US20140311146A1 - Fluorinated oxiranes as organic rankine cycle working fluids and methods of using same - Google Patents

Fluorinated oxiranes as organic rankine cycle working fluids and methods of using same Download PDF

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US20140311146A1
US20140311146A1 US14/007,057 US201214007057A US2014311146A1 US 20140311146 A1 US20140311146 A1 US 20140311146A1 US 201214007057 A US201214007057 A US 201214007057A US 2014311146 A1 US2014311146 A1 US 2014311146A1
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working fluid
rankine cycle
mechanical energy
fluorinated
oxirane
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Bamidele Fayemi
Zhongxing Zhang
Michael G. Costello
Michael J. Bulinski
John G. Owens
Phillip E. Tuma
Richard M. Minday
Richard M. Flynn
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
    • F01K25/10—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours the vapours being cold, e.g. ammonia, carbon dioxide, ether
    • 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
    • F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type
    • F25B15/02—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/11—Ethers
    • C09K2205/116—Halogenated cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/24—Only one single fluoro component present

Definitions

  • This disclosure relates to the use of fluorinated oxiranes as Rankine cycle working fluids.
  • Rankine cycle systems are commonly used for generating electrical power that can then be provided to a power distribution system, or grid for residential and commercial use.
  • the electrical power is generated by converting thermal energy into mechanical energy and then mechanical energy into electrical energy.
  • Closed Rankine systems include a heat source such as a boiler or evaporator of a motive fluid (working fluid), a turbine fed with the vapor from the boiler to drive a generator or other load, a condenser for condensing the exhaust vapors from the turbine, and a means to pump the recycled condensed fluid back to the heat source.
  • U.S. Pat. No. 3,393,515 (Tabor et al.) describes a self-starting power generating unit which operates on a closed Rankine cycle.
  • the motive fluid that has been used in such systems has often been water.
  • the heat source has been any form of fossil fuel, e.g., oil, coal, or natural gas.
  • Organic working fluids can boil at temperatures up to the critical temperature above which there is no boiling, fluids with higher critical temperatures result in higher Rankine cycle efficiency.
  • fluids such as 1,1,1,3,3-pentafluoropropane (R245fa Refrigerant, available from Honeywell, Morristown, N.J. under the trade designation GENETRON) has been used in Rankine cycle system devices.
  • R245fa Refrigerant 1,1,1,3,3-pentafluoropropane
  • GENETRON perfluorinated ketones having a higher critical temperature than R245fa (critical temperature of 150° C.) have been considered for use in Rankine cycle devices since these materials have a higher critical temperature than R245fa.
  • Brasz et al. discloses organic Rankine cycle systems that use other perfluorinated ketones with higher thermodynamic Rankine cycle efficiency than R245fa.
  • Brasz et al. discloses the use of CF 3 CF 2 C(O)CF(CF 3 ) 2 and other related compounds as Rankine working fluids.
  • fluorinated oxiranes for fire extinguishing has been disclosed, for example, in U.S. Ser. No. 61/431,119 entitled “Fluorinated Oxiranes as Fire Extinguishing Compositions and Methods of Extinguishing Fires Therewith”, filed Jan. 10, 2011.
  • fluorinated oxiranes as dielectric fluids has been disclosed, for example, in U.S. Ser. No. 61/435,867 entitled “Fluorinated Oxiranes as Dielectric Fluids”, filed Jan. 25, 2011.
  • Lubricants containing fluorinated oxiranes has been disclosed, for example, in U.S. Ser. No.
  • a process for converting thermal energy into mechanical energy in a Rankine cycle includes the steps of vaporizing a working fluid with a heat source to form a vaporized working fluid, expanding the vaporized working fluid through a turbine, cooling the vaporized working fluid using a cooling source to form a condensed working fluid, and pumping the condensed working fluid, wherein the working fluid comprises a fluorinated oxirane.
  • the fluorinated oxirane can contain substantially no hydrogen atoms bonded to carbon atoms and can have a total of from about 4 to about 9 carbon atoms.
  • the fluorinated oxirane can contain 6 carbon atoms.
  • the fluorinated oxirane can have a critical temperature of greater than about 150° C.
  • a process for recovering waste heat includes passing a liquid working fluid through a heat exchanger in communication with a process that produces waste heat to produce a vaporized working fluid, removing the vaporized working fluid from the heat exchanger, passing the vaporized working fluid through an expander, wherein the waste heat is converted into mechanical energy, and cooling the vaporized working fluid after it has been passed through the expander, wherein the fluorinated oxirane compound contains substantially no hydrogen atoms bonded to carbon atoms.
  • an apparatus for converting thermal energy into mechanical energy in a Rankine cycle includes a working fluid, a heat source to vaporize the working fluid and form a vaporized working fluid, a turbine through which the vaporized working fluid is passed thereby converting thermal energy into mechanical energy, a condenser to cool the vaporized working fluid after it is passed through the turbine, and a pump to recirculate the working fluid, wherein the working fluid comprises a fluorinated oxirane.
  • critical temperature and critical pressure refers to the temperature and pressure at which the density of the vapor of a liquid in a sealed system is the same as that of the liquid.
  • in-chain heteroatom refers to an atom other than carbon (for example, oxygen and nitrogen) that is bonded to carbon atoms in a carbon chain so as to form a carbon-heteroatom-carbon chain;
  • device refers to an object or contrivance which is heated, cooled, or maintained at a predetermined temperature
  • int refers to chemical compositions that are generally not chemically reactive under normal conditions of use
  • fluorinated refers to hydrocarbon compounds that have one or more C—H bonds replaced by C—F bonds;
  • oxirane refers to a substituted hydrocarbon that contains at least one epoxy group
  • perfluoro- (for example, in reference to a group or moiety, such as in the case of “perfluoroalkylene” or “perfluoroalkylcarbonyl” or “perfluorinated”) means completely fluorinated such that, except as may be otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable with fluorine.
  • the provided processes and apparatuses that include fluorinated oxiranes as organic Rankine cycle working fluids can have ever lower boiling points, higher critical pressures and temperatures as well as good thermal stabilities compared to conventionally used fluorinated compositions with comparable numbers of carbon atoms.
  • the provided Rankine cycle working fluids can be more efficient in energy transfer and can still be used in systems that have simple equipment design.
  • FIG. 1 is a schematic illustration of an apparatus for converting thermal energy into mechanical energy in a Rankine cycle.
  • FIG. 2 is a schematic illustration of a Rankine cycle apparatus that includes a recuperator.
  • FIG. 3 is a graph (Temperature-Entropy Diagram) for an embodiment of the provided process.
  • a process for converting thermal energy into mechanical energy in a Rankine cycle includes a working fluid comprising a fluorinated oxirane.
  • typical Rankine cycle system 100 is shown that includes evaporator/boiler 120 which receives heat from an external source. Evaporator/boiler 120 vaporizes an organic Rankine working fluid contained within closed system 100 .
  • Rankine cycle system 100 also includes turbine 160 which is driven by the vaporized working fluid in the system and is used to turn generator 180 thus producing electrical power. The vaporized working fluid is then channeled though condenser 140 removing excess heat and reliquifying the liquid working fluid.
  • Power pump 130 increases the pressure of liquid leaving condenser 140 and also pumps it back into evaporator/boiler 120 for further use in the cycle. Heat released from condenser 140 can then be used for other purposes including driving a secondary Rankine system (not shown).
  • FIG. 2 is an illustration of Rankine cycle system that includes a recuperator.
  • Rankine cycle system 200 includes evaporator/boiler 220 which receives heat from an external source. Evaporator/boiler 220 vaporizes an organic Rankine working fluid contained within closed system 200 . Rankine cycle system 200 also includes turbine 260 which is driven by the vaporized working fluid in the system and is used to turn generator 270 thus producing electrical power. The vaporized working fluid is then channeled though recuperator 280 removing some excess heat and from there to the condenser 250 , where the working fluid condenses back to liquid.
  • Power pump 240 increases the pressure of liquid leaving condenser 250 and also pumps it back into recuperator 280 , where it is preheated before going back into the evaporator/boiler 220 for further use in the cycle. Heat released from condenser 250 can then be used for other purposes including driving a secondary Rankine system (not shown).
  • the provided apparatuses and processes include fluorinated oxiranes.
  • Fluorinated oxiranes useful in the provided compositions and processes can be oxiranes that have a carbon backbone which is fully fluorinated (perfluorinated), i.e., substantially all of the hydrogen atoms in the carbon backbone have been replaced with fluorine or oxiranes that can have a carbon backbone which is fully or partially fluorinated having, in some embodiments, up to a maximum of three hydrogen atoms, or a combination thereof.
  • fluorinated oxiranes in an apparatus that includes a device and a mechanism for transferring heat to or from the device is disclosed in Applicants' copending application, U.S. Attorney Docket No. 67218US002, which has been filed on the same day herewith.
  • the fluorinated oxiranes In addition to providing the required thermophysical properties for use in organic Rankine systems, the fluorinated oxiranes also demonstrate desirable environmental benefits. Many compounds that display high stability in use have also been found to be quite stable in the environment. Perfluorocarbons and perfluoropolyethers exhibit high stability but also have been shown to have long atmospheric lifetimes which result in high global warming potentials. The atmospheric lifetimes of C 6 F 14 and CF 3 OCF(CF 3 )CF 2 OCF 2 OCF 3 are reported as 3200 years and 800 years, respectively (see climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on climate Change , Solomon, S., D. Qin, M. Manning, Z. Chen, M. Marquis, K. B.
  • 2-fluoro-2-pentafluoroethyl-3,3-bis-trifluoromethyl-oxirane demonstrates an estimated atmospheric lifetime of 77 years.
  • fluorinated oxiranes have lower global warming potentials and would be expected to make significantly less contribution to global warming as compared to perfluorocarbons and perfluoropolyethers.
  • the provided fluorinated oxiranes can be derived from fluorinated olefins that have been oxidized with epoxidizing agents.
  • the carbon backbone includes the whole carbon framework including the longest hydrocarbon chain (main chain) and any carbon chains branching off of the main chain.
  • there can be one or more catenated heteroatoms interrupting the carbon backbone such as oxygen and nitrogen, for example ether or trivalent amine functionalities.
  • the catenated heteroatoms are typically not directly bonded to the oxirane ring. In these cases the carbon backbone includes the heteroatoms and the carbon framework attached to the heteroatom.
  • halogen atoms attached to the carbon backbone are fluorine; most typically, substantially all of the halogen atoms are fluorine so that the oxirane is a perfluorinated oxirane.
  • the provided fluorinated oxiranes can have a total of 4 to 12 carbon atoms.
  • fluorinated oxirane compounds suitable for use in the provided processes and compositions include 2,3-difluoro-2,3-bis-trifluoromethyl-oxirane, 2,2,3-trifluoro-3-pentafluoroethyl-oxirane, 2,3-difluoro-2-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-3-trifluoromethyl-oxirane, 2-fluoro-2-pentafluoroethyl-3,3-bis-trifluoromethyl-oxirane, 1,2,2,3,3,4,4,5,5,6-decafluoro-7-oxa-bicyclo[4.1.0]heptane, 2,3-difluoro-2-trifluoromethyl-3-pentafluoroethyl-oxirane, 2,3-difluoro-2-nonafluorobutyl-3-trifluoromethyl-oxirane, 2,3-difluoro
  • 2-nonafluorobutyloxirane, 2-tridecafluorohexyloxirane, and oxiranes of HFP trimer including 2-pentafluoroethyl-2-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-3,3-bis-trifluoromethyl-oxirane, 2-fluoro-3,3-bis-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-2-trifluoromethyl-oxirane, 2-fluoro-3-heptafluoropropyl-2-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-3-trifluoromethyl-oxirane, 2-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-2,3,3-tris-trifluoromethyl-oxirane and 2-[1,1,2,3,3,3-hexafluoro-2
  • the provided fluorinated oxirane compounds can be prepared by epoxidation of the corresponding fluorinated olefin using an oxidizing agent such as sodium hypochlorite, hydrogen peroxide or other well known epoxidizing agent such as peroxycarboxylic acids such as meta-chloroperoxybenzoic acid or peracetic acid.
  • an oxidizing agent such as sodium hypochlorite, hydrogen peroxide or other well known epoxidizing agent such as peroxycarboxylic acids such as meta-chloroperoxybenzoic acid or peracetic acid.
  • the fluorinated olefinic precursors can be directly available as, for example, in the cases of 1,1,1,2,3,4,4,4-octafluoro-but-2-ene (for making 2,3-difluoro-2,3-bis-trifluoromethyl oxirane), 1,1,1,2,3,4,4,5,5,5-decafluoro-pent-2-ene or 1,2,3,3,4,4,5,5,6,6 decafluoro-cyclohexene (for making 1,2,2,3,3,4,4,5,5,6-decafluoro-7-oxa-bicyclo[4.1.0]heptane).
  • 1,1,1,2,3,4,4,4-octafluoro-but-2-ene for making 2,3-difluoro-2,3-bis-trifluoromethyl oxirane
  • 1,1,1,2,3,4,4,5,5,5-decafluoro-pent-2-ene or 1,2,3,3,4,4,5,5,6,6 decafluoro-cyclohexene
  • HFP oligomers can include oligomers of hexafluoropropene (HFP) and tetrafluoroethylene (TFE) such as dimers and trimers.
  • HFP oligomers can be prepared by contacting 1,1,2,3,3,3-hexafluoro-1-propene (hexafluoropropene) with a catalyst or mixture of catalysts selected from the group consisting of cyanide, cyanate, and thiocyanate salts of alkali metals, quaternary ammonium, and quaternary phosphonium in the presence of polar, aprotic solvents such as, for example, acetonitrile.
  • a catalyst or mixture of catalysts selected from the group consisting of cyanide, cyanate, and thiocyanate salts of alkali metals, quaternary ammonium, and quaternary phosphonium in the presence of polar, aprotic solvents such as, for example, acetonit
  • HFP oligomers include HFP trimers or HFP dimers.
  • HFP dimers include a mixture of cis- and trans-isomers of perfluoro-4-methyl-2-pentene as indicated in Table 1 in the Example section below.
  • HFP trimers include a mixture of isomers of C 9 F 18 . This mixture has six main components that are also listed in Table 1 in the Example section.
  • the provided fluorinated oxirane compounds can have a boiling point in a range of from about ⁇ 10° C. to about 150° C. In some embodiments, the fluorinated oxirane compounds can have a boiling point in the range of from about 0° C. to about 55° C. Some exemplary materials and their boiling point ranges are disclosed in the Examples section below.
  • the provided process for converting thermal energy into mechanical energy in a Rankine cycle includes using a heat source to vaporize a working fluid comprising fluorinated oxiranes to form a vaporized working fluid.
  • the heat is transferred from the heat source to the working fluid in an evaporator or boiler.
  • the vaporized working fluid is pressurized and can be used to do work by expansion.
  • the heat source can be of any form such as from fossil fuels, e.g., oil, coal, or natural gas. Additionally, in some embodiments, the heat source can come from nuclear power, solar power, or fuel cells.
  • the heat can be “waste heat” from other heat transfer systems that would otherwise be lost to the atmosphere.
  • the “waste heat”, in some embodiments, can be heat that is recovered from a second Rankine cycle system from the condenser or other cooling device in the second Rankine cycle.
  • waste heat can be found at landfills where methane gas is flared off.
  • the methane gas generated by the landfills can be burned by way of “flares” producing carbon dioxide and water which are both less harmful to the environment in terms of global warming potential than methane.
  • Other sources of “waste heat” that can be useful in the provided processes are geothermal sources and heat from other types of engines such as gas turbine engines that give off significant heat in their exhaust gases and to cooling liquids such as water and lubricants.
  • the vaporized working fluid is expanded though a device that can convert the pressurized working fluid into mechanical energy.
  • the vaporized working fluid is expanded through a turbine which can cause a shaft to rotate from the pressure of the vaporized working fluid expanding.
  • the turbine can then be used to do mechanical work such as, in some embodiments, operate a generator, thus generating electricity.
  • the turbine can be used to drive belts, wheels, gears, or other devices that can transfer mechanical work or energy for use in attached or linked devices.
  • the vaporized (and now expanded) working fluid can be condensed using a cooling source to liquefy for reuse.
  • the heat released by the condenser can be used for other purposes including being recycled into the same or another Rankine cycle system, thus saving energy.
  • the condensed working fluid can be pumped by way of a pump back into the boiler or evaporator for reuse in a closed system.
  • thermodynamic characteristics of organic Rankine cycle working fluids are well known to those of ordinary skill and are discussed, for example, in U.S. Pat. Appl. Publ. No. 2010/0139274 (Zyhowski et al.).
  • the thermodynamic efficiency is influenced by matching the working fluid to the heat source temperature. The closer the evaporating temperature of the working fluid to the source temperature, the higher the efficiency of the system. Toluene can be used, for example, in the temperature range of 79° C.
  • an apparatus for converting thermal energy into mechanical energy in a Rankine cycle that includes a working fluid that includes a fluorinated oxirane, a heat source to vaporize the working fluid and form a vaporized working fluid, a turbine to convert the thermal energy (and pressure) of the vaporized working fluid into mechanical energy, a condenser to cool the vaporized working fluid after it has transferred energy to the turbine and a pump to recirculate the working fluid and to build pressure.
  • the recirculated working fluid can then be reheated in an evaporator boiler in the provided method and as described above.
  • the apparatus is typically a closed loop
  • HFP Dimer 2 isomers; 3M Foam Additive FA-188, 3M, St. Paul, MN. 1,2,3,3,4,4,5,5,6,6 Available from Sigma- decafluoro-cyclohexene Aldrich, St. Louis, MO. HFP Trimer HFP Trimer 6 Isomers; (45%), U.S. Pat. No.
  • the product crude was then washed with 200 grams of water to remove solvent acetonitrile and then purified in a 40-tray Oldershaw fractionation column with condenser being cooled to 15° C.
  • the fractionation column was operated in such a way so that the reflux ratio (the distillate flow rate going back to the fractionation column to the distillate flow rate going to the product collection cylinder) was at 10:1.
  • the final product was collected as the condensate when the head temperature in the fractionation column was between 52° C. and 53° C.
  • the product crude was then washed with 100 grams of water to remove solvent acetonitrile and then purified in a 40-tray Oldershaw fractionation column with condenser being cooled to 15° C.
  • the fractionation column was operated in such a way that the reflux ratio (the distillate flow rate going back to the fractionation column to the distillate flow rate going to the product collection cylinder) was at 10:1.
  • the final product was collected as the condensate when the head temperature in the fractionation column was between 47° C. and 55° C.
  • the product crude was then washed with 200 grams of water to remove solvent acetonitrile and then purified in a 40-tray Oldershaw fractionation column with condenser being cooled to 15° C.
  • the fractionation column was operated in such a way so that the reflux ratio (the distillate flow rate going back to the fractionation column to the distillate flow rate going to the product collection cylinder) was at 10:1.
  • the final product was collected as the condensate when the head temperature in the fractionation column was between 120° C. and 122° C.
  • Table II shows some thermophysical properties of exemplary fluorinated oxiranes and a comparative material (docecafluoro-2-methylpentan-3-one).
  • the oxirane was prepared according to a modification of the procedure of WO2009/096265 (Daikin Industries Ltd.).
  • a 500 mL, magnetically stirred, three-necked round bottom flask was equipped with a water condensor, thermocouple and an addition funnel.
  • the flask was cooled in a water bath.
  • C 4 F 9 CH ⁇ CH 2 50 g, 0.2 mol, Alfa Aesar
  • N-bromosuccinimide 40 g, 0.22 mol, Aldrich Chemical Company
  • dichloromethane dichloromethane
  • Chlorosulfonic acid 50 g, 0.43 mol, Alfa Aesar
  • the entire reaction mixture was then poured carefully onto ice, the lower dichloromethane phase separated and washed once more with an equal volume of water and the solvent removed by rotary evaporation yielding 82 g of the chlorosulfite C 4 F 9 CHBrCH 2 OSO 2 Cl in about 65% purity by glc and which contained some C 4 F 9 CHBrCH 2 Br.
  • the chlorosulfite mixture was used without further purification in the next step.
  • the chlorosulfite, benzyltrimethylammonium chloride (0.6 g, 0.003 mol, Alfa Aesar) and water (350 mL) were placed in a 1 L, magnetically stirred, three-necked round bottom flask which was equipped with a water condensor, thermocouple and an addition funnel
  • a solution of potassium iodide (66.3 g, 0.4 mol, EMD Chemicals Inc.) dissolved in water (66 mL) was placed in the separatory funnel and added to the chlorosulfite solution dropwise over about 1.5 hours and the mixture stirred for 16 hours at ambient temperature.
  • the bromohydrin (82 g), diethyl ether solvent (200 mL) and tetrabutylammonium bromide (3.0 g, 0.009 mol, Aldrich) were placed in a 500 mL, magnetically stirred, round bottom flask equipped with a condensor and thermocouple. To this mixture was added all at once a solution of sodium hydroxide (24 g, 0.6 mol) in water (33 g). The mixture was stirred vigorously for four hours. The ether solution was then washed once with saturated sodium chloride solution and once with 5% HCl solution and subsequently dried over magnesium sulfate and the residue fractionally distilled through a concentric tube column with the fraction boiling at 101° C.
  • the product identity was confirmed by GCMS, H-1 and F-19 NMR spectroscopy.
  • a 1L, magnetically stirred, three-necked round bottom flask was equipped with a water condensor, thermocouple and an addition funnel. The flask was cooled in a water bath. Into the flask were placed fuming sulfuric acid (20% SO 3 content) (345 g, 0.86 mol SO 3 , Aldrich) and bromine (34.6 g, 0.216 mol, Aldrich). Into the addition funnel was placed C 6 F 13 CH ⁇ CH 2 (150 g, 0.433 mol, Alfa Aesar) which was added to the acid solution over a two hour period. There was no noticeable exotherm. The reaction mixture was stirred at ambient temperature for 16 hours.
  • the ether layer was washed with 5% by weight aqueous potassium hydroxide solution and the solvent removed by rotary evaporation to give 112 g of a white crystalline solid which was about 72% C 6 F 13 CHBrCH 2 OH, 8% C 6 F 13 CHBrCH 2 Br and 19% (C 6 F 13 CHBrCH 2 O)SO 2 .
  • the bromohydrin mixture was then placed in a 250 mL, magnetically stirred, round bottom flask equipped with a water condensor and thermocouple along with tetrabutylammonium bromide (1.5 g, 0.005 mol, Aldrich) dissolved in 5 g water and a solution of 8.2 g of sodium hydroxide (0.2 mol) dissolved in 15 g water. After one hour of vigorous stirring the reaction mixture was analyzed by glc which showed about a 40% conversion of the bromohydrin to the oxirane. The reaction was stirred for an additional 5 hours.
  • the product structure was confirmed by GCMS, H-1 and F-19 NMR.
  • hexafluoropropene dimer 300 g, 1.0 mol 3M Company
  • methanol 100 g, 3.12 mol, Aldrich
  • TAPEH t-amylperoxy-2-ethylhexanoate
  • the fluorinated alcohol product 2,3,4,5,5,5-hexafluoro-2,4-bis(trifluoromethyl)pentan-1-ol (257 g 0.77 mol) was charged to a 1L round bottom flask equipped with magnetic stirring, cold water condenser, thermocouple (J-Kem controller) and an addition funnel Thionyl chloride (202.25 g, 1.7 mol, Aldrich) was charged via the addition funnel to the fluorinated alcohol at room temperature. Once the addition was complete the temperature was increased to 85 deg. C. until no more offgas was observed. The water condenser was removed and a 1-plate distillation apparatus was put in place. The excess thionyl chloride was then distilled from the reaction mixture.
  • the critical temperature and pressure of the fluorinated oxiranes in Table II were determined from their molecular structures using the method of Wilson-Jasperson given in Reid, Prausnitz and Poling, The Properties of Gases and Liquids, 5 th ed., McGraw-Hill, 2000.
  • the critical densities were calculated using the method of Joback given in Reid, Prausnitz and Poling, The Properties of Gases and Liquids, 5 th edition, McGraw-Hill, 2000.
  • Exemplary fluorinated oxirane thermodynamic properties were derived using the Peng-Robinsion equation of state (Peng, D. Y., and Robinson, D. B., Ind . & Eng. Chem. Fund.
  • thermophysical property data were fitted to a Helmholtz equation of state, with the functional form described in Lemmon E. W., Mclinden M. O., and Wagner W., J. Chem. & Eng. Data, 54: 3141-3180., 2009.
  • FIG. 3 shows temperature-entropy diagrams for Examples 1, 2 and 3 (Ex. 1, Ex. 2, and Ex. 3), along with Comparative Example 1 (Comp. 1). Each plot was generated using the equations of state described above for each fluid. Though all the fluids have saturated vapor lines with a positive slope, Examples 1, 2 and 3 have greater positive slopes, thereby requiring less desuperheating (or recuperation) after expansion, which could be advantageous when sizing recuperator heat exchangers for the Rankine cycle configuration of FIG. 2 .
  • the Rankine cycle was modeled using the calculated thermodynamic properties from the equations of state and the procedure described in Cengel Y. A. and Boles M. A., Thermodynamics: An Engineering Approach, 5 th Edition ; McGraw Hill, 2006.
  • the heat input for the cycle was 1000 kW, with working fluid pump and expander efficiencies taken to be 60% and 80% respectively. Results are shown in Table III. Thermal efficiencies of the exemplary fluorinated oxiranes are greater than that of the comparative example.
  • thermodynamic efficiency in a Rankine cycle can be improved when the boiling point of the working fluid is close to that of the temperature of the heat source. Higher critical temperatures therefore lead to greater thermodynamic efficiencies.
  • Exemplary fluorinated oxiranes can have critical temperatures of greater than 175° C., greater than 200° C., or even greater than 230° C. as shown in Table II.
  • fluorinated oxiranes as organic rankine cycle working fluids and methods of using same according to aspects of the present invention.
  • Embodiment 1 is a process for converting thermal energy into mechanical energy in a Rankine cycle comprising: vaporizing a working fluid with a heat source to form a vaporized working fluid; expanding the vaporized working fluid through a turbine; cooling the vaporized working fluid using a cooling source to form a condensed working fluid; and pumping the condensed working fluid; wherein the working fluid comprises a fluorinated oxirane.
  • Embodiment 2 is a process for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 1, wherein the fluorinated oxirane compound includes up to a maximum of three hydrogen atoms.
  • Embodiment 3 is a process for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 1, wherein the fluorinated oxirane compound contains substantially no hydrogen atoms bonded to carbon atoms.
  • Embodiment 4 is a process for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 1, wherein the fluorinated oxirane has a total of from about 4 to about 9 carbon atoms.
  • Embodiment 5 is a process for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 4, wherein the fluorinated oxirane contains 6 carbon atoms.
  • Embodiment 6 is a process for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 1, wherein the fluorinated oxirane has a critical temperature greater than about 150° C.
  • Embodiment 7 is a process for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 1, wherein the turbine generates electrical energy.
  • Embodiment 8 is a process for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 1, wherein the vaporized working fluid is at a pressure greater than ambient pressure.
  • Embodiment 9 is a process for recovering waste heat comprising: passing a liquid working fluid through a heat exchanger in communication with a process that produces waste heat to produce a vaporized working fluid; removing the vaporized working fluid from the heat exchanger; passing the vaporized working fluid through an expander, wherein the waste heat is converted into mechanical energy; and cooling the vaporized working fluid after it has been passed through the expander, wherein the fluorinated oxirane compound contains substantially no hydrogen atoms bonded to carbon atoms.
  • Embodiment 10 is a process for recovering waste heat comprising according to embodiment 9, wherein the fluorinated oxirane has a total of from about 4 to about 9 carbon atoms.
  • Embodiment 11 is a process for recovering waste heat comprising according to embodiment 10, wherein the fluorinated oxirane contains 6 carbon atoms.
  • Embodiment 12 is a process for recovering waste heat comprising according to embodiment 10, wherein the fluorinated oxirane has a critical temperature of greater than about 150° C.
  • Embodiment 13 is an apparatus for converting thermal energy into mechanical energy in a Rankine cycle comprising: a working fluid; a heat source to vaporize the working fluid and form a vaporized working fluid; a turbine through which the vaporized working fluid is passed thereby converting thermal energy into mechanical energy; a condenser to cool the vaporized working fluid after it is passed through the turbine; and a pump to recirculate the working fluid, wherein the working fluid comprises a fluorinated oxirane.
  • Embodiment 14 is an apparatus for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 13, wherein the working fluid is in a closed loop.
  • Embodiment 15 is an apparatus for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 13, wherein the fluorinated oxirane contains substantially no hydrogen atoms bonded to carbon atoms.
  • Embodiment 16 is an apparatus for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 15, wherein the fluorinated oxirane has a total of from about 4 to about 9 carbon atoms.
  • Embodiment 17 is an apparatus for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 16, wherein the fluorinated oxirane contains 6 carbon atoms.
  • Embodiment 18 is an apparatus for converting thermal energy into mechanical energy in a Rankine cycle according to embodiment 13, wherein the fluorinated oxirane has a critical temperature greater than about 150° C.

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JP2018536439A (ja) * 2016-02-26 2018-12-13 シノケム ランティアン カンパニー リミテッドＳｉｎｏｃｈｅｍ Ｌａｎｔｉａｎ Ｃｏ．， Ｌｔｄ． フッ素含有ケトンを含む組成物
US20210325090A1 (en) * 2018-08-24 2021-10-21 Climasolutions Gmbh Method and device for obtaining useful energy from geothermal heat
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