WO2005067557A2 - Compositions refrigerantes hydrofluorocarbonees a base de 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane et leur mode d'emploi - Google Patents

Compositions refrigerantes hydrofluorocarbonees a base de 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane et leur mode d'emploi Download PDF

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WO2005067557A2
WO2005067557A2 PCT/US2005/001507 US2005001507W WO2005067557A2 WO 2005067557 A2 WO2005067557 A2 WO 2005067557A2 US 2005001507 W US2005001507 W US 2005001507W WO 2005067557 A2 WO2005067557 A2 WO 2005067557A2
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composition
weight percent
carbon atoms
difluorobutane
refrigeration
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PCT/US2005/001507
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English (en)
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WO2005067557A3 (fr
Inventor
Barbara Haviland Minor
Mario J. Nappa
Allen C. Sievert
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E.I. Dupont De Nemours And Company
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Priority claimed from US11/014,438 external-priority patent/US20050151112A1/en
Application filed by E.I. Dupont De Nemours And Company filed Critical E.I. Dupont De Nemours And Company
Priority to BRPI0506517-8A priority Critical patent/BRPI0506517A/pt
Priority to CA002552625A priority patent/CA2552625A1/fr
Priority to AU2005204954A priority patent/AU2005204954A1/en
Priority to EP05711558A priority patent/EP1723211A2/fr
Priority to JP2006549683A priority patent/JP2007517973A/ja
Publication of WO2005067557A2 publication Critical patent/WO2005067557A2/fr
Publication of WO2005067557A3 publication Critical patent/WO2005067557A3/fr
Priority to NO20063645A priority patent/NO20063645L/no

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/11—Ethers
    • C09K2205/112—Halogenated ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • 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

  • the present invention relates to compositions suitable for use in refrigeration and air conditioning apparatuses, wherein the compositions comprise at least one hydrofluoroether and hydrofluorocarbon. Further, the present invention relates to compositions suitable for use in refrigeration and air-conditioning apparatus employing a centrifugal compressor.
  • the compositions of the present invention may be azeotropic or near azeotropic in nature and are useful in processes for producing refrigeration or heat or as heat transfer fluids.
  • the object of the present invention is to provide novel refrigerant compositions and heat transfer fluids that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.
  • the present invention relates to refrigerant and heat transfer fluid compositions comprising C FgOCH 3 and a hydrofluorocarbon selected from the group consisting of:
  • the present invention further relates to the above listed compositions specifically suitable for use in refrigeration or air conditioning apparatus employing a centrifugal compressor.
  • the present invention further relates to the above listed compositions specifically suitable for use in refrigeration or air conditioning apparatus employing a 2-stage centrifugal compressor.
  • the present invention further relates to the above listed compositions specifically suitable for use in refrigeration or air conditioning apparatus employing a single pass/single slab heat exchanger.
  • the present invention further relates to azeotropic or near azeotropic refrigerant compositions. These compositions are useful in refrigeration or air conditioning apparatus.
  • the compositions are also useful in refrigeration or air conditioning apparatus employing a centrifugal compressor.
  • the present invention further relates to processes for producing refrigeration, heat, and transfer of heat from a heat source to a heat sink using the present inventive compositions.
  • the refrigerant compositions of the present invention comprise hydrofluoroether (HFOC) and hydrofluorocarbon (HFC).
  • the hydrofluoroether of the present invention comprises C 4 F 9 OCH 3 .
  • This hydrofluoroether compound may comprise a mixture of several isomers including CF 3 CF 2 CF 2 CF2OCH3 (1 ,1 ,1 ,2,2,3,3,4,4- nonalfuoro-4-methoxybutane, Cas reg no.
  • the hydrofluorocarbons of the present invention comprise compounds containing hydrogen, fluorine and carbon. These hydrofluorocarbons may be represented by the formula C ⁇ H 2 ⁇ +2-yF y or C ⁇ H 2 ⁇ -yF y . In the formulas, x may equal 3 to 8 and y may equal 1-17.
  • the hydrofluorocarbons may be straight chain, branched chain or cyclic; ⁇ saturated or unsaturated compounds having from about 3 to 8 carbon atoms. Representative hydrofluorocarbons are listed in Table 1.
  • compositions of the present invention have no ozone depletion potential and low global warming potential .
  • lightly fiuorinated hydrofluorocarbons and fluoroethers alone or in mixtures will have global warming potentials lower than many HFC refrigerants currently in use.
  • the compositions of the present invention that are mixtures may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
  • Representative refrigerant or heat transfer fluid compositions of the present invention include:
  • the refrigerant or heat transfer compositions of the present invention may be azeotropic or near azeotropic compositions.
  • An azeotropic composition is a liquid admixture of two or more substances that has a constant boiling point that may be above or below the boiling points of the individual components. As such an azeotropic composition will not fractionate within the refrigeration or air conditioning system during operation, which may reduce efficiency of the system. Additionally, an azeotropic composition will not fractionate upon leakage from the refrigeration or air conditioning system. In the situation where one component of a mixture is flammable, fractionation during leakage could lead to a flammable composition either within the system or outside of the system.
  • a near azeotropic composition is a substantially constant boiling, liquid admixture of two or more substances that behaves essentially as a single substance.
  • One way to characterize a near azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change.
  • Another way to characterize a near azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same.
  • a composition is near azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent.
  • the azeotropic refrigerant compositions of the present invention are listed in Table 2. TABLE 2
  • compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a thermal stabilizer such as nitromethane.
  • compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent.
  • UV dye is a useful component for detecting leaks of the refrigerant composition by permitting one observe the fluorescence of the dye in in the refrigerant or heat transfer fluid composition at a leak point in or the vicinity of refrigeration or air-conditioning apparatus. One may obserce the fluorosence of the dye under an ultra-violet light. Solubilizing agents may be needed due to poor solubility of such UV dyes in some refrigerants.
  • ultra-violet is meant a UV fluorescent composition that absorbs light in the ultra-violet or "near" ultra-violet region of the electromagnetic spectrum.
  • UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or combinations thereof.
  • Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1 ,1-trifluoroalkanes.
  • Hydrocarbon solubilizing agents of the present invention r comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only hydrogen with no other functional groups.
  • hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, and n-pentane. It should be noted that if the refrigerant is a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.
  • Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).
  • Polyoxyalkylene glycol ether solubilizing agents of the present invention are represented by the formula R 1 [(OR 2 ) x OR 3 ] y , wherein: x is an integer from 1-3; y is an integer from 1-4; R 1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R 1 and R 3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units.
  • x is preferably 1- 2; y is preferably 1 ; R 1 and R 3 are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R 2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units.
  • the R 1 and R 3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic.
  • R 1 and R 3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, ferf-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, and cyclohexyl.
  • R 1 and R 3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom.
  • the R 2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR 2 ) x - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals.
  • the oxyalkylene radical comprising R 2 in one polyoxyalkylene glycol ether solubilizing agent molecule may be the same, or one molecule may contain different R 2 oxyalkylene groups.
  • the present polyoxyalkylene glycol ether solubilizing agents preferably comprise at least one oxypropylene radical.
  • R 1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites
  • the radical may be linear, branched or cyclic.
  • Representative R 1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical.
  • R 1 aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritoi, 1,2,3- trihydroxycyclohexane and 1 ,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals.
  • Representative polyoxyalkylene glycol ether solubilizing agents include but are not limited to: CH 3 OCH 2 CH(CH 3 )O(H or CH 3 ) (propylene glycol methyl (or dimethyl) ether), CH 3 O[CH 2 CH(CH3)O] 2 (H or CH 3 ) (dipropylene glycol methyl (or dimethyl) ether), CH 3 O[CH 2 CH(CH3)O] 3 (H or CH 3 ) (tripropylene glycol methyl (or dimethyl) ether),
  • Amide solubilizing agents of the present invention comprise those represented by the formulae R 1 CONR 2 R 3 and cyclo-[R 4 CON(R 5 )-], wherein R 1 , R 2 , R 3 and R 5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units.
  • R 1 , R 2 , R 3 and R 5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 , R 2 , R 3 and R 5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen.
  • R 1 , R 2 , R 3 and R 5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, terf-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
  • a preferred embodiment of amide solubilizing agents are those wherein R 4 in the aforementioned formula cyclo-[R 4 CON(R 5 )-] may be represented by the hydrocarbylene radical (CR 6 R 7 ) n , in other words, the formula: cyclo- [(CR 6 R 7 ) n CON(R 5 )-] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to 5; R 5 is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R 6 and R 7 are independently selected (for each n) by the rules previously offered defining R 1"3 .
  • R 6 and R 7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms.
  • R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms.
  • amide solubilizing agents include but are not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5- methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1 -butyl-5-methylpiperid-2-one, 1 -pentyl-5-methylpiperid-2-one, 1 - hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1- pentylpiperid-2-one, 1 ,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1- butyl-pyrrolidin-2-one, 1 ,5-dimethylpiperid-2-one, 1-decyl-5- methylpyrrolidin-2-one, 1 -dodecyl pyrrolid-2-one, N,N-dibutylformamide and N,
  • Ketone solubilizing agents of the present invention comprise ketones represented by the formula R 1 COR 2 , wherein R 1 and R 2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units.
  • R 1 and R 2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms.
  • the molecular weight of said ketones is preferably from about 100 to 200 atomic mass units.
  • R 1 and R 2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone.
  • R 1 and R 2 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 and R 2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • heteroatom-substituted hydrocarbon radicals that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 1 and R 2 , and the presence of any such non- hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations.
  • R 1 and R 2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R 1 COR 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te/ ⁇ -butyl, pentyl, isopentyl, neopentyl, fe/f-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu rational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • ketone solubilizing agents include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3- heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4- decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.
  • Nitrile solubilizing agents of the present invention comprise nitriles represented by the formula R 1 CN, wherein R 1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units.
  • R 1 in said nitrile solubilizing agents is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms.
  • the molecular weight of said nitrile solubilizing agents is preferably from about 120 to about 140 atomic mass units.
  • R 1 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy).
  • R 1 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.
  • R 1 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R 1 CN include pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
  • nitrile solubilizing agents include but are not limited to: 1- cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1- cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1- cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.
  • Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RCI X , wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units.
  • the molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units.
  • R aliphatic and alicyclic hydrocarbon radicals in the general formula RCI X include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, terf-butyl, pentyl, isopentyl, neopentyl, terf-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
  • chlorocarbon solubilizing agents include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1- chlorohexane, 1 ,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1- chlorononane, 1-chlorodecane, and 1 ,1 ,1-trichlorodecane.
  • Ester solubilizing agents of the present invention comprise esters represented by the general formula R 1 CO 2 R 2 , wherein R 1 and R 2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals.
  • esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units.
  • Representative esters include but are not limited to: (CH 3 ) 2 CHCH 2 ⁇ OC(CH 2 ) 2-4 ⁇ COCH 2 CH(CH 3 ) 2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (a commercial C 7 alkyl acetate), "Exxate 800" (a commercial C 8 alkyl acetate), dibutyl phthalate, and tert-butyl acetate.
  • Lactone solubilizing agents of the present invention comprise lactones represented by structures [
  • lactones contain the functional group -CO 2 - in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], Ri through R 8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though Re may be connected forming a ring with another Ri through Rs.
  • the lactone may have an exocyclic alkylidene group as in structure [C], wherein Ri through R 6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though Re may be connected forming a ring with another Ri through R 6 .
  • the lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units.
  • lactone solubilizing agents include but are not limited to the compounds listed in Table 4. TABLE 4 I
  • Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 40°C.
  • gamma- undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl- 5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40°C.
  • Lactone solubilizing agents may be available commercially or prepared by methods as described in U. S. provisional patent application 10/910,495 (inventors being P. J. Fagan and C. J. Brandenburg), filed August 3, 2004, incorporated herein by reference.
  • Aryl ether solubilizing agents of the present invention further comprise aryl ethers represented by the formula R 1 OR 2 , wherein: R 1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units.
  • R 1 aryl radicals in the general formula R 1 OR 2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl.
  • R 2 aliphatic hydrocarbon radicals in the general formula R 1 OR 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and ferf-butyl.
  • Representative aromatic ether solubilizing agents include but are not limited to: methyl phenyl ether (anisole), 1 ,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.
  • Fluoroether solubilizing agents of the present invention comprise those represented by the general formula R 1 OCF 2 CF 2 H, wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals.
  • Representative fluoroether solubilizing agents include but are not limited to: C 8 H ⁇ 7 OCF 2 CF 2 H and C 6 H 13 OCF 2 CF 2 H. It should be noted that if the refrigerant is a fluoroether, then the solubilizing agent may not be the same fluoroether.
  • 1 ,1 ,1-Trifluoroalkane solubilizing agents of the present invention comprise 1 ,1 ,1-trifluoroalkanes represented by the general formula CF3R 1 , wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals.
  • Representative 1 ,1 ,1- trifluoroalkane solubilizing agents include but are not limited to: 1,1 ,1- trifluorohexane and 1 ,1 ,1-trifluorododecane.
  • Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether.
  • the present compositions comprising refrigerant and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent. Solubility of these UV fluorescent dyes in refrigerants may be poor.
  • US patent no. RE 36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration or air conditioning apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air conditioning apparatus are described in the literature. Ideally, the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration or air conditioning apparatus. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system directly in the refrigerant.
  • compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent in the refrigerant.
  • the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent in the refrigerant, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
  • commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance performance and system stability.
  • These additives are known within the field of refrigeration, and include, but are not limited to, anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, and foam control agents,.
  • these additives are present in the inventive compositions in small amounts relative to the overall composition. Typically concentrations of from less than about 0.1 weight percent to as much as about 3 weight percent of each additive are used. These additives are selected on the basis of the individual system requirements.
  • additives include members of the triaryl phosphate family of EP (extreme pressure) lubricity additives, such as butylated triphenyl phosphates (BTPP), or other alkylated triaryl phosphate esters, e.g. Syn- 0-Ad 8478 from Akzo Chemicals, tricrecyl phosphates and related compounds. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1375 and other members of this family of chemicals may be used in compositions of the present invention.
  • Other antiwear additives include natural product oils and asymmetrical polyhydroxyl lubrication additives, such as Synergol TMS (International Lubricants).
  • stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed.
  • Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.
  • Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance.
  • Typical examples of odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel or sold by Intercontinental Fragrance, as well as d- limonene and pinene.
  • Such odor masking agents may be used at concentrations of from about 0.001 % to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent.
  • the present invention further relates to a method of using the refrigerant or heat transfer fluid compositions further comprising ultraviolet fluorescent dye, and optionally, solubilizing agent, in refrigeration or air conditioning apparatus.
  • the method comprises introducing the refrigerant or heat transfer fluid composition into the refrigeration or air conditioning apparatus. This may be done by dissolving the UV fluorescent dye in the refrigerant or heat transfer fluid composition in the presence of a solubilizing agent and introducing the combination into the apparatus.
  • this may be done by combining solubilizing agent and and UV fluorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid.
  • the resulting composition is may be used in the refrigeration or air conditioning apparatus.
  • the present invention further relates to a method of using the refrigerant or heat transfer fluid compositions comprising ultraviolet fluorescent dye to detect leaks.
  • the presence of the dye in the compositions allows for detection of leaking refrigerant in the refrigeration or air conditioning apparatus. Leak detection helps to address, resolve or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps one contain chemicals used in the operation of the apparatus.
  • the method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye as described herein, and optionally, a solubilizing agent as described herein, to refrigeration and air conditioning apparatus and employing a suitable means for detecting the UV fluorescent dye-containing refrigerant.
  • suitable means for detecting the dye include, but are not limited to, ultra-violet lamp, often referred to as a "black light” or "blue light”. Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose.
  • the present invention further relates to a method of using the compositions of the present invention for producing refrigeration or heat, wherein the method comprises producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition; or producing heat by condensing the said composition in the vicinity of the body to be heated and thereafter evaporating said composition.
  • Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device.
  • a vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows.
  • Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling.
  • the low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature.
  • the higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment.
  • the refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.
  • compressors There are various types of compressors that may be used in refrigeration applications.
  • Compressors can be generally classified as 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), depending on how the mechanical elements act on the fluid to be compressed. Either positive displacement or dynamic compressors may be used in the present inventive process.
  • a centrifugal type compressor is the preferred equipment for the present refrigerant compositions.
  • a centrifugal compressor uses rotating elements to accelerate the refrigerant radially, and typically includes an impeller and diffuser housed in a casing.
  • Centrifugal compressors usually take fluid in at an impeller eye, or central inlet of a circulating impeller, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but most of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure.
  • Each impeller-diffuser set is a stage of the compressor.
  • Centrifugal compressors are built with from 1 to 12 or more stages, depending on the final pressure desired and the volume of refrigerant to be handled.
  • the pressure ratio, or compression ratio, of a compressor is the ratio of absolute discharge pressure to the absolute inlet pressure.
  • Pressure delivered by a centrifugal compressor is practically constant over a relatively wide range of capacities.
  • Positive displacement compressors draw vapor into a chamber, and the chamber decreases in volume to compress the vapor. After being compressed , the vapor is forced from the chamber by further decreasing the volume of the chamber to zero or nearly zero.
  • a positive displacement compressor can build up a pressure, which is limited only by the volumetric efficiency and the strength of the parts to withstand the pressure.
  • a centrifugal compressor depends entirely on the centrifugal force of the high-speed impeller to compress the vapor passing through the impeller. There is no positive displacement, but rather what is called dynamic-compression. The pressure a centrifugal compressor can develop depends on the tip speed of the impeller.
  • Tip speed is the speed of the impeller measured at its tip and is related to the diameter of the impeller and its revolutions per minute.
  • the capacity of the centrifugal compressor is determined by the size of the passages through the impeller. This makes the size of the compressor more dependent on the pressure required than the capacity. Because of its high-speed operation, a centrifugal compressor is fundamentally a high volume, low-pressure machine.
  • a centrifugal compressor works best with a low-pressure refrigerant, such as trichlorofluoromethane (CFC-11) or 1 ,2,2-trichlorotrifluoroethane (CFC- 113). Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm).
  • Small turbine centrifugal compressors are designed for high speeds, from about 40,000 to about 70,000 (rpm), and have small impeller sizes, typically less than 0.15 meters.
  • a multi-stage impeller may be used in a centrifugal compressor to improve compressor efficiency thus requiring less power in use.
  • the discharge of the first stage impeller goes to the suction intake of a second impeller.
  • Both impellers may operate by use of a single shaft (or axle).
  • Each stage can build up a compression ratio of about 4 to 1 ; that is, the absolute discharge pressure can be four times the absolute suction pressure.
  • An example of a two- stage centrifugal compressor system, in this case for automotive applications, is described in US 5,065,990, incorporated herein by reference.
  • the compositions of the present invention suitable for use in a refrigeration or air conditioning apparatus employing a centrifugal compressor comprise at least one of: C 4 FgOCH 3 and 1 ,1 ,2,2,3-pentafluoropropane;
  • compositions of the present invention are also suitable for use in two- stage centrifugal compressor apparatus and suitable for use in refrigeration or air conditioning apparatus employing a single slab/single pass heat exchanger:
  • the compositions of the present invention may be used in stationary air-conditioning, heat pumps or mobile air-conditioning and refrigeration systems.
  • Stationary air conditioning and heat pump applications include window, ductless, ducted, packaged terminal, chillers and commercial, 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 transport refrigeration systems.
  • the compositions of the present invention may additionally be used in air-conditioning, heating and refrigeration systems that employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers.
  • Conventional microchannel heat exchangers may not be ideal for the low pressure refrigerant compositions of the present invention.
  • the low operating pressure and density result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design may be modified.
  • a single slab/single pass heat exchanger arrangement may be used. Therefore, a preferred heat exchanger for the low pressure refrigerants of the present invention is a single slab/single pass heat exchanger.
  • the compositions of the present invention are particularly useful in small turbine centrifugal compressors, which can be used in auto and window air conditioning or heat pump as well as other applications. These high efficiency miniature centrifugal compressors may be driven by an electric motor and can therefore be operated independently of the engine speed.
  • a constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for efficiency improvements especially at higher engine speeds as compared to a conventional R-134a automobile air-conditioning system.
  • the present invention relates to a process for producing refrigeration comprising evaporating the compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions.
  • the present invention further relates to a process for producing heat comprising condensing the compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions.
  • the present invention further relates to a process for transfer of heat from a heat source to a heat sink wherein the compositions of the present invention serve as heat transfer fluids.
  • Said process for heat transfer comprises transferring the compositions of the present invention from a heat source to a heat sink.
  • Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or convection.
  • a heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense).
  • a heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat.
  • Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air conditioning, or the passenger compartment of an automobile requiring air conditioning.
  • a heat sink may be defined as any space, location, object or body capable of absorbing heat.
  • a vapor compression refrigeration system is one example of such a heat sink.
  • a vessel is charged with an initial composition at a specified temperature, and the initial vapor pressure of the composition is measured.
  • the composition is allowed to leak from the vessel, while the temperature is held constant, until 50 weight percent of the initial composition is removed, at which time the vapor pressure of the composition remaining in the vessel is measured.
  • Table 4 The results are summarized in Table 4 below.
  • compositions of the present invention are azeotropic or near-azeotrope. Where an azeotrope is present, the data show compositions of the present invention have an initial vapor pressure higher than the vapor pressure of either pure component.
  • EXAMPLE 2 Tip Speed to Develop Pressure Tip speed can be estimated by making some fundamental relationships for refrigeration equipment that use centrifugal compressors.
  • T m*(v2*r2-v ⁇ *r ⁇ ) Equation 1
  • T torque
  • N*m m mass rate of flow
  • kg/s V2 tangential velocity of refrigerant leaving impeller (tip speed)
  • m/s r2 radius of exit impeller
  • tangential velocity of refrigerant entering impeller
  • m/s r-j radius of inlet of impeller
  • T m*V2*r2 Equation 2
  • Equation 8 is based on some fundamental assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip speeds of refrigerants.
  • Table 6 shows theoretical tip speeds that are calculated for 1 ,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the present invention. The conditions assumed for this comparison are:
  • Table 7 shows the performance of various refrigerants compared to CFC-113. The data are based on the following conditions. Evaporator temperature 40.0°F (4.4°C) Condenser temperature 110.0°F (43.3°C) Subcool temperature 10.0°F (5.5°C) Return gas temperature 75.0°F (23.8°C) Compressor efficiency is 70%
  • compositions of the present invention have evaporator and condenser pressures similar to CFC-113. Some compositions also have higher capacity or energy efficiency (COP) than CFC-113.
  • COP energy efficiency

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Abstract

L'invention porte sur des compositions réfrigérantes ou des compositions à fluide caloporteur comprenant en outre du fluoroether, 1,1,1,2,2,3,3,4,4-nonafluoro-4-méthoxybutane et des hydrofluorocarbones, qui sont d'utilité dans les appareils de réfrigération ou de climatisation ou en tant que fluides caloporteurs. Lesdites compositions sont également utiles dans les compresseurs centrifuges qui font appel à des compresseurs à double étage ou à des échangeurs thermiques mono-étage et/ou à passage unique.
PCT/US2005/001507 2004-01-14 2005-01-12 Compositions refrigerantes hydrofluorocarbonees a base de 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane et leur mode d'emploi WO2005067557A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BRPI0506517-8A BRPI0506517A (pt) 2004-01-14 2005-01-12 composições refrigerantes, composições azeotrópicas, processo para a produção de refrigeração e de calor e métodos de utilização da composição
CA002552625A CA2552625A1 (fr) 2004-01-14 2005-01-12 Compositions refrigerantes hydrofluorocarbonees a base de 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane et leur mode d'emploi
AU2005204954A AU2005204954A1 (en) 2004-01-14 2005-01-12 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane refrigerant compositions comprising hydrofluorocarbon, and uses thereof
EP05711558A EP1723211A2 (fr) 2004-01-14 2005-01-12 Compositions refrigerantes hydrofluorocarbonees a base de 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane et leur mode d'emploi
JP2006549683A JP2007517973A (ja) 2004-01-14 2005-01-12 ヒドロフルオロカーボンを含む１，１，１，２，２，３，３，４，４−ノナフルオロ−４−メトキシブタン冷媒組成物、およびその使用
NO20063645A NO20063645L (no) 2004-01-14 2006-08-11 1,1,2,2,3,3,4,4,4-nonametoksybutan kjolemedium-sammensetninger som omfatter hydrofluorkarbon og anvendelser derav

Applications Claiming Priority (4)

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US53681904P 2004-01-14 2004-01-14
US60/536,819 2004-01-14
US11/014,438 US20050151112A1 (en) 2004-01-14 2004-12-16 1,1,1,2,2,3,3,4,4-Nonafluoro-4-methoxybutane refrigerant compositions comprising hydrofluorocarbon, and uses thereof
US11/014,438 2004-12-16

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JP2010185048A (ja) * 2009-02-13 2010-08-26 Daikin Ind Ltd 熱伝達装置および熱伝達方法、ならびにそれに用いる熱伝達流体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5580906A (en) * 1995-05-19 1996-12-03 E. I. Du Pont De Nemours And Company Ternary azeotropic compositions
US5672293A (en) * 1994-03-11 1997-09-30 E. I. Du Pont De Nemours And Company Hydrofluorocarbon compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5672293A (en) * 1994-03-11 1997-09-30 E. I. Du Pont De Nemours And Company Hydrofluorocarbon compositions
US5580906A (en) * 1995-05-19 1996-12-03 E. I. Du Pont De Nemours And Company Ternary azeotropic compositions

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CA2552625A1 (fr) 2005-07-28
BRPI0506517A (pt) 2007-02-27
WO2005067557A3 (fr) 2005-12-01
EP1723211A2 (fr) 2006-11-22
KR20060122923A (ko) 2006-11-30
AR048146A1 (es) 2006-04-05
NO20063645L (no) 2006-10-04
RU2006129275A (ru) 2008-02-20

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