AU2011213781B2 - Tracer-containing compositions - Google Patents

Abstract

The present invention relates to the field of compression refrigeration and air conditioning. Specifically, the present invention relates to a tracer-containing composition comprising: a 5 refrigeration/heating fluid comprising a fluorocarbon refrigerant selected from an unsaturated or other functionalized fluorocarbon refrigerant; and at least one tracer compound(s). Additionally, the present invention relates to a method for detecting tracer compounds to identify gases after leaving the custody of the original manufacturer or prior source, and the 10 verification of authenticity. The aforementioned method provides for the detection of tracer compounds, which in turn, may alert the refrigeration industry to when dilution, adulteration, contamination or other unauthorized practices have occurred with refrigeration products.

Description

P/00/011 Regulation 3.2 AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION FOR A DIVISIONAL PATENT ORIGINAL Name of Applicant: E. I. DU PONT DE NEMOURS AND COMPANY Actual Inventor(s): Thomas J. LECK, Stuart C. BRICKER and Allen C. SIEVERT Address for Service: Houlihan 2 , Level 1, 70 Doncaster Road, Balwyn North, Victoria 3104, Australia Invention Title: TRACER-CONTAINING COMPOSITIONS The following statement is a full description of this invention, including the best method of performing it known to the Applicant: - 1 - TITLE OF INVENTION TRACER-CONTAINING COMPOSITIONS CROSS REFERENCE(S) TO RELATED APPLICATION(S) 5 The present application is a divisional application from Australian patent application number 2005217616. The entire disclosures of Australian patent application number 2005217616 and its corresponding International application, PCT/US2005/005595, are incorporated herein by 10 reference. This application claims the priority benefit of U.S. Provisional Patent Application 60/548,085, filed February 26, 2004, which is hereby incorporated herein by reference. BACKGROUND OF THE INVENTION 15 1. Field of the Invention. The present invention relates to the field of compression refrigeration and air conditioning. Specifically, the present invention relates to a composition comprising refrigerant and tracer compound(s). 20 Additionally, the present invention relates to a method for the identification of refrigerant gases after leaving the custody of the original manufacturer and the verification of refrigerant authenticity. The aforementioned method provides for the detection of tracer compounds, which in turn, may alert the refrigeration industry to the occurrence of dilution, adulteration, 25 contamination or other unauthorized modification of refrigeration products. 2. Description of Related Art. Environmental concerns have led the refrigeration industry to high levels of consciousness around the responsible use of refrigerants. The 30 refrigeration industry, as well as the society at large, benefits when everyone who manufactures, distributes, uses refrigerants, or services refrigeration and air conditioning equipment uses all applicable measures to keep equipment operating at the highest achievable level of energy efficiency. This reduces the amount of energy consumed by the 35 equipment. Higher than necessary energy consumption, as well as leakage of refrigerants, can contribute to unnecessary pollution of our -2atmosphere and waste of existing resources. This unnecessary waste also comes at a cost to the consumer for replacement of leaked refrigerant. In response to environmental concerns, manufacturers of 5 refrigerants have developed new refrigerant products that allow higher levels of energy efficiency when used in properly designed equipment. The new generation HFC refrigerants have less impact on the environment than older generation chlorinated refrigerants in the event that they inadvertently leak into the atmosphere. The HFC refrigerants 10 have zero ozone depletion potential, and in general have less tropospheric climate change potential than the refrigerants they replace. In addition, industry practices now mandate the elimination of leaks from most types of operating equipment, and require that refrigerant gas be recovered from equipment when that equipment is taken out of service or is opened to 15 allow service work to be performed. While the new high efficiency refrigerants and new responsible use policies are benefiting the environment, the benefit is not as great as it could be. In some instances, the recovered refrigerant gases are not properly reclaimed or recycled. The recovered refrigerant may be re 20 installed back into other pieces of equipment without being properly reclaimed and cleaned to remove any harmful or energy efficiency reducing impurities which may have been introduced in handling or as a result of poorly performing or damaged equipment. The equipment into which this refrigerant is introduced will then not operate at peak efficiency, 25 and will consume more energy than necessary. In addition, used refrigerant can be blended with virgin refrigerant, which generally results in a non-standard refrigerant gas composition. Similarly, used refrigerant can be re-packaged and sold as virgin refrigerant, without certification of purity and quality. These practices may 30 result in increased atmospheric pollution and increased energy use, and places expensive refrigeration hardware at risk of being damaged. In addition to negative environmental and equipment impact , there are economic losses to the refrigerant manufacturers and distributors. Refrigerant manufacturers make significant investments into the 35 development of the quality new refrigerants products. Refrigerant distributors similarly have invested in equipment for the proper protection of refrigerants from contamination during packaging, storage, and -3distribution of refrigerants. When refrigerants are diluted or blended with recovered refrigerants, and sold as virgin refrigerant, manufacturers and distributors do not receive the benefit of their investment. For the foregoing reasons, there has been a need for the ability to 5 positively determine when a refrigerant composition is diluted or altered in any way, in a manner that does not compromise performance or the product properties to any measurable extent. The present invention addresses this need by providing a highly secure way to label virgin refrigerant product. 10 BRIEF SUMMARY OF THE INVENTION The present invention is directed to a tracer-containing composition, said composition comprising: a refrigeration/heating fluid comprising a fluorocarbon refrigerant selected from an unsaturated fluorocarbon 15 refrigerant or a functionalized fluorocarbon refrigerant; and at least one tracer compound, said tracer compound being analytically detectable and selected from the group consisting of hydrofluorocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes and ketones, 20 nitrous oxide and combinations thereof with the proviso that said refrigerant/heating fluid is different from said tracer compound. Additionally, the present invention relates to a composition as stated above wherein at least one of said tracer compound is present as a single pre-determined isomer. 25 The unsaturated fluorocarbon refrigerant or functionalized fluorocarbon refrigerant of the composition is preferably an unsaturated fluorocarbon refrigerant. The tracer compound is preferably a perfluorocarbon. The refrigeration/heating fluid of the present invention preferably 30 comprises a mixture of said unsaturated fluorocarbon refrigerant or functionalized fluorocarbon refrigerant with at least one other refrigerant selected from the group consisting of hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, fluorocarbon ethers, hydrocarbons, carbon dioxide and ammonia. 35 The at least one other refrigerant included in the refrigeration/heating fluid of the present invention may be any common refrigeration/heating fluid used in the refrigeration industry. Such other refrigerant may be hydrofluorocarbons (HFCs), hydrochlorofluorocarbons -4- (HCFCs), perfluorocarbons (PFCs), fluorocarbon ethers (HFEs), hydrocarbons, carbon dioxide (CO 2 ), ammonia (NH 3 ), or mixtures thereof. The fluorinated refrigeration/heating fluids, HFCs, HCFCs, HFEs and PFCs may be referred to as fluorocarbon refrigerants. 5 The at least one fluorocarbon refrigerant of the present invention may have 1-8 carbon atoms, contain at least one fluorine atom, optionally contain chlorine and oxygen atoms, and have a normal boiling point of from -90 0 C to 80 0 C. The said fluorocarbon refrigerant may be represented by the general formula CF2w+2-yHxClyO, wherein w is 1-6, x is 0-9, y is 0 10 3, and z is 0-2, and wherein 2w+2-x-y is a positive integer. Preferred of the said fluorocarbon refrigerant/s of the present invention are those in which w is 1-6, x is 1-5, y is 0-1, and z is 0-1. The present invention is particularly useful with hydrofluorocarbon and hydrochlorofluorocarbon-based refrigerants as the said fluorocarbon 15 refrigerant, which include but which are not limited to: CHCIF 2 (HCFC-22),

CHF

3 (HFC-23), CH 2

F

2 (HFC-32), CH 3 F (HFC-41), CF 3

CF

3 (FC-116),

CHCIFCF

3 (HCFC-124), CHF 2

CF

3 (HFC-125), CH 2

CICF

3 (HCFC-133a),

CHF

2

CHF

2 (HFC-134), CH 2

FCF

3 (HFC-134a), CCIF 2

CH

3 (HCFC-142b),

CHF

2

CH

2 F (HFC-143), CF 3

CH

3 (HFC-143a), CHF 2

CH

3 (HFC-152a), 20 CHF 2

CF

2

CF

3 (HFC-227ca), CF 3

CFHCF

3 (HFC-227ea), CHF 2

CF

2

CHF

2 (HFC-236ca), CH 2

FCF

2

CF

3 (HFC-236cb), CHF 2

CHFCF

3 (HFC-236ea),

CF

3

CH

2

CF

3 (HFC-236fa), CH 2

FCF

2

CHF

2 (HFC-245ca), CH 3

CF

2

CF

3

(HFC

245cb), CHF 2

CHFCHF

2 (HFC-245ea), CH 2

FCHFCF

3 (HFC-245eb),

CHF

2

CH

2

CF

3 (HFC-245fa), CH 2

FCF

2

CH

2 F (HFC-254ca), CH 3

CF

2

CHF

2 25 (HFC-254cb), CH 2

FCHFCHF

2 (HFC-254ea), CH 3

CHFCF

3 (HFC-254eb),

CHF

2

CH

2

CHF

2 (HFC-254fa), CH 2

FCH

2

CF

3 (HFC-254fb), CH 3

CF

2

CH

3 (HFC-272ca), CH 3

CHFCH

2 F (HFC-272ea), CH 2

FCH

2

CH

2 F (HFC-272fa),

CH

3

CH

2

CF

2 H (HFC-272fb), CH 3

CHFCH

3 (HFC-281ea), CH 3

CH

2

CH

2 F (HFC-281fa), CHF 2

CF

2

CF

2

CF

2 H (HFC-338pcc), CF 3

CH

2

CF

2

CH

3

(HFC

30 365mfc), CF 3

CF

2

CF

2 0CHFCF 3 (Freon@ El), CF 3

CHFCHFCF

2

CF

3

(HFC

43-10mee), C 4

F

9 0CH 3 , and C 4

F

9

OC

2

H

5 . The present invention further relates to a method of using the present inventive tracer-containing compositions, said method comprising combining said tracer compound with said unsaturated fluorocarbon 35 refrigerant or functionalized fluorocarbon refrigerant to make a tracer containing refrigerant composition, and detecting the presence of said tracer compound in said tracer-containing refrigerant composition. Said method may comprise -5detecting the occurrence of dilution, adulteration or contamination of said composition. Also, the present invention relates to use of the tracer-containing composition in a method for producing refrigeration comprising 5 evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition. The present invention additionally relates to a method of using the tracer-containing refrigerant composition for producing heat comprising condensing said composition in the vicinity of a body to be heated and thereafter evaporating said 10 composition. DETAILED DESCRIPTION OF THE INVENTION Applicants specifically incorporate the entire contents of all cited references in this disclosure. Further, when an amount, concentration, or 15 other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such ranges are separately disclosed. Where 20 a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the present invention be limited to the specific values recited when defining a range. The unsaturated or other functionalized fluorocarbon refrigerant of 25 the present invention is preferably represented by the general formula CwF2w-xHxOz, wherein w is 3 to 8 and x is 0-15 and z is 0 to 2, and wherein 2w-x is a positive integer. Such unsaturated compounds and other functionalized fluorocarbons include CF 3

(CF

2

)

3

CH=CH

2 (perfluorobutylethylene, PFBE), CF 3

CF

2

C(O)CF(CF

3

)

2 30 (perfluoroethylisopropylketone, PEIK), and CF 3

C(O)CF(CF

3

)

2 (perfluoromethylisopropylketone, PMIK). Fluorocarbon refrigerants are commercial products available from a number of sources such as E. I. du Pont de Nemours & Co., Fluoroproducts, Wilmington, DE, 19898, USA, or are available from 35 custom chemical synthesis companies such as PCR Inc., P.O. Box 1466, Gainesville, Florida, 32602, USA, and additionally by synthetic processes disclosed in publications such as Chemistry of Organic Fluorine -6- Compounds 2 nd (revised edition), edited by Milos Hudlicky, published by Ellis Harwood-Prentice Hall Publishers, 1992. The unsaturated compounds and other functionalized fluorocarbon refrigerants of the present invention may optionally further comprise up to 5 10 weight percent of dimethyl ether, or at least one C 3 to C 5 hydrocarbon, e.g., propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, cyclopentane and neopentane (2,2-dimethylpropane). The tracer compound of the present invention is selected from the group consisting of hydrofluorocarbon, deuterated hydrocarbon or 10 hydrofluorocarbon, perfluorocarbon, fluoroether, brominated compound, iodated compound, alcohol, aldehydes and ketone, nitrous oxide (N 2 0) and combinations thereof. Suitable tracer compound candidates are listed in Table 1. TABLE 1 15 Compound Name Chemical Structure CAS registry no. Deuterated hydrocarbon or HFC compounds Ethane-d6 CD3-CD3 1632-99-1 Propane-d8 CD3-CD2-CD3 2875-94-7 HFC-32-d2 CD 2

F

2 594-24-1 HFC-134a-d2 CD 2

F-CF

3 496024-52-3 HFC-143a-d3 CD 3

-CF

3 558-59-8 HFC-125-d CDF 2

-CF

3 87458-21-7 HFC-227ea-d CF 3

-CDF-CF

3 119117-94-1 HFC-227ca-d CF 3

-CF

2

-CDF

2 662-02-2 HFC-134-d2 CDF 2

-CDF

2 274689-13-3 HFC-236fa-d2 CF 3

-CD

2

-CF

3 72256-43-0 HFC-245cb-d3 CF 3

-CF

2

-CD

3 38878-30-7 HFC-263fb-d2* CF 3

-CD

2

-CH

3 7370-99-2 HFC-263fb-d3 CF 2

-CH

2

-CD

3 7371-43-9 Fluoroethers HFOC-125E CHF 2 -0-CF 3 3822-68-2 HFOC-1 34aE CH 2

F-O-CF

3 2261-01-0 HFOC-143aE CH 3

-O-CF

3 421-14-7 HFOC-227eaE CF 3

-O-CHF-CF

3 2356-62-9 -7- HFOC-236faE CF 3

-O-CH

2

-CF

3 20193-67-3 HFOC-245faEpy or CHF 2 -0-CH 2

CF

3 1885-48-9 HFOC-245faEap (or CHF 2

CH

2 -0-CF 3 ) (or 84011-15-4) HFOC-245cbEpy or CH 3

-O-CF

2

-CF

3 22410-44-2 HFOC-245cbasp (or CH 3

-CF

2 -0-CF 3 ) (or HFE-42-1 1 mcc (or Freon@ CF 3

-CF

2

-CF

2 -0-CHF-CF 3 3330-15-2 El) Freon® E2 CF 3

-CF

2

-CF

2 -0-CF(CF3) CF 2 -0- 3330-14-1

CHF-CF

3 Hydrofluorocarbons HFC-23 CHF 3 75-46-7 HFC-161 CH 3

-CH

2 F 353-36-3 HFC-152a CH 3

-CHF

2 75-37-6 HFC-134 CHF 2

-CHF

2 359-35-3 HFC-227ea CF 3

-CHF-CF

3 431-89-0 HFC-227ca CHF 2

-CF

2

-CF

3 2252-84-8 HFC-236cb CH 2

F-CF

2

-CF

3 677-56-5 HFC-236ea CF 3

-CHF-CHF

2 431-63-0 HFC-236fa CF 3

-CH

2

-CF

3 690-39-1 HFC-245cb CF 3

-CF

2

-CH

3 1814-88-6 HFC-245fa CHF 2

-CH

2

-CF

3 460-73-1 HFC-254cb CHF 2

-CF

2

-CH

3 40723-63-5 HFC-254eb CF 3

-CHF-CH

3 421-48-7 HFC-263fb CF 3

-CH

2

-CH

3 421-07-8 HFC-272ca CH 3

-CF

2

-CH

3 420-45-1 HFC-281ea CH 3

-CHF-CH

3 420-26-8 HFC-281fa CH 2

F-CH

2

-CH

3 460-13-9 HFC-329p CHF 2

-CF

2

CF

2

CF

3 375-17-7 HFC-329mmz (CH 3 ) 2

-CH-CF

3 382-24-1 HFC-338mf CF 3

-CH

2

-CF

2

-CF

3 2924-29-0 HFC-338pcc CHF 2

-CF

2

-CF

2

-CHF

2 377-36-6 HFC-347s CH 3

-CF

2

-CF

2

-CF

3 662-00-0 HFC-43-10mee CF 3

-CHF-CHF-CF

2

-CF

3 138495-42-8 Perfluorocarbons PFC-116 CF 3

-CF

3 76-16-4 PFC-C216 Cyclo(-CF 2

-CF

2

-CF

2 -) 931-91-9 -8- PFC-218 CF 3

CF

2

CF

3 76-19-7 PFC-C318 Cyclo(-CF 2

-CF

2

-CF

2

-CF

2 -) 115-25-3 PFC-31-1 Omc CF 3

-CF

2

-CF

2

-CF

3 355-25-9 PFC-31-1 Omy (CF 3 ) 2

CF-CF

3 354-92-7 PFC-C51-12mycm Cyclo(-CF(CF 3

)-CF

2

-CF(CF

3

)-CF

2 -) 2994-71-0 PFC-C51-12mym, trans Cyclo(-CF 2

-CF(CF

3

)-CF(CF

3

)-CF

2 -) 1583-98-8 PFC-C51-12mym, cis Cyclo(-CF 2

-CF(CF

3

)-CF(CF

3

)-CF

2 -) 1583-97-7 Perfluoromethylcyclo- Cyclo(-CF 2

-CF

2

(CF

3 ) -CF 2

-CF

2 - 1805-22-7 pentane

CF

2 -) Perfluoromethylcyclo- Cyclo(CF 2

-CF

2

(CF

3

)-CF

2

-CF

2

-CF

2 - 355-02-2 hexane

CF

2 -) Perfluorodimethylcyclo- Cyclo(-CF 2

-CF

2

(CF

3

)-CF

2

-CF

2

(CF

3 ) ortho - 306-89-9 hexane (ortho, meta, or -CF 2 -) meta - 335-27-3 para) para - 374-77-6 Perfluoroethylcyclohexane Cyclo(-CF 2

-CF

2

(CF

2

CF

3

)-CF

2

-CF

2 - 335-21-7

CF

2

-CF

2 -) Perfluoroindan C 9 FOo (see structure below) 1736-47-6 F F F F F Perfluorotrimethylcyclo- Cyclo(-CF 2

(CF

3

)-CF

2

(CF

3

)-CF

2 - 374-76-5 hexane (all possible CF 2

(CF

3

)-CF

2 -) isomers) Perfluoroisopropylcyclo- Cyclo(-CF 2

CF

2

(CF

2

(CF

3 ) 2

)CF

2

CF

2 423-02-9 hexane

CF

2

CF

2 -) Perfluorodecalin (cis or ClOF 18 (see structure below) 306-94-5 trans, trans shown) F F F F F F F F F F -9- Perfluoromethyldecalin C, F 20 (see structure below) 306-92-3 (cis or trans and all

CF

3 F F additional possible F F F FF isomers) F F Brominated Compounds Bromomethane CH 3 Br 74-83-9 Bromofluoromethane CH 2 FBr 373-52-4 Bromodifluoromethane CHF 2 Br 1511-62-2 Dibromofluoromethane CHFBr 2 1868-53-7 Tribromomethane CHBr 3 75-25-2 Bromoethane CH 3

-CH

2 Br 74-96-4 Bromoethene CH 2 =CHBr 593-60-2 1,2-dibromoethane CH 2 Br-CH 2 Br 106-93-4 1-bromo-1,2- CFBr=CHF 358-99-6 difluoroethene lodated compounds lodotrifluoromethane CF 3 1 2314-97-8 Difluoroiodomethane CHF 2 1 1493-03-4 Fluoroiodomethane CH 2 FI 373-53-5 1,1,2-trifluoro-1- CF 2 1-CH 2 F 20705-05-9 iodoethane 1,1,2,2-tetrafluoro-1- CF 2 1-CHF 2 354-41-6 iodoethane 1,1,2,2-tetrafluoro-1,2- CF 2 1-CF 2 1 354-65-4 diiodoethane lodopentafluorobenzene C 6

F

5 1 827-15-6 Alcohols Ethanol CH 3

-CH

2 -OH 64-17-5 n-propanol CH 3

-CH

2

-CH

2 -OH 71-23-8 Isopropanol CH 3

-CH(OH)-CH

3 67-63-0 Aldehydes and Ketones Acetone (2-propanone) CH 3

-CO-CH

3 67-64-1 n-propanal CH 3

-CH

2 -CHO 123-38-6 n-butanal CH 3

-CH

2

-CH

2 -CHO 123-72-8 Methyl ethyl ketone (2- CH 3

-CO-CH

2

-CH

3 78-93-3 - 10butanone) Other Nitrous oxide N 2 0 10024-97-2 The compounds listed in Table 1 are available commercially (from chemical supply houses, such as Aldrich, Milwaukee, WI) or may be prepared by processes known in the art. 5 Single tracer compounds may be used in combination with an unsaturated or other functionalised fluorocarbon refrigerant in the compositions of the present invention or multiple tracer compounds may be combined in any proportion to serve as a tracer blend. The tracer blend may contain multiple tracer compounds from the same class of 10 compounds or multiple tracer compounds from different classes of compounds. For example, a tracer blend may contain 2 or more deuterated unsaturated or other functionalized fluorocarbons, or one deuterated unsaturated or other functionalized fluorocarbon in combination with one or more perfluorocarbons. 15 Additionally, some of the compounds in Table 1 exist as multiple isomers, structural or optical. Single isomers or multiple isomers of the same compound may be used in any proportion to prepare the tracer compound. Further, single or multiple isomers of a given compound may be combined in any proportion with any number of other compounds to 20 serve as a tracer blend. The tracer-containing refrigerant compositions of the present invention may be prepared by any convenient method to combine the desired amount of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the 25 components in an appropriate vessel. Agitation may be used, if desired. By "analytically detectable" is meant that the tracer or tracer blend may be detected by any analytical method capable of differentiating the tracer from the unsaturated or other functionalized fluorocarbon refrigerant or capable of determining the quantity of tracer present. In the case where 30 a dilution of the tracer-containing composition may have occurred, the tracer compound may be present in a lesser quantity than originally added to the unsaturated or other functionalized fluorocarbon refrigerant. Analytical detection of the lesser quantity would aid the refrigeration industry. Such detection is capable of alerting the industry to the - 11 occurrence of dilution, adulteration, or contamination. Additionally, manufacturers, distributors and purchasers would be able to verify or authenticate the source (ie., supplier) of the refrigerant composition by comparing any quantity of detected tracer to the quantity that was 5 intentionally combined with unsaturated or other functionalized fluorocarbon refrigerant by the source. Gas chromatography (GC) is one analytical method that may be used to detect and quantify the tracer or tracer blended with the unsaturated or other functionalized fluorocarbon refrigerant. Any GC 10 detector may be used that is capable of detecting and quantifying the tracer compound. Such detectors include, but are not limited, to flame ionization detector (FID), thermal conductivity detector (TCD), electron capture detector (ECD), photo-ionization detector (PID), infrared detectors (IRD) and mass spectrometer detectors (usually referred to as GC-MS 15 when combined with a gas chromatograph). Other analytical methods may be utilized which do not require the gas chromatographic separation prior to detection. Such additional analytical methods include but are not limited to nuclear magnetic resonance (NMR) or infrared (IR) spectrometry. 20 When mixtures of this invention are analyzed using gas chromatography, conditions capable of identifying and quantifying the tracer in the presence of the unsaturated or other functionalized fluorocarbon refrigerant may be used. The GC column used for the analysis must be chosen so as to be capable of separating the tracer 25 compound or components of the tracer blend from the unsaturated or other functionalized fluorocarbon refrigerant. Both packed and capillary GC columns may be used. The preferred GC columns are those known to provide separation of fluorocarbon compounds from each other and classes of candidate tracer compounds of the present invention. 30 The packed GC columns that may be useful in the present invention are from about 1 meter to about 12 meters in length. Generally, packed GC columns are constructed of stainless steel. The commercially available packed GC columns that may be useful in the present invention include but are not limited to: porous polymer stationary phase, such as 35 Porapak* Q or Porapak* T; silicone polymer stationary phases, such as SP*-1000 on Carbopack* B support or SP*-2100 (methyl silicone) on Supelcoport* support, perfluorinated polymer stationary phase, Fluorcol* - 12on Carbopack * B support; and polyethylene glycol stationary phases, such as Carbowax* on Carbopack* C support. For those packed GC columns that are packed with a polymer coated support, the polymer loading may range from about 0.1% to about 10%. Packed GC columns 5 listed here are available from Supelco (Bellefonte, PA). Capillary GC columns which are found useful in the present invention are available commercially. Capillary columns may vary in length from about 10 meters to about 105 meters, but may also be longer if two or more columns are joined together (e.g. 120 meters by joining two 10 60 meter capillary GC columns). The capillary GC columns that may be of use in the present invention are generally constructed of fused silica tubing and vary in inner diameter (ID) from about 0.1 millimeter to about 0.53 millimeter. The stationary phase for the capillary GC columns is coated on the interior surface of the column and may vary in thickness 15 from about 0.1 micrometer to about 5 micrometers. The stationary phases that may be of use in the present invention, include but are not limited to the commercially available liquid polymer phases: RTx*-1 ((Crossbond* 100% dimethyl polysiloxane), RTx*-200 (Crossbond* trifluoropropylmethyl polysiloxane), RTx*-1 301 (Crossbond@ 6% cyanopropylphenyl/94% 20 dimethyl polysiloxane), RTx*-1701 (Crossbond* 14% cyanopropylphenyl/86% dimethyl polysiloxane) from Restek Corporation (Bellefonte, PA). Porous layer open tubular (PLOT) capillary columns may also be useful in the present invention. Such PLOT capillary GC columns include, but are not limited to, the CP-PoraPLOT* Q (100% styrene 25 divinylbenzene) column from Varian Chrompack (Middelburg, The Netherlands). Temperature and pressure conditions for the GC analysis will vary depending upon the unsaturated or other functionalized fluorocarbon refrigerant and the tracer being used in the composition. Cryogenic 30 temperatures (sub-ambient, requiring liquid nitrogen, dry ice or liquid carbon dioxide) may be used in order to provide separation of low boiling components (either unsaturated or other functionalsied fluorocarbon refrigerant or tracer compound(s)), when necessary. Tracer compounds or blends may be present in concentrations that 35 are detectable by whichever analytical method is chosen. Additionally, the tracer concentration must be chosen such that the quantity of tracer or tracer blend does not interfere with the performance of the unsaturated or - 13other functionalized fluorocarbon refrigerant. The tracer compound or tracer blend may be present at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm. Preferably, the tracer compound or tracer blend is present at a total concentration of about 50 5 ppm to about 500 ppm and most preferably, the tracer compound or tracer blend is present at a total concentration of about 100 ppm to about 300 ppm. The present invention further relates to a method of using the present inventive tracer-containing refrigerant compositions, said method 10 comprising combining said tracer compound with said unsaturated or other functionalsied fluorocarbon refrigerant to make a tracer-containing refrigerant composition, and detecting the presence of said tracer compound in said tracer-containing refrigerant composition. The present method is useful to (i) determine the occurrence of dilution, adulteration or 15 contamination or (ii) verify the source of the refrigerant composition of said composition. The present invention further relates to a method of using the present inventive tracer-containing refrigerant composition, said method comprising: (i) producing refrigeration by evaporating the tracer 20 containing refrigerant composition in the vicinity of a body to be cooled and thereafter condensing said composition; or (ii) producing heat by condensing the tracer-containing refrigerant composition in the vicinity of the body to be heated and thereafter evaporating said composition. Vapor-compression refrigeration systems include an evaporator, a 25 compressor, a condenser, a liquid storage receiver and an expansion device. A vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid 30 refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The high pressure gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The 35 refrigerant returns to the expansion device through which the liquid expands from the high-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle. - 14 - Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of 5 one or more other feature, integer, step, component or group thereof. Further, any prior art reference or statement provided in the specification is not to be taken as an admission that such art constitutes, or is to be understood as constituting, part of the common general knowledge in Australia. 10 - 15-

Claims (20)

1. A tracer-containing composition comprising: (i) a refrigeration/heating fluid comprising a fluorocarbon 5 refrigerant selected from an unsaturated fluorocarbon refrigerant or a functionalized fluorocarbon refrigerant selected from the group consisting of CF 3 CF

2 C(O)CF(CF 3 ) 2 (perfluoroethylisopropylketone, PEIK), and CF 3 C(O)CF(CF 3 ) 2 (perfluoromethylisopropylketone, PMIK); and 10 (ii) at least one tracer compound, said tracer compound being analytically detectable and selected from the group consisting of hydrofluorocarbons, deuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, 15 iodated compounds, alcohols, aldehydes and ketones, nitrous oxide and combinations thereof with the proviso that said refrigeration/heating fluid is different from said tracer compound. 20 2. The tracer-containing composition according to Claim 1, wherein said refrigeration/heating fluid comprises a mixture of said unsaturated fluorocarbon refrigerant or functionalized fluorocarbon refrigerant with at least one other refrigerant selected from the group consisting of hydrofluorocarbons, hydrochlorofluorocarbons, 25 perfluorocarbons, fluorocarbon ethers, hydrocarbons, carbon dioxide and ammonia.

3. The tracer-containing composition according to Claim 1, wherein said unsaturated fluorocarbon refrigerant or functionalized 30 fluorocarbon refrigerant is represented by the general formula CwF2w-xHxOz, wherein w is 3 to 8 and x is 0-15 and z is 0 to 2, and wherein 2w-x is a positive integer.

4. The tracer-containing composition according to Claim 1, wherein 35 said unsaturated fluorocarbon refrigerant or functionalized fluorocarbon refrigerant is an unsaturated fluorocarbon refrigerant. - 16-

5. The tracer-containing composition according to Claim 1, wherein said unsaturated fluorocarbon refrigerant or functionalized fluorocarbon refrigerant is perfluorobutylethylene. 5

6. The tracer-containing composition according to any one of Claims 1 to 5, wherein said composition comprises a single tracer compound.

7. The tracer-containing composition according to any one of Claims 1 10 to 5, wherein said composition comprises a tracer blend.

8. The tracer-containing composition according to any one of Claims 1 to 5, wherein at least one of said tracer compounds is present as a single pre-determined isomer. 15

9. The tracer-containing composition according to any one of Claims 1 to 5, wherein at least one of said tracer compound is present as multiple pre-determined isomers. 20

10. The tracer-containing composition according to Claim 6 or Claim 7, wherein said composition comprises a tracer compound or tracer blend in an amount ranging from about 50 ppm to about 1000 ppm.

11. The tracer-containing composition according to Claim 10, wherein 25 said tracer compound or tracer blend is in an amount ranging from about 50 ppm to about 500 ppm.

12. The tracer-containing composition according to Claim 11, wherein said tracer compound or tracer blend is in an amount ranging from 30 about 100 ppm to about 300 ppm.

13. The tracer-containing composition according to any one of Claims 1 to 5, wherein said tracer compound is at least one compound selected from HFOC-125E, HFOC-134aE, HFOC-143aE, HFOC 35 227eaE, HFOC-236faE, HFOC-245faEpy or HFOC-245faEup, HFOC-245cbEpy or HFOC-245cbap, HFE-42-1 1 mcc (or CF 3 -CF 2 CF 2 -0-CHF-CF 3 ), CF 3 -CF 2 -CF 2 -0-CF(CF 3 )CF 2 -0-CHF-CF 3 , - 17- HFC-23, HFC-161, HFC-152a, HFC-134, HFC-227ea, HFC-227ca, HFC-236cb, HFC-236ea, HFC-236fa, HFC-245cb, HFC-245fa, HFC-254cb, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC-338mf, HFC-338pcc, 5 HFC-347s, HFC-43-10mee, PFC-116, PFC-C216, PFC-218, PFC C318, PFC-31-10mc, PFC-31-10my, PFC-C51-12mycm, PFC-C51 12mym, trans, PFC-C51-12mym, cis, Perfluoromethylcyclo pentane, Perfluoromethylcyclo-hexane, Perfluorodimethylcyclo hexane (ortho, meta, or para), Perfluoroethylcyclohexane, 10 Perfluoroindan, Perfluorotrimethylcyclo-hexane and isomers thereof, Perfluoroisopropylcyclo-hexane, cis-Perfluorodecalin, trans-Perfluorodecalin, cis- or trans- Perfluoromethyldecalin and isomers thereof, Bromomethane, Bromofluoromethane, Bromodifluoromethane, Dibromofluoromethane, Tribromomethane, 15 Bromoethane, Bromoethene, 1,2-dibromoethane, 1-bromo-1,2 difluoroethene, lodotrifluoromethane, Difluoroiodomethane, Fluoroiodomethane, 1,1,2-trifluoro-1-iodoethane, 1,1,2,2-tetrafluoro 1-iodoethane, 1,1,2,2-tetrafluoro-1,2-diiodoethane, lodopentafluorobenzene, Ethanol, n-propanol, Isopropanol, 20 Acetone (2-propanone), n-propanal, n-butanal, Methyl ethyl ketone (2-butanone), Nitrous oxide, and combinations thereof.

14. The tracer-containing composition according to Claim 13, wherein the tracer compound is at least one compound selected from PFC 25 116, PFC-C216, PFC-218, PFC-C318, PFC-31-10mc, PFC-31 10my, PFC-C51-12mycm, PFC-C51-12mym, trans, PFC-C51 12mym, cis, Perfluoromethylcyclo-pentane, Perfluoromethylcyclo hexane, Perfluorodimethylcyclo-hexane (ortho, meta, or para), Perfluoroethylcyclohexane, Perfluoroindan, Perfluorotrimethylcyclo 30 hexane and isomers thereof, Perfluoroisopropylcyclo-hexane, cis Perfluorodecalin, trans-Perfluorodecalin, cis- or trans Perfluoromethyldecalin and isomers thereof.

15. A method of using the tracer-containing composition of any one of 35 Claims 1 to 14 comprising: combining said tracer compound with said unsaturated fluorocarbon refrigerant or functionalized fluorocarbon refrigerant to make a tracer-containing refrigerant - 18- composition, and detecting said tracer compound in said tracer containing refrigerant composition.

16. The method of Claim 15, wherein said detecting comprises 5 detecting the presence of said tracer, detecting the quantity of said tracer, or both presence and quantity of said tracer compound.

17. A method of producing refrigeration using the tracer-containing composition of any one of Claims 1 to 14, said method comprising: 10 evaporating the tracer-containing refrigerant composition in the vicinity of a body to be cooled and thereafter condensing said composition.

18. A method of producing refrigeration using the tracer-containing 15 composition of any one of Claims 1 to 14, said method comprising: condensing the tracer-containing refrigerant composition in the vicinity of the body to be heated and thereafter evaporating said composition. 20

19. A method for making the tracer-containing composition of any one of Claims 1 to 14, said method comprising: combining an unsaturated fluorocarbon refrigerant or a functionalized fluorocarbon refrigerant with a tracer compound selected from the group consisting of hydrofluorocarbons, deuterated 25 hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof.

20. Use of the tracer-containing composition according to any one of 30 Claims 1 to 14, substantially as hereinbefore described. -19-