Tracer-containing compositions

The present invention relates to compression cooling and air conditioning. Specifically, the present invention relates to a composition containing a refrigerant and a tracer compound. Furthermore, the present invention relates to the identification of the refrigerant gas after leaving the control of the authorized manufacturer and the verification of the reliability of the refrigerant. The method described above alerts the cooling company that the tracer compound has been detected and that any dilution, modification, or contamination has occurred, or that any other modification not approved for the cooling product has been made.

Cross-reference of related applications This application claims the priority benefit of US Provisional Patent Application No. 60 / 548,085, filed February 26, 2004. This is incorporated herein by reference.

Environmental issues have raised a high level of awareness of the cooling industry regarding the responsible use of refrigerants. All applicable means to ensure that everyone who manufactures, sells, and uses refrigerants, or who operates cooling and air conditioning equipment, keeps the equipment operating at the highest level of energy efficiency achievable. When used, it benefits the cooling industry as well as society as a whole. This reduces the amount of energy consumed by the device. As with refrigerant leaks, excessive energy consumption can contribute to unnecessary pollution of our atmosphere and unnecessary waste of existing resources. This unnecessary waste brings consumers the cost of replacing the leaked refrigerant.

In response to environmental issues, refrigerant manufacturers have developed new refrigerant products that enable high levels of energy efficiency when used in well-designed equipment. New-generation HFC refrigerants have less environmental impact than older-generation chlorinated refrigerants if inadvertently leaked into the atmosphere. HFC refrigerants have a zero ozone depletion potential and are less likely to change the tropospheric climate than refrigerants that replace HFC refrigerants. In addition, industry practice now mandates the elimination of leaks from most types of operating equipment, and when the equipment is inactive or open to perform inspection work. In addition, it is necessary to recover the refrigerant gas.

New high-efficiency refrigerants and responsible use policies benefit the environment, but the benefits are not as great as possible. For example, the recovered refrigerant gas may not be properly regenerated or reused. The recovered refrigerant may have been re-installed in another part of the device without proper regeneration and proper cleaning to remove harmful or energy efficient impurities. .. This impurity can be contaminated during handling or due to poor performance or damaged equipment. A device into which such a refrigerant is introduced does not operate at maximum efficiency and consumes more energy than necessary.

In addition, the used refrigerant can be mixed with unused refrigerant, which is generally a non-standard refrigerant gas composition. Similarly, the used refrigerant can be repackaged and sold as an unused refrigerant without warranty of purity and quality. Such practices lead to increased air pollution and increased energy use, putting expensive cooling equipment at risk of damage.

In addition to adverse effects on the environment and equipment, it also results in economic loss for refrigerant manufacturers and distributors. Refrigerant manufacturers are investing enormously in developing new, high-quality refrigerant products. Refrigerant distributors are also investing in equipment to adequately protect the refrigerant from contamination during packaging, storage and sale. Manufacturers and distributors do not benefit from their investment if the refrigerant is diluted or blended with the recovered refrigerant and sold as unused refrigerant.

<p><nplcit num="1"><text>"Chemistry of Organic Fluorine Compounds 2nd (revised edition)", edited by Milos Hudlicky, Ellis Harwood-Prentice Hall Publishers), 1992</text></nplcit></p>

<p> For the above reasons, the ability to clearly determine when a refrigerant composition has been diluted or altered in some way without compromising performance and quality characteristics to a measurable degree is required.</p><p> The present invention addresses such demands by providing a reliable method for labeling unused refrigerant products.</p>

<p> The present invention relates to a tracer-containing composition, wherein the composition comprises a cooling / heating fluid and at least one tracer compound, the tracer compound is present in an analytically detectable state, hydrofluorocarbon, dehydrofluorocarbon. , Perfluorocarbons, fluoroethers, brominated compounds, iodide compounds, alcohols, aldehydes and ketones, nitrogen phosphite, and combinations thereof. Furthermore, the present invention relates to a composition as described above in which at least one of the tracer compounds is present as a single predetermined isomer.</p><p> The present invention further relates to a method of using the tracer-containing composition of the present invention, wherein the method combines the tracer compound with the cooling / heating fluid to produce a refrigerant composition containing the tracer, and the tracer. The step of detecting the presence of the tracer compound in the contained refrigerant composition is included. The method comprises the steps of detecting the occurrence of dilution, modification, or contamination of the composition.</p><p> Furthermore, the present invention relates to using a tracer-containing composition in a method of causing cooling, which comprises the step of evaporating the composition in the vicinity of the object to be cooled and then condensing the composition. The present invention also relates to a method of using a tracer-containing refrigerant composition to generate heat, comprising the step of condensing the composition in the vicinity of a heated object and then evaporating the composition.</p>

Applicants specifically incorporate the full content of all references listed. Further, if an amount, concentration, or other value or parameter is given as either a range, a suitable range, or a list of preferred upper and lower limits, such ranges are disclosed separately. It is understood that this specifically discloses the entire range formed from any combination of a range upper bound or preferred value and a range lower bound or preferred value, whether or not. When a range of numbers is described herein, the range is intended to include its endpoints and to include all integers and fractions within that range, unless otherwise stated. If a range is defined, it is not intended to limit the scope of the invention to the particular values described.

The cooling / heating fluid of the present invention may be any common cooling / heating fluid used in the cooling industry. Such cooling / heating fluids include hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), perfluorocarbons (PFCs), fluorocarbon ethers (HFEs), hydrocarbons, carbon dioxide (CO).₂), Ammonia (NH₃), Or a mixture thereof. Fluorinated cooling / heating fluids, HFCs, HCFCs, HFEs, and PFCs may be referred to as fluorocarbon refrigerants.

The fluorocarbon refrigerant of the present invention has 1 to 8 carbon atoms, contains at least one fluorine atom, optionally contains chlorine and oxygen atoms, and has a standard boiling point of -90 ° C to 80 ° C. is there. These fluorocarbons have the general formula C_wF_{2w + 2-xy}H_xCl_yO_zWhere w is 1 ~ 6, x is 0 ~ 9, y is 0 ~ 3, z is 0 ~ 2, and here 2w + 2-xy is a positive integer.

Suitable fluorocarbons are those with w of 1 to 6, x of 1 to 5, y of 0 to 1, and z of 0 to 1. The present invention is particularly useful for hydrofluorocarbon refrigerants and hydrochlorofluorocarbon-based refrigerants. Fluorocarbon refrigerants are commercially available from a number of sources, including the patent applicants of the present application, or are commissioned by PCR Inc., PO Box 1466, Gainesville, Florida, 32602, USA, PO Box 1466, Gainesville, Florida, USA, 32602, USA. It is commercially available from chemical synthesis companies and is also available by synthetic processes disclosed in publications such as (Non-Patent Document 1). Typical fluorocarbons include, but are not limited to: CHClF:₂(HCFC-22), CHF₃(HFC-23), CH₂F₂(HFC-32), CH₃F (HFC-41), CF₃CF₃(FC-116), CHClFCF₃(HCFC-124), CHF₂CF₃(HFC-125), CH₂ClCF₃(HCFC-133a), CHF₂CHF₂(HFC-134), CH₂FCF₃(HFC-134a), CClF₂CH₃(HCFC-142b), CHF₂CH₂F (HFC-143), CF₃CH₃(HFC-143a), CHF₂CH₃(HFC-152a), CHF₂CF₂CF₃(HFC-227ca), CF₃CFHCF₃(HFC-227ea), CHF₂CF₂CHF₂(HFC-236ca), CH₂FCF₂CF₃(HFC-236cb), CHF₂CHFCF₃(HFC-236ea), CF₃CH₂CF₃(HFC-236fa), CH₂FCF₂CHF₂(HFC-245ca), CH₃CF₂CF₃(HFC-245cb), CHF₂CHFCHF₂(HFC-245ea), CH₂FCHFCF₃(HFC-245eb), CHF₂CH₂CF₃(HFC-245fa), CH₂FCF₂CH₂F (HFC-254ca), CH₃CF₂CHF₂(HFC-254cb), CH₂FCHFCHF₂(HFC-254ea), CH₃CHFCF₃(HFC-254eb), CHF₂CH₂CHF₂(HFC-254fa), CH₂FCH₂CF₃(HFC-254fb), CH₃CF₂CH₃(HFC-272ca), CH₃CHFCH₂F (HFC-272ea), CH₂FCH₂CH₂F (HFC-272fa), CH₃CH₂CF₂H (HFC-272fb), CH₃CHFCH₃(HFC-281ea), CH₃CH₂CH₂F (HFC-281fa), CHF₂CF₂CF₂CF₂H (HFC-338pcc), CF₃CH₂CF₂CH₃(HFC-365mfc), CF₃CF₂CF₂OCHFCF₃(Freon® E1), CF₃CHFCHFCF₂CF₃(HFC-43-10mee), C₄F₉OCH₃, And C₄F₉OC₂H₅。

Further, the fluorocarbon refrigerant of the present invention has the general formula C._wF_2w-xH_xO_zRepresented by, where w is equal to 3-8, x is equal to 0-17, and z is equal to 0-2, where 2w-x is a positive integer. Such fluorocarbon refrigerants are CF₃(CF₂)₃CH = CH₂(Perfluorobutylethylene, PFBE), CF₃CF₂C (O) CF (CF)₃)₂(Perfluoroethyl isopropyl ketone, PEIK), and CF₃C (O) CF (CF)₃)₂Examples include unsaturated compounds such as (perfluoromethylisopropylketone, PMIK) and other functionalized fluorocarbons.

A more preferred fluorocarbon refrigerant is CHClF₂(HCFC-22), CHF₃(HFC-23), CH₂F₂(HFC-32), CHClFCF₃(HCFC-124), CHF₂CF₃(HFC-125), CHF₂CHF₂(HFC-134), CH₂FCF₃(HFC-134a), CF₃CH₃(HFC-143a), CHF₂CH₃(HFC-152a), CHF₂CF₂CF₃(HFC-227ca), CF₃CFHCF₃(HFC-227ea), CF₃CH₂CF₃(HFC-236fa), CHF₂CH₂CF₃(HFC-245fa), CHF₂CF₂CF₂CF₂H (HFC-338pcc), CF₃CHFCHFCF₂CF₃(HFC-43-10mee), CF₃(CF₂)₃CH = CH₂(Perfluorobutylethylene, PFBE), CF₃CF₂C (O) CF (CF)₃)₂(Perfluoroethyl isopropyl ketone, PEIK), CF₃C (O) CF (CF)₃)₂Hydrofluorocarbon-based refrigerants such as (perfluoromethylisopropylketone, PMIK) and hydrochlorofluorocarbon-based refrigerants, and HCFC-22 / HFC-152a / HCFC-124 (American Society for Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE) trade names R-401A, R- Known by 401B and R-401C), HFC-125 / HFC-143a / HFC-134a (known by ASHRAE trade name R-404A), HFC-32 / HFC-125 / HFC-134a (ASHRAE) (Known by trade name R-407A, R-407B and R-407C), HCFC-22 / HFC-143a / HFC-125 (known by ASHRAE trade name R-408A), HCFC-22 / HCFC -124 / HCFC-142b (known by ASHRAE trade name R-409A), HFC-32 / HFC-125 (R-410A), and HFC-125 / HFC-143a (known by ASHRAE trade name R-507) ) And other co-boiling and co-boiling-like fluorocarbon refrigerant compositions.

The fluorocarbon refrigerant of the present invention optionally comprises 10 weight percent or less of dimethyl ether or at least one C.₃~ C₅Hydrocarbons such as propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, cyclopentane, and neopentane (2,2-dimethylpropane) may be further included. C like this₃~ C₅Examples of fluorocarbons containing hydrocarbons are HCFC-22 / HFC-125 / Propane (known by ASHRAE trade names R-402A and R-402B), HCFC-22 / Octafluoropropane / Propane (ASHRAE trade name). (Known by R-403A and R-403B), Octafluoropropane / HFC-134a / Isobutane (known by ASHRAE trade name R-413A), HCFC-22 / HCFC-124 / HCFC-142b / Isobutane (Known by ASHRAE trade names R-414A and R-414B), HFC-134a / HCFC-124 / n-butane (known by ASHRAE trade name R-416A), HFC-125 / HFC-134a / n-butane (known by ASHRAE trade name R-417A), HFC-125 / HFC-134a / dimethyl ether (known by ASHRAE trade name R-419A), and HFC-125 / HFC-134a / An isobutane-like composition of isobutane (known by ASHRAE trade name R-422A).

The tracer compounds of the present invention include hydrofluorocarbons, deuterated hydrocarbons or deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodide compounds, alcohols, aldehydes and ketones, and nitrogen phosphite (N).₂It is selected from the group consisting of O) and combinations thereof. The same composition acts as both elements of a given composition, although there may be overlap between the chemical compound defined as the cooling / heating fluid and the chemical compound defined as the tracer compound. It is not possible. Candidates for suitable tracer compounds are listed in Table 1.

<tables num="1"><img file="JP2012082425A_D0001.tif" /></tables>

<tables num="2"><img file="JP2012082425A_D0002.tif" /></tables>

<tables num="3"><img file="JP2012082425A_D0003.tif" /></tables>

<tables num="4"><img file="JP2012082425A_D0004.tif" /></tables>

The compounds listed in Table 1 may be commercially available (from a drug supplier such as Aldrich in Milwaukee, WI, Wyoming) or may be prepared by a process known in the art.

In the composition of the present invention, a single tracer compound may be used in combination with a cooling / heating fluid, or a plurality of tracer compounds may be combined in any ratio and provided as a tracer blend. The tracer blend may include multiple tracer compounds from the same type of compound or multiple tracer compounds from different types of compounds. For example, the tracer blend may include two or more deuterated hydrofluorocarbons or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.

In addition, some of the compounds in Table 1 are structurally or optically present as multiple isomers. A single isomer or multiple isomers of the same compound may be used in any proportion that prepares the tracer compound. The single or multiple isomers of a given compound may be served as a tracer blend in any proportion in combination with any number of other compounds.

The tracer-containing cooling composition of the present invention may be prepared by any convenient method of combining the desired amounts of individual components. In a preferred method, the desired amount of ingredients is weighed and then the ingredients are combined in a suitable container. If desired, stirring may be used.

"Analytical detectable" means detecting a tracer or tracer blend by an analytical method capable of distinguishing the tracer from the cooling / heating fluid or measuring the amount of tracer present. Means. When dilution of the tracer-containing composition occurs, the tracer compound is present in an amount less than the amount initially added to the cooling / heating fluid. A small amount of analytical detection helps the cooling industry. Such detection makes it possible to alert companies to the occurrence of dilution, modification, or contamination. In addition, the manufacturer, distributor, and purchaser can compare the amount of tracer detected to the amount intentionally mixed with the cooling / heating fluid by the source to supply the cooling composition. (That is, the supplier) can be verified or certified.

Gas chromatography (GC) is one of the analytical methods that can be used to detect and quantify tracers or tracer blends in a cooling / heating fluid. Any GC detector capable of detecting and quantifying the tracer compound may be used. Such detectors are, but are not limited to, frame ionization detectors (FIDs), thermal conductivity detectors (TCDs), electron capture detectors (ECDs), photoionization detectors ( PID), infrared detector (IRD), and mass spectrometer detector (usually referred to as GC-MS when combined with a gas chromatograph). Other analytical methods that do not require gas chromatograph separation prior to detection may be used. Such additional analytical methods include, but are not limited to, nuclear magnetic resonance (NMR) or infrared (IR) spectroscopy.

When analyzing a mixture of the invention using gas chromatography, conditions may be used that allow the tracer to be identified and quantified in the presence of a cooling / heating fluid. The GC column used for the analysis must be selected so that the tracer compound, or component of the tracer blend, can be separated from the cooling / heating fluid. Both filled GC columns and capillary GC columns may be used. Suitable GC columns are known to separate fluorocarbon compounds from each other and to separate candidate types of tracer compounds of the invention.

Filled GC columns useful in the present invention are from about 1 meter to about 12 meters in length. Generally, the filled GC column is made of stainless steel. Commercially available packed GC columns that may be useful in the present invention are not limited to these, porous polymer stationary phases such as Porapack Q or Porapack T, Carbopack ( Carbopack® B Support SP®-1000 or Supelcoport® Support SP®-2100 (methyl silicone), perfluoropolymer stationary phase, Carbopack (Registered Trademark)) Silicone polymer stationary phase such as B-support Fluorcol (registered trademark) and polyethylene glycol fixation such as Carbopack (registered trademark) C-supported Carbowax (registered trademark). There is a phase. For packed GC columns packed with polymer coating supports, the polymer loading is in the range of about 0.1% to about 10%. The filled GC columns listed here are commercially available from Supelco (Bellefonte, PA, PA).

Capillary GC columns that appear to be useful in the present invention are commercially available. Capillary columns may vary in length from about 10 meters to about 105 meters, but may be longer when connecting two or more columns (eg, two 60 meter capillary GC columns joined together). And make it 120 meters). Capillary GC columns useful in the present invention are generally composed of fused quartz tube material and have an inner diameter (ID) that varies between about 0.1 mm and about 0.53 mm. The stationary phase for a capillary GC column is coated on the inner surface of the column and varies in thickness from about 0.1 micrometer to about 5 micrometers. The stationary phase useful in the present invention is not limited to these, but is a commercially available polymer phase, RT manufactured by Restek Corporation (Bellefonte, PA) in Bellefonte, PA._x(Registered Trademark) -1 (Crossbond® dimethylpolysiloxane 100%), RT_x(Registered Trademark)-200 (Crossbond® trifluoropropylmethylpolysiloxane), RT_x(Registered Trademark) -1301 (Crossbond® cyanopropylphenyl 6% / dimethylpolysiloxane 94%), RT_x(Registered Trademark) -1701 (Crossbond® cyanopropylphenyl 14% / dimethylpolysiloxane 86%). Porous layer open tube (PLOT) capillary columns are also useful in the present invention. One such PLOT capillary GC column is the CP-PoraPLOT® Q (100% Styrene Divinylbenzene) column from Varian Chrompack (Middelburg, Netherlands). Not limited.

The temperature and pressure conditions for GC analysis will vary depending on the cooling / heating fluid and tracer used in the composition. If necessary, use cryogenic temperatures (below ambient temperature, requiring liquid nitrogen, dry ice, or liquid carbon dioxide) to provide separation of low boiling components (either cooling / heating fluids or tracer compounds). You can do it.

The tracer compound or blend may be present at a concentration that is detectable by any analytical method chosen. In addition, the tracer concentration must be selected such that the tracer or tracer blend does not interfere with the performance of the cooling / heating fluid. The tracer compound or blend may be present in a total concentration of about 50 ppm by weight to about 1000 ppm. Preferably, the tracer compound or tracer blend is present in a total concentration of about 50 ppm to about 500 ppm, and most preferably the tracer compound or tracer blend is present in a total concentration of about 100 ppm to about 300 ppm.

The present invention further relates to a method of using the tracer-containing composition of the present invention, wherein the method is a step of combining the tracer compound with the cooling / heating fluid to produce a tracer-containing refrigerant composition, and the tracer-containing refrigerant. The step of detecting the presence of the tracer compound in the composition is included. This method is useful for (i) determining the occurrence of dilution, modification, or contamination, or (ii) confirming the source of the refrigerant composition of the above composition.

The present invention further relates to a method of using the tracer-containing refrigerant composition of the present invention, wherein the method (i) causes cooling by evaporating the tracer-containing refrigerant composition in the vicinity of an object to be cooled, and then the composition. It comprises the steps of condensing an object or (ii) generating heat by condensing the tracer-containing refrigerant composition in the vicinity of the object to be heated and then evaporating the composition.

Vapor-compression refrigeration systems include evaporators, compressors, condensers, liquid storage vessels, and expansion devices. In the steam compression cycle, the refrigerant is reused in multiple steps that produce a cooling effect in one step and a heating effect in one different step. This cycle can be briefly explained as follows. The liquid refrigerant enters the evaporator via an expansion device and evaporates at a low temperature in the evaporator to form a gas and cause cooling. Low-pressure gas enters the compressor, where it is compressed and the pressure and temperature rise. The high-pressure gaseous refrigerant then enters the capacitor, where the refrigerant is condensed and releases heat into the environment. The refrigerant returns to the expansion device and expands the liquid from the high pressure level at the condenser to the low pressure level at the evaporator, which repeats this cycle.

<p> The tracer-containing cooling composition of the present invention was then prepared and then analyzed under different analytical conditions using several different GC columns. Retention times for the cooling / heating fluid and tracer compound have been defined and are given in each example. Note that the exact retention time measured on a particular gas chromatograph on a particular GC column will be slightly different from the retention time measured on different instruments and columns.</p><p> All samples were analyzed on an Agilent 6890 gas chromatograph and the data were collected and processed by Agilent Chemstation® software. Both are commercially available from Agilent Technologies (Palo Alto, CA, CA).</p><p> (Example 1) A sample of R22 (refrigerant HCFC-22, chlorodifluoromethane) was spiked with 100 ppm (ppm by weight) PFC-C318 (perfluorocyclobutane). Samples were then analyzed by GC using the conditions described below.</p><p>Column: RT_X(Registered Trademark)-1701 (Crossbond® 14% cyanopropylphenyl / 86% dimethylpolysiloxane) Length: 105 meters Inner diameter: 0.25 mm Fixed phase film thickness: 0.25 μm Carrier gas and flow rate: He, 1.0 ml / min Oven temperature: Initial temperature: -20 ° C Initial retention time: 15 minutes Temperature gradient: 10 ° C / min Final temperature: 50 ° C Last retention time: 0 minutes (no final retention time) Detector: Frame ionization detector (FID) Temperature: 250 ° C Hydrogen flow rate: 42 ml / min Air flow rate: 450 ml / min Injection port: split Temperature: 150 ° C Head pressure: 22psi Sample type: Gas phase, manual syringe injection Sample size: 1.0 ml Split ratio: 50: 1</p><p> Table 2 shows the retention times of the refrigerant, R-22 and tracer, and PFC-C318.</p><p><tables num="5"><img file="JP2012082425A_D0005.tif" /></tables></p><p> (Example 2) A sample of R-134a (refrigerant HFC-134a, 1,1,1,2-tetrafluoroethane) was used as a sample of 100 ppm (weight ppm) of HFC-236fa (1,1,1,3,3,3-hexafluoropropane). ) Spike. Samples were then analyzed by GC using the conditions described below.</p><p>Column: RT_x(Registered Trademark) -1 (Crossbond® 100% Dimethylpolysiloxane) Length: 105 meters Inner diameter: 0.25 mm Fixed phase film thickness: 1.0 micrometer Carrier gas and flow rate: helium, 0.75 ml / min Oven temperature: Initial temperature: -20 ° C Initial retention time: 13 minutes Temperature gradient: 5 ° C / min Final temperature: 50 ° C Last retention time: 10 minutes Detector: Frame ionization detector (FID) Temperature: 250 ° C Hydrogen pressure: 20psi Pneumatic: 45psi Injection port: split Temperature: 175 ° C Head pressure: 38psi Sample type: Gas phase, manual syringe injection Sample size: 1.0 ml Split ratio: 75: 1</p><p> Table 3 shows the retention times of the refrigerant, R-134a and tracer, and HFC-236fa.</p><p><tables num="6"><img file="JP2012082425A_D0006.tif" /></tables></p><p> (Example 3) A sample of R-410A (refrigerant blend, 50% by weight R-32, difluoromethane and 50% by weight R-125, pentafluoroethane) was sampled at 100ppm (ppm) HFE-236fa (1-trifluoromethoxy-). 2,2,2-trifluoroethane) spiked. Samples were then analyzed by GC using the conditions described below.</p><p>Column: Carbopack B60 / 80 mesh Fluorcol Length: 20 feet (6.1 meters) Inner diameter: 1/8 inch (0.32 cm) Carrier gas and flow rate: helium, 30 ml / min Oven temperature: Initial temperature: 60 ° C Initial retention time: 3 minutes Temperature gradient: 8 ° C / min Final temperature: 180 ° C Last retention time: 10 minutes Detector: Frame ionization detector (FID) Temperature: 250 ° C Hydrogen pressure: 20psi Pneumatic: 45psi Injection port: filling Temperature: 250 ° C Head pressure: 67psi Sample type: Gas phase, sample valve injection Sample size: 50 microliters</p><p> Table 4 shows the retention times of the refrigerant, R-410A, specifically R-32 and R-125, and the tracer, HFE236fa.</p><p><tables num="7"><img file="JP2012082425A_D0007.tif" /></tables></p>