US20050211949A1 - Detectable refrigerant compositions and uses thereof - Google Patents

Detectable refrigerant compositions and uses thereof Download PDF

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Publication number
US20050211949A1
US20050211949A1 US10/984,530 US98453004A US2005211949A1 US 20050211949 A1 US20050211949 A1 US 20050211949A1 US 98453004 A US98453004 A US 98453004A US 2005211949 A1 US2005211949 A1 US 2005211949A1
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United States
Prior art keywords
hfc
refrigerant
hfe
cbrf
ocf
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US10/984,530
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Donald Bivens
Thomas Leck
Mack McFarland
Barbara Minor
John Steichen
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EIDP Inc
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Individual
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Priority to US10/984,530 priority Critical patent/US20050211949A1/en
Priority to CA2543979A priority patent/CA2543979C/en
Priority to ARP040104179A priority patent/AR048659A1/en
Priority to BRPI0415805-9A priority patent/BRPI0415805A/en
Priority to CN2004800335071A priority patent/CN1882671B/en
Priority to RU2006120449/04A priority patent/RU2006120449A/en
Priority to JP2006539959A priority patent/JP2007512396A/en
Priority to KR1020127001511A priority patent/KR20120025617A/en
Priority to AU2004291895A priority patent/AU2004291895B2/en
Priority to KR1020067009253A priority patent/KR101227269B1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BIVENS, DONALD BERNARD, MCFARLAND, MACK, MINOR, BARBARA HAVILAND, LECK, THOMAS J., STEICHEN, JOHN CARL
Publication of US20050211949A1 publication Critical patent/US20050211949A1/en
Priority to NO20062742A priority patent/NO20062742L/en
Priority to US12/414,022 priority patent/US7779668B2/en
Priority to US12/820,678 priority patent/US20100251803A1/en
Abandoned legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G01M3/00—Investigating fluid-tightness of structures
    • G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
    • G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
    • G01M3/20—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material
    • G01M3/22—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material for pipes, cables or tubes; for pipe joints or seals; for valves; for welds; for containers, e.g. radiators
    • G01M3/226—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material for pipes, cables or tubes; for pipe joints or seals; for valves; for welds; for containers, e.g. radiators for containers, e.g. radiators
    • G01M3/228—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material for pipes, cables or tubes; for pipe joints or seals; for valves; for welds; for containers, e.g. radiators for containers, e.g. radiators for radiators

Definitions

  • the present invention relates to detectable refrigerant compositions having tracers that are useful in vapor compression refrigeration systems.
  • the detectable tracers permit detection of the composition upon leaking.
  • HFC-134a 1,1,1,2-tetrafluoroethane
  • CFC chlorofluorocarbon
  • Refrigeration and air conditioning industry solutions include designing essentially leak-free hydrofluorocarbon-based refrigeration systems, as well as possibly transitioning from higher GWP to lower GWP refrigerants, including certain hydrofluorocarbons (e.g., 1,1-difluoroethane (HFC-152a)) and hydrocarbons as well as compounds such as carbon dioxide, ammonia, and dimethyl ether.
  • hydrofluorocarbons e.g., 1,1-difluoroethane (HFC-152a)
  • hydrocarbons as well as compounds such as carbon dioxide, ammonia, and dimethyl ether.
  • the solution involves carbon dioxide used as a refrigerant
  • detection differentiating from background (atmospheric) carbon dioxide concentration (which may vary, e.g., in a sealed space depending on occupant respiration, efficiency of combustion and emission control apparatus, etc.), and quantifying leaking carbon dioxide refrigerant is a difficult problem to solve with current apparatus and methods.
  • background atmospheric
  • HFC-152a 1,1-difluoroethane
  • detection differentiating from background 1,1-difluoroethane concentration (which may be separately present due to usage of HFC-152a as aerosol propellant and polymer foam blowing agent), and quantifying leaking 1,1-difluoroethane refrigerant is a difficult problem to solve with currently available apparatus and methods.
  • Some current detectors are also less sensitive to hydrofluorocarbons and have more difficulty detecting HFC leaks than compounds containing chlorine.
  • compositions of the present invention meet the industry needs.
  • a detectable refrigerant composition comprising: at least one refrigerant selected from the group consisting of: hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, and an effective amount of a tracer wherein said tracer is different from said refrigerant.
  • a further disclosure is a method for analyzing at least one gas component in the detectable refrigerant composition of claim the present invention, said method comprising: providing an array of at least two chemo/electro-active materials, each chemo/electro-active material exhibiting a different electrical response characteristic upon exposure to the individual gas component in said refrigerant than each other chemo/electro-active material; exposing said array to said refrigerant-composition; determining an electrical response of each chemo/electro-active material upon exposure of said array to said refrigerant; and analyzing the individual gas component from the electrical response values.
  • Another disclosure is a detectable refrigerant composition, wherein said refrigerant is at least one member selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, and an effective amount of a tracer, to produce a detectable refrigerant composition or to improve the detectability of refrigerant composition, wherein said refrigerant composition is in a vessel, exterior of said vessel having a means for detecting said tracer in said refrigerant-tracer combination.
  • the present invention relates in part to a detectable refrigerant composition
  • a detectable refrigerant composition comprising at least one refrigerant, and an effective amount of a tracer wherein said tracer is different from said refrigerant.
  • Refrigerant of the present invention is preferred to have a normal boiling point of about 80° C. or less.
  • the refrigerant of the present invention is at least one refrigerant selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether.
  • Representative hydrofluorocarbon refrigerants include fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134) and 1,1,1,2,2-pentafluoroethane (HFC-125).
  • fluoromethane HFC-41
  • difluoromethane HFC-32
  • trifluoromethane HFC-23
  • fluoroethane HFC-161
  • 1,1-difluoroethane HFC-152a
  • 1,1,1-trifluoroethane HFC-143a
  • 1,1,1,2-tetrafluoroethanethane H
  • hydrochlorofluorocarbon refrigerants include chlorodifluoromethane (HCFC-22), 2-chloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) and 1-chloro-1,1-difluoroethane (HCFC-142b).
  • perfluorocarbon refrigerants include tetrafluoromethane (PFC-14), hexafluoroethane (PFC-116), octafluoropropane (PFC-218) and decafluorobutane (PFC-31-10).
  • Representative hydrofluorocarbon ether refrigerants include CF 3 OCHF 2 (HFE-125), CF 3 OCH 3 (HFE-143a), CF 3 OCH 2 F (HFE-134a), CHF 2 OCHF 2 (HFC-134), cyclo-(CF 2 CF 2 CF 2 O—) (HFE-c216), CF 3 CF 2 OCH 3 (HFE-245cbEbg), CHF 2 OCHFCF 3 (HFE-236eaEbg), CHF 2 CF 2 OCH 3 (HFE-254cb2), C 4 F 9 OCH 3 (HFE-7100) and C 4 F 9 OC 2 H 5 (HFE-7200).
  • Representative perfluorocarbon ether refrigerants include CF 3 OCF 3 , CF 3 OC 2 F 5 , C 2 F 5 OC 2 F 5 and CF 3 OCF(CF 3 )CF(CF 3 )OCF 3 .
  • Representative hydrocarbon refrigerants include methane, ethane, propane, cyclopropane, propylene, n-butane, cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane, cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane and dimethylcyclopropane isomers.
  • Another aspect of the present invention is wherein said refrigerant composition is in a vessel, exterior of said vessel having either a mobile, transportable, hand-held or stationary means for detecting said tracer in said refrigerant-tracer combination.
  • the tracer is at least one member selected from the group consisting of C 1-5 hydrofluorocarbon, C 1-2 hydrochlorofluorocarbon, C 1-4 hydrochlorocarbon, C 2-6 fluoroether, C 1-5 hydrocarbon, C 1-3 hydrocarbon alcohol, C 1-3 hydrocarbon amine, C 1-3 hydrocarbon mercaptan, C 1-4 hydrocarbon ether, C 3-4 hydrocarbon ketone, C 3-4 bromofluoroketone, C 2-4 hydrocarbon aldehyde, 1,1,1-trifluorotoluene, p-chloro-1,1,1-trifluorotoluene, sulfur dioxide, nitrogen oxide, ethanolamine, ammonia, perfluoromethyl iodide, and perfluoroethyl iodide.
  • Representative hydrofluorocarbon tracer compositions of the present invention include fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and 1,1,2,2,3,3,4,4,-octafluorobutane (HFC-338 pcc).
  • fluoromethane HFC-41
  • hydrochlorofluorocarbon tracer compositions of the present invention include chlorodifluoromethane (HCFC-22), 2-chloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) and 1-chloro-1,1-difluoroethane (HCFC-142b).
  • hydrochlorocarbon tracer compositions of the present invention include methyl chloride, methylene chloride, ethyl chloride, trans-1,2-dichloroethylene, 1-propyl chloride and 2-propyl chloride.
  • Representative fluoroether tracer compositions of the present invention include CF 3 OCHF 2 (HFE-125), CF 3 OCH 3 (HFE-143a), CF 3 OCH 2 F (HFE-134a), CHF 2 OCHF 2 (HFC-134), cyclo-(CF 2 CF 2 CF 2 O—) (HFE-c216), CF 3 CF 2 OCH 3 (HFE-245cbEbg), CHF 2 OCHFCF 3 (HFE-236eaEbg); C 4 F 9 OCH 3 (HFE-7100) and C 4 F 9 OC 2 H 5 (HFE-7200).
  • Representative hydrocarbon tracer compositions of the present invention include methane, ethane, propane, cyclopropane, propylene, n-butane, cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane, cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane and dimethylcyclopropane isomers.
  • hydrocarbon alcohol tracer compositions of the present invention methanol, ethanol, 1-propanol and 2-propanol.
  • hydrocarbon amine tracer compositions of the present invention are methyl amine or ethyl amine,
  • a representative hydrocarbon mercaptan tracer composition of the present invention is ethyl mercaptan.
  • hydrocarbon ether tracer compositions of the present invention include dimethyl ether, ethyl methyl ether and diethyl ether.
  • hydrocarbon ketone tracer compositions of the present invention include propanone and butanone,
  • bromofluoroketone tracer compositions of the present invention are selected from the group consisting of CF 3 C(O)CBrFCF 2 CF 3 ; CF 3 C(O)CF 2 CF 2 CBrF 2 ; CBrF 2 C(O)CF(CF 3 ) 2 ; CF 3 C(O)CBr(CF 3 ) 2 ; CBrF 2 CF 2 C(O)CF 2 CF 3 ; CF 3 CBrFC(O)CF 2 CF 3 ; CF 3 CBrFC(O)CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 3 ; CF 3 CF 2 C(O)CF 2 CF 2 CBrF 2 ; CF 3 C(O)CBr(CF 3 )CF 2 CF 3 ; CF 3 C(O)CBrFCF 3 ; CF 3 C(O)CBrFCF 3 ; CF 3 C(O
  • hydrocarbon aldehyde tracer compositions of the present invention are acetaldehyde or propionaldehyde.
  • Additional tracer compositions of the present invention include sulfur dioxide, and a nitrogen oxide selected from nitric oxide or nitrous oxide.
  • effective amount of tracer is meant an amount of at least one tracer component that when combined with refrigerants of the present will result in a detectable refrigerant-tracer mixture.
  • the effective amount of tracer is preferably sufficient to allow for accurate, reproducible, and optionally quantifiable detection of a refrigerant leak.
  • An effective amount of tracer is generally from about 0.001 to about 5 weight percent of tracer, and more preferably from about 0.01 to about 1 weight percent of tracer, based on the total weight of refrigerant and tracer.
  • the tracer of the present invention has a vapor pressure (neat) at 25° C. of generally from about 0.01 to about 500 times, preferably from about 1 to about 300 times, the vapor pressure at 25° C. of said refrigerant (neat).
  • Tracer is preferably selected for a given refrigerant such that it may be accurately and reproducibly detected in the presence of background gases using an appropriate means for detecting said tracer.
  • refrigerant and tracer form a low boiling (maximum pressure) azeotropic or azeotrope-like mixture.
  • a low boiling (maximum pressure) azeotropic or azeotrope-like mixture is preferred in the instance where refrigerant and an effective amount of tracer, under temperature and pressure conditions where a vessel containing said mixture is leaking, allow for accurate detection of a refrigerant leak, via detection of tracer.
  • Preferred refrigerants are the relatively low GWP compounds difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), propane, cyclopropane, propylene, n-butane, 2-methylpropane, carbon dioxide, ammonia, and dimethyl ether.
  • the tracers include ammonia, nitric oxide, 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), 1,1,1,2-tetrafluoroethane (HFC-134a) and dimethyl ether.
  • the refrigerant is 1,1-difluoroethane (HFC-152a)
  • the tracer is preferably selected from at least one of ammonia, nitric oxide or dimethyl ether
  • the means for detecting tracer is preferably a chemo/electro-active array detector, corona discharge detector, heated electrochemical detector or heated diode detector.
  • the present invention also relates to a method of using the refrigerant composition of the present invention to detect its presence wherein said refrigerant is at least one member selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, said method comprising providing a detector having a means for detecting said tracer in the vicinity of said refrigerant composition.
  • the method described herein may be used to detect leaks in a vapor compression refrigeration or air conditioning system or heat pump system.
  • the detection is carried out by a means for detecting said tracer, wherein in the absence of the tracer component would not be detectable, or at best difficult to detect, or unreliably detectable.
  • the means for detecting said tracer is selected from the group consisting of a chemo/electro-active array detector, corona discharge detector, heated diode detector, heated electrochemical detector, photoionization detector, infra red detector, ultrasonic detector and an electron capture detector.
  • the present invention also relates to a method for analyzing at least one gas component in the detectable refrigerant composition of the present invention, said method comprising: providing an array of at least two chemo/electro-active materials, each chemo/electro-active material exhibiting a different electrical response characteristic upon exposure to the individual gas component in said refrigerant than each other chemo/electro-active material; exposing said array to said refrigerant-composition; determining an electrical response of each chemo/electro-active material upon exposure of said array to said refrigerant; and analyzing the individual gas component from the electrical response values.
  • the method described herein optionally may further comprise determining a value for the temperature of said refrigerant composition independently of the determination of the electrical responses of the chemo/electro-active materials; optionally, digitizing the electrical responses and the temperature value, so as to permit calculation of a value from the digitized electrical responses and temperature value, and optionally, analyzing the gas component.
  • Suitable array detectors are described in U.S. patent application Ser. No. 09/977,791, filed Oct. 15, 2001, published U.S. 2002-121,440 and U.S. patent application Ser. No. 10/1117,472, filed Apr. 5, 2002, both incorporated herein by reference.
  • Representative means for detecting tracer include a corona discharge detector as disclosed in U.S. Pat. No. 6,333,632, U.S. Pat. No. 4,609,875 and U.S. Pat. No. 4,488,118, all of which are incorporated herein by reference.
  • Representative means for detecting tracer include a heated diode detector as disclosed in U.S. Pat. No. 5,932,176, herein incorporated by reference.
  • Representative means for detecting tracer include a heated electrochemical sensor as disclosed in U.S. Pat. No. 4,400,260, herein incorporated by reference.
  • Representative means for detecting tracer include a photoionization detector as disclosed in U.S. Pat. No. 5,393,979, herein incorporated by reference.
  • Representative means for detecting tracer include an ultrasonic detector as disclosed in European patent publication EP 0 319 133 A2, herein incorporated by reference.
  • Representative means for detecting tracer include infra red detectors as disclosed in U.S. Pat. No. 5,528,792 and U.S. Pat. No. 6,373,056, both incorporated herein by reference.
  • Representative means for detecting tracer further include electron capture detectors.
  • the present invention involves a method for detecting refrigerant leaking from a vessel.
  • vessel any sealed vessel containing refrigerant, including but not limited to, lab and commercial scale cylinders, railroad and tractor-trailer tank cars, piping, and vapor compression refrigeration and air conditioning (AC) apparatus and associated piping and storage containers that may be found in stationary (e.g., home or commercial AC) or mobile (e.g., automobile, train, boat, airplane) installations.
  • stationary e.g., home or commercial AC
  • mobile e.g., automobile, train, boat, airplane
  • compositions of the present invention were prepared a suitable container. Comparative compositions that did not contain tracer compositions were also prepared. Compositions were then leaked in the vapor phase in the presence of a hand-held Ritchie Yellow Jacket® Accuprobe® heated electrochemical detector. The digital readout scale was 0 (for no detection) to 9 (for maximum detection). Results are shown below. Detector Digital Composition Reading CO 2 0 CO 2 /0.05 wt % trans- 8 1,2-dichloroethylene CO 2 /0.1 wt % HFC- 5 152a The data show that addition of tracer enables the detector to detect a CO2 leak, whereas it was unable to detect the leak without tracer present.
  • compositions of the present invention were prepared in a suitable container. Comparative compositions that did not contain tracer compositions were also prepared. Compositions were then leaked in the vapor phase in the presence of a hand-held TIF Instruments 5650 corona discharge halogen leak detector and the detector reading was recorded based on number of red lights illuminated. Results are shown below. Detector Reading Composition (number of red lights) HFC-134a 2 HFC-134a/0.1 wt % 4 trans-1,2- dichloroethylene CO2 2 CO2/0.1 wt % HFC- 5 152a The data show that addition of tracer improves the ability of the detector to detect an HFC-134a or CO 2 refrigerant leak.
  • compositions of the present were prepared in a suitable container. Comparative compositions that did not contain tracer compositions were also prepared. Compositions were then leaked in the vapor phase in the presence of a hand-held Ritchie Yellow Jacket® Accuprobe® heated electrochemical detector. The digital readout scale was 0 for no detection to 9 for maximum detection. Results are shown below. Detector Digital Composition Reading HFC-152a 1 HFC-152a/0.03 4 wt % trans-1,2- dichloroethylene HFC-152a/0.1 wt % 4 HCFC-22 The data show that addition of tracer improves the ability of the detector to detect an HFC-152a refrigerant leak.
  • compositions of the present were prepared in a suitable container. Comparative compositions that did not contain tracer compositions were also prepared. Compositions were then leaked in the vapor phase in the presence of a hand-held TIF Instruments 5650 corona discharge halogen leak detector and the detector reading was recorded based on number of red lights illuminated. Results are shown below.
  • Detector Reading Composition (number of red lights) HFC-152a 0 HFC-152a/0.03 wt % 6 trans-1,2- dichloroethylene HFC-152a/0.1% 6 HCFC-22 The data show that addition of tracer enables the detector to detect presence of an HFC-152a leak, whereas it was unable to detect the leak without tracer present.

Abstract

Disclosed herein are detectable refrigerant compositions, comprising from about 0.001 to about 5 weight percent tracer compositions, which are useful to identify leaking in a vapor compression refrigeration and/or air conditioning system. The presence of the tracers make the refrigerant compositions detectable by chemo/electro-active array, corona discharge, heated diode, electrochemical, photoionization, infra red, ultrasonic and electron capture detectors.

Description

    CROSS REFERENCE(S) TO RELATED APPLICATION(S)
  • This application claims the priority benefit of U.S. Provisional Application 60/519,790, filed Nov. 13, 2003.
    • FIELD OF THE INVENTION
  • The present invention relates to detectable refrigerant compositions having tracers that are useful in vapor compression refrigeration systems. The detectable tracers permit detection of the composition upon leaking.
    • BACKGROUND OF THE INVENTION
  • Certain highly fluorinated hydrofluorocarbon refrigerants, 1,1,1,2-tetrafluoroethane (HFC-134a) for example, developed in the mid-1980s and commercialized in the early 1990s to replace ozone depleting chlorofluorocarbon (CFC) refrigerants, are coming under increased regulatory pressure due to their relatively high global warming potential (GWP) and purported impact on global warming. Refrigeration and air conditioning industry solutions include designing essentially leak-free hydrofluorocarbon-based refrigeration systems, as well as possibly transitioning from higher GWP to lower GWP refrigerants, including certain hydrofluorocarbons (e.g., 1,1-difluoroethane (HFC-152a)) and hydrocarbons as well as compounds such as carbon dioxide, ammonia, and dimethyl ether. These new solutions are accompanied by concerns related to leak-free designs, as well as concerns around flammability and toxicity of the lower GWP refrigerants. The industry needs to be able to detect and/or differentiate from background gases, and optionally quantify leaking refrigerants as it transitions to lower GWP refrigerants, preferably, doing so accurately, reproducibly and cost effectively.
  • For example, where the solution involves carbon dioxide used as a refrigerant, detection, differentiating from background (atmospheric) carbon dioxide concentration (which may vary, e.g., in a sealed space depending on occupant respiration, efficiency of combustion and emission control apparatus, etc.), and quantifying leaking carbon dioxide refrigerant is a difficult problem to solve with current apparatus and methods.
  • Also, where the solution involves 1,1-difluoroethane (HFC-152a) as the working fluid in a sealed vehicle's air conditioning system, detection, differentiating from background 1,1-difluoroethane concentration (which may be separately present due to usage of HFC-152a as aerosol propellant and polymer foam blowing agent), and quantifying leaking 1,1-difluoroethane refrigerant is a difficult problem to solve with currently available apparatus and methods. Some current detectors are also less sensitive to hydrofluorocarbons and have more difficulty detecting HFC leaks than compounds containing chlorine.
  • The present invention, the use of the compositions of the present invention, and the method for detecting the compositions of the present invention meet the industry needs.
    • BRIEF SUMMARY OF THE INVENTION
  • Disclosed herein is a detectable refrigerant composition comprising: at least one refrigerant selected from the group consisting of: hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, and an effective amount of a tracer wherein said tracer is different from said refrigerant.
  • Also disclosed is a method of using the refrigerant composition of the present invention to detect its presence wherein said refrigerant is at least one member selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, said method comprising providing a detector having a means for detecting said tracer in the vicinity of said refrigerant composition.
  • A further disclosure is a method for analyzing at least one gas component in the detectable refrigerant composition of claim the present invention, said method comprising: providing an array of at least two chemo/electro-active materials, each chemo/electro-active material exhibiting a different electrical response characteristic upon exposure to the individual gas component in said refrigerant than each other chemo/electro-active material; exposing said array to said refrigerant-composition; determining an electrical response of each chemo/electro-active material upon exposure of said array to said refrigerant; and analyzing the individual gas component from the electrical response values.
  • Another disclosure is a detectable refrigerant composition, wherein said refrigerant is at least one member selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, and an effective amount of a tracer, to produce a detectable refrigerant composition or to improve the detectability of refrigerant composition, wherein said refrigerant composition is in a vessel, exterior of said vessel having a means for detecting said tracer in said refrigerant-tracer combination.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention relates in part to a detectable refrigerant composition comprising at least one refrigerant, and an effective amount of a tracer wherein said tracer is different from said refrigerant. Refrigerant of the present invention is preferred to have a normal boiling point of about 80° C. or less.
  • The refrigerant of the present invention is at least one refrigerant selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether.
  • Representative hydrofluorocarbon refrigerants include fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134) and 1,1,1,2,2-pentafluoroethane (HFC-125).
  • Representative hydrochlorofluorocarbon refrigerants include chlorodifluoromethane (HCFC-22), 2-chloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) and 1-chloro-1,1-difluoroethane (HCFC-142b).
  • Representative perfluorocarbon refrigerants include tetrafluoromethane (PFC-14), hexafluoroethane (PFC-116), octafluoropropane (PFC-218) and decafluorobutane (PFC-31-10).
  • Representative hydrofluorocarbon ether refrigerants include CF3OCHF2 (HFE-125), CF3OCH3 (HFE-143a), CF3OCH2F (HFE-134a), CHF2OCHF2 (HFC-134), cyclo-(CF2CF2CF2O—) (HFE-c216), CF3CF2OCH3 (HFE-245cbEbg), CHF2OCHFCF3 (HFE-236eaEbg), CHF2CF2OCH3 (HFE-254cb2), C4F9OCH3 (HFE-7100) and C4F9OC2H5 (HFE-7200).
  • Representative perfluorocarbon ether refrigerants include CF3OCF3, CF3OC2F5, C2F5OC2F5 and CF3OCF(CF3)CF(CF3)OCF3.
  • Representative hydrocarbon refrigerants include methane, ethane, propane, cyclopropane, propylene, n-butane, cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane, cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane and dimethylcyclopropane isomers.
  • Another aspect of the present invention is wherein said refrigerant composition is in a vessel, exterior of said vessel having either a mobile, transportable, hand-held or stationary means for detecting said tracer in said refrigerant-tracer combination.
  • In the composition of the present invention the tracer is at least one member selected from the group consisting of C1-5 hydrofluorocarbon, C1-2 hydrochlorofluorocarbon, C1-4 hydrochlorocarbon, C2-6 fluoroether, C1-5 hydrocarbon, C1-3 hydrocarbon alcohol, C1-3 hydrocarbon amine, C1-3 hydrocarbon mercaptan, C1-4 hydrocarbon ether, C3-4 hydrocarbon ketone, C3-4 bromofluoroketone, C2-4 hydrocarbon aldehyde, 1,1,1-trifluorotoluene, p-chloro-1,1,1-trifluorotoluene, sulfur dioxide, nitrogen oxide, ethanolamine, ammonia, perfluoromethyl iodide, and perfluoroethyl iodide.
  • Representative hydrofluorocarbon tracer compositions of the present invention include fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and 1,1,2,2,3,3,4,4,-octafluorobutane (HFC-338 pcc).
  • Representative hydrochlorofluorocarbon tracer compositions of the present invention include chlorodifluoromethane (HCFC-22), 2-chloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) and 1-chloro-1,1-difluoroethane (HCFC-142b).
  • Representative hydrochlorocarbon tracer compositions of the present invention include methyl chloride, methylene chloride, ethyl chloride, trans-1,2-dichloroethylene, 1-propyl chloride and 2-propyl chloride.
  • Representative fluoroether tracer compositions of the present invention include CF3OCHF2 (HFE-125), CF3OCH3 (HFE-143a), CF3OCH2F (HFE-134a), CHF2OCHF2 (HFC-134), cyclo-(CF2CF2CF2O—) (HFE-c216), CF3CF2OCH3 (HFE-245cbEbg), CHF2OCHFCF3 (HFE-236eaEbg); C4F9OCH3 (HFE-7100) and C4F9OC2H5 (HFE-7200).
  • Representative hydrocarbon tracer compositions of the present invention include methane, ethane, propane, cyclopropane, propylene, n-butane, cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane, cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane and dimethylcyclopropane isomers.
  • Representative hydrocarbon alcohol tracer compositions of the present invention methanol, ethanol, 1-propanol and 2-propanol.
  • Representative hydrocarbon amine tracer compositions of the present invention are methyl amine or ethyl amine,
  • A representative hydrocarbon mercaptan tracer composition of the present invention is ethyl mercaptan.
  • Representative hydrocarbon ether tracer compositions of the present invention include dimethyl ether, ethyl methyl ether and diethyl ether.
  • Representative hydrocarbon ketone tracer compositions of the present invention include propanone and butanone,
  • Representative bromofluoroketone tracer compositions of the present invention are selected from the group consisting of CF3C(O)CBrFCF2CF3; CF3C(O)CF2CF2CBrF2; CBrF2C(O)CF(CF3)2; CF3C(O)CBr(CF3)2; CBrF2CF2C(O)CF2CF3; CF3CBrFC(O)CF2CF3; CF3CBrFC(O)CF2CF2CF3; CF3CF2C(O)CBrFCF2CF3; CF3CF2C(O)CF2CF2CBrF2; CF3C(O)CBr(CF3)CF2CF3; CF3C(O)CF(CF3)CBrFCF3; CF3C(O)CBrFCF2CF2CF2CF3; CF3C(O)CF2CF2CF2CF2CBrF2; CF3CBrFC(O)CF2CF2CF2CF3; CF3CF2C(O)CBrFCF2CF2CF3; CF3CF2C(O)CF2CF2CF2CBrF2; CF3CF2CBrFC(O)CF2CF2CF3; CBrF2CF2C(O)CF(CF3)CF2CF3; CF3CBrFC(O)CF(CF3)CF2CF3; CF3CF2C(O)CBr(CF3)CF2CF3; CF3CF2C(O)CF(CBrF2)CF2CF3; CBrF2CF2CF2C(O)CF(CF3)2; CF3CF2CBrFC(O)CF(CF3)2; CF3CF2CF2C(O)CBr(CF3)2; (CF3)2CBrC(O)CF(CF3)2; CF3CBrFCF2C(O)CF(CF3)2; CHF2CF2C(O)CBr(CF3)2; (CF3)2CHC(O)CBr(CF3)2; CH F2CF2C(O)CBrFCF3; (CF3)2CHC(O)CBrFCF3; (CF3)2CHC(O)CBrF2; CBrF2CF2C(O)CH(CF3)2; CBrF2C(O)CF(CF3)OCF3; CBrF2CF2C(O)CF(CF3)OCF3; CBrF2CF2CF2C(O)CF(CF3)OCF3; CBrF2C(O)CF(CF3)OC2F5; CBrF2CF2C(O)CF(CF3)OC2F5; CBrF2C(O)CF(CF3)OCF2C2F5; CBrF2CF2C(O)CF(CF3)OCF2C2F5; CBrF2C(O)CF(CF3)OCF(CF3)2; CBrF2CF2C(O)CF(CF3)OCF(CF3)2; CF3CBrFC(O)CF(CF3)OCF(CF3)2; CF3CBrFC(O)CF(CF3)OCF3; CF3CBrFC(O)CF(CF3)OC2F5; CF3CBrFC(O)CF(CF3)OCF3; (CF3)2CBrC(O)CF(CF3)OCF3; CF3CBrFC(O)CF(CF3)OC2F5; (CF3)2CBrC(O)CF(CF3)OC2F5; CF3CBrFC(O)CF(CF3)OCF2C2F5; CF3CBrFC(O)CF(CF3)OCF(CF3)2; CBrF2C(O)CF(OCF2CHF2)CF3; CBrF2C(O)CH(OCF2CHF2)CF3; CBrF2C(O)CF(OCH3)CF3; CBrF2C(O)CF(CF2OCH3)CF3; CClF2CFBrC(O)CF2CF3; CBrF2CFClC(O)CF2CF3; CClF2CFBrC(O)CF(CF3)2; CBrF2CFClC(O)CF(CF3)2; CClF2CFBrC(O)CF(CF3)(C2F5); CBrF2CFClC(O)CF(CF3)(C2F5); CClF2C(O)CBr(CF3)2; CClF2CF2C(O)CBr(CF3)2; CF3CClFC(O)CBr(CF3)2; CClF2C(O)CBrFCF3; CClF2CF2(O)CCBrFCF3; CF3CClFC(O)CBrFCF3; CBrF2C(O)CCl(CF3)2; CBrF2CF2C(O)CCl(CF3)2; CBrF2C(O)CClFCF3; and CBrF2CF2C(O)CClFCF3.
  • Representative hydrocarbon aldehyde tracer compositions of the present invention are acetaldehyde or propionaldehyde.
  • Additional tracer compositions of the present invention include sulfur dioxide, and a nitrogen oxide selected from nitric oxide or nitrous oxide.
  • By effective amount of tracer is meant an amount of at least one tracer component that when combined with refrigerants of the present will result in a detectable refrigerant-tracer mixture. The effective amount of tracer is preferably sufficient to allow for accurate, reproducible, and optionally quantifiable detection of a refrigerant leak. An effective amount of tracer is generally from about 0.001 to about 5 weight percent of tracer, and more preferably from about 0.01 to about 1 weight percent of tracer, based on the total weight of refrigerant and tracer.
  • The tracer of the present invention has a vapor pressure (neat) at 25° C. of generally from about 0.01 to about 500 times, preferably from about 1 to about 300 times, the vapor pressure at 25° C. of said refrigerant (neat). Tracer is preferably selected for a given refrigerant such that it may be accurately and reproducibly detected in the presence of background gases using an appropriate means for detecting said tracer.
  • It is acceptable if refrigerant and tracer form a low boiling (maximum pressure) azeotropic or azeotrope-like mixture. Such a mixture is preferred in the instance where refrigerant and an effective amount of tracer, under temperature and pressure conditions where a vessel containing said mixture is leaking, allow for accurate detection of a refrigerant leak, via detection of tracer. Preferred refrigerants are the relatively low GWP compounds difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), propane, cyclopropane, propylene, n-butane, 2-methylpropane, carbon dioxide, ammonia, and dimethyl ether. Preferred amongst the tracers include ammonia, nitric oxide, 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), 1,1,1,2-tetrafluoroethane (HFC-134a) and dimethyl ether. Where the refrigerant is 1,1-difluoroethane (HFC-152a), the tracer is preferably selected from at least one of ammonia, nitric oxide or dimethyl ether, and the means for detecting tracer is preferably a chemo/electro-active array detector, corona discharge detector, heated electrochemical detector or heated diode detector.
  • The present invention also relates to a method of using the refrigerant composition of the present invention to detect its presence wherein said refrigerant is at least one member selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, said method comprising providing a detector having a means for detecting said tracer in the vicinity of said refrigerant composition.
  • The method described herein may be used to detect leaks in a vapor compression refrigeration or air conditioning system or heat pump system. The detection is carried out by a means for detecting said tracer, wherein in the absence of the tracer component would not be detectable, or at best difficult to detect, or unreliably detectable.
  • In the method disclosed herein, the means for detecting said tracer is selected from the group consisting of a chemo/electro-active array detector, corona discharge detector, heated diode detector, heated electrochemical detector, photoionization detector, infra red detector, ultrasonic detector and an electron capture detector.
  • The present invention also relates to a method for analyzing at least one gas component in the detectable refrigerant composition of the present invention, said method comprising: providing an array of at least two chemo/electro-active materials, each chemo/electro-active material exhibiting a different electrical response characteristic upon exposure to the individual gas component in said refrigerant than each other chemo/electro-active material; exposing said array to said refrigerant-composition; determining an electrical response of each chemo/electro-active material upon exposure of said array to said refrigerant; and analyzing the individual gas component from the electrical response values.
  • The method described herein optionally may further comprise determining a value for the temperature of said refrigerant composition independently of the determination of the electrical responses of the chemo/electro-active materials; optionally, digitizing the electrical responses and the temperature value, so as to permit calculation of a value from the digitized electrical responses and temperature value, and optionally, analyzing the gas component.
  • Suitable array detectors are described in U.S. patent application Ser. No. 09/977,791, filed Oct. 15, 2001, published U.S. 2002-121,440 and U.S. patent application Ser. No. 10/1117,472, filed Apr. 5, 2002, both incorporated herein by reference.
  • Representative means for detecting tracer include a corona discharge detector as disclosed in U.S. Pat. No. 6,333,632, U.S. Pat. No. 4,609,875 and U.S. Pat. No. 4,488,118, all of which are incorporated herein by reference.
  • Representative means for detecting tracer include a heated diode detector as disclosed in U.S. Pat. No. 5,932,176, herein incorporated by reference.
  • Representative means for detecting tracer include a heated electrochemical sensor as disclosed in U.S. Pat. No. 4,400,260, herein incorporated by reference.
  • Representative means for detecting tracer include a photoionization detector as disclosed in U.S. Pat. No. 5,393,979, herein incorporated by reference.
  • Representative means for detecting tracer include an ultrasonic detector as disclosed in European patent publication EP 0 319 133 A2, herein incorporated by reference.
  • Representative means for detecting tracer include infra red detectors as disclosed in U.S. Pat. No. 5,528,792 and U.S. Pat. No. 6,373,056, both incorporated herein by reference.
  • Representative means for detecting tracer further include electron capture detectors.
  • The present invention involves a method for detecting refrigerant leaking from a vessel. By vessel is meant any sealed vessel containing refrigerant, including but not limited to, lab and commercial scale cylinders, railroad and tractor-trailer tank cars, piping, and vapor compression refrigeration and air conditioning (AC) apparatus and associated piping and storage containers that may be found in stationary (e.g., home or commercial AC) or mobile (e.g., automobile, train, boat, airplane) installations.
    • EXAMPLES Example 1
  • Compositions of the present invention were prepared a suitable container. Comparative compositions that did not contain tracer compositions were also prepared. Compositions were then leaked in the vapor phase in the presence of a hand-held Ritchie Yellow Jacket® Accuprobe® heated electrochemical detector. The digital readout scale was 0 (for no detection) to 9 (for maximum detection). Results are shown below.
    Detector Digital
    Composition Reading
    CO2 0
    CO2/0.05 wt % trans- 8
    1,2-dichloroethylene
    CO2/0.1 wt % HFC- 5
    152a

    The data show that addition of tracer enables the detector to detect a CO2 leak, whereas it was unable to detect the leak without tracer present.
    • Example 2
  • Compositions of the present invention were prepared in a suitable container. Comparative compositions that did not contain tracer compositions were also prepared. Compositions were then leaked in the vapor phase in the presence of a hand-held TIF Instruments 5650 corona discharge halogen leak detector and the detector reading was recorded based on number of red lights illuminated. Results are shown below.
    Detector Reading
    Composition (number of red lights)
    HFC-134a 2
    HFC-134a/0.1 wt % 4
    trans-1,2-
    dichloroethylene
    CO2 2
    CO2/0.1 wt % HFC- 5
    152a

    The data show that addition of tracer improves the ability of the detector to detect an HFC-134a or CO2 refrigerant leak.
    • Example 3
  • Compositions of the present were prepared in a suitable container. Comparative compositions that did not contain tracer compositions were also prepared. Compositions were then leaked in the vapor phase in the presence of a hand-held Ritchie Yellow Jacket® Accuprobe® heated electrochemical detector. The digital readout scale was 0 for no detection to 9 for maximum detection. Results are shown below.
    Detector Digital
    Composition Reading
    HFC-152a 1
    HFC-152a/0.03 4
    wt % trans-1,2-
    dichloroethylene
    HFC-152a/0.1 wt % 4
    HCFC-22

    The data show that addition of tracer improves the ability of the detector to detect an HFC-152a refrigerant leak.
    • Example 4
  • Compositions of the present were prepared in a suitable container. Comparative compositions that did not contain tracer compositions were also prepared. Compositions were then leaked in the vapor phase in the presence of a hand-held TIF Instruments 5650 corona discharge halogen leak detector and the detector reading was recorded based on number of red lights illuminated. Results are shown below.
    Detector Reading
    Composition (number of red lights)
    HFC-152a 0
    HFC-152a/0.03 wt % 6
    trans-1,2-
    dichloroethylene
    HFC-152a/0.1% 6
    HCFC-22

    The data show that addition of tracer enables the detector to detect presence of an HFC-152a leak, whereas it was unable to detect the leak without tracer present.

Claims (16)

1. A detectable refrigerant composition comprising:
(a) at least one refrigerant selected from the group consisting of:
hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, and
(b) an effective amount of a tracer wherein said tracer is different from said refrigerant.
2. The composition of claim 1 wherein said refrigerant is a hydrofluorocarbon refrigerant selected from fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134) or 1,1,1,2,2-pentafluoroethane (HFC-125),
a hydrochlorofluorocarbon refrigerant selected from chlorodifluoromethane (HCFC-22), 2-chloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) or 1-chloro-1,1-difluoroethane (HCFC-142b),
a perfluorocarbon refrigerant selected from tetrafluoromethane (PFC-14), hexafluoroethane (PFC-116), octafluoropropane (PFC-218) or decafluorobutane (PFC-31-10),
a hydrofluorocarbon ether refrigerant selected from CF3OCHF2 (HFE-125), CF3OCH3 (HFE-143a), CF3OCH2F (HFE-134a), CHF2OCHF2 (HFC-134), cyclo-(CF2CF2CF2O—) (HFE-c216), CF3CF2OCH3 (HFE-245cbEbg) CHF2OCHFCF3 (HFE-236eaEbg), CHF2CF2OCH3 (HFE-254cb2), C4F9OCH3 (HFE-7100); or C4F9OC2H5 (HFE-7200);
a perfluorocarbon ether refrigerant selected from CF3OCF3, CF3OC2F5 or C2F5OC2F5 or CF3OCF(CF3)CF(CF3)OCF3, and
a hydrocarbon refrigerant selected from methane, ethane, propane, cyclopropane, propylene, n-butane, cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane, cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane or dimethylcyclopropane isomers.
3. A method of using the refrigerant composition of claim 1 to detect its presence wherein said refrigerant is at least one member selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, said method comprising providing a detector having a means for detecting said tracer in the vicinity of said refrigerant composition.
4. The method of claim 3, wherein said method is used to detect leaks in a vapor compression refrigeration or air conditioning system, or heat pump system.
5. A method for analyzing at least one gas component in the detectable refrigerant composition of claim 1, said method comprising:
(a) providing an array of at least two chemo/electro-active materials, each chemo/electro-active material exhibiting a different electrical response characteristic upon exposure to the individual gas component in said refrigerant than each other chemo/electro-active material;
(b) exposing said array to said refrigerant-composition;
(c) determining an electrical response of each chemo/electro-active material upon exposure of said array to said refrigerant; and
(d) analyzing the individual gas component from the electrical response values.
6. The method of claim 3, 4 or 5 wherein said refrigerant is a hydrofluorocarbon refrigerant selected from fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134) or 1,1,1,2,2-pentafluoroethane (HFC-125),
a hydrochlorofluorocarbon refrigerant selected from chlorodifluoromethane (HCFC-22), 2-chloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) or 1-chloro-1,1-difluoroethane (HCFC-142b),
a perfluorocarbon refrigerant selected from tetrafluoromethane (PFC-14), hexafluoroethane (PFC-116), octafluoropropane (PFC-218) or decafluorobutane (PFC-31-10),
a hydrofluorocarbon ether refrigerant selected from CF3OCHF2 (HFE-125), CF3OCH3 (HFE-143a), CF3OCH2F (HFE-134a), CHF2OCHF2 (HFC-134), cyclo-(CF2CF2CF2O—) (HFE-c216), CF3CF2OCH3 (HFE-245cbEbg) or CHF2OCHFCF3 (HFE-236eaEbg), CHF2CF2OCH3 (HFE-254cb2), C4F9OCH3 (HFE-7100) or C4F9OC2H5 (HFE-7200);
a perfluorocarbon ether refrigerant selected from CF3OCF3, CF3OC2F5 or C2F5OC2F5 or CF3OCF(CF3)CF(CF3)OCF3;
a hydrocarbon refrigerant selected from methane, ethane, propane, cyclopropane, propylene, n-butane, cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane, cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane or dimethylcyclopropane isomers.
7. The method of claim 5, said method further comprising:
optionally, determining a value for the temperature of said refrigerant composition independently of the determination of the electrical responses of the chemo/electro-active materials; and
optionally, digitizing the electrical responses and the temperature value, so as to permit calculation of a value from the digitized electrical responses and temperature value, and optionally,
analyzing the gas component.
8. A detectable refrigerant composition, wherein said refrigerant is at least one member selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, perfluorocarbon, hydrofluorocarbon ether, perfluorocarbon ether, hydrocarbon, carbon dioxide, ammonia, and dimethyl ether, and an effective amount of a tracer, to produce a detectable refrigerant composition, wherein said refrigerant composition is in a vessel, exterior of said vessel having a means for detecting said tracer in said refrigerant-tracer combination.
9. The composition of claim 8 wherein said:
hydrofluorocarbon refrigerant is fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134) or 1,1,1,2,2-pentafluoroethane (HFC-125),
hydrochlorofluorocarbon refrigerant is chlorodifluoromethane (HCFC-22), 2-chloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) or 1-chloro-1,1-difluoroethane (HCFC-142b),
perfluorocarbon refrigerant is tetrafluoromethane (PFC-14), hexafluoroethane (PFC-116), octafluoropropane (PFC-218) or decafluorobutane (PFC-31-10),
hydrofluorocarbon ether refrigerant is CF3OCHF2 (HFE-125), CF3OCH3 (HFE-143a), CF3OCH2F (HFE-134a), CHF2OCHF2 (HFC-134), cyclo-(CF2CF2CF2O—) (HFE-c216), CF3CF2OCH3 (HFE-245cbEbg) CHF2OCHFCF3 (HFE-236eaEbg), CHF2CF2OCH3 (HFE-254cb2), C4F9OCH3 (HFE-7100); or C4F9OC2H5 (HFE-7200);
perfluorocarbon ether refrigerant is CF3OCF3, CF3OC2F5 or C2F5OC2F5 or CF3OCF(CF3)CF(CF3)OCF3;
hydrocarbon refrigerant is methane, ethane, propane, cyclopropane, propylene, n-butane, cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane, cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane or dimethylcyclopropane isomers.
10. The composition of claim 1 wherein said tracer is at least one member selected from the group consisting of
C1-5 hydrofluorocarbon,
C1-2 hydrochlorofluorocarbon,
C1-4 hydrochlorocarbon,
C2-6 fluoroether,
C1-5 hydrocarbon,
C1-3 hydrocarbon alcohol,
C1-3 hydrocarbon amine,
C1-3 hydrocarbon mercaptan,
C1-4 hydrocarbon ether,
C3-4 hydrocarbon ketone,
C3-4 bromofluoroketone,
C2-4 hydrocarbon aldehyde,
1,1,1-trifluorotoluene
p-chloro-1,1,1-trifluorotoluene
sulfur dioxide,
nitrogen oxide,
ethanolamine,
ammonia,
perfluoromethyl iodide, and
perfluoroethyl iodide.
11. The composition of claim 1 wherein said tracer is at least one of:
a hydrofluorocarbon selected from fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134) 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) or 1,1,2,2,3,3,4,4,-octafluorobutane (HFC-338 pcc),
a hydrochlorofluorocarbon is selected from chlorodifluoromethane (HCFC-22), 2-chloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) or 1-chloro-1,1-difluoroethane (HCFC-142b),
a hydrochlorocarbon is selected from trans-1,2-dichloroethylene, methyl chloride, methylene chloride, ethyl chloride, 1-propyl chloride or 2-propyl chloride;
a fluoroether selected from CF3OCHF2 (HFE-125), CF3OCH3 (HFE-143a), CF3OCH2F (HFE-134a), CHF2OCHF2 (HFC-134), cyclo-(CF2CF2CF2O—) (HFE-c216), CF3CF2OCH3 (HFE-245cbEbg), CHF2OCHFCF3 (HFE-236eaEbg), C4F9OCH3 (HFE-7100), or C4F9OC2H5 (HFE-7200);
a hydrocarbon is selected from methane, ethane, propane, cyclopropane, propylene, n-butane, cyclobutane, 2-methylpropane, methylcyclopropane, n-pentane, cyclopentane, 2-methylbutane, methylcyclobutane, 2,2-dimethylpropane or dimethylcyclopropane isomers,
a hydrocarbon alcohol selected from methanol, ethanol, 1-propanol or 2-propanol,
a hydrocarbon amine is selected from methyl amine or ethyl amine,
a hydrocarbon mercaptan is selected from ethyl mercaptan,
a hydrocarbon ether is selected from dimethyl ether, ethyl methyl ether or diethyl ether,
a hydrocarbon ketone is selected from propanone or butanone,
a bromofluoroketone is selected from CF3C(O)CBrFCF2CF3; CF3C(O)CF2CF2CBrF2; CBrF2C(O)CF(CF3)2; CF3C(O)CBr(CF3)2; CBrF2CF2C(O)CF2CF3; CF3CBrFC(O)CF2CF3; CF3CBrFC(O)CF2CF2CF3; CF3CF2C(O)CBrFCF2CF3; CF3CF2C(O)CF2CF2CBrF2; CF3C(O)CBr(CF3)CF2CF3; CF3C(O)CF(CF3)CBrFCF3; CF3C(O)CBrFCF2CF2CF2CF3; CF3C(O)CF2CF2CF2CF2CBrF2; CF3CBrFC(O)CF2CF2CF2CF3; CF3CF2C(O)CBrFCF2CF2CF3; CF3CF2C(O)CF2CF2CF2CBrF2; CF3CF2CBrFC(O)CF2CF2CF3; CBrF2CF2C(O)CF(CF3)CF2CF3; CF3CBrFC(O)CF(CF3)CF2CF3; CF3CF2C(O)CBr(CF3)CF2CF3; CF3CF2C(O)CF(CBrF2)CF2CF3; CBrF2CF2CF2C(O)CF(CF3)2; CF3CF2CBrFC(O)CF(CF3)2; CF3CF2CF2C(O)CBr(CF3)2; (CF3)2CBrC(O)CF(CF3)2; CF3CBrFCF2C(O)CF(CF3)2; CHF2CF2C(O)CBr(CF3)2; (CF3)2CHC(O)CBr(CF3)2; CHF2CF2C(O)CBrFCF3; (CF3)2CHC(O)CBrFCF3; (CF3)2CHC(O)CBrF2; CBrF2CF2C(O)CH(CF3)2; CBrF2C(O)CF(CF3)OCF3; CBrF2CF2C(O)CF(CF3)OCF3; CBrF2CF2CF2C(O)CF(CF3)OCF3; CBrF2C(O)CF(CF3)OC2F5; CBrF2CF2C(O)CF(CF3)OC2F5; CBrF2C(O)CF(CF3)OCF2C2F5; CBrF2CF2C(O)CF(CF3)OCF2C2F5; CBrF2C(O)CF(CF3)OCF(CF3)2; CBrF2CF2C(O)CF(CF3)OCF(CF3)2; CF3CBrFC(O)CF(CF3)OCF(CF3)2; CF3CBrFC(O)CF(CF3)OCF3; CF3CBrFC(O)CF(CF3)OC2F5; CF3CBrFC(O)CF(CF3)OCF3; (CF3)2CBrC(O)CF(CF3)OCF3; CF3CBrFC(O)CF(CF3)OC2F5; (CF3)2CBrC(O)CF(CF3)OC2F5; CF3CBrFC(O)CF(CF3)OCF2C2F5; CF3CBrFC(O)CF(CF3)OCF(CF3)2; CBrF2C(O)CF(OCF2CHF2)CF3; CBrF2C(O)CH(OCF2CHF2)CF3; CBrF2C(O)CF(OCH3)CF3; CBrF2C(O)CF(CF2OCH3)CF3; CClF2CFBrC(O)CF2CF3; CBrF2CFClC(O)CF2CF3; CClF2CFBrC(O)CF(CF3)2; CBrF2CFClC(O)CF(CF3)2; CClF2CFBrC(O)CF(CF3)(C2F5); CBrF2CFClC(O)CF(CF3)(C2F5); CClF2C(O)CBr(CF3)2; CClF2CF2C(O)CBr(CF3)2; CF3CClFC(O)CBr(CF3)2; CClF2C(O)CBrFCF3; CClF2CF2(O)CCBrFCF3; CF3CClFC(O)CBrFCF3; CBrF2C(O)CCl(CF3)2; CBrF2CF2C(O)CCl(CF3)2; CBrF2C(O)CClFCF3; or CBrF2CF2C(O)CClFCF3;
a hydrocarbon aldehyde is selected from acetaldehyde or propionaldehyde,
sulfur dioxide, or
a nitrogen oxide is selected from nitric oxide or nitrous oxide.
12. The composition of claim 1 wherein the composition comprises from about 0.001 to about 5 weight percent of tracer, based on the total weight of said refrigerant and said tracer.
13. The composition of claim 1 wherein the composition comprises from about 0.01 to about 1 weight percent of tracer, based on the total weight of said refrigerant and said tracer.
14. The composition of claim 1 wherein said tracer has a vapor pressure at 25° C. of from about 0.01 to about 500 times the vapor pressure at 25° C. of said refrigerant.
15. The composition of claim 1 wherein said tracer has a vapor pressure at 25° C. of from about 1 to about 300 times the vapor pressure at 25° C. of said refrigerant.
16. The method of claim 3 wherein said means for detecting said tracer comprises a chemo/electro-active array detector, corona discharge detector, heated diode detector, heated electrochemical detector, photoionization detector, infrared detector, ultrasonic detector or an electron capture detector.
US10/984,530 2003-11-13 2004-11-09 Detectable refrigerant compositions and uses thereof Abandoned US20050211949A1 (en)

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050230657A1 (en) * 2004-02-26 2005-10-20 Leck Thomas J Tracer-containing compositions
US20070267597A1 (en) * 2004-06-04 2007-11-22 Japan Petroleum Exploration Co., Ltd. Refrigerant Mixture of Dimethyl Ether and Carbon Dioxide
US20090045375A1 (en) * 2005-09-27 2009-02-19 Japan Petroleum Exploration Co., Ltd. Refrigerant Composition
US20090092556A1 (en) * 2004-04-16 2009-04-09 Honeywell International Inc. Azeotrope-like compositions of difluoromethane and trifluoroiodomethane
US20090260373A1 (en) * 2005-08-17 2009-10-22 Japan Petroleum Exploration Co., Ltd. Refrigerant Composition
US20090267018A1 (en) * 2005-11-25 2009-10-29 Seijyuro Maiya Refrigerant Composition
US20090278075A1 (en) * 2008-05-07 2009-11-12 E. I. Du Pont De Nemours And Company Compositions comprising 1,1,1,2,3-pentafluoropropane or 2,3,3,3- tetrafluoropropene
US20100090156A1 (en) * 2008-10-10 2010-04-15 E. I. Du Pont De Nemours And Company Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride
WO2010049569A1 (en) * 2008-10-31 2010-05-06 Eads Construcciones Aeronauticas, S.A Methods and systems for analysing sealing in fluid deposits
US20100155652A1 (en) * 2006-03-10 2010-06-24 Honeywell International Inc. Method for generating pollution credits
US20100251803A1 (en) * 2003-11-13 2010-10-07 E. I. Du Pont De Nemours And Company Detectable refrigerant compositions and uses thereof
US20140150492A1 (en) * 2012-12-04 2014-06-05 Conocophillips Company Use of alternate refrigerants in optimized cascade process
TWI455918B (en) * 2006-12-06 2014-10-11 3M Innovative Properties Co Hydrofluoroether compounds and processes for their preparation and use
US8877086B2 (en) 2008-05-07 2014-11-04 E I Du Pont De Nemours And Company Compositions comprising 2,3-dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane or 2,3,3,3-tetrafluoropropene
US9051500B2 (en) 2009-12-22 2015-06-09 E I Du Pont De Nemours And Company Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetra-chloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane
US20150185193A1 (en) * 2010-08-27 2015-07-02 Empire Technology Development Llc Hydrofluorocarbon detection device
DE102014104110A1 (en) * 2014-03-25 2015-10-01 Technische Universität Dresden Working mixture for devices for heat transport and method for operating a refrigerant circuit of the device
US20160137897A1 (en) * 2013-06-21 2016-05-19 Zhejiang Lantian Environmental Protection Hi-Tech Co. Ltd. Mixed refrigerant
JP2018529936A (en) * 2015-07-28 2018-10-11 キャリア コーポレイションＣａｒｒｉｅｒ Ｃｏｒｐｏｒａｔｉｏｎ Refrigerant analyzer and method of using refrigerant analyzer
US10151663B2 (en) 2015-09-15 2018-12-11 Emerson Climate Technologies, Inc. Leak detector sensor systems using tag-sensitized refrigerants
WO2022046826A1 (en) * 2020-08-28 2022-03-03 Kla Corporation Coolant microleak sensor for a vacuum system
US11802700B2 (en) 2017-04-06 2023-10-31 Carrier Corporation Moderate-to-low global warming potential value refrigerant leak detection

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2011213781B2 (en) * 2004-02-26 2014-02-27 E. I. Du Pont De Nemours And Company Tracer-containing compositions
EP3351609B1 (en) 2005-03-04 2020-08-26 The Chemours Company FC, LLC Method for replacing a high gwp refrigerant by compositions comprising hfc-1234yf
US7569170B2 (en) * 2005-03-04 2009-08-04 E.I. Du Pont De Nemours And Company Compositions comprising a fluoroolefin
WO2007053697A2 (en) * 2005-11-01 2007-05-10 E. I. Du Pont De Nemours And Company Compositions comprising fluoroolefins and uses thereof
DE102006053231A1 (en) 2006-11-11 2008-05-15 GM Global Technology Operations, Inc., Detroit Refrigeration system with CO2 as refrigerant
DE102006053230A1 (en) * 2006-11-11 2008-05-15 GM Global Technology Operations, Inc., Detroit Air conditioning for a motor vehicle
GB2454879A (en) * 2007-11-20 2009-05-27 Vulkan Ind Ltd Leakage test for refrigerant carrying pipe.
US8444873B2 (en) 2009-06-12 2013-05-21 Solvay Fluor Gmbh Refrigerant composition
JP5595110B2 (en) * 2010-05-10 2014-09-24 三菱重工業株式会社 Iodine filter leak test method, leak test apparatus, and fluorine-containing reagent
US8530241B2 (en) * 2010-08-27 2013-09-10 Empire Technology Development Llc Hydrofluorocarbon sensing and elimination device and method
JP2014224611A (en) * 2011-09-16 2014-12-04 パナソニック株式会社 Air conditioner
EP2778657B1 (en) * 2013-03-15 2018-12-12 Airbus Defence and Space GmbH Detection device for detecting at least one fault condition
CN104277765B (en) * 2013-07-05 2017-12-08 中化蓝天集团有限公司 A kind of environment-friendly type near azeotropic mixed refrigerant
DE102014200161A1 (en) * 2014-01-09 2015-07-09 Bayerische Motoren Werke Aktiengesellschaft A method of detecting a leak in an air conditioning circuit
CN103900312B (en) * 2014-03-31 2016-06-22 华南理工大学 A kind of method utilizing ultrasound wave to regulate refrigeration system Cycle Component concentration
CN103965836B (en) * 2014-04-02 2017-04-19 浙江大学 Environment-friendly refrigerant for automobile air conditioner and preparation method of refrigerant
US9488629B2 (en) * 2014-04-10 2016-11-08 General Electric Company Method for detecting coolant leaks in generators
JP2015215111A (en) * 2014-05-09 2015-12-03 パナソニックＩｐマネジメント株式会社 Heat pump device
CN104089381B (en) * 2014-06-24 2016-12-21 珠海格力电器股份有限公司 Device, method and the air-conditioner of detection combustible refrigerant leakage
WO2016029005A1 (en) 2014-08-20 2016-02-25 Carrier Corporation Detection of refrigerant contaminants
DE102014112294A1 (en) * 2014-08-27 2016-03-03 Technische Universität Dresden Working mixture for devices for heat transport
US10488065B2 (en) 2014-12-17 2019-11-26 Carrier Corporation Leak detection unit for refrigerant system
US10975216B2 (en) * 2015-02-06 2021-04-13 The Chemours Company Fc, Llc Compositions comprising Z-1,1,1,4,4,4-hexafluoro-2-butene and uses thereof
PL3536760T3 (en) 2015-02-19 2022-04-04 Daikin Industries, Ltd. Composition containing mixture of fluorinated hydrocarbons, and method for producing same
CN108627305B (en) * 2017-03-23 2020-05-29 青岛海尔空调器有限总公司 Air conditioning system and method for detecting air conditioning system tightness
CN108148556A (en) * 2017-12-25 2018-06-12 洛阳名力科技开发有限公司 A kind of air-conditioning refrigerant
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CN109971434A (en) * 2019-05-16 2019-07-05 青岛营上电器有限公司 A kind of low-temperature mixed refrigerant
CN113429936A (en) * 2021-05-25 2021-09-24 宁波奥克斯电气股份有限公司 Refrigerant and refrigerating system
CN114992919B (en) * 2022-06-27 2023-06-06 珠海格力电器股份有限公司 Refrigerating medium, refrigerant and refrigerating system
CN115260019B (en) * 2022-08-04 2024-03-26 三明市海斯福化工有限责任公司 Hyperbranched perfluoro-ketone and application thereof in heat conduction operation

Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901672A (en) * 1973-12-26 1975-08-26 Gen Electric Filter system for halogen gas detector
US4294716A (en) * 1980-05-14 1981-10-13 Saccavino Joseph F Halocarbon and azeotrope refrigerant compositions containing offensive warning component
US4488118A (en) * 1981-09-22 1984-12-11 Control Power Systems Inc. Halogen gas leak detector
US4609875A (en) * 1983-08-26 1986-09-02 Jeffers Edward A Corona discharge freon gas sensor having electrical wind pumping action
US5064560A (en) * 1990-10-11 1991-11-12 E. I. Du Pont De Nemours And Company Ternary azeotropic compositions of 43-10mee (CF3 CHFCHFCH2 CF.sub.
US5264833A (en) * 1991-06-28 1993-11-23 Edward Jeffers Automatic leak detector
US5351037A (en) * 1993-01-22 1994-09-27 J And N Associates, Inc. Refrigerant gas leak detector
US5371467A (en) * 1992-01-24 1994-12-06 Jeffers; Edward A. Gas sensor probe tip with integrating filter
US5393979A (en) * 1993-05-12 1995-02-28 Rae Systems, Inc. Photo-ionization detector for detecting volatile organic gases
US5421192A (en) * 1993-06-25 1995-06-06 Bright Solutions, Inc. Leak detection in heating, ventilating and air conditioning systems using an environmentally safe material
US5932176A (en) * 1998-07-07 1999-08-03 Bacharach, Inc. Halogen gas detector
US6076372A (en) * 1998-12-30 2000-06-20 Praxair Technology, Inc. Variable load refrigeration system particularly for cryogenic temperatures
US6100229A (en) * 1998-01-12 2000-08-08 Alliedsignal Inc. Compositions of 1,1,1,3,3,-pentafluoropropane and chlorinated ethylenes
US6178809B1 (en) * 1996-07-22 2001-01-30 Bright Solutions, Inc. Leak detection in heating, ventilating, refrigeration, and air conditioning systems utilizing adsorptive materials
US6333632B1 (en) * 1999-09-16 2001-12-25 Rae Systems, Inc. Alternating current discharge ionization detector
US6373056B1 (en) * 1997-12-04 2002-04-16 Ion Optics, Inc. Gas detection apparatus using a combined infrared source and high temperature bolometer
US20020066555A1 (en) * 2000-12-05 2002-06-06 Mulder Eric P. Geothermal heat pump cleaning control system and method
US20020121440A1 (en) * 2000-10-16 2002-09-05 Morris Patricia A. Method and apparatus for analyzing mixtures of gases
US20020162343A1 (en) * 2001-05-07 2002-11-07 Herrick Todd W. Evacuation volume for a refrigeration system
US6498046B2 (en) * 2000-10-16 2002-12-24 E. I. Du Pont De Nemours And Company Infrared thermographic screening technique for semiconductor-based chemical sensors
US20030010093A1 (en) * 2001-07-12 2003-01-16 Michael Barjesteh Hand held flexible mount leak detector
US6526674B1 (en) * 1998-12-09 2003-03-04 Domnick Hunter Limited Gas dryer
US20030046975A1 (en) * 2001-09-08 2003-03-13 Manning Systems, Inc. Gas monitoring system and environmentally controlled housing therefore
US20030074903A1 (en) * 2001-10-23 2003-04-24 Shashank Upadhye Timed container warmer and cooler
US20030178597A1 (en) * 2000-09-06 2003-09-25 Seung-Yon Cho Refrigerant mixture for low back pressure condition
US20040006321A1 (en) * 1999-06-29 2004-01-08 Cheng Gordon C. Personal urine management system for human males
US20040005589A1 (en) * 2000-08-29 2004-01-08 Birch Robert George Isomaltulose synthases, polynucleotides encoding them and uses therefor
US20040012628A1 (en) * 2002-07-16 2004-01-22 Kropf Linn James Device interface customization
US20050006387A1 (en) * 2003-07-07 2005-01-13 Jackson Bruce D. Reclosable dispenser

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3572085A (en) * 1968-12-18 1971-03-23 Joseph J Packo Method of detecting leaks in fluid-containing equipment
GB1266832A (en) * 1970-04-27 1972-03-15
DE3120159A1 (en) * 1981-05-21 1982-12-09 Bosch Gmbh Robert ELECTROCHEMICAL PROBE FOR DETERMINING THE OXYGEN CONTENT IN GASES
JPS5813687A (en) 1981-07-17 1983-01-26 Showa Denko Kk Fluid composition for refrigerant
DE319133T1 (en) 1987-11-30 1991-03-21 Kent-Moore Corp., Warren, Mich., Us PORTABLE COOLANT LEAK DETECTOR.
EP0602022B1 (en) * 1990-07-26 1997-05-21 E.I. Du Pont De Nemours And Company Near-azeotropic blends for use as refrigerants
US5725791A (en) * 1991-03-28 1998-03-10 E. I. Du Pont De Nemours And Company Azeotropic and azeotrope-like compositions of 1,1,2,2-tetrafluoroethane
US5156768A (en) * 1991-04-05 1992-10-20 Allied-Signal Inc. Stabilized chlorine-containing refrigeration compositions
DE4116274C2 (en) * 1991-05-17 1998-03-19 Forschungszentrum Fuer Kaeltet Refrigerant
US5762818A (en) * 1992-07-15 1998-06-09 E. I. Du Pont De Nemours And Company Compositions which include 1,1,2,2- tetrafluoroethane and fluoroethane
US6214624B1 (en) * 1992-12-31 2001-04-10 Shell Oil Company Use of perfluorocarbons as tracers in chemical compositions
US5458798A (en) * 1993-02-05 1995-10-17 E. I. Du Pont De Nemours And Company Azeotropic and azeotrope-like compositions of a hydrofluorocarbon and a hydrocarbon
JPH0797585A (en) * 1993-09-30 1995-04-11 Toshiba Corp Freezing apparatus
US5698750A (en) * 1994-03-07 1997-12-16 Commodore Laboratories, Inc. Methods for purifying and recovering contaminated refrigerants with aqueous solutions of bases
US6001273A (en) * 1994-03-11 1999-12-14 Minor; Barbara Haviland Binary azeotropes of difluoromethane and hydrocarbons
US5528792A (en) * 1994-12-12 1996-06-25 Nazemi; Ataollah F. Axially pivotable dual configuration shower brush
JPH08245952A (en) * 1995-03-13 1996-09-24 Daikin Ind Ltd Odorized refrigerant composition
US6070455A (en) * 1995-07-21 2000-06-06 Bright Solutions, Inc. Leak detection additives
US5767390A (en) * 1996-06-14 1998-06-16 Environmental Fuel Systems, Inc. System and method for storage system leak detection
US5969198A (en) * 1997-06-27 1999-10-19 Alliedsignal Inc. Process for the preparation of 1,1,1,3,3-pentafluoropropane
JPH11351711A (en) * 1998-06-11 1999-12-24 Sanyo Electric Co Ltd Freezer with refrigerant recovery device
JP2000105034A (en) * 1998-09-29 2000-04-11 Sanyo Electric Co Ltd Cooling storage
JP3485006B2 (en) * 1998-12-22 2004-01-13 三菱電機株式会社 Refrigeration air conditioner using flammable refrigerant
JP2000192025A (en) * 1998-12-25 2000-07-11 Sanden Corp Vapor compression refrigeration cycle
US6148634A (en) * 1999-04-26 2000-11-21 3M Innovative Properties Company Multistage rapid product refrigeration apparatus and method
JP4599699B2 (en) * 2000-09-26 2010-12-15 ダイキン工業株式会社 Air conditioner
US6526764B1 (en) * 2000-09-27 2003-03-04 Honeywell International Inc. Hydrofluorocarbon refrigerant compositions soluble in lubricating oil
US6849239B2 (en) * 2000-10-16 2005-02-01 E. I. Du Pont De Nemours And Company Method and apparatus for analyzing mixtures of gases
JP2002195707A (en) * 2000-12-22 2002-07-10 Mitsubishi Electric Corp Refrigerating cycle apparatus
US7487662B2 (en) 2001-12-13 2009-02-10 The University Of Wyoming Research Corporation Volatile organic compound sensor system
KR101074956B1 (en) 2002-04-05 2011-10-18 이 아이 듀폰 디 네모아 앤드 캄파니 Apparatus for analyzing mixtures of gases
US20050211949A1 (en) * 2003-11-13 2005-09-29 Bivens Donald B Detectable refrigerant compositions and uses thereof

Patent Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901672A (en) * 1973-12-26 1975-08-26 Gen Electric Filter system for halogen gas detector
US4294716A (en) * 1980-05-14 1981-10-13 Saccavino Joseph F Halocarbon and azeotrope refrigerant compositions containing offensive warning component
US4488118A (en) * 1981-09-22 1984-12-11 Control Power Systems Inc. Halogen gas leak detector
US4609875A (en) * 1983-08-26 1986-09-02 Jeffers Edward A Corona discharge freon gas sensor having electrical wind pumping action
US5064560A (en) * 1990-10-11 1991-11-12 E. I. Du Pont De Nemours And Company Ternary azeotropic compositions of 43-10mee (CF3 CHFCHFCH2 CF.sub.
US5264833A (en) * 1991-06-28 1993-11-23 Edward Jeffers Automatic leak detector
US5371467A (en) * 1992-01-24 1994-12-06 Jeffers; Edward A. Gas sensor probe tip with integrating filter
US5351037A (en) * 1993-01-22 1994-09-27 J And N Associates, Inc. Refrigerant gas leak detector
US5393979A (en) * 1993-05-12 1995-02-28 Rae Systems, Inc. Photo-ionization detector for detecting volatile organic gases
US5421192A (en) * 1993-06-25 1995-06-06 Bright Solutions, Inc. Leak detection in heating, ventilating and air conditioning systems using an environmentally safe material
US6178809B1 (en) * 1996-07-22 2001-01-30 Bright Solutions, Inc. Leak detection in heating, ventilating, refrigeration, and air conditioning systems utilizing adsorptive materials
US6528792B2 (en) * 1997-12-04 2003-03-04 Ion Optics, Inc. Gas detection apparatus using a combined infrared source and high temperature bolometer
US6373056B1 (en) * 1997-12-04 2002-04-16 Ion Optics, Inc. Gas detection apparatus using a combined infrared source and high temperature bolometer
US6100229A (en) * 1998-01-12 2000-08-08 Alliedsignal Inc. Compositions of 1,1,1,3,3,-pentafluoropropane and chlorinated ethylenes
US5932176A (en) * 1998-07-07 1999-08-03 Bacharach, Inc. Halogen gas detector
US6526674B1 (en) * 1998-12-09 2003-03-04 Domnick Hunter Limited Gas dryer
US6076372A (en) * 1998-12-30 2000-06-20 Praxair Technology, Inc. Variable load refrigeration system particularly for cryogenic temperatures
US20040006321A1 (en) * 1999-06-29 2004-01-08 Cheng Gordon C. Personal urine management system for human males
US6333632B1 (en) * 1999-09-16 2001-12-25 Rae Systems, Inc. Alternating current discharge ionization detector
US20040005589A1 (en) * 2000-08-29 2004-01-08 Birch Robert George Isomaltulose synthases, polynucleotides encoding them and uses therefor
US20030178597A1 (en) * 2000-09-06 2003-09-25 Seung-Yon Cho Refrigerant mixture for low back pressure condition
US20020121440A1 (en) * 2000-10-16 2002-09-05 Morris Patricia A. Method and apparatus for analyzing mixtures of gases
US6498046B2 (en) * 2000-10-16 2002-12-24 E. I. Du Pont De Nemours And Company Infrared thermographic screening technique for semiconductor-based chemical sensors
US20020066555A1 (en) * 2000-12-05 2002-06-06 Mulder Eric P. Geothermal heat pump cleaning control system and method
US20020162343A1 (en) * 2001-05-07 2002-11-07 Herrick Todd W. Evacuation volume for a refrigeration system
US6571565B2 (en) * 2001-05-07 2003-06-03 Tecumseh Products Company Evacuation volume for a refrigeration system
US20030010093A1 (en) * 2001-07-12 2003-01-16 Michael Barjesteh Hand held flexible mount leak detector
US20030046975A1 (en) * 2001-09-08 2003-03-13 Manning Systems, Inc. Gas monitoring system and environmentally controlled housing therefore
US20030074903A1 (en) * 2001-10-23 2003-04-24 Shashank Upadhye Timed container warmer and cooler
US20040012628A1 (en) * 2002-07-16 2004-01-22 Kropf Linn James Device interface customization
US20050006387A1 (en) * 2003-07-07 2005-01-13 Jackson Bruce D. Reclosable dispenser

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100251803A1 (en) * 2003-11-13 2010-10-07 E. I. Du Pont De Nemours And Company Detectable refrigerant compositions and uses thereof
US20050230657A1 (en) * 2004-02-26 2005-10-20 Leck Thomas J Tracer-containing compositions
US7641809B2 (en) * 2004-02-26 2010-01-05 E. I. Du Pont De Nemours And Company Tracer-containing compositions
US20100065772A1 (en) * 2004-02-26 2010-03-18 E.I. Du Pont De Nemours And Company Tracer-containing compositions
US8562853B2 (en) * 2004-02-26 2013-10-22 E I Du Pont De Nemours And Company Tracer-containing compositions
US8163689B2 (en) * 2004-04-16 2012-04-24 Honeywell International Inc. Azeotrope-like compositions of difluoromethane and trifluoroiodomethane
US8492327B2 (en) 2004-04-16 2013-07-23 Honeywell International Inc. Azeotrope-like compositions of difluoromethane and trifluoroiodomethane
US20090092556A1 (en) * 2004-04-16 2009-04-09 Honeywell International Inc. Azeotrope-like compositions of difluoromethane and trifluoroiodomethane
US20070267597A1 (en) * 2004-06-04 2007-11-22 Japan Petroleum Exploration Co., Ltd. Refrigerant Mixture of Dimethyl Ether and Carbon Dioxide
US20110017941A1 (en) * 2005-08-17 2011-01-27 Japan Petroleum Exploration Co., Ltd. Refrigerant Composition
US20090260373A1 (en) * 2005-08-17 2009-10-22 Japan Petroleum Exploration Co., Ltd. Refrigerant Composition
US7976721B2 (en) 2005-09-27 2011-07-12 Japan Petroleum Exploration Co., Ltd. Refrigerant composition
US20090045375A1 (en) * 2005-09-27 2009-02-19 Japan Petroleum Exploration Co., Ltd. Refrigerant Composition
US20110017940A1 (en) * 2005-09-27 2011-01-27 Japan Petroleum Exploration Co., Ltd. Refrigerant Composition
US20090267018A1 (en) * 2005-11-25 2009-10-29 Seijyuro Maiya Refrigerant Composition
US20100155652A1 (en) * 2006-03-10 2010-06-24 Honeywell International Inc. Method for generating pollution credits
TWI455918B (en) * 2006-12-06 2014-10-11 3M Innovative Properties Co Hydrofluoroether compounds and processes for their preparation and use
US8692037B2 (en) 2008-05-07 2014-04-08 E I Du Pont De Nemours And Company Compositions comprising 1,1,1,2,3-pentafluoropropane or 2,3,3,3-tetrafluoropropene
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US20140150492A1 (en) * 2012-12-04 2014-06-05 Conocophillips Company Use of alternate refrigerants in optimized cascade process
US20160137897A1 (en) * 2013-06-21 2016-05-19 Zhejiang Lantian Environmental Protection Hi-Tech Co. Ltd. Mixed refrigerant
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US10151663B2 (en) 2015-09-15 2018-12-11 Emerson Climate Technologies, Inc. Leak detector sensor systems using tag-sensitized refrigerants
US11802700B2 (en) 2017-04-06 2023-10-31 Carrier Corporation Moderate-to-low global warming potential value refrigerant leak detection
WO2022046826A1 (en) * 2020-08-28 2022-03-03 Kla Corporation Coolant microleak sensor for a vacuum system

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