Classifications

• • 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 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 further relates to the above listed compositions specifically suitable for use in refrigeration or air conditioning apparatus employing a centrifugal compressor; employing a multi-stage, preferably a two-stage, centrifugal compressor or 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 or heat transfer fluid compositions of the present invention comprise 1,1,1,3,3-pentafluorobutane, commonly referred to as HFC-365mfc, in combination with fluoroether.
• the fluoroethers of the present invention comprise compounds containing hydrogen, fluorine, carbon and at least one ether group oxygen.
• the fluoroethers may be represented by the formula R 1 OR 2 , wherein R 1 and R 2 are independently selected from straight or branched chain aliphatic fluorinated hydrocarbon radicals. R 1 and R 2 may be joined to form a cyclic fluoroether ring.
• the fluoroethers may contain from about 2 to 8 carbon atoms.
• Preferred fluoroethers have from 3 to 6 carbon atoms.
• Representative fluoroethers are listed in Table 1.
• Representative refrigerant and heat transfer fluids of the present invention include: 1,1,1 ,3,3-pentafluorobutane and 1 , 1 -difluoro-2-methoxyethane; 1 ,1,1 ,3,3-pentafluorobutane and 1-(2,2-difluoroethoxy)-1 ,1 ,2,2,2- pentafluoroethane; 1 ,1,1 ,3,3-pentafluorobutane and 3-(difluoromethoxy)-1 ,1 ,1 ,2,2- pentafluoropropane; 1 ,1 ,1 ,3,3-pentafluorobutane and 1 ,1 ,2,2-tetrafluoro-3- (trifluorometho ⁇ y)propane; 1,1 ,1 ,3,3-penta
• the refrigerant or heat transfer fluid compositions of the present invention comprising 1,1 ,1,3,3-pentafluorobutane and a fluoroether selected from the group consisting of:
• 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.
• 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
• the azeotropic or near azeotropic 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.
• the 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.
• UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of these dyes and 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, hydrofluoroethers and 1 , 1 , 1 -trifluoroalkanes.
• Hydrocarbon solubilizing agents of the present invention 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.
• Representative 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).
• 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, fetf-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.
• R 1 aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 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 0[CH 2 CH(CH 3 )0] 2 (H or CH 3 ) (dipropylene glycol methyl (or dimethyl) ether), CH 3 O[CH 2 CH(CH 3 )0] 3 (H or CH 3 ) (tripropylene glycol methyl (or dimethyl) ether), C 2 H 5 ⁇ CH 2 CH(CH 3 )0(H or C 2 H 5 ) (propylene glycol ethyl (or diethyl) ether), C 2 H 5 ⁇ [CH 2 CH(CH 3 )0] 2 (H or C 2 H 5 ) (dipropylene glycol ethyl (or diethyl) ether), C 2 H 5 0[CH 2 CH(CH 3 )Oj 3 (H or C
• 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.
• 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"3 .
• 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 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.
• 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.
• 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.
• 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.
• 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 refrigerant or heat transfer fluid compositions described herein comprising 1 ,1 ,1 ,3,3- pentafluorobutane and fluoroether are also suitable for use in refrigeration or air conditioning apparatus employing a single slab/single pass heat exchanger.
• HFC-365mfc/HFOC-254cbE ⁇ (28 .3 °C) 51.4/48.6 14.71 101.42 14.71 101.42 0.0% 20/80 13.78 95.01 12.55 86.53 8.9% 18/82 13.61 93.84 12.29 84.74 9.7% 0/100 10.72 73.91 10.72 73.91 0.0% 78/22 14.13 97.42 12.85 88.60 9.1% 79/21 14.07 97.01 12.66 87.29 10.0% 100/0 9.84 67.84 9.84 67.84 0.0%
• HFC-365mfc/HFOC-254ebE ⁇ (29 .9 °C) 55.4/44.6 14.70 101.35 14.70 101.35 0.0% 20/80 13.52 93.22 12.63 87.08 6.6% 10/90 12.53 86.39 11.71 80.74 6.5% 1/99 11.22 77.36 11.10 76.53 1.1% 0/100 11.05 76.19 11.05 76.19 0.0% 83/17 14.00 96.53 12.65 87.22 9.6% 100/0 10.42 71.84 10.42 71.84 0.0%
• HFC-365mfc/HFOC-356mecE ⁇ (37. 2 °C) 73.5/26.5 14.67 101.15 14.67 101.15 0.0% 90/10 14.35 98.94 14.10 97.22 1.7% 99/1 13.54 93.36 13.45 92.74 0.7% 100/0 13.39 92.32 13.39 92.32 0.0% 40/60 13.79 95.08 12.76 87.98 7.5% 35/65 13.46 92.80 12.11 83.50 10.0% 0/100 8.11 55.92 8.11 55.92 0.0%
• HFC-365mfc/HFOC-365mcE ⁇ (38.8 i °C) 75.2/24.8 14.72 101.49 14.72 101.49 0.0% 90/10 14.54 100.25 14.50 99.97 0.3% 99/1 14.18 97.77 14.17 97.70 0.1% 100/0 14.12 97.35 14.12 97.35 0.0% 40/60 13.94 96.11 13.56 93.49 2.7% 20/80 12.70 87.56 12.05 83.08 5.1% 10/90 11.77 81.15 11.25 77.57 4.4% 1/99 10.70 73.77 10.62 73.22 0.7% 0/100 10.56 72.81 10.56 72.81 0.0%
• HFC-365mfc/HFOC-374mefE ⁇ (39. 1 °C) 86.5/13.5 14.70 101.35 14.70 101.35 0.0% 95/5 14.56 100.39 14.52 100.11 0.3% 99/1 14.34 98.87 14.32 98.73 0.1% 100/0 14.27 98.39 14.27 98.39 0.0% 60/40 14.05 96.87 13.48 92.94 4.1% 45/55 13.20 91.01 11.89 81.98 9.9% 0/100 7.63 52.61 7.63 52.61 0.0%
• HFC-365mfc/HFOC-383peE ⁇ (33.7 °C) 73.6/26.4 14.71 101.42 14.71 101.42 0.0% 92/8 14.19 97.84 12.76 87.98 10.1% 91/9 14.28 98.46 13.01 89.70 8.9% 100/0 11.89 81.98 11.89 81.98 0.0% 45/55 14.07 97.01 12.72 87.70 9.6% 0/100 7.66 52.81 7.66 52.81 0.0%
• Equation 8 m*Hj*(1 OOOJ/kJ) Equation 7
• Hj Difference in enthalpy of the refrigerant from a saturated vapor at the evaporating conditions to saturated condensing conditions, kJ/kg.
• V2*V2 1000*Hj Equation 8
• 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 below 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:
• Example shows that compounds of the present invention have tip speeds within about +/- 20 percent of CFC-113 and would be effective replacements for CFC-113 with minimal compressor design changes. Most preferred compositions have tip speeds within about +/-15 percent of CFC-113.
• 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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• 2005
  • 2005-01-12 CA CA002553431A patent/CA2553431A1/en not_active Abandoned
  • 2005-01-12 RU RU2006129285/04A patent/RU2006129285A/ru not_active Application Discontinuation
  • 2005-01-12 AU AU2005204953A patent/AU2005204953A1/en not_active Abandoned
  • 2005-01-12 WO PCT/US2005/001506 patent/WO2005067556A2/en not_active Ceased
  • 2005-01-12 BR BRPI0506520-8A patent/BRPI0506520A/pt not_active Application Discontinuation
  • 2005-01-12 KR KR1020067016227A patent/KR20060122922A/ko not_active Withdrawn
  • 2005-01-12 JP JP2006549682A patent/JP2007517972A/ja not_active Withdrawn
  • 2005-01-12 EP EP05705841A patent/EP1704198A2/en not_active Withdrawn
  • 2005-01-14 AR ARP050100139A patent/AR049615A1/es unknown
• 2006
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