GB2624981A (en) * 2021-06-16 2024-06-05 Univ Colorado State Res Found Air source heat pump system and method of use for industrial steam generation
US12006274B2 (en) 2022-11-03 2024-06-11 The Chemours Company Fc, Llc Compositions including olefin and hydrofluoroalkane

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MX2012005191A (es) 2012-06-08
CN102686957B (zh) 2015-06-03
IN2012DN03407A (pt) 2015-10-23
AU2010315264B2 (en) 2016-03-31
RU2012122709A (ru) 2013-12-10
BR112012010481A2 (pt) 2016-03-15
WO2011056824A3 (en) 2011-07-07
WO2011056824A2 (en) 2011-05-12
EP2591296A2 (en) 2013-05-15
CA2779093A1 (en) 2011-05-12
AR078902A1 (es) 2011-12-14
CO6541600A2 (es) 2012-10-16
TW201124687A (en) 2011-07-16
JP2013510286A (ja) 2013-03-21
AU2010315264A1 (en) 2012-05-03
KR20120102673A (ko) 2012-09-18

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