Detectable refrigerant compositions and uses thereof

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.

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 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), CHF2CF2OCH3 (HFE-254cb2), C 4 F 9 OCH 3  (HFE-7100); or C4F9OC 2 H 5  (HFE-7200);    a perfluorocarbon ether refrigerant selected from CF 3 OCF 3 , CF 3 OC 2 F 5  or C 2 F 5 OC 2 F 5  or CF 3 OCF(CF 3 )CF(CF 3 )OCF 3 , 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 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) or CHF 2 OCHFCF 3  (HFE-236eaEbg), CHF2CF2OCH3 (HFE-254cb2), C 4 F 9 OCH 3  (HFE-7100) or C4F9OC 2 H 5  (HFE-7200);    a perfluorocarbon ether refrigerant selected from CF 3 OCF 3 , CF 3 OC 2 F 5  or C 2 F 5 OC 2 F 5  or CF 3 OCF(CF 3 )CF(CF 3 )OCF 3 ;    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 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), CHF2CF2OCH3 (HFE-254cb2), C 4 F 9 OCH 3  (HFE-7100); or C 4 F 9 OC 2 H 5  (HFE-7200);    perfluorocarbon ether refrigerant is CF 3 OCF 3 , CF 3 OC 2 F 5  or C 2 F 5 OC 2 F 5  or CF 3 OCF(CF 3 )CF(CF 3 )OCF 3 ;    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 
 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.    
     
     
         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 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), or C 4 F 9 OC 2 H 5  (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 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)CF(CF 3 )CBrFCF 3 ; CF 3 C(O)CBrFCF 2 CF 2 CF 2 CF 3 ; CF 3 C(O)CF 2 CF 2 CF 2 CF 2 CBrF 2 ; CF 3 CBrFC(O)CF 2 CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CF 2 CF 2 CF 2 CBrF 2 ; CF 3 CF 2 CBrFC(O)CF 2 CF 2 CF 3 ; CBrF 2 CF 2 C(O)CF(CF 3 )CF 2 CF 3 ; CF 3 CBrFC(O)CF(CF 3 )CF 2 CF 3 ; CF 3 CF 2 C(O)CBr(CF 3 )CF 2 CF 3 ; CF 3 CF 2 C(O)CF(CBrF 2 )CF 2 CF 3 ; CBrF 2 CF 2 CF 2 C(O)CF(CF 3 ) 2 ; CF 3 CF 2 CBrFC(O)CF(CF 3 ) 2 ; CF 3 CF 2 CF 2 C(O)CBr(CF 3 ) 2 ; (CF 3 ) 2 CBrC(O)CF(CF 3 ) 2 ; CF 3 CBrFCF 2 C(O)CF(CF 3 ) 2 ; CHF 2 CF 2 C(O)CBr(CF 3 ) 2 ; (CF 3 ) 2 CHC(O)CBr(CF 3 ) 2 ; CHF 2 CF 2 C(O)CBrFCF 3 ; (CF 3 ) 2 CHC(O)CBrFCF 3 ; (CF 3 ) 2 CHC(O)CBrF 2 ; CBrF 2 CF 2 C(O)CH(CF 3 ) 2 ; CBrF 2 C(O)CF(CF 3 )OCF 3 ; CBrF 2 CF 2 C(O)CF(CF 3 )OCF 3 ; CBrF 2 CF 2 CF 2 C(O)CF(CF 3 )OCF 3 ; CBrF 2 C(O)CF(CF 3 )OC 2 F 5 ; CBrF 2 CF 2 C(O)CF(CF 3 )OC 2 F 5 ; CBrF 2 C(O)CF(CF 3 )OCF 2 C 2 F 5 ; CBrF 2 CF 2 C(O)CF(CF 3 )OCF 2 C 2 F 5 ; CBrF 2 C(O)CF(CF 3 )OCF(CF 3 ) 2 ; CBrF 2 CF 2 C(O)CF(CF 3 )OCF(CF 3 ) 2 ; CF 3 CBrFC(O)CF(CF 3 )OCF(CF 3 ) 2 ; CF 3 CBrFC(O)CF(CF 3 )OCF 3 ; CF 3 CBrFC(O)CF(CF 3 )OC 2 F 5 ; CF 3 CBrFC(O)CF(CF 3 )OCF 3 ; (CF 3 ) 2 CBrC(O)CF(CF 3 )OCF 3 ; CF 3 CBrFC(O)CF(CF 3 )OC 2 F 5 ; (CF 3 ) 2 CBrC(O)CF(CF 3 )OC 2 F 5 ; CF 3 CBrFC(O)CF(CF 3 )OCF 2 C 2 F 5 ; CF 3 CBrFC(O)CF(CF 3 )OCF(CF 3 ) 2 ; CBrF 2 C(O)CF(OCF 2 CHF 2 )CF 3 ; CBrF 2 C(O)CH(OCF 2 CHF 2 )CF 3 ; CBrF 2 C(O)CF(OCH 3 )CF 3 ; CBrF 2 C(O)CF(CF 2 OCH 3 )CF 3 ; CClF 2 CFBrC(O)CF 2 CF 3 ; CBrF 2 CFClC(O)CF 2 CF 3 ; CClF 2 CFBrC(O)CF(CF 3 ) 2 ; CBrF 2 CFClC(O)CF(CF 3 ) 2 ; CClF 2 CFBrC(O)CF(CF 3 )(C 2 F 5 ); CBrF 2 CFClC(O)CF(CF 3 )(C 2 F 5 ); CClF 2 C(O)CBr(CF 3 ) 2 ; CClF 2 CF 2 C(O)CBr(CF 3 ) 2 ; CF 3 CClFC(O)CBr(CF 3 ) 2 ; CClF 2 C(O)CBrFCF 3 ; CClF 2 CF 2 (O)CCBrFCF 3 ; CF 3 CClFC(O)CBrFCF 3 ; CBrF 2 C(O)CCl(CF 3 ) 2 ; CBrF 2 CF 2 C(O)CCl(CF 3 ) 2 ; CBrF 2 C(O)CClFCF 3 ; or CBrF 2 CF 2 C(O)CClFCF 3 ;    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.