US20090120619A1 - Method for exchanging heat in vapor compression heat transfer systems - Google Patents

Method for exchanging heat in vapor compression heat transfer systems Download PDF

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Publication number
US20090120619A1
US20090120619A1 US12/119,023 US11902308A US2009120619A1 US 20090120619 A1 US20090120619 A1 US 20090120619A1 US 11902308 A US11902308 A US 11902308A US 2009120619 A1 US2009120619 A1 US 2009120619A1
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United States
Prior art keywords
butene
chf
trifluoromethyl
cfcf
working fluid
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Abandoned
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US12/119,023
Inventor
Allen Capron Sievert
Mario Joseph Nappa
Barbara Haviland Minor
Thomas J. Leck
Velliyur Nott Mallikarjuna Rao
Ekaterina N. SWEARINGEN
Corneille Schmitz
Nandini C. Mouli
Deepak Perti
Denis Clodic
Mary E. Koban
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority claimed from PCT/US2007/025675 external-priority patent/WO2008085314A2/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US12/119,023 priority Critical patent/US20090120619A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SWEARINGEN, EKATERINA N, CLODIC, DENIS, SCHMITZ, CORNEILLE, SIEVERT, ALLEN CAPRON, KOBAN, MARY E, LECK, THOMAS J, MINOR, BARBARA HAVILAND, MOULI, NANDINI C, NAPPA, MARIO JOSEPH, PERTI, DEEPAK, RAO, VELLIYUR NOTT MALLIKARJUNA
Publication of US20090120619A1 publication Critical patent/US20090120619A1/en
Priority to US13/207,557 priority patent/US20110290447A1/en
Priority to US15/939,644 priority patent/US11624534B2/en
Priority to US18/084,201 priority patent/US11867436B2/en
Abandoned legal-status Critical Current

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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
    • F25B40/00—Subcoolers, desuperheaters or superheaters
    • 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
    • F25B40/00—Subcoolers, desuperheaters or superheaters
    • F25B40/02—Subcoolers
    • 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
    • F25B49/00—Arrangement or mounting of control or safety devices
    • F25B49/02—Arrangement or mounting of control or safety devices for compression type machines, plants or systems
    • 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
    • F25B49/00—Arrangement or mounting of control or safety devices
    • F25B49/02—Arrangement or mounting of control or safety devices for compression type machines, plants or systems
    • F25B49/027—Condenser control arrangements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D1/00—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators
    • F28D1/02—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid
    • F28D1/04—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits
    • F28D1/0408—Multi-circuit heat exchangers, e.g. integrating different heat exchange sections in the same unit or heat exchangers for more than two fluids
    • F28D1/0426—Multi-circuit heat exchangers, e.g. integrating different heat exchange sections in the same unit or heat exchangers for more than two fluids with units having particular arrangement relative to the large body of fluid, e.g. with interleaved units or with adjacent heat exchange units in common air flow or with units extending at an angle to each other or with units arranged around a central element
    • F28D1/0452—Combination of units extending one behind the other with units extending one beside or one above the other
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D1/00—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators
    • F28D1/02—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid
    • F28D1/04—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits
    • F28D1/053—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being straight
    • F28D1/05316—Assemblies of conduits connected to common headers, e.g. core type radiators
    • F28D1/05333—Assemblies of conduits connected to common headers, e.g. core type radiators with multiple rows of conduits or with multi-channel conduits
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D1/00—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators
    • F28D1/02—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid
    • F28D1/04—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits
    • F28D1/053—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being straight
    • F28D1/0535—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being straight the conduits having a non-circular cross-section
    • F28D1/05366—Assemblies of conduits connected to common headers, e.g. core type radiators
    • F28D1/05383—Assemblies of conduits connected to common headers, e.g. core type radiators with multiple rows of conduits or with multi-channel conduits
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D1/00—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators
    • F28D1/02—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid
    • F28D1/04—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits
    • F28D1/053—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being straight
    • F28D1/0535—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being straight the conduits having a non-circular cross-section
    • F28D1/05366—Assemblies of conduits connected to common headers, e.g. core type radiators
    • F28D1/05391—Assemblies of conduits connected to common headers, e.g. core type radiators with multiple rows of conduits or with multi-channel conduits combined with a particular flow pattern, e.g. multi-row multi-stage radiators
    • 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
    • F25B2339/00—Details of evaporators; Details of condensers
    • F25B2339/04—Details of condensers
    • F25B2339/046—Condensers with refrigerant heat exchange tubes positioned inside or around a vessel containing water or pcm to cool the refrigerant gas
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/0068—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for refrigerant cycles
    • F28D2021/007—Condensers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/0068—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for refrigerant cycles
    • F28D2021/0071—Evaporators

Definitions

  • the present disclosure relates to a method for exchanging heat in a vapor compression heat transfer system.
  • it relates to use of an intermediate heat exchanger to improve performance of a vapor compression heat transfer system utilizing a working fluid comprising at least one fluoroolefin.
  • Applicants have found that the use of an internal heat exchanger in a vapor compression heat transfer system that uses a fluoroolefin provides unexpected benefits due to sub-cooling of the working fluid exiting out of the condenser.
  • subcooling is meant the reduction of the temperature of a liquid below that liquid's saturation point for a given pressure. The saturation point is the temperature at which the vapor usually would condense to a liquid, but subcooling produces a lower temperature vapor at the given pressure.
  • Sub-cooling thereby improves cooling capacity and energy efficiency of a system, such as vapor compression heat transfer systems, which comprise fluoroolefins.
  • the present disclosure provides a method of exchanging heat in a vapor compression heat transfer system, comprising:
  • the fluorolefin is a compound selected from the group consisting of:
  • sub-cooling has been found to enhance the performance and efficiency of systems which use cross-current/counter-current heat exchange, such as those which employ either a dual-row condenser or a dual-row evaporator.
  • the condensing step may comprise:
  • the evaporating step may comprise:
  • a vapor compression heat transfer system for exchanging heat comprising an intermediate heat exchanger in combination with a dual-row condenser or a dual-row evaporator, or both.
  • FIG. 1 is a schematic diagram of one embodiment of a vapor compression heat transfer system including an intermediate heat exchanger, used to practice the method of circulating a working fluid comprising a fluoroolefin through this system according to the present invention.
  • FIG. 1A is a cross-sectional view of one embodiment of an intermediate heat exchanger.
  • FIG. 2 is a perspective view of a dual-row condenser which can be used with the vapor compression heat transfer system of FIG. 1 .
  • FIG. 3 is a perspective view of a dual-row evaporator used which can be used with the vapor compression heat transfer system of FIG. 1 .
  • One embodiment of the present disclosure provides a method of circulating a working fluid comprising a fluoroolefin through a vapor compression heat transfer system.
  • a vapor-compression heat transfer system is a closed loop system which re-uses working fluid in multiple steps producing a cooling effect in one step and a heating effect in a different step.
  • Such a system generally includes an evaporator, a compressor, a condenser and an expansion device, and is known in the art. Reference will be made to FIG. 1 in describing this method. With reference to FIG. 1 , liquid working fluid from a condenser 41 flows through a line to an intermediate heat exchanger, or simply IHX.
  • the intermediate heat exchanger includes a first tube 30 , which contains a relatively hot liquid working fluid, and a second tube 50 , which contains a relatively colder gaseous working fluid.
  • the first tube of the IHX is connected to the outlet line of the condenser.
  • the liquid working fluid then flows through an expansion device 52 and through a line 62 to an evaporator 42 , which is located in the vicinity of a body to cooled. In the evaporator, the working fluid is evaporated, and the vaporization of the working fluid provides cooling.
  • the expansion device 52 may be an expansion valve, a capillary tube, an orifice tube or any other device where the working fluid may undergo an abrupt reduction in pressure.
  • the evaporator has an outlet, through which the cold gaseous working fluid flows to the second tube 50 of the IHX, wherein the cold gaseous working fluid comes in thermal contact with the hot liquid working fluid in the first tube 30 of the IHX, and thus the cold gaseous working fluid is warmed somewhat.
  • the gaseous working fluid flows from the second tube of the IHX through a line 63 to the inlet of a compressor 12 .
  • the gas is compressed in the compressor, and the compressed gaseous working fluid is discharged from the compressor and flows to the condenser 41 through a line 61 wherein the working fluid is condensed, thus giving off heat, and the cycle then repeats.
  • the first tube containing the relatively hotter liquid working fluid and the second tube containing the relatively colder gaseous working fluid are in thermal contact, thus allowing transfer of heat from the hot liquid to the cold gas.
  • the means by which the two tubes are in thermal contact may vary.
  • the first tube has a larger diameter than the second tube, and the second tube is disposed concentrically in the first tube, and a hot liquid in the first tube surrounds a cold gas in the second tube. This embodiment is shown in FIG. 1A , where the first tube ( 30 a ) surrounds the second tube ( 50 a ).
  • the working fluid in the second tube of the internal heat exchanger may flow in a countercurrent direction to the direction of flow of the working fluid in the first tube, thereby cooling the working fluid in the first tube and heating the working fluid in the second tube.
  • Cross-current/counter-current heat exchange may be provided in the system of FIG. 1 by a dual-row condenser or a dual-row evaporator, although it should be noted that this system is not limited to such a dual-row condensers or evaporators.
  • Such condensers and evaporators are described in detail in U.S. Provisional Patent Application No. 60/875,982, filed Dec. 19, 2006 (now International Application PCT/US07/25675, filed Dec. 17, 2007), and may be designed particularly for working fluids that comprise non-azeotropic or near-azeotropic compositions.
  • a vapor compression heat transfer system which comprises either a dual-row condenser, or a dual-row evaporator, or both.
  • a vapor compression heat transfer system which comprises either a dual-row condenser, or a dual-row evaporator, or both.
  • FIG. 2 A dual-row condenser is shown at 41 in FIG. 2 .
  • a hot working fluid enters the condenser through a first, or back row 14 , passes through the first row, and exits the condenser through a second, or front row 13 .
  • the working fluid enters first row 14 via a collector 6 inside a first pass 2 of the first row.
  • the working fluid is cooled in a counter current manner by air, which has been heated by the second, or front row 13 of this dual-row condenser.
  • the working fluid goes from first pass 2 of the first row 14 , to a pass 3 of the second, or front row 13 by a connection 7 .
  • the working fluid then flows from pass 3 to a pass 4 in second row 13 through a connection 8 , and then flows from pass 4 to a pass 5 through a connection 9 .
  • the sub-cooled working fluid exits the condenser by a connection 10 .
  • Air is circulated in a counter-current manner relative to the working fluid flow, as indicated by the arrow having points 11 and 12 of FIG. 2 .
  • the design shown in FIG. 2 is generic and can be used for any air-to-refrigerant condenser in stationary applications as well as in mobile applications.
  • FIG. 3 A dual-row evaporator is shown at 42 in FIG. 3 .
  • working fluid enters the evaporator through a first, or front row 17 , passes through the first row, and exits the condenser through a second, or back row 18 .
  • the working fluid enters the evaporator 19 at the lowest temperature through a collector 24 as shown in FIG. 3 .
  • the working fluid flows downwards through a tank 20 to a tank 21 through a collector 25 , then from tank 21 to a tank 22 in the back row through a collector 26 .
  • the working fluid then flows from tank 22 to a tank 23 through a collector 27 , and finally exits the evaporator through a collector 28 .
  • Air is circulated in a cross-countercurrent arrangement as indicated by the arrow having points 29 and 30 , of FIG. 3 .
  • the connecting lines between the components of the vapor compression heat transfer system, through which the working fluid may flow may be constructed of any typical conduit material known for such purpose.
  • metal piping or metal tubing such as aluminum or copper or copper alloy tubing
  • hoses constructed of various materials, such as polymers or elastomers, or combinations of such materials with reinforcing materials such as metal mesh etc, may be used in the system.
  • a hose design for heat transfer systems, in particular for automobile air conditioning systems is provided in U.S. Provisional Patent Application No. 60/841,713, filed Sep.
  • compressors may be used in the vapor compression heat transfer system of the embodiments of the present invention, including reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive-displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet).
  • positive-displacement e.g., reciprocating, scroll or screw
  • dynamic e.g., centrifugal or jet
  • the heat transfer systems as disclosed herein may employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers, among others for both the evaporator and condenser.
  • the closed loop vapor compression heat transfer system as described herein may be used in stationary refrigeration, air-conditioning, and heat pumps or mobile air-conditioning and refrigeration systems.
  • Stationary air-conditioning and heat pump applications include window, ductless, ducted, packaged terminal, chillers and light commercial and commercial air-conditioning systems, including packaged rooftop.
  • Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self-contained coolers and freezers, walk-in coolers and freezers and supermarket systems, and transport refrigeration systems.
  • Mobile refrigeration or mobile air-conditioning systems refer to any refrigeration or air-conditioning system incorporated into a transportation unit for the road, rail, sea or air.
  • apparatus which are meant to provide refrigeration or air-conditioning for a system independent of any moving carrier, known as “intermodal” systems, are included in the present invention.
  • intermodal systems include “containers” (combined sea/land transport) as well as “swap bodies” (combined road and rail transport).
  • the present invention is particularly useful for road transport refrigerating or air-conditioning apparatus, such as automobile air-conditioning apparatus or refrigerated road transport equipment.
  • the working fluid utilized in the vapor compression heat transfer system comprises at least one fluoroolefin.
  • fluoroolefin is meant any compound containing carbon, fluorine and optionally, hydrogen or oxygen that also contains at least one double bond. These fluoroolefins may be linear, branched or cyclic.
  • Fluoroolefins have a variety of utilities in working fluids, which include use as foaming agents, blowing agents, fire extinguishing agents, heat transfer mediums (such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air-conditioning systems, heat pumps, chillers, and the like), to name a few.
  • working fluids include use as foaming agents, blowing agents, fire extinguishing agents, heat transfer mediums (such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air-conditioning systems, heat pumps, chillers, and the like), to name a few.
  • heat transfer compositions may comprise fluoroolefins comprising at least one compound with 2 to 12 carbon atoms, in another embodiment 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 present methods use working fluids comprising 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 about 4 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula I have at least about 5 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 11 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 21 with a perfluoroalkyltrihydroolefin of the formula R 1 CH ⁇ CH 2 .
  • Said 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 take 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.
  • fluoroolefins comprise 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.
  • Representative cyclic fluoroolefins of Formula II are listed in Table 2.
  • compositions 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.
  • fluoroolefins may comprise 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.
  • CHF 2 CH 2 CHFCF 3 1,1,1,2,4,4-hexafluorobutane
  • the synthesis of 1,1,1,2,4,4-hexafluorobutane is described in U.S. Pat. No. 6,066,768, incorporated herein by reference.
  • 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.
  • the synthesis of 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.
  • 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 working fluid may further comprise at least one compound selected from hydrofluorocarbons, fluoroethers, hydrocarbons, dimethyl ether (DME), carbon dioxide (CO 2 ), ammonia (NH 3 ), and iodotrifluoromethane (CF 3 I).
  • DME dimethyl ether
  • CO 2 carbon dioxide
  • NH 3 ammonia
  • CF 3 I iodotrifluoromethane
  • the working fluid may further comprise hydrofluorocarbons comprising at least one saturated compound containing carbon, hydrogen, and fluorine.
  • hydrofluorocarbons comprising at least one saturated compound containing carbon, hydrogen, and fluorine.
  • hydrofluorocarbons having 1 to 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
  • working fluids may further comprise fluoroethers comprising 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-236eaE ⁇ , 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-347 mmzE ⁇ , or CH 2 FOCH(CF 3 ) 2 ); 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFOC-356 mmzE ⁇ , or CH 3 OCH(CH 3 ) 2 ); 1,1,1,
  • working fluids may further comprise hydrocarbons comprising compounds having only carbon and hydrogen.
  • hydrocarbons comprising compounds having only carbon and hydrogen.
  • 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, and cycloheptane.
  • the working fluid may comprise hydrocarbons containing heteroatoms, such as dimethylether (DME, CH 3 OCH 3 ).
  • DME dimethylether
  • CH 3 OCH 3 dimethylether
  • working fluids 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
  • working fluids 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 working fluid further comprises at least one compound selected from hydrofluorocarbons, fluoroethers, hydrocarbons, dimethyl ether (DME), carbon dioxide (CO 2 ), ammonia (NH 3 ), and iodotrifluoromethane (CF 3 I).
  • the working fluid comprises 1,2,3,3,3-pentafluoropropene (HFC-1225ye). In another embodiment, the working fluid further comprises difluoromethane (HFC-32). In yet another embodiment, the working fluid further comprises 1,1,1,2-tetrafluoroethane (HFC-134a).
  • the working fluid comprises 2,3,3,3-tetrafluoropropene (HFC-1234yf). In another embodiment, the working fluid comprises HFC-1225ye and HFC-1234yf.
  • the working fluid comprises 1,3,3,3-tetrafluoropropene (HFC-1234ze). In another embodiment, the working fluid comprises E-HFC-1234ze (or trans-HFC-1234ze).
  • the working fluid further comprises at least one compound from the group consisting of HFC-134a, HFC-32, HFC-125, HFC-152a, and CF 3 I.
  • working fluids may comprise a composition selected from the group consisting of:
  • HFC-32, HFC-134a, and HFC-1225ye are HFC-32, HFC-134a, and HFC-1225ye;
  • HFC-32, HFC-125, and HFC-1225ye
  • HFC-32, HFC-1225ye, and HFC-1234yf
  • HFC-125, HFC-1225ye, and HFC-1234yf are HFC-125, HFC-1225ye, and HFC-1234yf;
  • HFC-134a HFC-1225ye, and HFC-1234yf
  • HFC-32, HFC-125, and HFC-1234yf
  • HFC-152a n-butane, and HFC-1234yf
  • HFC-134a propane, and HFC-1234yf
  • HFC-125, HFC-152a, and HFC-1234yf are HFC-125, HFC-152a, and HFC-1234yf;
  • HFC-125, HFC-134a, and HFC-1234yf are HFC-125, HFC-134a, and HFC-1234yf;
  • HFC-32, HFC-1234ze, and HFC-1234yf are HFC-32, HFC-1234ze, and HFC-1234yf;
  • HFC-125, HFC-1234ze, and HFC-1234yf are HFC-125, HFC-1234ze, and HFC-1234yf;
  • HFC-134a HFC-1234ze, and HFC-1234yf
  • HFC-32, HFC-134a, and HFC-1234ze
  • HFC-152a, HFC-134a, and HFC-1234ze
  • HFC-152a n-butane, and HFC-1234ze
  • HFC-134a propane, and HFC-1234ze
  • HFC-125, HFC-152a, and HFC-1234ze are HFC-125, HFC-152a, and HFC-1234ze.
  • HFC-125, HFC-134a, and HFC-1234ze are HFC-125, HFC-134a, and HFC-1234ze.
  • the working fluid was a blend of 95% by weight HFC-1225ye and 5% by weight of HFC-32.
  • Each system had a condenser, evaporator, compressor and a thermal expansion device.
  • the ambient air temperature was 30° C. at the evaporator and the condenser inlets. Tests were performed for 2 compressor speeds, 1000 and 2000 rpm, and for 3 vehicle speeds: 25, 30, and 36 km/h.
  • the volumetric flow rate of air on the evaporator was 380 m 3 /h.
  • the cooling capacity for the system with an IHX shows an increase of 4 to 7% as compared to the system with no IHX.
  • the COP also showed an increase of 2.5 to 4% for the system with the IHX as compared to a system with no IHX.
  • Cooling performance is calculated for HFC-134a and HFC-1234yf both with and without an IHX.
  • the conditions used are as follows:
  • the subcool difference arises from the differences in molecular weight, liquid density and liquid heat capacity for HFC-1234yf as compared to HFC-134a. Based on these parameters it was estimated that there would be a difference in subcool achieved with the different compounds. When the HFC-134a subcool was set to 5° C., the corresponding subcool for HFC-1234yf was calculated to be 5.8° C.

Abstract

The present disclosure relates to a method for exchanging heat in a vapor compression heat transfer system. In particular, it relates to use of an intermediate heat exchanger to improve performance of a vapor compression heat transfer system utilizing a working fluid comprising at least one fluoroolefin. In addition, the present disclosure relates to a vapor compression heat transfer system comprising an intermediate heat exchanger in combination with a dual-row evaporator or a dual-row condenser, or both.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application claims the priority benefit of U.S. Provisional Application 60/928,826, filed May 11, 2007, U.S. Provisional Application 60/988,562, filed Nov. 16, 2007 and PCT Application No. U.S. Ser. No. 07/25675, filed Dec. 17, 2007.
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present disclosure relates to a method for exchanging heat in a vapor compression heat transfer system. In particular, it relates to use of an intermediate heat exchanger to improve performance of a vapor compression heat transfer system utilizing a working fluid comprising at least one fluoroolefin.
  • 2. Description of Related Art
  • Methods for improving the performance of heat transfer systems, such as refrigeration systems and air conditioners, are always being sought, in order to reduce cost of operation of such systems.
  • When new working fluids for heat transfer systems, including vapor compression heat transfer systems, are being proposed it is important to be able to provide means of improving cooling capacity and energy efficiency for the new working fluids.
    • SUMMARY OF THE INVENTION
  • Applicants have found that the use of an internal heat exchanger in a vapor compression heat transfer system that uses a fluoroolefin provides unexpected benefits due to sub-cooling of the working fluid exiting out of the condenser. By “subcooling” is meant the reduction of the temperature of a liquid below that liquid's saturation point for a given pressure. The saturation point is the temperature at which the vapor usually would condense to a liquid, but subcooling produces a lower temperature vapor at the given pressure. By cooling a vapor below the saturation point, the net refrigeration capacity can be increased. Sub-cooling thereby improves cooling capacity and energy efficiency of a system, such as vapor compression heat transfer systems, which comprise fluoroolefins.
  • In particular, when the fluoroolefin 2,3,3,3-tetrafluoropropene (HFC-1234yf) is used as the working fluid, surprising results have been achieved with respect to coefficient of performance and capacity of the working fluid, as compared to the use of known working fluids such as 1,1,1,2-tetrafluoroethane (HFC-124a).
  • Therefore, in accordance with the present invention, the present disclosure provides a method of exchanging heat in a vapor compression heat transfer system, comprising:
  • (a) circulating a working fluid comprising a fluoroolefin to an inlet of a first tube of an internal heat exchanger, through the internal heat exchanger and to an outlet thereof;
  • (b) circulating the working fluid from the outlet of the first tube of the internal heat exchanger to an inlet of an evaporator, through the evaporator to evaporate the working fluid into a gas, and through an outlet of the evaporator;
  • (c) circulating the working fluid from the outlet of the evaporator to an inlet of a second tube of the internal heat exchanger to transfer heat from the liquid working fluid from the condenser to the gaseous working fluid from the evaporator, through the internal heat exchanger, and to an outlet of the second tube;
  • (d) circulating the working fluid from the outlet of the second tube of the internal heat exchanger to an inlet of a compressor, through the compressor to compress the working fluid gas, and to an outlet of the compressor;
  • (e) circulating the working fluid from the outlet of the compressor to an inlet of a condenser and through the condenser to condense the compressed working fluid gas into a liquid, and to an outlet of the condenser;
  • (f) circulating the working fluid from the outlet of the condenser to an inlet of the first tube of the intermediate heat exchanger to transfer heat from the liquid from the condenser to the gas from the evaporator, and to an outlet of the second tube; and
  • (g) circulating the working fluid from the outlet of the second tube of the internal heat exchanger back to the evaporator.
  • The fluorolefin is a compound selected from the group consisting of:
      • (i) fluoroolefins of the formula E- or Z-R1CH═CHR2, wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups;
      • (ii) cyclic fluoroolefins of the formula cyclo-[CX═CY(CZW)n—], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and
      • (iii) fluoroolefins selected from the group consisting of:
        • 1,2,3,3,3-pentafluoro-1-propene (CHF═CFCF3), 1,1,3,3,3-pentafluoro-1-propene (CF2═CHCF3), 1,1,2,3,3-pentafluoro-1-propene (CF2═CFCHF2), 1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF2), 2,3,3,3-tetrafluoro-1-propene (CH2═CFCF3), 1,3,3,3-tetrafluoro-1-propene (CHF═CHCF3), 1,1,2,3-tetrafluoro-1-propene (CF2═CFCH2F), 1,1,3,3-tetrafluoro-1-propene (CF2═CHCHF2), 1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF2), 3,3,3-trifluoro-1-propene (CH2═CHCF3), 2,3,3-trifluoro-1-propene (CHF2CF═CH2); 1,1,2-trifluoro-1-propene (CH3CF═CF2); 1,2,3-trifluoro-1-propene (CH2FCF═CF2); 1,1,3-trifluoro-1-propene (CH2FCH═CF2); 1,3,3-trifluoro-1-propene (CHF2CH═CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF3CF═CFCF3); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF3CF2CF═CF2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF═CHCF3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF2CF3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF2CF═CFCF3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF3)2C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF2═CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF2═CFCHFCF3); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF2═CFCF2CHF2); 2,3,3,4,4,4-hexafluoro-1-butene (CF3CF2CF═CH2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF═CFCHFCF3); 1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF2CHF2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF2CF═CFCHF2); 1,1,1,2,3,4-hexafluoro-2-butene (CH2FCF═CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF2CH═CFCF3); 1,1,1,3,4,4-hexafluoro-2-butene (CF3CH═CFCHF2); 1,1,2,3,3,4-hexafluoro-1-butene (CF2═CFCF2CH2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF2═CFCHFCHF2); 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH2═C(CF3)2); 1,1,1,2,4-pentafluoro-2-butene (CH2FCH═CFCF3); 1,1,1,3,4-pentafluoro-2-butene (CF3CH═CFCH2F); 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH═CH2); 1,1,1,4,4-pentafluoro-2-butene (CHF2CH═CHCF3); 1,1,1,2,3-pentafluoro-2-butene (CH3CF═CFCF3); 2,3,3,4,4-pentafluoro-1-butene (CH2═CFCF2CHF2); 1,1,2,4,4-pentafluoro-2-butene (CHF2CF═CHCHF2); 1,1,2,3,3-pentafluoro-1-butene (CH3CF2CF═CF2); 1,1,2,3,4-pentafluoro-2-butene (CH2FCF═CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2═C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH2═C(CHF2)(CF3)); 2,3,4,4,4-pentafluoro-1-butene (CH2═CFCHFCF3); 1,2,4,4,4-pentafluoro-1-butene (CHF═CFCH2CF3); 1,3,4,4,4-pentafluoro-1-butene (CHF═CHCHFCF3); 1,3,3,4,4-pentafluoro-1-butene (CHF═CHCF2CHF2); 1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF2); 3,3,4,4-tetrafluoro-1-butene (CH2═CHCF2CHF2); 1,1-difluoro-2-(difluoromethyl)-1-propene (CF2═C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2-methyl-1-propene (CHF═C(CF3)(CH3)); 3,3-difluoro-2-(difluoromethyl)-1-propene (CH2═C(CHF2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF═CHCH3); 1,1,1,3-tetrafluoro-2-butene (CH3CF═CHCF3); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF3CF═CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF2═CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene ((CF3)2C═CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF═CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH═CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene (CHF═CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2═CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2═CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF═CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF═CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF═CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF═CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2═CFCH(CF3)2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH═C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2═CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1-pentene (CH2═CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF═CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH2═C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CF2═CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2═C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH═CH2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH═CH2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH2═CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2═CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF═C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH2═CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH═C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF═C(CF3)2); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C═CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF═CHCH3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF3C(CH3)═CHCF3); 3,3,4,5,5,5-hexafluoro-1-pentene (CH2═CHCF2CHFCF3); 4,4,4-trifluoro-2-(trifluoromethyl)-1-butene (CH2═C(CF3)CH2CF3); 1, 1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF3(CF2)3CF═CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF3CF2CF═CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF3)2C═C(CF3)2); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF═CFCF3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C═CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF═CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF3CF2CF2CF2CH═CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2═CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene ((CF3)2C═C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene (CH2═CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF3CF═C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene (CF3CH═CHCH(CF3)2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF3CF2CF2CF═CHCH3); 3,3,4,4,5,5,6,6-octafluoro1-hexene (CH2═CHCF2CF2CF2CHF2); 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C═CHCF2CH3); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene (CH2═C(CF3)CH2C2F5); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF3CF2CF2C(CH3)═CH2); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF3CF2CF2CH═CHCH3); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH2═CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF═CFC2H5); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH2═CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF3CF═CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C═CFC2H5); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF═CCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (CF3CF2CF═CFCF2C2F5); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CH═CFCF2CF2C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CF═CHCF2CF2C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CH═CFCF2C2F5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CF═CHCF2C2F5); pentafluoroethyl trifluorovinyl ether (CF2═CFOCF2CF3); and trifluoromethyl trifluorovinyl ether (CF2═CFOCF3).
  • In addition, sub-cooling has been found to enhance the performance and efficiency of systems which use cross-current/counter-current heat exchange, such as those which employ either a dual-row condenser or a dual-row evaporator.
  • Therefore, further in accordance with the method of the present invention, the present disclosure also provides that the condensing step may comprise:
      • (i) circulating the working fluid to a back row of the dual-row condenser, where the back row receives the working fluid at a first temperature; and
      • (ii) circulating the working fluid to a front row of the dual-row condenser, where the front row receives the working fluid at a second temperature, where the second temperature is less than the first temperature, so that air which travels across the front row and the back row is preheated, whereby the temperature of the air is greater when it reaches the back row than when it reaches the front row.
  • Further in accordance with the method of the present invention, the present disclosure also provides that the evaporating step may comprise:
      • (i) passing the working fluid through an inlet of a dual-row evaporator having a first row and a second row,
      • (ii) circulating the working fluid in a first row in a direction perpendicular to the flow of fluid through the inlet of the evaporator, and
      • (iii) circulating the working fluid in a second row in a direction generally counter to the direction of the flow of the working fluid through the inlet.
  • Also in accordance with the present invention, there is provided a vapor compression heat transfer system for exchanging heat comprising an intermediate heat exchanger in combination with a dual-row condenser or a dual-row evaporator, or both.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The present invention may be better understood with reference to the following figures, wherein:
  • FIG. 1 is a schematic diagram of one embodiment of a vapor compression heat transfer system including an intermediate heat exchanger, used to practice the method of circulating a working fluid comprising a fluoroolefin through this system according to the present invention.
  • FIG. 1A is a cross-sectional view of one embodiment of an intermediate heat exchanger.
  • FIG. 2 is a perspective view of a dual-row condenser which can be used with the vapor compression heat transfer system of FIG. 1.
  • FIG. 3 is a perspective view of a dual-row evaporator used which can be used with the vapor compression heat transfer system of FIG. 1.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • One embodiment of the present disclosure provides a method of circulating a working fluid comprising a fluoroolefin through a vapor compression heat transfer system. A vapor-compression heat transfer system is a closed loop system which re-uses working fluid in multiple steps producing a cooling effect in one step and a heating effect in a different step. Such a system generally includes an evaporator, a compressor, a condenser and an expansion device, and is known in the art. Reference will be made to FIG. 1 in describing this method. With reference to FIG. 1, liquid working fluid from a condenser 41 flows through a line to an intermediate heat exchanger, or simply IHX. The intermediate heat exchanger includes a first tube 30, which contains a relatively hot liquid working fluid, and a second tube 50, which contains a relatively colder gaseous working fluid. The first tube of the IHX is connected to the outlet line of the condenser. The liquid working fluid then flows through an expansion device 52 and through a line 62 to an evaporator 42, which is located in the vicinity of a body to cooled. In the evaporator, the working fluid is evaporated, and the vaporization of the working fluid provides cooling. The expansion device 52 may be an expansion valve, a capillary tube, an orifice tube or any other device where the working fluid may undergo an abrupt reduction in pressure. The evaporator has an outlet, through which the cold gaseous working fluid flows to the second tube 50 of the IHX, wherein the cold gaseous working fluid comes in thermal contact with the hot liquid working fluid in the first tube 30 of the IHX, and thus the cold gaseous working fluid is warmed somewhat. The gaseous working fluid flows from the second tube of the IHX through a line 63 to the inlet of a compressor 12. The gas is compressed in the compressor, and the compressed gaseous working fluid is discharged from the compressor and flows to the condenser 41 through a line 61 wherein the working fluid is condensed, thus giving off heat, and the cycle then repeats.
  • In an intermediate heat exchanger, the first tube containing the relatively hotter liquid working fluid and the second tube containing the relatively colder gaseous working fluid are in thermal contact, thus allowing transfer of heat from the hot liquid to the cold gas. The means by which the two tubes are in thermal contact may vary. In one embodiment, the first tube has a larger diameter than the second tube, and the second tube is disposed concentrically in the first tube, and a hot liquid in the first tube surrounds a cold gas in the second tube. This embodiment is shown in FIG. 1A, where the first tube (30 a) surrounds the second tube (50 a).
  • Also, in one embodiment, the working fluid in the second tube of the internal heat exchanger may flow in a countercurrent direction to the direction of flow of the working fluid in the first tube, thereby cooling the working fluid in the first tube and heating the working fluid in the second tube.
  • Cross-current/counter-current heat exchange may be provided in the system of FIG. 1 by a dual-row condenser or a dual-row evaporator, although it should be noted that this system is not limited to such a dual-row condensers or evaporators. Such condensers and evaporators are described in detail in U.S. Provisional Patent Application No. 60/875,982, filed Dec. 19, 2006 (now International Application PCT/US07/25675, filed Dec. 17, 2007), and may be designed particularly for working fluids that comprise non-azeotropic or near-azeotropic compositions. Therefore, in accordance with the present invention, there is provided a vapor compression heat transfer system which comprises either a dual-row condenser, or a dual-row evaporator, or both. Such a system is the same as that described above with respect to FIG. 1, except for the description of the dual-row condenser or the dual-row evaporator.
  • Reference will be made to FIG. 2 to describe such a system which includes a dual-row condenser. A dual-row condenser is shown at 41 in FIG. 2. In this dual-row cross-current/counter-current design, a hot working fluid enters the condenser through a first, or back row 14, passes through the first row, and exits the condenser through a second, or front row 13. The working fluid enters first row 14 via a collector 6 inside a first pass 2 of the first row. In the first, or back row, the working fluid is cooled in a counter current manner by air, which has been heated by the second, or front row 13 of this dual-row condenser. The working fluid goes from first pass 2 of the first row 14, to a pass 3 of the second, or front row 13 by a connection 7. The working fluid then flows from pass 3 to a pass 4 in second row 13 through a connection 8, and then flows from pass 4 to a pass 5 through a connection 9. Then the sub-cooled working fluid exits the condenser by a connection 10. Air is circulated in a counter-current manner relative to the working fluid flow, as indicated by the arrow having points 11 and 12 of FIG. 2. The design shown in FIG. 2 is generic and can be used for any air-to-refrigerant condenser in stationary applications as well as in mobile applications.
  • Reference will be made to FIG. 3 in describing a vapor compression heat transfer system comprising a dual-row evaporator. A dual-row evaporator is shown at 42 in FIG. 3. In this dual-row cross-current/counter-current design, working fluid enters the evaporator through a first, or front row 17, passes through the first row, and exits the condenser through a second, or back row 18. In particular, the working fluid enters the evaporator 19 at the lowest temperature through a collector 24 as shown in FIG. 3. Then the working fluid flows downwards through a tank 20 to a tank 21 through a collector 25, then from tank 21 to a tank 22 in the back row through a collector 26. The working fluid then flows from tank 22 to a tank 23 through a collector 27, and finally exits the evaporator through a collector 28. Air is circulated in a cross-countercurrent arrangement as indicated by the arrow having points 29 and 30, of FIG. 3.
  • In the embodiments as shown in FIGS. 1, 1A, 2 and 3, the connecting lines between the components of the vapor compression heat transfer system, through which the working fluid may flow, may be constructed of any typical conduit material known for such purpose. In one embodiment, metal piping or metal tubing (such as aluminum or copper or copper alloy tubing) may be used to connect the components of the heat transfer system. In another embodiment, hoses, constructed of various materials, such as polymers or elastomers, or combinations of such materials with reinforcing materials such as metal mesh etc, may be used in the system. One example of a hose design for heat transfer systems, in particular for automobile air conditioning systems, is provided in U.S. Provisional Patent Application No. 60/841,713, filed Sep. 1, 2006 (now International Application PCT/US07/019,205 filed Aug. 31, 2007 and published as WO2008-027255A1 on Mar. 6, 2008). For the tubes of the IHX, metal piping or tubing provides more efficient transfer of heat from the hot liquid working fluid to the cold gaseous working fluid.
  • Various types of compressors may be used in the vapor compression heat transfer system of the embodiments of the present invention, including reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive-displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet).
  • In certain embodiments the heat transfer systems as disclosed herein may employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers, among others for both the evaporator and condenser.
  • The closed loop vapor compression heat transfer system as described herein may be used in stationary refrigeration, air-conditioning, and heat pumps or mobile air-conditioning and refrigeration systems. Stationary air-conditioning and heat pump applications include window, ductless, ducted, packaged terminal, chillers and light commercial and commercial air-conditioning systems, including packaged rooftop. Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self-contained coolers and freezers, walk-in coolers and freezers and supermarket systems, and transport refrigeration systems.
  • Mobile refrigeration or mobile air-conditioning systems refer to any refrigeration or air-conditioning system incorporated into a transportation unit for the road, rail, sea or air. In addition, apparatus, which are meant to provide refrigeration or air-conditioning for a system independent of any moving carrier, known as “intermodal” systems, are included in the present invention. Such intermodal systems include “containers” (combined sea/land transport) as well as “swap bodies” (combined road and rail transport). The present invention is particularly useful for road transport refrigerating or air-conditioning apparatus, such as automobile air-conditioning apparatus or refrigerated road transport equipment.
  • The working fluid utilized in the vapor compression heat transfer system comprises at least one fluoroolefin. By fluoroolefin is meant any compound containing carbon, fluorine and optionally, hydrogen or oxygen that also contains at least one double bond. These fluoroolefins may be linear, branched or cyclic.
  • Fluoroolefins have a variety of utilities in working fluids, which include use as foaming agents, blowing agents, fire extinguishing agents, heat transfer mediums (such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air-conditioning systems, heat pumps, chillers, and the like), to name a few.
  • In some embodiments, heat transfer compositions may comprise fluoroolefins comprising at least one compound with 2 to 12 carbon atoms, in another embodiment 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.
  • In one embodiment, the present methods use working fluids comprising fluoroolefins having the formula E- or Z-R1CH═CHR2 (Formula I), wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups. Examples of R1 and R2 groups include, but are not limited to, CF3, C2F5, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3, CF(CF3)CF2CF3, CF2CF(CF3)2, C(CF3)3, CF2CF2CF2CF2CF3, CF2CF2CF(CF3)2, C(CF3)2C2F5, CF2CF2CF2CF2CF2CF3, CF(CF3) CF2CF2C2F5, and C(CF3)2CF2C2F5. In one embodiment the fluoroolefins of Formula I, have at least about 4 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula I have at least about 5 carbon atoms in the molecule. Exemplary, non-limiting Formula I compounds are presented in Table 1.
  • TABLE 1
    Code Structure Chemical Name
    F11E CF3CH═CHCF3 1,1,1,4,4,4-hexafluorobut-2-ene
    F12E CF3CH═CHC2F5 1,1,1,4,4,5,5,5-octafluoropent-2-ene
    F13E CF3CH═CHCF2C2F5 1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene
    F13iE CF3CH═CHCF(CF3)2 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-
    ene
    F22E C2F5CH═CHC2F5 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene
    F14E CF3CH═CH(CF2)3CF3 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene
    F14iE CF3CH═CHCF2CF—(CF3)2 1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-
    ene
    F14sE CF3CH═CHCF(CF3)—C2F5 1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-
    ene
    F14tE CF3CH═CHC(CF3)3 1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-
    ene
    F23E C2F5CH═CHCF2C2F5 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene
    F23iE C2F5CH═CHCF(CF3)2 1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-
    ene
    F15E CF3CH═CH(CF2)4CF3 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene
    F15iE CF3CH═CH—CF2CF2CF(CF3)2 1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-
    (trifluoromethyl)hept-2-ene
    F15tE CF3CH═CH—C(CF3)2C2F5 1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-
    2-ene
    F24E C2F5CH═CH(CF2)3CF3 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene
    F24iE C2F5CH═CHCF2CF—(CF3)2 1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-
    (trifluoromethyl)hept-3-ene
    F24sE C2F5CH═CHCF(CF3)—C2F5 1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-
    (trifluoromethyl)hept-3-ene
    F24tE C2F5CH═CHC(CF3)3 1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-
    3-ene
    F33E C2F5CF2CH═CH—CF2C2F5 1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene
    F3i3iE (CF3)2CFCH═CH—CF(CF3)2 1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-
    3-ene
    F33iE C2F5CF2CH═CH—CF(CF3)2 1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-
    (trifluoromethyl)hept-3-ene
    F16E CF3CH═CH(CF2)5CF3 1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-
    ene
    F16sE CF3CH═CHCF(CF3)(CF2)2C2F5 1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-
    (trifluoromethyl)hept-2-ene
    F16tE CF3CH═CHC(CF3)2CF2C2F5 1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-
    ene
    F25E C2F5CH═CH(CF2)4CF3 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-
    ene
    F25iE C2F5CH═CH—CF2CF2CF(CF3)2 1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-
    (trifluoromethyl)oct-3-ene
    F25tE C2F5CH═CH—C(CF3)2C2F5 1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-
    bis(trifluoromethyl)hept-3-ene
    F34E C2F5CF2CH═CH—(CF2)3CF3 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-
    ene
    F34iE C2F5CF2CH═CH—CF2CF(CF3)2 1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-
    (trifluoromethyl)oct-4-ene
    F34sE C2F5CF2CH═CH—CF(CF3)C2F5 1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-
    (trifluoromethyl)oct-4-ene
    F34tE C2F5CF2CH═CH—C(CF3)3 1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-
    bis(trifluoromethyl)hept-3-ene
    F3i4E (CF3)2CFCH═CH—(CF2)3CF3 1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-
    2(trifluoromethyl)oct-3-ene
    F3i4iE (CF3)2CFCH═CH—CF2CF(CF3)2 1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-
    bis(trifluoromethyl)hept-3-ene
    F3i4sE (CF3)2CFCH═CH—CF(CF3)C2F5 1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-
    bis(trifluoromethyl)hept-3-ene
    F3i4tE (CF3)2CFCH═CH—C(CF3)3 1,1,1,2,6,6,6-heptafluoro-2,5,5-
    tris(trifluoromethyl)hex-3-ene
    F26E C2F5CH═CH(CF2)5CF3 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-
    octadecafluorodec-3-ene
    F26sE C2F5CH═CHCF(CF3)(CF2)2C2F5 1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-
    (trifluoromethyl)non-3-ene
    F26tE C2F5CH═CHC(CF3)2CF2C2F5 1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-
    bis(trifluoromethyl)oct-3-ene
    F35E C2F5CF2CH═CH—(CF2)4CF3 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-
    octadecafluorodec-4-ene
    F35iE C2F5CF2CH═CH—CF2CF2CF(CF3)2 1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-
    (trifluoromethyl)non-4-ene
    F35tE C2F5CF2CH═CH—C(CF3)2C2F5 1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-
    bis(trifluoromethyl)oct-4-ene
    F3i5E (CF3)2CFCH═CH—(CF2)4CF3 1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-
    (trifluoromethyl)non-3-ene
    F3i5iE (CF3)2CFCH═CH—CF2CF2CF(CF3)2 1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-
    bis(trifluoromethyl)oct-3-ene
    F3i5tE (CF3)2CFCH═CH—C(CF3)2C2F5 1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-
    tris(trifluoromethyl)hept-3-ene
    F44E CF3(CF2)3CH═CH—(CF2)3CF3 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-
    octadecafluorodec-5-ene
    F44iE CF3(CF2)3CH═CH—CF2CF(CF3)2 1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-
    (trifluoromethyl)non-4-ene
    F44sE CF3(CF2)3CH═CH—CF(CF3)C2F5 1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-
    (trifluoromethyl)non-4-ene
    F44tE CF3(CF2)3CH═CH—C(CF3)3 1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-
    bis(trifluoromethyl)oct-3-ene
    F4i4iE (CF3)2CFCF2CH═CH—CF2CF(CF3)2 1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-
    bis(trifluoromethyl)oct-4-ene
    F4i4sE (CF3)2CFCF2CH═CH—CF(CF3)C2F5 1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-
    bis(trifluoromethyl)oct-4-ene
    F4i4tE (CF3)2CFCF2CH═CH—C(CF3)3 1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-
    tris(trifluoromethyl)hept-3-ene
    F4s4sE C2F5CF(CF3)CH═CH—CF(CF3)C2F5 1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-
    bis(trifluoromethyl)oct-4-ene
    F4s4tE C2F5CF(CF3)CH═CH—C(CF3)3 1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-
    tris(trifluoromethyl)hept-3-ene
    F4t4tE (CF3)3CCH═CH—C(CF3)3 1,1,1,6,6,6-hexafluoro-2,2,5,5-
    tetrakis(trifluoromethyl)hex-3-ene
  • Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide of the formula R11 with a perfluoroalkyltrihydroolefin of the formula R2CH═CH2 to form a trihydroiodoperfluoroalkane of the formula R1CH2CHIR2. This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R1CH═CHR2. Alternatively, the olefin R1CH═CHR2 may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R1CHICH2R2 formed in turn by reacting a perfluoroalkyl iodide of the formula R21 with a perfluoroalkyltrihydroolefin of the formula R1CH═CH2.
  • Said 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.
  • Alternatively, the reaction may take 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.
  • 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.
  • Said contacting of the trihydroiodoperfluoroalkane with a basic substance may take place in the liquid phase preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. 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. The choice of solvent may depend on the boiling point product and the ease of separation of traces of the solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for the reaction.
  • Typically, 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. Of note are dehydroiodination reactions in which the compound of Formula I is distilled out of the reaction vessel as it is formed.
  • Alternatively, 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. 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).
  • Alternatively, 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.
  • In another embodiment of the present invention, fluoroolefins comprise 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). In one embodiment the fluoroolefins of Formula II, have at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula II have at least about 4 carbon atoms in the molecule. In yet another embodiment, the fluoroolefins of Formula II have at least about 5 carbon atoms in the molecule. Representative cyclic fluoroolefins of Formula II are listed in Table 2.
  • TABLE 2
    Cyclic
    fluoroolefins Structure Chemical name
    FC-C1316cc cyclo-CF2CF2CF═CF— 1,2,3,3,4,4-hexafluorocyclobutene
    HFC-C1334cc cyclo-CF2CF2CH═CH— 3,3,4,4-tetrafluorocyclobutene
    HFC-C1436 cyclo-CF2CF2CF2CH═CH— 3,3,4,4,5,5,-hexafluorocyclopentene
    FC-C1418y cyclo-CF2CF═CFCF2CF2— 1,2,3,3,4,4,5,5-octafluorocyclopentene
    FC-C151-10y cyclo-CF2CF═CFCF2CF2CF2— 1,2,3,3,4,4,5,5,6,6-
    decafluorocyclohexene
  • The compositions 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.
  • In another embodiment, fluoroolefins may comprise those compounds listed in Table 3.
  • TABLE 3
    Name Structure Chemical name
    HFC-1225ye CF3CF═CHF 1,2,3,3,3-pentafluoro-1-propene
    HFC-1225zc CF3CH═CF2 1,1,3,3,3-pentafluoro-1-propene
    HFC-1225yc CHF2CF═CF2 1,1,2,3,3-pentafluoro-1-propene
    HFC-1234ye CHF2CF═CHF 1,2,3,3-tetrafluoro-1-propene
    HFC-1234yf CF3CF═CH2 2,3,3,3-tetrafluoro-1-propene
    HFC-1234ze CF3CH═CHF 1,3,3,3-tetrafluoro-1-propene
    HFC-1234yc CH2FCF═CF2 1,1,2,3-tetrafluoro-1-propene
    HFC-1234zc CHF2CH═CF2 1,1,3,3-tetrafluoro-1-propene
    HFC-1243yf CHF2CF═CH2 2,3,3-trifluoro-1-propene
    HFC-1243zf CF3CH═CH2 3,3,3-trifluoro-1-propene
    HFC-1243yc CH3CF═CF2 1,1,2-trifluoro-1-propene
    HFC-1243zc CH2FCH═CF2 1,1,3-trifluoro-1-propene
    HFC-1243ye CH2FCF═CHF 1,2,3-trifluoro-1-propene
    HFC-1243ze CHF2CH═CHF 1,3,3-trifluoro-1-propene
    FC-1318my CF3CF═CFCF3 1,1,1,2,3,4,4,4-octafluoro-2-butene
    FC-1318cy CF3CF2CF═CF2 1,1,2,3,3,4,4,4-octafluoro-1-butene
    HFC-1327my CF3CF═CHCF3 1,1,1,2,4,4,4-heptafluoro-2-butene
    HFC-1327ye CHF═CFCF2CF3 1,2,3,3,4,4,4-heptafluoro-1-butene
    HFC-1327py CHF2CF═CFCF3 1,1,1,2,3,4,4-heptafluoro-2-butene
    HFC-1327et (CF3)2C═CHF 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-
    propene
    HFC-1327cz CF2═CHCF2CF3 1,1,3,3,4,4,4-heptafluoro-1-butene
    HFC-1327cye CF2═CFCHFCF3 1,1,2,3,4,4,4-heptafluoro-1-butene
    HFC-1327cyc CF2═CFCF2CHF2 1,1,2,3,3,4,4-heptafluoro-1-butene
    HFC-1336yf CF3CF2CF═CH2 2,3,3,4,4,4-hexafluoro-1-butene
    HFC-1336ze CHF═CHCF2CF3 1,3,3,4,4,4-hexafluoro-1-butene
    HFC-1336eye CHF═CFCHFCF3 1,2,3,4,4,4-hexafluoro-1-butene
    HFC-1336eyc CHF═CFCF2CHF2 1,2,3,3,4,4-hexafluoro-1-butene
    HFC-1336pyy CHF2CF═CFCHF2 1,1,2,3,4,4-hexafluoro-2-butene
    HFC-1336qy CH2FCF═CFCF3 1,1,1,2,3,4-hexafluoro-2-butene
    HFC-1336pz CHF2CH═CFCF3 1,1,1,2,4,4-hexafluoro-2-butene
    HFC-1336mzy CF3CH═CFCHF2 1,1,1,3,4,4-hexafluoro-2-butene
    HFC-1336qc CF2═CFCF2CH2F 1,1,2,3,3,4-hexafluoro-1-butene
    HFC-1336pe CF2═CFCHFCHF2 1,1,2,3,4,4-hexafluoro-1-butene
    HFC-1336ft CH2═C(CF3)2 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene
    HFC-1345qz CH2FCH═CFCF3 1,1,1,2,4-pentafluoro-2-butene
    HFC-1345mzy CF3CH═CFCH2F 1,1,1,3,4-pentafluoro-2-butene
    HFC-1345fz CF3CF2CH═CH2 3,3,4,4,4-pentafluoro-1-butene
    HFC-1345mzz CHF2CH═CHCF3 1,1,1,4,4-pentafluoro-2-butene
    HFC-1345sy CH3CF═CFCF3 1,1,1,2,3-pentafluoro-2-butene
    HFC-1345fyc CH2═CFCF2CHF2 2,3,3,4,4-pentafluoro-1-butene
    HFC-1345pyz CHF2CF═CHCHF2 1,1,2,4,4-pentafluoro-2-butene
    HFC-1345cyc CH3CF2CF═CF2 1,1,2,3,3-pentafluoro-1-butene
    HFC-1345pyy CH2FCF═CFCHF2 1,1,2,3,4-pentafluoro-2-butene
    HFC-1345eyc CH2FCF2CF═CHF 1,2,3,3,4-pentafluoro-1-butene
    HFC-1345ctm CF2═C(CF3)(CH3) 1,1,3,3,3-pentafluoro-2-methyl-1-propene
    HFC-1345ftp CH2═C(CHF2)(CF3) 2-(difluoromethyl)-3,3,3-trifluoro-1-propene
    HFC1345fye CH2═CFCHFCF3 2,3,4,4,4-pentafluoro-1-butene
    HFC-1345eyf CHF═CFCH2CF3 1,2,4,4,4-pentafluoro-1-butene
    HFC-1345eze CHF═CHCHFCF3 1,3,4,4,4-pentafluoro-1-butene
    HFC-1345ezc CHF═CHCF2CHF2 1,3,3,4,4-pentafluoro-1-butene
    HFC-1345eye CHF═CFCHFCHF2 1,2,3,4,4-pentafluoro-1-butene
    HFC-1354fzc CH2═CHCF2CHF2 3,3,4,4-tetrafluoro-1-butene
    HFC-1354ctp CF2═C(CHF2)(CH3) 1,1,3,3-tetrafluoro-2-methyl-1-propene
    HFC-1354etm CHF═C(CF3)(CH3) 1,3,3,3-tetrafluoro-2-methyl-1-propene
    HFC-1354tfp CH2═C(CHF2)2 2-(difluoromethyl)-3,3-difluoro-1-propene
    HFC-1354my CF3CF═CHCH3 1,1,1,2-tetrafluoro-2-butene
    HFC-1354mzy CH3CF═CHCF3 1,1,1,3-tetrafluoro-2-butene
    FC-141-10myy CF3CF═CFCF2CF3 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene
    FC-141-10cy CF2═CFCF2CF2CF3 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene
    HFC-1429mzt (CF3)2C═CHCF3 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-
    butene
    HFC-1429myz CF3CF═CHCF2CF3 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene
    HFC-1429mzy CF3CH═CFCF2CF3 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene
    HFC-1429eyc CHF═CFCF2CF2CF3 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene
    HFC-1429czc CF2═CHCF2CF2CF3 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene
    HFC-1429cycc CF2═CFCF2CF2CHF2 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene
    HFC-1429pyy CHF2CF═CFCF2CF3 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene
    HFC-1429myyc CF3CF═CFCF2CHF2 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene
    HFC-1429myye CF3CF═CFCHFCF3 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene
    HFC-1429eyym CHF═CFCF(CF3)2 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-
    butene
    HFC-1429cyzm CF2═CFCH(CF3)2 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-
    butene
    HFC-1429mzt CF3CH═C(CF3)2 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-
    butene
    HFC-1429czym CF2═CHCF(CF3)2 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-
    butene
    HFC-1438fy CH2═CFCF2CF2CF3 2,3,3,4,4,5,5,5-octafluoro-1-pentene
    HFC-1438eycc CHF═CFCF2CF2CHF2 1,2,3,3,4,4,5,5-octafluoro-1-pentene
    HFC-1438ftmc CH2═C(CF3)CF2CF3 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-
    butene
    HFC-1438czzm CF2═CHCH(CF3)2 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-
    butene
    HFC-1438ezym CHF═CHCF(CF3)2 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-
    butene
    HFC-1438ctmf CF2═C(CF3)CH2CF3 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-
    butene
    HFC-1447fzy (CF3)2CFCH═CH2 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-
    butene
    HFC-1447fz CF3CF2CF2CH═CH2 3,3,4,4,5,5,5-heptafluoro-1-pentene
    HFC-1447fycc CH2═CFCF2CF2CHF2 2,3,3,4,4,5,5-heptafluoro-1-pentene
    HFC-1447czcf CF2═CHCF2CH2CF3 1,1,3,3,5,5,5-heptafluoro-1-pentene
    HFC-1447mytm CF3CF═C(CF3)(CH3) 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-
    butene
    HFC-1447fyz CH2═CFCH(CF3)2 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-
    butene
    HFC-1447ezz CHF═CHCH(CF3)2 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-
    butene
    HFC-1447qzt CH2FCH═C(CF3)2 1,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-
    butene
    HFC-1447syt CH3CF═C(CF3)2 2,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-
    butene
    HFC-1456szt (CF3)2C═CHCH3 3-(trifluoromethyl)-4,4,4-trifluoro-2-butene
    HFC-1456szy CF3CF2CF═CHCH3 3,4,4,5,5,5-hexafluoro-2-pentene
    HFC-1456mstz CF3C(CH3)═CHCF3 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene
    HFC-1456fzce CH2═CHCF2CHFCF3 3,3,4,5,5,5-hexafluoro-1-pentene
    HFC-1456ftmf CH2═C(CF3)CH2CF3 4,4,4-trifluoro-2-(trifluoromethyl)-1-butene
    FC-151-12c CF3(CF2)3CF═CF2 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-
    hexene (or perfluoro-1-hexene)
    FC-151-12mcy CF3CF2CF═CFCF2CF3 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-
    hexene (or perfluoro-3-hexene)
    FC-151-12mmtt (CF3)2C═C(CF3)2 1,1,1,4,4,4-hexafluoro-2,3-
    bis(trifluoromethyl)-2-butene
    FC-151-12mmzz (CF3)2CFCF═CFCF3 1,1,1,2,3,4,5,5,5-nonafluoro-4-
    (trifluoromethyl)-2-pentene
    HFC-152-11mmtz (CF3)2C═CHC2F5 1,1,1,4,4,5,5,5-octafluoro-2-
    (trifluoromethyl)-2-pentene
    HFC-152- (CF3)2CFCF═CHCF3 1,1,1,3,4,5,5,5-octafluoro-4-
    11mmyyz (trifluoromethyl)-2-pentene
    PFBE CF3CF2CF2CF2CH═CH2 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (or
    (or HFC-1549fz) perfluorobutylethylene)
    HFC-1549fztmm CH2═CHC(CF3)3 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-
    butene
    HFC-1549mmtts (CF3)2C═C(CH3)(CF3) 1,1,1,4,4,4-hexafluoro-3-methyl-2-
    (trifluoromethyl)-2-butene
    HFC-1549fycz CH2═CFCF2CH(CF3)2 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-
    pentene
    HFC-1549myts CF3CF═C(CH3)CF2CF3 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-
    pentene
    HFC-1549mzzz CF3CH═CHCH(CF3)2 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-
    pentene
    HFC-1558szy CF3CF2CF2CF═CHCH3 3,4,4,5,5,6,6,6-octafluoro-2-hexene
    HFC-1558fzccc CH2═CHCF2CF2CF2CHF2 3,3,4,4,5,5,6,6-octafluoro-2-hexene
    HFC-1558mmtzc (CF3)2C═CHCF2CH3 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-
    pentene
    HFC-1558ftmf CH2═C(CF3)CH2C2F5 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-
    pentene
    HFC-1567fts CF3CF2CF2C(CH3)═CH2 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-
    pentene
    HFC-1567szz CF3CF2CF2CH═CHCH3 4,4,5,5,6,6,6-heptafluoro-2-hexene
    HFC-1567fzfc CH2═CHCH2CF2C2F5 4,4,5,5,6,6,6-heptafluoro-1-hexene
    HFC-1567sfyy CF3CF2CF═CFC2H5 1,1,1,2,2,3,4-heptafluoro-3-hexene
    HFC-1567fzfy CH2═CHCH2CF(CF3)2 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-
    pentene
    HFC-1567myzzm CF3CF═CHCH(CF3)(CH3) 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-
    pentene
    HFC-1567mmtyf (CF3)2C═CFC2H5 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-
    pentene
    FC-161-14myy CF3CF═CFCF2CF2C2F5 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-
    2-heptene
    FC-161-14mcyy CF3CF2CF═CFCF2C2F5 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-
    2-heptene
    HFC-162-13mzy CF3CH═CFCF2CF2C2F5 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-
    heptene
    HFC162-13myz CF3CF═CHCF2CF2C2F5 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-
    heptene
    HFC-162-13mczy CF3CF2CH═CFCF2C2F5 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-
    heptene
    HFC-162-13mcyz CF3CF2CF═CHCF2C2F5 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-
    heptene
    PEVE CF2═CFOCF2CF3 pentafluoroethyl trifluorovinyl ether
    PMVE CF2═CFOCF3 trifluoromethyl trifluorovinyl ether
  • The compounds listed in Table 2 and Table 3 are available commercially or may be prepared by processes known in the art or as described herein.
  • 1,1,1,4,4-pentafluoro-2-butene may be prepared from 1,1,1,2,4,4-hexafluorobutane (CHF2CH2CHFCF3) 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, incorporated herein by reference.
  • 1,1,1,4,4,4-hexafluoro-2-butene may be prepared from 1,1,1,4,4,4-hexafluoro-2-iodobutane (CF3CHICH2CF3) by reaction with KOH using a phase transfer catalyst at about 60° C. The synthesis of 1,1,1,4,4,4-hexafluoro-2-iodobutane may be carried out by reaction of perfluoromethyl iodide (CF3I) and 3,3,3-trifluoropropene (CF3CH═CH2) at about 200° C. under autogenous pressure for about 8 hours.
  • 3,4,4,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorination of 1,1,1,2,2,3,3-heptafluoropentane (CF3CF2CF2CH2CH3) 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 (CF3CF2CF2CH═CH2).
  • 1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,3,3,4-heptafluorobutane (CH2FCF2CHFCF3) 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 (CHF2CH2CF2CF3) 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 (CF3CH2CF2CHF2) using solid KOH.
  • 1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,2,3-hexafluorobutane (CH2FCH2CF2CF3) using solid KOH.
  • 1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,3,3,4-hexafluorobutane (CF3CH2CF2CH2F) using solid KOH.
  • 1,1,1,3-tetrafluoro-2-butene may be prepared by reacting 1,1,1,3,3-pentafluorobutane (CF3CH2CF2CH3) with aqueous KOH at 120° C.
  • 1,1,1,4,4,5,5,5-octafluoro-2-pentene may be prepared from (CF3CHICH2CF2CF3) 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 (CF3CF2I) 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 (CF3CF2CHICH2CF2CF3) 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 (CF3CF2I) and 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH═CH2) 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 (CF3CHICH2CF(CF3)2) with KOH in isopropanol. CF3CHICH2CF(CF3)2 is made from reaction of (CF3)2CFI with CF3CH═CH2 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 (CF3CH═CHCF3) with tetrafluoroethylene (CF2═CF2) and antimony pentafluoride (SbF5).
  • 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.
  • Many of the compounds of Formula I, Formula II, Table 1, Table 2, and Table 3 exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the described composition is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, F11E is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. As another example, HFC-1225ye is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio, with the Z isomer preferred.
  • In some embodiments, the working fluid may further comprise at least one compound selected from hydrofluorocarbons, fluoroethers, hydrocarbons, dimethyl ether (DME), carbon dioxide (CO2), ammonia (NH3), and iodotrifluoromethane (CF3I).
  • In some embodiments, the working fluid may further comprise hydrofluorocarbons comprising at least one saturated compound containing carbon, hydrogen, and fluorine. Of particular utility are hydrofluorocarbons having 1 to 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. Representative hydrofluorocarbon compounds include but are not limited to fluoromethane (CH3F, HFC-41), difluoromethane (CH2F2, HFC-32), trifluoromethane (CHF3, HFC-23), pentafluoroethane (CF3CHF2, HFC-125), 1,1,2,2-tetrafluoroethane (CHF2CHF2, HFC-134), 1,1,1,2-tetrafluoroethane (CF3CH2F, HFC-134a), 1,1,1-trifluoroethane (CF3CH3, HFC-143a), 1,1-difluoroethane (CHF2CH3, HFC-152a), fluoroethane (CH3CH2F, HFC-161), 1,1,1,2,2,3,3-heptafluoropropane (CF3CF2CHF2, HFC-227ca), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea), 1,1,2,2,3,3-hexafluoropropane (CHF2CF2CHF2, HFC-236ca), 1,1,1,2,2,3-hexafluoropropane (CF3CF3CH2F, HFC-236cb), 1,1,1,2,3,3-hexafluoropropane (CF3CHFCHF2, HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3, HFC-236fa), 1,1,2,2,3-pentafluoropropane (CHF2CF2CH2F, HFC-245ca), 1,1,1,2,2-pentafluoropropane (CF3CF2CH3, HFC-245cb), 1,1,2,3,3-pentafluoropropane (CHF2CHFCHF2, HFC-245ea), 1,1,1,2,3-pentafluoropropane (CF3CHFCH2F, HFC-245eb), 1,1,1,3,3-pentafluoropropane (CF3CH2CHF2, HFC-245fa), 1,2,2,3-tetrafluoropropane (CH2FCF2CH2F, HFC-254ca), 1,1,2,2-tetrafluoropropane (CHF2CF2CH3, HFC-254cb), 1,1,2,3-tetrafluoropropane (CHF2CHFCH2F, HFC-254ea), 1,1,1,2-tetrafluoropropane (CF3CHFCH3, HFC-254eb), 1,1,3,3-tetrafluoropropane (CHF2CH2CHF2, HFC-254fa), 1,1,1,3-tetrafluoropropane (CF3CH2CH2F, HFC-254fb), 1,1,1-trifluoropropane (CF3CH2CH3, HFC-263fb), 2,2-difluoropropane (CH3CF2CH3, HFC-272ca), 1,2-difluoropropane (CH2FCHFCH3, HFC-272ea), 1,3-difluoropropane (CH2FCH2CH2F, HFC-272fa), 1,1-difluoropropane (CHF2CH2CH3, HFC-272fb), 2-fluoropropane (CH3CHFCH3, HFC-281ea), 1-fluoropropane (CH2FCH2CH3, HFC-281fa), 1,1,2,2,3,3,4,4-octafluorobutane (CHF2CF2CF2CHF2, HFC-338pcc), 1,1,1,2,2,4,4,4-octafluorobutane (CF3CH2CF2CF3, HFC-338mf), 1,1,1,3,3-pentafluorobutane (CF3CH2CHF2, HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF3CHFCHFCF2CF3, HFC-43-10mee), and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane (CF3CF2CHFCHFCF2CF2CF3, HFC-63-14mee).
  • In some embodiments, working fluids may further comprise fluoroethers comprising 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. Representative fluoroethers include but are not limited to nonafluoromethoxybutane (C4F9OCH3, any or all possible isomers or mixtures thereof); nonafluoroethoxybutane (C4F9OC2H5, any or all possible isomers or mixtures thereof); 2-difluoromethoxy-1,1,1,2-tetrafluoroethane (HFOC-236eaEβγ, or CHF2OCHFCF3); 1,1-difluoro-2-methoxyethane (HFOC-272fbEβγ, CH3OCH2CHF2); 1,1,1,3,3,3-hexafluoro-2-(fluoromethoxy)propane (HFOC-347 mmzEβγ, or CH2FOCH(CF3)2); 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFOC-356 mmzEβγ, or CH3OCH(CH3)2); 1,1,1,2,2-pentafluoro-3-methoxypropane (HFOC-365mcEγδ, or CF3CF2CH2OCH3); 2-ethoxy-1,1,1,2,3,3,3-heptafluoropropane (HFOC-467 mmyEβγ, or CH3CH2OCF(CF3)2; and mixtures thereof.
  • In some embodiments, working fluids may further comprise hydrocarbons comprising compounds having only carbon and hydrogen. Of particular utility are compounds having 3 to 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, and cycloheptane.
  • In some embodiments, the working fluid may comprise hydrocarbons containing heteroatoms, such as dimethylether (DME, CH3OCH3). DME is commercially available.
  • In some embodiments, working fluids may further comprise carbon dioxide (CO2), which is commercially available from various sources or may be prepared by methods known in the art.
  • In some embodiments, working fluids may further comprise ammonia (NH3), which is commercially available from various sources or may be prepared by methods known in the art.
  • In some embodiments, the working fluid further comprises at least one compound selected from hydrofluorocarbons, fluoroethers, hydrocarbons, dimethyl ether (DME), carbon dioxide (CO2), ammonia (NH3), and iodotrifluoromethane (CF3I).
  • In one embodiment, the working fluid comprises 1,2,3,3,3-pentafluoropropene (HFC-1225ye). In another embodiment, the working fluid further comprises difluoromethane (HFC-32). In yet another embodiment, the working fluid further comprises 1,1,1,2-tetrafluoroethane (HFC-134a).
  • In one embodiment, the working fluid comprises 2,3,3,3-tetrafluoropropene (HFC-1234yf). In another embodiment, the working fluid comprises HFC-1225ye and HFC-1234yf.
  • In one embodiment, the working fluid comprises 1,3,3,3-tetrafluoropropene (HFC-1234ze). In another embodiment, the working fluid comprises E-HFC-1234ze (or trans-HFC-1234ze).
  • In yet another embodiment, the working fluid further comprises at least one compound from the group consisting of HFC-134a, HFC-32, HFC-125, HFC-152a, and CF3I.
  • In certain embodiments, working fluids may comprise a composition selected from the group consisting of:
    • HFC-32 and HFC-1225ye; HFC-1234yf and CF3I; HFC-32, HFC-134a, and HFC-1225ye; HFC-32, HFC-125, and HFC-1225ye; HFC-32, HFC-1225ye, and HFC-1234yf; HFC-125, HFC-1225ye, and HFC-1234yf; HFC-32, HFC-1225ye, HFC-1234yf, and CF3I; HFC-134a, HFC-1225ye, and HFC-1234yf; HFC-134a and HFC-1234yf; HFC-32 and HFC-1234yf; HFC-125 and HFC-1234yf; HFC-32, HFC-125, and HFC-1234yf; HFC-32, HFC-134a, and HFC-1234yf; DME and HFC-1234yf; HFC-152a and HFC-1234yf; HFC-152a, HFC-134a, and HFC-1234yf;
  • HFC-152a, n-butane, and HFC-1234yf;
    HFC-134a, propane, and HFC-1234yf;
    • HFC-125, HFC-152a, and HFC-1234yf; HFC-125, HFC-134a, and HFC-1234yf; HFC-32, HFC-1234ze, and HFC-1234yf; HFC-125, HFC-1234ze, and HFC-1234yf; HFC-32, HFC-1234ze, HFC-1234yf, and CF3I; HFC-134a, HFC-1234ze, and HFC-1234yf; HFC-134a and HFC-1234ze; HFC-32 and HFC-1234ze; HFC-125 and HFC-1234ze; HFC-32, HFC-125, and HFC-1234ze; HFC-32, HFC-134a, and HFC-1234ze; DME and HFC-1234ze; HFC-152a and HFC-1234ze; HFC-152a, HFC-134a, and HFC-1234ze;
  • HFC-152a, n-butane, and HFC-1234ze;
    HFC-134a, propane, and HFC-1234ze;
    • HFC-125, HFC-152a, and HFC-1234ze; or HFC-125, HFC-134a, and HFC-1234ze. EXAMPLES Example 1 Performance Comparison
  • Automobile air conditioning systems with and without an intermediate heat exchanger were tested to determine if an improvement is seen with the IHX. The working fluid was a blend of 95% by weight HFC-1225ye and 5% by weight of HFC-32. Each system had a condenser, evaporator, compressor and a thermal expansion device. The ambient air temperature was 30° C. at the evaporator and the condenser inlets. Tests were performed for 2 compressor speeds, 1000 and 2000 rpm, and for 3 vehicle speeds: 25, 30, and 36 km/h. The volumetric flow rate of air on the evaporator was 380 m3/h.
  • The cooling capacity for the system with an IHX shows an increase of 4 to 7% as compared to the system with no IHX. The COP also showed an increase of 2.5 to 4% for the system with the IHX as compared to a system with no IHX.
    • Example 2 Improvement in Performance with Internal Heat Exchanger
  • Cooling performance is calculated for HFC-134a and HFC-1234yf both with and without an IHX. The conditions used are as follows:
  •
    Condenser temperature 55° C.
    Evaporator temperature
     5° C.
    Superheat (absolute) 15° C.
  • The data illustrating relative performance is shown in TABLE 5.
  • TABLE 5
    Subcool, Capacity Compressor
    Test ° C. COP kJ/m3 work, kJ/kg
    HFC-134a, without 0 4.74 2250.86 29.6
    IHX
    HFC-134a, with IHX 5.0 5.02 2381.34 29.6
    HFC-134a, % 5.91 5.80
    increase with IHX
    HFC-1234yf, 0 4.64 2172.43 24.37
    without IHX
    HFC-1234yf with 5.8 5.00 2335.38 24.37
    IHX
    HFC-1234yf, % 7.76 7.50
    increase with IHX

    The data above demonstrate an unexpected level of improvement in energy efficiency (COP) and cooling capacity for the fluoroolefin (HFC-1234yf) with the IHX, as compared to that gained by HFC-134a with the IHX. In particular, COP was increased by 7.67% and cooling capacity increased by 7.50%.
  • It should be noted that the subcool difference arises from the differences in molecular weight, liquid density and liquid heat capacity for HFC-1234yf as compared to HFC-134a. Based on these parameters it was estimated that there would be a difference in subcool achieved with the different compounds. When the HFC-134a subcool was set to 5° C., the corresponding subcool for HFC-1234yf was calculated to be 5.8° C.

Claims (11)

1. A method for exchanging heat in a vapor compression heat transfer system having a working fluid circulating therethrough, comprising the steps of:
(a) circulating a working fluid comprising a fluoroolefin to an inlet of a first tube of an internal heat exchanger, through the internal heat exchanger and to an outlet thereof;
(b) circulating the working fluid from the outlet of the first tube of the internal heat exchanger to an inlet of an evaporator, through the evaporator to evaporate the working fluid and convert it into a gas, and through an outlet of the evaporator;
(c) circulating the working fluid from the outlet of the evaporator to an inlet of a second tube of the internal heat exchanger to transfer heat from the liquid working fluid from the condenser to the gaseous working fluid from the evaporator, through the internal heat exchanger, and to an outlet of the second tube;
(d) circulating the working fluid from the outlet of the second tube of the internal heat exchanger to an inlet of a compressor, through the compressor to compress the working fluid gas, and to an outlet of the compressor;
(e) circulating the working fluid from the outlet of the compressor to an inlet of a condenser and through the condenser to condense the compressed working fluid gas into a liquid, and to an outlet of the condenser;
(f) circulating the working fluid from the outlet of the condenser to an inlet of the first tube of the intermediate heat exchanger to transfer heat from the liquid from the condenser to the gas from the evaporator, and to an outlet of the second tube; and
(g) circulating the working fluid from the outlet of the second tube of the internal heat exchanger back to the evaporator.
2. The method of claim 1, where the fluoroolefin is at least one compound selected from the group consisting of:
(i) fluoroolefins of the formula E- or Z-R1CH═CHR2, wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups;
(ii) cyclic fluoroolefins of the formula cyclo-[CX═CY(CZW)n—], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and
(iii) fluoroolefins selected from the group consisting of: 1,1,2,3,3,3-pentafluoro-1-propene (CHF═CFCF3), 1,1,3,3,3-pentafluoro-1-propene (CF2═CHCF3), 1,1,2,3,3-pentafluoro-1-propene (CF2═CFCHF2), 1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF2), 2,3,3,3-tetrafluoro-1-propene (CH2═CFCF3), 1,3,3,3-tetrafluoro-1-propeneCHF═CHCF3), 1,1,2,3-tetrafluoro-1-propene (CF2═CFCH2F), 1,1,3,3-tetrafluoro-1-propene (CF2═CHCHF2), 1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF2), 3,3,3-trifluoro-1-propene (CH2═CHCF3), 2,3,3-trifluoro-1-propene (CHF2CF═CH2); 1,1,2-trifluoro-1-propene (CH3CF═CF2); 1,2,3-trifluoro-1-propene (CH2FCF═CF2); 1,1,3-trifluoro-1-propene (CH2FCH═CF2); 1,3,3-trifluoro-1-propene (CHF2CH═CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF3CF═CFCF3); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF3CF2CF═CF2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF═CHCF3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF2CF3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF2CF═CFCF3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF3)2C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF2═CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF2═CFCHFCF3); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF2═CFCF2CHF2); 2,3,3,4,4,4-hexafluoro-1-butene (CF3CF2CF═CH2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF═CFCHFCF3); 1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF2CHF2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF2CF═CFCHF2); 1,1,1,2,3,4-hexafluoro-2-butene (CH2FCF═CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF2CH═CFCF3); 1,1,1,3,4,4-hexafluoro-2-butene (CF3CH═CFCHF2); 1,1,2,3,3,4-hexafluoro-1-butene (CF2═CFCF2CH2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF2═CFCHFCHF2); 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH2═C(CF3)2); 1,1,1,2,4-pentafluoro-2-butene (CH2FCH═CFCF3); 1,1,1,3,4-pentafluoro-2-butene (CF3CH═CFCH2F); 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH═CH2); 1,1,1,4,4-pentafluoro-2-butene (CHF2CH═CHCF3); 1,1,1,2,3-pentafluoro-2-butene (CH3CF═CFCF3); 2,3,3,4,4-pentafluoro-1-butene (CH2═CFCF2CHF2); 1,1,2,4,4-pentafluoro-2-butene (CHF2CF═CHCHF2); 1,1,2,3,3-pentafluoro-1-butene (CH3CF2CF═CF2); 1,1,2,3,4-pentafluoro-2-butene (CH2FCF═CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2═C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH2═C(CHF2)(CF3)); 2,3,4,4,4-pentafluoro-1-butene (CH2═CFCHFCF3); 1,2,4,4,4-pentafluoro-1-butene (CHF═CFCH2CF3); 1,3,4,4,4-pentafluoro-1-butene (CHF═CHCHFCF3); 1,3,3,4,4-pentafluoro-1-butene (CHF═CHCF2CHF2); 1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF2); 3,3,4,4-tetrafluoro-1-butene (CH2═CHCF2CHF2); 1,1-difluoro-2-(difluoromethyl)-1-propene (CF2═C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2-methyl-1-propene (CHF═C(CF3)(CH3)); 3,3-difluoro-2-(difluoromethyl)-1-propene (CH2═C(CHF2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF═CHCH3); 1,1,1,3-tetrafluoro-2-butene (CH3CF═CHCF3); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF3CF═CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF2═CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene ((CF3)2C═CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF═CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH═CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene (CHF═CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2═CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2═CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF═CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF═CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF═CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF═CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2═CFCH(CF3)2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH═C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2═CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1-pentene (CH2═CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1-pentene (CHF═CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH2═C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CF2═CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2═C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH═CH2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH═CH2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH2═CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2═CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF═C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH2═CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH═C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF═C(CF3)2); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C═CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF═CHCH3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF3C(CH3)═CHCF3); 3,3,4,5,5,5-hexafluoro-1-pentene (CH2═CHCF2CHFCF3); 4,4,4-trifluoro-2-(trifluoromethyl)-1-butene (CH2═C(CF3)CH2CF3); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF3(CF2)3CF═CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF3CF2CF═CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF3)2C═C(CF3)2); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF═CFCF3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C═CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF═CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF3CF2CF2CF2CH═CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2═CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene ((CF3)2C═C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene (CH2═CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF3CF═C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene (CF3CH═CHCH(CF3)2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF3CF2CF2CF═CHCH3); 3,3,4,4,5,5,6,6-octafluoro1-hexene (CH2═CHCF2CF2CF2CHF2); 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C═CHCF2CH3); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene (CH2═C(CF3)CH2C2F5); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF3CF2CF2C(CH3)═CH2); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF3CF2CF2CH═CHCH3); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH2═CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF═CFC2H5); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH2═CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF3CF═CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C═CFC2H5); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF═CFCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (CF3CF2CF═CFCF2C2F5); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CH═CFCF2CF2C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CF═CHCF2CF2C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CH═CFCF2C2F5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CF═CHCF2C2F5); pentafluoroethyl trifluorovinyl ether (CF2═CFOCF2CF3); and trifluoromethyl trifluorovinyl ether (CF2═CFOCF3).
3. The method of claim 1, where the working fluid in the second tube flows in a countercurrent direction to the direction of flow of the working fluid in the first tube, thereby cooling the working fluid in the first tube and heating the working fluid in the second tube.
4. The method of claim 1, where the first tube has a larger diameter than the second tube, and the second tube is disposed concentrically in the first tube, and a hot liquid in the first tube surrounds a cool gas in the second tube.
5. The method of claim 1, wherein the condensing step comprises:
(i) circulating the working fluid to a back row of a dual-row condenser, where the back row receives the working fluid at a first temperature; and
(ii) circulating the working fluid to a front row of the dual-row condenser, where the front row receives the working fluid at a second temperature, where the second temperature is less than the first temperature, so that air which travels across the front row and the back row is preheated, whereby the temperature of the air is greater when it reaches the back row than when it reaches the front row.
6. The method of claim 1, wherein the evaporating step comprises
(i) passing the working fluid through an inlet of a dual-row evaporator having a first row and a second row,
(ii) circulating the working fluid in the first row in a direction perpendicular to the flow of fluid through the inlet of the evaporator, and
(iii) circulating the working fluid in the second row in a direction generally counter to the direction of the flow of the working fluid through the inlet
7. The method of claim 1, 5, or 6, wherein the working fluid further comprises at least one compound selected from hydrofluorocarbons, fluoroethers, hydrocarbons, dimethyl ether (DME), carbon dioxide (CO2), ammonia (NH3), and iodotrifluoromethane (CF3I).
8. The method of claims 1, 5, or 6 wherein the fluoroolefin comprises HFC-1234yf.
9. The method of claim 8, wherein the coefficient of performance and the cooling capacity of the system is increased by at least 7.5% as compared to a system which uses HFC-134a as the working fluid.
10. A vapor compression heat transfer system for exchanging heat, comprising:
(a) an evaporator having an inlet and an outlet;
(b) a compressor having an inlet and an outlet, wherein the inlet is connected to the outlet of the evaporator;
(c) a dual row-condenser connected to the outlet of the compressor, the dual-row condenser having:
(i) an inlet,
(ii) a first row connected to the inlet, the first row comprising a first inlet manifold and a plurality of channels for allowing a working fluid at a first temperature to flow into the manifold and then through the channels in at least one direction and collect in a second outlet manifold,
(iii) a second row connected to the first row, the second row comprising a plurality of channels for conducting a working fluid at a second temperature less than the refrigerant in the first row,
(iv) a conduit connecting the first row to the second row; and
(d) an intermediate heat exchanger, having:
(i) a first tube having an inlet connected to an exit of the condenser and an outlet, and
(ii) a second tube having an inlet connected to an outlet and an outlet connected to an inlet of the dual-row condenser; and
wherein the inlet of the evaporator is connected to the outlet of the first tube of the intermediate heat exchanger
11. A vapor compression heat transfer system for exchanging heat, comprising:
(a) a dual-row evaporator for evaporating a working fluid, the evaporator having an inlet and an outlet;
(b) a compressor having an inlet and an outlet, wherein the inlet is connected to the outlet of the evaporator;
(c) a condenser having an inlet and an outlet, wherein the inlet is connected to the outlet of the compressor; and
(d) an intermediate heat exchanger having:
(i) a first tube having an inlet connected to an exit line of a condenser and an outlet connected to an inlet line of the evaporator;
(ii) a second tube having an inlet connected to an outlet line of the evaporator having an outlet.
US12/119,023 2007-05-11 2008-05-12 Method for exchanging heat in vapor compression heat transfer systems Abandoned US20090120619A1 (en)

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US15/939,644 US11624534B2 (en) 2007-05-11 2018-03-29 Method for exchanging heat in vapor compression heat transfer systems and vapor compression heat transfer systems comprising intermediate heat exchangers with dual-row evaporators or condensers
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KR20100029761A (en) 2010-03-17
US11867436B2 (en) 2024-01-09
CA2682312A1 (en) 2008-11-20
EP3091320A1 (en) 2016-11-09
EP4160127A1 (en) 2023-04-05
CA3002834A1 (en) 2008-11-20

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