TW201412966A - Method of recharging equipment designed for chlorodifluoromethane - Google Patents

Abstract

In accordance with the present invention a method is provided for recharging or topping-off refrigerant. The method comprises adding a second refrigerant to a refrigeration, air conditioning, heat pump or power cycle system containing HCFC-22 as a first refrigerant wherein said second refrigerant comprises at least one refrigerant selected from the group consisting of HFC-143a, HFC-125, and mixtures thereof, and optionally HCFC-22, thus producing a refrigerant composition comprising the first refrigerant and the second refrigerant. Also in accordance with the present invention another method is provided. This method comprises replacing HCFC-22 in a refrigeration, air conditioning, heat pump or power cycle system with a refrigerant composition comprising at least one refrigerant selected from the group consisting of HFC-143a, HFC-125, and mixtures thereof, and optionally HCFC-22.

Description

Refilling method for equipment designed for difluorochloromethane

The present disclosure is directed to a method of refilling or replenishing a refrigerant charge in an apparatus designed to use difluorochloromethane. The method of the present invention can be used to add or supplement refrigerant in a refrigeration unit, an air conditioning unit, a heat pump unit, or a power cycle unit.

Over the past few decades, the refrigeration industry has been looking for alternative refrigerants to replace ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which will be phased out due to the Montreal Protocol. The solution for most refrigerant manufacturers is the commercialization of hydrofluorocarbon (HFC) refrigerants. Among the new HFC refrigerants, HFC-134a is currently the most widely used user. Such refrigerants do not have ozone depletion potential and are therefore not affected by the Montreal Protocol's regulations that specific refrigerants must be phased out.

However, further environmental regulations may eventually result in the global decommissioning of certain HFC refrigerants. Currently, the refrigerant industry is constrained by the Global Warming Potential (GWP) and Ozone Depletion Potential (ODP) regulations. If these specifications are expanded in the future, they will show greater demand for refrigerants in all aspects of the refrigeration and air-conditioning industry. Since it is not yet possible to determine the final regulatory specifications for GWP and ODP, the industry has been forced to consider a variety of candidate compounds and mixtures.

Alternative refrigerants for the proposed HFC refrigerant must have low toxicity, low flammability or non-flammability and improved energy efficiency, in addition to low global warming potential and low or no ozone depletion potential.

As the use of certain refrigerants is banned or restricted, a need arises for refrigerants that are compatible with existing equipment. During normal operation, the refrigerant will escape from the system and new refrigerant needs to be added. If the original refrigerant is available in limited quantities or cannot be obtained, it is necessary to find a compatible refrigerant or to change or replace the equipment to provide similar performance.

Some existing refrigerants have been found to have suitable properties that allow them to be used as a substitute for difluorochloromethane. In addition, their refrigerants can be used as a suitable refrigerant to fill the foot candidates.

The present invention provides a method of filling or supplementing a refrigerant. The method comprises adding a second refrigerant to a refrigeration system, an air conditioning system, a heat pump system or a power cycle system containing HCFC-22 as a first refrigerant, wherein the second refrigerant comprises at least one selected from the group consisting of HFC-143a, HFC-125 or The refrigerant of the group consisting of the mixture, and optionally HCFC-22, produces a refrigerant composition comprising the first refrigerant and the second refrigerant.

The invention also provides another method. The method comprises refilling a refrigerant composition containing HCFC-22, the refrigerant composition comprising at least one refrigerant selected from the group consisting of HFC-143a, HFC-125, and mixtures thereof, and optionally HCFC- twenty two.

The invention also provides another method. The method comprises replacing HCFC-22 in a refrigeration system, an air conditioning system, a heat pump system or a power cycle system with a refrigerant composition comprising at least one group selected from the group consisting of HFC-143a, HFC-125, and mixtures thereof The refrigerant and, if appropriate, HCFC-22.

Certain terms are defined or clarified before the details of the embodiments described below are presented.

definition

As used herein, the term heat transfer liquid means a composition for carrying heat from a heat source to a heat sink.

A heat source is defined as any space, location, object, or subject that is intended to join, transfer, move, or remove heat. Examples of heat sources include spaces that need to be frozen or cooled (open or closed), such as freezer or freezer in a supermarket, building space requiring air conditioning, industrial water chillers, or car passenger compartments that require air conditioning. In certain embodiments, the heat transfer composition can maintain a steady state (i.e., not evaporate or condense) throughout the transfer. In other embodiments, the evaporative cooling process may also utilize a heat transfer composition.

A heat sink is defined as any space, location, object or body that is capable of absorbing heat. A vapor compression refrigeration system is an example of such a heat sink.

A refrigerant is defined as a heat transfer liquid that undergoes a phase change during the cycle for conducting heat, from a liquid state to a gaseous state and back to a liquid state.

Refrigerant filling is cold that is filled in order to operate the equipment at maximum performance. The total amount of media. Refilling (or replenishment or refilling) means adding additional refrigerant to restore the system to maximum performance when it is lost or partially leaking from the equipment.

a heat transfer system for generating a heating or cold in a specific space But the system (or device) of the effect. The heat transfer system can be a mobile system or a stationary system.

Examples of heat transfer systems are any type of refrigeration system and air conditioning system Systems, including but not limited to air conditioners, freezers, refrigerators, heat pumps, water coolers, submersible evaporative coolers, direct expansion coolers, walk-in refrigerated cabinets, mobile refrigerators, mobile air conditioning units, dehumidifiers and Its combination.

As used herein, a mobile heat transfer system refers to any combination of Refrigeration, air conditioning or heating for road, rail, sea or air transport units. In addition, mobile freeze or air conditioner units include those that are independent of any mobile vehicle and are known as "intermodal" systems. Such joint transport systems include "containers" (joint sea/land transport) and "swap bodies" (joint road/rail transport).

As used herein, a stationary heat transfer system is positionally fixed during operation Set the system. The fixed heat transfer system can be combined or connected to a variety of different buildings, or can be a separate device located outside the door, such as a refreshing beverage vending machine. Their fixed applications can be fixed air conditioners and heat pumps, including but not limited to coolers, high temperature heat pumps, domestic, commercial or industrial air conditioning systems (including domestic heat pumps), and include windows, no pipes, pipes, and terminal units ( Packaged terminal) and external but linked to the building For example, a roof system. In stationary refrigeration applications, the disclosed compositions can be used in equipment including commercial, industrial or domestic freezers and freezers, ice machines, self-contained coolers and freezers, submerged evaporative coolers, direct expansion coolers , walk-in and reach-in refrigerators and freezers, and combined systems. In certain embodiments, the disclosed compositions can be used in a supermarket refrigeration system. In addition, stationary applications may utilize an auxiliary circulation system that uses a primary refrigerant to produce a cooling effect at a location and deliver it to a remote location via an auxiliary heat transfer fluid.

The term freezing capacity (also known as cooling capacity) is defined as an evaporator The amount of refrigerant per pound of circulating refrigerant changes, or the heat (volume capacity) of the refrigerant removed per unit volume of refrigerant vapor in the evaporator as it leaves the evaporator. The ability to freeze is used to assess the ability of a refrigerant or heat transfer composition to produce cooling. Therefore, the higher the capacity, the greater the resulting cooling. The cooling rate means the heat of refrigerant removal in the evaporator per unit time.

Coefficient of performance (COP) is the amount of heat removed divided by the amount required to operate the cycle Energy input. The higher the COP, the higher the energy efficiency. COP is directly related to energy efficiency ratio (EER), which refers to the efficiency rating of refrigeration or air conditioning equipment at a specific set of internal and external temperatures.

The term "subcooling" refers to a liquid whose temperature drops below the saturation point of the liquid at a given pressure. The saturation point is the temperature at which the vapor is completely condensed to a liquid, but subcooling will continue to cool the liquid to a lower temperature liquid (at that given pressure). By cooling a liquid to below the saturation temperature (or bubble point temperature), its net freezing capacity can be increased. Subcooling thus improves the refrigeration capacity and energy efficiency of a system. The amount of subcooling is the amount of cooling (in degrees) below the saturation temperature.

Overheating is defined as a heating of a vapor composition over its saturated vapor temperature. The term (saturated vapor temperature is the temperature at which the first drop of liquid is formed if the composition is cooled, also referred to as "dew point").

Temperature glide (sometimes just called "slip") The absolute difference between the start and end temperatures of a phase change process in a component of a refrigerant system, and excludes any overcooling or overheating. This term can be used to describe the condensation or evaporation of a near azeotropic or non-azeotropic composition. When referring to the temperature slip of a refrigeration, air conditioning or heat pump system, the average temperature slip typically provided is the average of the temperature slip in the evaporator and the temperature slip in the condenser.

The azeotropic composition means a constant boiling mixture of two or more substances. A substance that behaves like a single substance. A method of characterizing an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid (the vapor is evaporated or distilled from the liquid), that is, the mixture does not distill/reflow. A composition change occurred. Azeotrope compositions are characterized by azeotropic properties because they exhibit a highest or lowest boiling point compared to a non-azeotropic mixture of the same compound. During operation, the azeotropic composition does not undergo fractionation in a refrigeration or air conditioning system. In addition, the azeotrope does not undergo fractionation when leaking from a refrigeration or air conditioning system.

Azeotrope-like compositions (also known as "near azeotropes") are two Or a substantially constant boiling liquid admixture of the above material, which behaves substantially as a single substance. A method of characterizing an azeotrope-like composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the vaporized or distilled liquid, in other words, the blend does not undergo substantial compositional changes. Distillation/return flow. Another characterization of the azeotrope-like composition is such that the bubble point vapor pressure of the composition is substantially the same as the dew point vapor pressure at a certain temperature. As used herein, if 50 weight percent of the composition is removed (eg, by evaporation or boiling), the vapor pressure between the original composition and the composition remaining after removal of 50 weight percent of the original composition If the difference is less than 10%, the composition is defined as an azeotrope-like one.

a non-azeotropic (also known as non-azeotropic) composition of one or two or more A mixture of substances that behaves as a simple mixture rather than as a single substance. A method of characterizing a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a composition substantially different from that of the liquid which is vaporized or distilled from the liquid, that is, the mixture is distilled/reflowed. A substantial compositional change occurs. Another way to characterize the non-azeotropic composition is that the bubble point vapor pressure of the composition is substantially different from the dew point vapor pressure at a particular temperature. Herein, if a composition is removed by 50% by weight, for example by evaporation or boiling, the vapor pressure difference between the original composition and the 50% by weight removed composition is greater than about 10%, then the composition The substance is non-azeotropic.

As used herein, the term "lubricant" means any added to one. The composition or material of a compressor (and any heat transfer composition used in any heat transfer system) to provide lubrication of the compressor to help avoid component jamming.

As used herein, a compatibilizer is enhanced A compound of the solubility of a hydrofluorocarbon of a composition in a heat transfer system lubricant. In certain embodiments, the compatibilizer returns oil to the compressor Ability has improved. In certain embodiments, the composition is used with a system lubricant to reduce the viscosity of the oil-rich phase.

As used herein, oil return refers to a heat transfer composition carrying a lubricant The ability to pass a heat transfer system and bring the lubricant back to the compressor. That is, in use, it is not unusual for the heat transfer composition to carry certain portions of the compressor lubricant away from the compressor and into other portions of the system. In such systems, if the lubricant is not effectively returned to the compressor, the compressor will eventually fail due to lack of lubrication.

As used herein, an "ultraviolet" dye is defined as a UV fluorescent or A phosphorescent composition that absorbs light in the ultraviolet region of the electromagnetic spectrum or in the "near" ultraviolet region. Fluorescence of the UV fluorochrome dye produced by exposure to UV light can be detected by at least some of the radiation having a wavelength in the range of from 10 nanometers to about 775 nanometers.

The term flammability means the energy of a composition to burn and/or spread flames. force. For refrigerants and other heat transfer compositions, the lower flammability limit ("LFL") is the lowest concentration of heat transfer composition in the air, which can be tested under the test conditions specified by ASTM (American Society for Testing and Materials) E681-04. The flame is continued through a homogeneous mixture of air and composition. The upper limit of flammability ("UFL") is the highest concentration of heat transfer composition in the air that sustains the flame through a homogeneous mixture of composition and air under the same test conditions. In order to be classified as non-flammable by ASHRAE (American Association of Heating, Refrigerating and Air-Conditioning Engineers), a refrigerant must be non-flammable under ASTM E681-04 conditions and liquid phase caused during leakage conditions when formulated into a liquid phase and a vapor phase. Both the vapor phase and the vapor phase must be non-flammable.

The Global Warming Potential (GWP) is an index that measures the relative emissions of one kilogram of specific greenhouse gases based on one kilogram of carbon dioxide emissions. Global warming contribution. By calculating the GWP for different time horizons, you can understand the effect of a particular gas remaining in the atmosphere. The GWP is usually referenced over a hundred years. For mixtures, the weighted average can be calculated based on the individual GWP of each component.

The Ozone Depletion Potential (ODP) is a quantitative representation of ozone depletion caused by a substance. ODP is the ratio of the impact of a chemical on ozone compared to the impact of a comparable quality of CFC-11 (fluorotrichloromethane). Therefore, the ODP of CFC-11 is defined as 1.0. Other CFCs and HCFCs have ODPs ranging from 0.01 to 1.0. HFCs have zero ODP because they do not contain chlorine.

The terms "comprising," "comprising," "having," or "said" or "comprising", as used herein, are intended to encompass non-exclusive inclusions. For example, a composition, process, method, article, or device containing the plural elements listed in the list is not necessarily limited to the elements listed on the list, but may include not explicitly listed or the composition, process , methods, articles or other elements inherent in the device. In addition, unless expressly stated to the contrary, “or” is an inclusive “or” rather than an exclusive “or”. For example: one of the following satisfies condition A or B: A is true (or exists) and B is pseudo (or non-existent), A is pseudo (or nonexistent) and B is true (or exists) , and both A and B are true (or exist).

The conjunction "consisting of" excludes any element, step or component that is not specifically described. If used in the scope of patent application, in addition to the impurities normally associated with it, this language should limit the scope of the patent application to the scope of the materials listed. When the phrase "consisting of" appears in one of the clauses of the request, Rather than immediately following the preceding text, it is limited only to the elements presented in the clause; other elements are generally not excluded from the scope of the patent application.

The word "consisting essentially of" is used to define a composition, method or device that includes materials, steps, features, components or elements other than those disclosed in the text, provided that such additional The materials, steps, features, components or elements are included to substantially affect the basic and novel features of the invention. The meaning of the phrase "mainly composed of" is between "contains" and "consisting of". In general, the components of the refrigerant mixture and their refrigerant mixture may themselves contain small amounts (eg, less than about 0.5 weight percent total) of impurities and/or by-products (eg, from the manufacture of the refrigerant component or from other systems). The refrigerant component is reused, which does not substantially affect the novel and basic characteristics of the refrigerant mixture.

An applicant who defines an invention or part thereof in an open-ended language such as "including" means that (unless otherwise stated) the statement should be construed as being "consisting mainly of" or "consisting of" The invention.

Also, "a" or "an" is used to describe the elements and components described herein. This is done for convenience only and provides a general sense of the scope of the invention. This description should be understood to include one or at least one, and the singular also includes the plural.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning meaning meaning Although materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the disclosed compositions, suitable methods and materials are described below. Unless a specific paragraph is quoted, All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference in their entirety. In the event of a conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting.

Difluorochloromethane (also known as HCFC-22 or R22), 1,1,1-trifluoroethane (also known as HFC-143a or R143a), pentafluoroethane (also known as HFC-125 or R125) 1,1,2,2-tetrafluoroethane (also known as HFC-134 or R134), 1,1,1,2-tetrafluoroethane (also known as HFC-134a or R134a), difluoromethane (also known as HFC-32 or R32), difluoromethoxytrifluoromethane (CF ₃ OCHF ₂ , also known as HFE-125E), propane, propylene, cyclopropane, n-butane, isobutane, n-pentane 2-methylbutane, 2,2-dimethylpropane and cyclopentane are commercially available from a variety of chemical suppliers or refrigerant suppliers.

2,3,3,3-tetrafluoropropene may also be referred to as HFO-1234yf, HFC-1234yf or R1234yf. HFO-1234yf can be prepared by conventional methods in the art, such as dehydrofluorinated 1,1,1,2,3-pentafluoropropane (HFC-245eb) or 1,1,1,2,2- Pentafluoropropane (HFC-245cb).

E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze) can be obtained by 1,1,1,2,3-pentafluoropropane (HFC-245eb, CF ₃ CHFCH ₂ F) or 1 1,1,3,3-pentafluoropropane (HFC-245fa, CF ₃ CH ₂ CHF ₂ ) was prepared by dehydrofluorination. The dehydrofluorination reaction can be carried out in the presence or absence of a catalyst in the vapor phase, and can also be carried out in the liquid phase by reaction with a caustic such as NaOH or KOH. Their reactions are described in more detail in U.S. Patent Publication No. 2006/0106263, which is incorporated herein by reference. HFO-1234ze can exist in the form of one of two conformational isomers (cis- or trans-, also referred to as E- and Z-isomers, respectively). E-HFO-1234ze is available from certain fluorocarbon manufacturers.

Method of refilling or replenishing

During normal use of refrigeration equipment, air conditioning equipment, heat pump equipment, or power cycle equipment, refrigerant (or working fluid) may escape from the system, thereby reducing the performance of the equipment. To restore performance, new refrigerants can be added to replace the lost. HCFC-22 refrigerant loss may be fully filled from less than 1% by weight of the filling to accidental loss per year depending on the type of equipment and the conditions of use.

In one embodiment, a method of refilling or supplementing the refrigerant charge is provided. The method comprises adding a second refrigerant to a refrigeration system, an air conditioning system, a heat pump system or a power cycle system comprising HCFC-22 as a first refrigerant, wherein the second refrigerant comprises at least one refrigerant selected from the group consisting of: HFC-143a, HFC-125, HFC-32, HFC-134, HFC-134a, HFE-125E, propylene, propane, cyclopropane, n-butane, isobutane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, HFO-1234yf, and E-HFO-1234ze, and optionally HCFC-22, thereby producing a refrigerant composition comprising the first refrigerant and the second refrigerant.

In an embodiment, the second refrigerant comprises HFC-143a.

In another embodiment, the second refrigerant further comprises HCFC-22. In another embodiment, the second refrigerant further comprises HFC-125. In another embodiment, the second refrigerant comprises a HFC-143a and a non-flammable refrigerant mixture selected from the group consisting of HCFC-22, HFC-125, and mixtures thereof. Expected to contain less A mixture of HFC-143a and HCFC-22 or HFC-125 at about 60 weight percent HFC-143a would be non-flammable. Thus in another embodiment, the second refrigerant mixture comprises at least about 40 weight percent HCFC-22, HFC-125, or a mixture thereof. In another embodiment, the second refrigerant comprises from about 40 weight percent to about 99 weight percent HCFC-22, HFC-125, or a mixture thereof.

In an embodiment, the second refrigerant comprises HFC-32. In another embodiment, the second refrigerant comprises HFC-134. In another embodiment, the second refrigerant comprises HFC-134a. In another embodiment, the second refrigerant comprises a mixture of HFC-134 and HFC-134a. In another embodiment, the second refrigerant comprises HFE-125E. In another embodiment, the second refrigerant comprises propylene. In another embodiment, the second refrigerant comprises propane. In another embodiment, the second refrigerant comprises cyclopropane. In another embodiment, the second refrigerant comprises n-butane. In another embodiment, the second refrigerant comprises isobutane. In another embodiment, the second refrigerant comprises n-pentane. In another embodiment, the second refrigerant comprises 2-methylbutane. In another embodiment, the second refrigerant comprises 2,2-dimethylpropane. In another embodiment, the second refrigerant comprises cyclopentane. In another embodiment, the second refrigerant comprises HFO-1234yf. In another embodiment, the second refrigerant comprises E-HFO-1234ze. In another embodiment, the second refrigerant comprises a mixture of at least two of: HFC-143a, HFC-125, HFC-32, HFC-134, HFC-134a, HFE-125E, propylene, propane, cyclopropane , n-butane, isobutane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, HFO-1234yf, E-HFO-1234ze or HCFC-22. In another embodiment, the second refrigerant comprises a mixture of at least two of: HFC-143a, HFC-125 or HCFC-22.

In one embodiment, the refrigeration system, air conditioning system, heat pump system, or power cycle system includes a refrigerant composition comprising HCFC-22 in an amount ranging from greater than 0 weight percent to less than 100 weight percent and a content greater than zero The weight percentage is less than 100% by weight of the second refrigerant.

In another embodiment, the refrigeration system, air conditioning system, heat pump system or power cycle system comprises a refrigerant composition comprising HCFC-22 in an amount ranging from about 40 weight percent to less than 100 weight percent and a content greater than 0% by weight to about 60% by weight of the second refrigerant. In another embodiment, the refrigeration system, air conditioning system, heat pump system, or power cycle system includes a refrigerant composition comprising HCFC-22 in an amount ranging from about 40 weight percent to about 99 weight percent and having a content of about 1% by weight to about 60% by weight of the second refrigerant.

The vapor compression air conditioning system and the heat pump system include an evaporator, a compressor, a condenser, and an expansion device. The refrigerating cycle of the refrigerant is reused in a plurality of stages to produce a cooling effect in one stage and a heating effect in another step.

Compressors used in refrigeration systems, air conditioning systems, or heat pump systems include dynamic (eg, shaft or centrifugal) compressors or positive displacement (eg, reciprocating, screw or scroll) compressors. In an embodiment, the refrigeration system, air conditioning system or heat pump system comprises a centrifugal compressor. In another embodiment, the refrigeration system, air conditioning system or heat pump system includes a positive displacement compressor.

In one embodiment, the refrigeration system, air conditioning system, heat pump system, or power cycle system includes a centrifugal compressor, and the centrifugal compressor includes an impeller.

Expanders for use in powertrain systems include dynamic (eg, shaft or centrifugal) expanders or positive displacement (eg, reciprocating, screw or scroll) expanders. In an embodiment, the power cycle system includes a centrifugal expander (ie, a turbine). In another embodiment, the power cycle system includes a positive displacement expander.

In an embodiment of the method of the invention, the refrigeration system, air conditioning system, heat pump system or power cycle system comprises a cooler. In another embodiment, the cooler is a centrifugal cooler.

In an embodiment of the method of the invention, the refrigeration system, air conditioning system, heat pump system or power cycle system comprises a heat pump. In another embodiment, the heat pump is a centrifugal heat pump.

In an embodiment of the method of the invention, the refrigeration system, air conditioning system, heat pump system or power cycle system comprises an organic Rankine cycle system.

In order to fully benefit from the method of the present disclosure, an existing device containing R22 as a refrigerant will be used and a second refrigerant will be added. Compared to the optimum conditions of the R22 refrigerant, the performance provided by refilling or supplementing the second refrigerant necessarily has a certain degree of limitation. Thus, in one embodiment, the average temperature slip is maintained at less than about 1 °C. In another embodiment, the average temperature slip is maintained at less than about 0.75 °C. In another embodiment, the average temperature slip is maintained at less than about 0.5 °C. In another embodiment, the average temperature slip is maintained at less than about 0.25 °C. In another embodiment, the average temperature slip is maintained at less than about 0.16 °C.

In an embodiment, the refrigeration system, air conditioning system, heat pump system, or power cycle system includes a submerged evaporator, a submerged condenser, or a combination thereof. Immersion evaporators and/or condenser systems do not operate efficiently as temperature slip increases. Therefore, in order to make their systems efficient, it is necessary to minimize slippage of the compositions and methods of the present invention.

In one embodiment, the cooling capacity of the system after the addition of the second refrigerant is maintained within 10 percent of the cooling capacity of the system operating when filled with HCFC-22. In another embodiment, the cooling capacity is maintained within 7 percent of the cooling capacity of the system operating when filled with HCFC-22. In another embodiment, the cooling capacity is maintained within 5 percent of the cooling capacity of the system operating when filled with HCFC-22. In another embodiment, the cooling capacity is maintained within 3 percent of the cooling capacity of the system operating when filled with HCFC-22. In another embodiment, the cooling capacity is maintained within 2% of the cooling capacity of the system operating when filled with HCFC-22. In another embodiment, the cooling capacity remains maintained when the system is operated with HCFC-22. Within 1% of the cooling capacity.

In one embodiment, when the refrigeration system, air conditioning system, heat pump system, or power cycle system includes a centrifugal compressor, the impeller tip speed of the centrifugal compressor is maintained while the system is operating with HCFC-22 Centrifugal compressors have an impeller tip rate of less than 10 percent. In another embodiment, the impeller tip speed of the centrifugal compressor is maintained within 7 percent of the impeller tip rate of the centrifugal compressor operating at HCFC-22. In another embodiment, the impeller tip speed of the centrifugal compressor is maintained at a centrifuge that operates when the system is filled with HCFC-22. The compressor has an impeller tip rate of less than 5 percent. In another embodiment, the impeller tip speed of the centrifugal compressor is maintained within 3 percent of the impeller tip rate of the centrifugal compressor operating at HCFC-22. In another embodiment, the impeller tip speed of the centrifugal compressor is maintained within 2 percent of the impeller tip rate of the centrifugal compressor operating at HCFC-22. In another embodiment, the impeller tip speed of the centrifugal compressor is maintained within 1 percent of the impeller tip rate of the centrifugal compressor operating at HCFC-22.

The vapor compression refrigeration system, air conditioning system, heat pump system or power cycle system also contains at least one lubricant that lubricates the moving parts of the compressor or expander and avoids jamming. The lubricant is selected according to the refrigerant used in the system. Systems using R22 as a refrigerant generally use a mineral oil type lubricant. As a hydrofluorocarbon (HFC) or hydrofluoroolefin (HFO) refrigerant (such as HFC-143a, etc.) is added to a system as a make-up or refilling refrigerant (second refrigerant), miscibility with mineral oil-type lubricants Will be reduced accordingly. In order to keep the system operating properly, it is necessary to add other lubricants that are more miscible with HFC-type refrigerants. Accordingly, in an embodiment of the method, further comprising adding at least one lubricant. In another embodiment, the refrigeration system, air conditioning system, heat pump system, or power cycle system includes a first lubricant, and the method further includes replacing at least a portion of the first lubricant with a second lubricant.

In one embodiment, the lubricant to be added is selected from the group consisting of polyol esters (POE), polyvinyl ethers (PVE), mineral oils, or mixtures thereof.

In certain embodiments, the lubricant is a mineral oil lubricant. In certain embodiments, the mineral oil lubricant is selected from the group consisting of paraffin waxes (including straight carbon chain saturated hydrocarbons, a combination of a branched carbon chain saturated hydrocarbon and the above substances), a cycloalkane (including a saturated cyclic and cyclic structure), an aromatic (having an unsaturated hydrocarbon having one or more rings, wherein the one or more rings are characterized It is a group consisting of alternating carbon-carbon double bonds) and non-hydrocarbons (molecules containing atoms such as sulfur, nitrogen, oxygen, and a mixture of the above atoms) and mixtures and combinations thereof.

Certain embodiments may contain one or more synthetic lubricants. In certain embodiments, the synthetic lubricant is selected from the group consisting of alkyl substituted aromatics (eg, benzene or naphthalene substituted with a mixture of linear, branched, or linear and branched alkyl groups, Commonly known as alkyl benzene), synthetic paraffin and naphthenic, poly(alpha olefin), polyglycol (including polyolefin diol), dibasic acid ester, polyester, polyol ester, neopentyl ester, polyethylene Ethers (PVEs), polyoxyxides, phthalates, fluorinated compounds, phosphates, polycarbonates, and mixtures thereof (ie, mixtures of any of the lubricants disclosed in this paragraph).

The lubricants disclosed herein may be commercially available lubricants. For example, the lubricant can (sold by the name of the BVM 100N BVA Oils) is a paraffinic mineral oil by Crompton Co. under the trademark Suniso ^® 1GS, Suniso ^® 3GS and Suniso ^® 5GS naphthenic sold on the mineral oil Naphthenic mineral oil sold by Pennzoil under the trademark Sontex ^® 372LT, naphthenic mineral oil sold under the trade name Calumet ^® RO-30 by Calumet Lubricants, Zerol ^® 75, Zerol ^® 150 by Shrieve Chemicals And linear alkyl benzene sold under the trademark Zerol ^® 500, and branched alkyl benzene sold under the name HAB 22 by Nippon Oil, and polyol ester sold by Castrol, United Kingdom under the trademark Castrol ^® 100 (POEs) Polyolefin diols (PAGs) (such as RL-488A from Dow (Dow Chemical, Midland, Michigan)) and mixtures of the foregoing (meaning a mixture of any of the lubricants disclosed in this paragraph).

Lubricants for use with the present invention can be designed for use with hydrofluorocarbon refrigerants and are miscible with the compositions disclosed herein under the operating conditions of a compression refrigeration and air conditioning unit. In certain embodiments, the lubricant is selected by considering the requirements of a given compressor or expander and the environment in which the lubricant will be exposed.

Although the weight ratios of the above compositions have been disclosed herein, it should be understood that although certain compositions have been used in some heat transfer systems, one or more of the equipment components of the heat transfer system may still require additional lubricant. For example, in some refrigeration systems, air conditioning systems, heat pump systems, or power cycle systems, the lubricant may be filled in a compressor and/or compressor lubricant sump or expander. This lubricant is other than the lubricating additive present in the refrigerant of this system. In use, when the refrigerant composition is in the compressor or the expander, it is possible to pick up some amount of equipment lubricant and change the refrigerant-lubricant composition to be different from the initial ratio.

In certain embodiments, the composition comprising R22 and a second refrigerant may comprise a selective non-refrigerant component (also referred to herein as an additive). The selective non-refrigerant component in the compositions disclosed herein may comprise one or more components selected from the group consisting of dyes (including UV dyes), solubilizers, compatibilizers, stabilizers, Tracer, perfluoropolyether, antiwear agent, extreme pressure agent, corrosion and oxidation inhibitor, metal surface energy reducer, metal surface deactivator, free radical scavenger, foam control agent, viscosity index improver, flow Point drop agents, detergents, viscosity modifiers, and mixtures thereof. Actually, Many of their selective non-refrigerant components are suitable for one or more of their classification and may have properties that enable them to achieve one or more performance characteristics.

In certain embodiments, one or more non-refrigerant compositions are present in small amounts relative to the total composition. In certain embodiments, the amount of additive concentration in the disclosed composition is less than about 0.1 weight percent to up to about 5 weight percent of the total composition. In certain embodiments of the invention, the additive is present in the disclosed compositions in an amount between about 0.1 weight percent to about 5 weight percent total composition, or between about 0.1 weight percent to about 3.5 weight percent. Between percentages. The additive component(s) selected for the disclosed compositions are selected for use and/or individual device component or system requirements.

In the compositions of the invention comprising a lubricant, the lubricant is present in an amount less than 5.0 weight percent relative to the total composition. In other embodiments, the lubricant is present in an amount between about 0.1 and 3.5 weight percent of the total composition.

The non-refrigerant component for use with the compositions of the present invention can include at least one dye. The dye can be at least one ultraviolet (UV) dye. The UV dye can be a fluorescent dye. The fluorescent dye may be selected from naphthalimides, guanidine, coumarin, phenanthracenes, xanthenes, thioxanthenes, naphthalene. Combination of naphthoxanthenes, fluorescein and derivatives of the dyes with a combination of the foregoing, meaning a mixture of any of the foregoing dyes or derivatives thereof as disclosed in this paragraph.

In certain embodiments, the disclosed compositions contain from about 0.001 weight percent to about 1.0 weight percent UV dye. In other embodiments, the UV dye is present in an amount from about 0.005 weight percent to about 0.5 weight percent; and in other embodiments, the UV dye is present in an amount from about 0.01 weight percent to about 0.25 weight percent of the total composition. .

UV dyes are useful components for detecting leakage of a composition by allowing others to observe the fluorescence emitted by the dye near a leak or leak point in a device, such as a freezer, air conditioner, or heat pump. The UV emission (e.g., fluorescence from the dye) can be observed under exposure to ultraviolet light. Therefore, if a composition containing the UV dye leaks from a specific point of a device, fluorescence can be detected at or near the leak point.

Other non-refrigerant components that can be used with the compositions of the present invention can include at least one co-solvent that is selected to improve the solubility of one or more dyes in the disclosed compositions. In certain embodiments, the weight ratio of dye to co-solvent ranges from about 99:1 to about 1:1. The co-solvent comprises at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (eg, dipropylene glycol dimethyl ether), decylamine, nitriles, ketones, chlorocarbons (eg, Methylene chloride, trichloroethylene, chloroform or a mixture thereof, esters, lactones, aromatic esters, fluoroethers and 1,1,1-trifluoroalkane and mixtures thereof, ie any mixture of cosolvents disclosed in this paragraph.

In certain embodiments, the non-refrigerant component comprises at least one compatibilizer for improving the compatibility of one or more lubricant lubricants with the disclosed composition. The compatibilizer comprises at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, and polyoxygen extensions. An alkanediol ether (such as dipropylene glycol dimethyl ether), a guanamine, a nitrile, a ketone, a chlorocarbon (such as dichloromethane, trichloroethane, chloroform or a mixture thereof), an ester, a lactone, an aromatic ether, A group consisting of fluoroether, 1,1,1-trifluoroalkane, and mixtures thereof, meaning a mixture of any compatibilizers disclosed in this paragraph.

The co-solvent and/or compatibilizer may be selected from the group consisting of a hydrocarbon ether consisting of an ether containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME), and mixtures thereof, the mixture means A mixture of any of the hydrocarbon ethers disclosed in the paragraph.

The compatibilizer can be a linear or cyclic aliphatic or aromatic hydrocarbon compatibilizer and contains from 3 to 15 carbon atoms. For the second refrigerant hydrocarbon (for example: propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, 2-methylbutane, 2,2-dimethylpropane or cyclopentane) For the system, a compatibilizer of mineral oil lubricant is not necessary. However, for HFC and HFO refrigerant hydrocarbons (including propane, propylene, cyclopropane and especially selected from n-butane, isobutane, n-pentane, isopentane, hexane, octane, decane and decane) It is necessary for the other of the groups). Commercially available hydrocarbon compatibilizing agents include but are not limited to, available from Exxon Chemical (USA) under the trademark Isopar ^® H (who is undecane (C ₁₁₎ and a mixture of dodecane (C ₁₂₎ of (C ₁₁ to high purity C ₁₂ isoparaffin), Aromatic 150 (C ₉ to C ₁₁ aromatic hydrocarbon), Aromatic 200 (C ₉ to C ₁₅ aromatic hydrocarbon) and Naptha 140 (C ₅ to C ₁₁ paraffin, naphthenic and aromatic hydrocarbons) Mixtures) and mixtures thereof, which means a mixture of any of the hydrocarbons disclosed in this paragraph.

The compatibilizer may additionally be at least one polymerizable compatibilizer. The polymerizable compatibilizer may be a scrambled copolymer of fluorinated and non-fluorinated acrylate, wherein the polymer comprises repeating units of at least one monomer represented by the formula CH ₂ =C(R ¹ ) CO ₂ R ² , CH ₂ =C(R ³ )C ₆ H ₄ R ⁴ and CH ₂ =C(R ⁵ )C ₆ H ₄ XR ⁶ , wherein X is oxygen or sulfur; R ¹ , R ³ and R ⁵ Is independently selected from the group consisting of H and C ₁ -C ₄ alkyl radicals; and R ² , R ⁴ and R ⁶ are independently selected from the group consisting of a group containing a carbon chain of C and F. And may further comprise, H, Cl, ether oxygen or sulfur (in the form of a thioether), a mixture of an anthracene or anthracene group and the above. Examples of such polymeric compatibilizers include those commercially available from EI du Pont de Nemours and Company (Wilmington, DE, 1989, USA) under the trademark Zonyl ^® PHS. Zonyl ^® PHS is a messy copolymer, 40 weight percent of a polymeric _{CH 2 = C (CH 3)} CO 2 CH 2 CH 2 (CF 2 CF 2) m F ( also referred to as Zonyl ^® fluoromethyl acrylate or ZFM, Wherein m is from 1 to 12, mainly from 2 to 8) and 60% by weight of lauryl methacrylate (CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₁₁ CH ₃ , also known as LMA).

In certain embodiments, the compatibilizer component contains from about 0.01 to 30 weight percent (based on the total amount of compatibilizer) of an additive that reduces metallic copper, aluminum, steel, or other metals found in the heat exchanger. Or the surface energy of the metal alloy, and to some extent reduce the adhesion of the lubricant to the metal. Examples of metal surface energy reducing agents include those commercially available from DuPont and under the trademarks Zonyl ^® FSA, Zonyl ^® FSP and Zonyl ^® FSJ.

Other non-refrigerant components that can be used with the compositions of the present invention can be a metal surface deactivator. The metal surface deactivator is selected from the group consisting of (grassyl bis(benzylidene) hydrazine (CAS accession number 6629-10-3), N,N'-bis (3,5-di-tertiary butyl- 4-Hydroxyhydrocincine 醯 肼 (CAS accession number 32687-78-8), 2, 2, '- oxalyl bis-ethyl-(3,5-di-tri-butyl-4-hydroxy hydrogenated cassia Acid ester (CAS registration number 70331-94-1), N,N'-(disialidyl)-1,2-diaminopropane (CAS Accession No. 94-91-7) and ethylenediaminetetraacetic acid (CAS Registry No. 60-00-4) and its salts Mixture with the above materials means a mixture of any of the metal surface deactivators disclosed in this paragraph.

The non-refrigerant component for use with the composition of the present invention may alternatively be a stabilizer selected from the group consisting of hindered phenol, thiophosphate, butylated triphenyl phosphinosulfuric acid. Butylated triphenylphosphorothionates, organophosphates or phosphites, arylalkyl ethers, terpenes, terpenoids, epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols, lactones , thioether, amine, nitromethane, alkyl decane, diphenyl ketone derivative, aryl sulfide, divinyl phthalic acid, diphenyl citric acid, ionic liquid, and mixtures thereof, the mixture means Any mixture of stabilizers as disclosed in this paragraph.

The stabilizer may be selected from the group consisting of tocopherol; hydroquinone; tertiary butyl hydroquinone; monothiophosphate; and dithiophosphate, commercially available from Ciba Specialty Chemicals ( Basel, Switzerland, hereinafter referred to as "Ciba") and under the trademark Irgalube ^® 63; dialkyl phosphorothioates commercially available from Ciba under the trademarks Irgalube ^® 353 and Irgalube ^® 350; butylated Triphenylphosphorylsulfonate, commercially available from Ciba under the trademark Irgalube ^® 232; amine phosphate, commercially available from Ciba and trademarked as Irgalube ^® 349 (Ciba); hindered phosphite, commercially Available from Ciba as Irgafos ^® 168, and ginseng-(di-terp-butylphenyl) phosphite, commercially available from Ciba under the trademark Irgafos ^® OPH; (di-n-octyl phosphite) And isodecyl diphenyl phosphite, commercially available from Ciba and under the trademark Irgafos ^® DDPP; trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate , trioctyl phosphate and tris(2-ethylhexyl) phosphate; triaryl phosphate, including Triphenyl phthalate, tricresyl phosphate and trixylenyl phosphate; mixed alkyl-aryl phosphates, including isopropyl phenyl phosphate (IPPP) and bis(tris) yl) phenyl ester (TBPP); butylated triphenyl phosphates, for example in their commercially Syn-O-Ad ^® is a trademark of commercially available, including Syn-O-Ad ^® 8784; three Butylated triphenyl phosphates, for example, which are commercially available under the trademark Durat ^® 620; isopropylated triphenyl phosphates, for example, which are commercially available as Durad ^® 220 and Durad ^® 110 Trademark purchaser; anisole; 1,4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene; myrcene, allolocene, Terpene (specifically d-limonene); retinal aldehyde; terpene; menthol; geranyl alcohol; phytol alcohol; phytol; vitamin A; terpinene; (delta-3-carene); terpinolene; anise; terpenes; dipentene; carotenoids, such as lycopene, beta carotene and lutein, such as zeaxanthin; Such as epoxy vitamin A and different dimensions A; decane; 1,2-propylene oxide; 1,2-butene oxide; n-butyl epoxypropyl ether; trifluoromethyl oxirane; 1,1-bis(trifluoromethyl) Ethylene oxide; 3-ethyl-3-hydroxymethyl-propylene oxide, such as OXT-101 (Toagosei Co., Ltd); 3-ethyl-3-((phenoxy)methyl) - propylene oxide, such as OXT-211 (Toagosei Co., Ltd); 3-ethyl-3-((2-ethylenehexyl)methyl)-epoxypropane, such as OXT-212 (Toagosei Co., Ltd. Ascorbic acid; methyl mercaptan (methyl mercaptan); ethanethiol (ethyl mercaptan); coenzyme A; dimercaptosuccinic acid (DMSA); grapefruit thiol ((R)-2-( 4-methylcyclohex-3-enyl)propane-2-thiol)); cysteine ((R)-2-amino-3-thio-propionic acid); lipoamide 1,2-dithiolane-3-pentanamide); 5,7-bis(1,1-dimethylethyl)-3-[2,3 (or 3 , 4)-xylyl]-2(3H)-benzofuranone, commercially available from Ciba and under the trademark Irganox ^® HP-136; benzyl phenyl sulfide; diphenyl sulfide; Propylamine; bis(octadecyl) 3,3'-thiodipropionate commercially available from Ciba under the trademark Irganox ^® PS 802 (Ciba); 3,3 '-Tetradecyl thiopropionate, commercially available from Ciba and under the trademark Irganox ^® PS 800; bis-(2,2,6,6-tetramethyl-4-piperidinyl)sebacate Salt, commercially available from Ciba under the trademark Tinuvin ^® 770; poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidinyl succinate, commercially available Available from Ciba and sold under the trademark Tinuvin ^® 622LD (Ciba); methyl double tallow amine; double tallow amine; phenol-α-naphthylamine; bis(dimethylamino)methane (DMAMS); Base alkyl) decane (TTMSS); vinyl triethoxy decane; vinyl trimethoxy decane; 2,5-difluorodiphenyl ketone; 2', 5'-dihydroxyacetophenone; Diphenyl ketone; 2-chlorodiphenyl ketone: benzyl phenyl sulfide; diphenyl thioether; dibenzyl sulfide; ionic liquid; mixture and combination with the above.

The additive used with the composition of the present invention may alternatively be an ionic liquid stabilizer. The ionic liquid stabilizer may be selected from the group consisting of organic salts, which are liquid at room temperature (about 25 ° C), and the salts thereof are selected from the group consisting of pyridinium cations, pyridazine cations, pyrimidine oximes, pyrazine cations, and imidazoles. a cation of a group consisting of a cation, an azole cation, a thiazole cation, an oxazole cation, and a triazole cation, and mixtures thereof; and selected from the group consisting of [BF ₄ ]-, [PF ₆ ]-, [SbF ₆ ]-, [CF ₃ SO ₃ ]-, [HCF ₂ CF ₂ SO ₃ ]-, [CF ₃ HFCCF ₂ SO ₃ ]-, [HCClFCF ₂ SO ₃ ]-, [(CF ₃ SO ₂ ) ₂ N]-, [(CF ₃ CF ₂ An anion of the group consisting of SO ₂ ) ₂ N]-, [(CF ₃ SO ₂ ) ₃ C]-, [CF ₃ CO ₂ ]-, and F- and mixtures thereof. In certain embodiments, the ionic liquid stabilizer is selected from the group consisting of emim BF ₄ (1-ethyl-3-methylimidazolium cation tetrafluoroborate); bmim BF ₄ (1-butyl) 3-methylimidazolium cation tetraborate); emim PF ₆ (1-ethyl-3-methylimidazolium cation hexafluorophosphate); and bmim PF ₆ (1-butyl-3-methylimidazolium cation) Hexafluorophosphate salt, all of which are available from Fluka (Sigma-Aldrich).

In certain embodiments, the stabilizer may be a hindered phenol which is any substituted phenolic compound, including phenols containing one or more substituted or cyclic, linear or branched aliphatic substituent groups , such as alkylated monophenols, which include 2,6-ditributyl-4-methylphenol; 2,6-ditributyl-4-acetol; 2,4-dimethyl-6- Tertiary butyl phenol; tocopherol; and similar, hydroquinone and alkylated hydroquinone, which include tertiary butyl hydroquinone, other derivatives of hydroquinone; and similarly, hydroxylated thiodiphenyl ether, Including 4,4'-thio-bis(2-methyl-6-tertiary butyl phenol); 4,4'-thiobis(3-methyl-6-tertiary butyl phenol); 2,2' -thio bis(4methyl-6-tertiary butyl phenol); and analogs, alkylidene bisphenols, including: 4,4'-methylenebis(2,6-di-tributylphenol) ; 4,4'-bis(2,6-di-tri-n-butylphenol); derivative of 2,2'- or 4,4-biphenyl glycol; 2,2'-methylene double (4- Ethyl-6-tertiary butyl phenol); 2,2'-methylenebis(4-methyl-6-tertiary butyl phenol); 4,4-butylene bis(3-methyl-6-three Butyl phenol); 4,4-isopropylidene bis(2,6-ditriphenylbutanol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2 '-Isobutyl bis(4,6-xylenol); 2,2'-methylenebis(4-methyl-6-cyclohexanol, 2,2- or 4,4-biphenyl a diol comprising 2,2'-methylenebis(4-ethyl-6-tertiary butyl phenol); butylated hydroxytoluene (BHT, or 2,6-ditributyl-4-yl-4-) a phenol containing a hetero atom, which comprises 2,6-di-tris-α-dimethylamino-p-cresol and 4,4-thiobis(6-tertiary butyl-inter) -cresol); and class Like; guanamine phenol; 2,6-ditributyl butyl-4 (N,N'-dimethylamino cresol); thioether, which includes: bis(3-methyl-4-hydroxy- 5-tris-butylbenzyl) sulfide; bis(3,5-ditributyl-4-hydroxybenzyl) sulfide and mixtures thereof, the mixture means a mixture of any of the phenols disclosed in this paragraph.

The non-refrigerant component used with the compositions of the present invention may alternatively be a tracer. The tracer can be two or more tracer compounds and are derived from the same species of compound or from different classes of compounds. In certain embodiments, the total concentration of the tracer present in the composition is from about 50 parts per million (ppm) to about 1000 ppm by weight, based on the weight of the total composition. In other embodiments, the tracer is present in a total concentration of from about 50 ppm to about 500 ppm. Alternatively, the tracer is present in a total concentration of from about 100 ppm to about 300 ppm.

The tracer may be selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes and ketones, nitrous oxide and the above. A group of combinations of substances. Alternatively, the tracer may be selected from the group consisting of fluoroethane, 1,1,-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 1,1,1 , 2,3,4,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,4,5,5,6,6,7,7,7-13 Fluoroheptane, iodine trifluoromethane, deuterated hydrocarbon, deuterated hydrogen fluorocarbon, perfluorocarbon, fluoroether, brominated compound, iodinated compound, alcohol, aldehyde, ketone, nitrous oxide (N ₂ O ) a group of its mixture. In certain embodiments, the tracer is a blend of two or more hydrofluorocarbons, or a combination of a hydrofluorocarbon and one or more perfluorocarbons.

The tracer can be added to the compositions of the invention in a predetermined amount to enable detection of dilution, contamination or other changes in any of the compositions.

Additives which may be used with the compositions of the invention may additionally be perfluoropolyethers as detailed in US 2007-0284555, which is incorporated herein by reference.

Some of the additives mentioned above that are suitable for use in the non-refrigerant component have been recognized as potential refrigerants. However, in accordance with the present invention, when such additives are used, they will be present in amounts that will not affect the novel and essential characteristics of the refrigerant mixture of the present invention.

In one embodiment, the compositions disclosed herein can be prepared in any convenient manner to combine the individual components in the desired amounts. A preferred method is to weigh the desired component weights and then combine the components in a suitable container. Stirring can be used if needed.

Device, method and usage flow

The compositions disclosed herein can be used as a heat transfer composition or a refrigerant.

The mechanical vapor compression refrigeration system, the air conditioning system, and the heat pump system include an evaporator, a compressor, a condenser, and an expansion device. The refrigerating cycle of the refrigerant is reused in a plurality of stages to produce a cooling effect in one stage and a heating effect in another step. This cycle can be briefly described as follows. The liquid refrigerant enters an evaporator via an expansion device, and the liquid refrigerant boils in the evaporator by taking heat away from the environment or steam or the object to be cooled, forming a vapor at a low temperature and generating cooling. Typically, air or a heat transfer liquid flows through or around the evaporator to conduct a cooling effect caused by evaporation of the refrigerant in the evaporator to the object to be cooled. The low pressure vapor enters a pressure The compressor is compressed here to increase its pressure and pressure. The higher pressure (compressed) gaseous refrigerant then enters the condenser where it condenses and vents its heat to the environment or vapor or the object to be heated. The refrigerant is returned to the expansion device, through which the liquid expands to a lower pressure level (in the evaporator) from a higher pressure level (in the condenser), thereby repeating the cycle. A power cycle system includes a heat source, a working fluid heater, an expander, a condenser, and a pump. The working fluid is heated by a heat source in the heater. The heated working fluid expands in the expander. The expansion process causes at least a portion of the thermal energy provided by the heat source to be converted to mechanical shaft power. Depending on the desired speed and required torque, this shaft power can be used for any mechanical work by using the traditional configuration of belts, pulleys, gears, transmissions and similar devices. The working fluid leaving the expander, still in vapor form, continues to be directed to the condenser where sufficient heat is removed to condense the fluid into a liquid phase. The liquid phase working fluid flows to the pump, which raises the fluid pressure so that the fluid can be directed back into the heater, thereby completing the power cycle loop.

A method is provided to replace HCFC-22 in refrigeration systems, air conditioning systems, heat pump systems, or power cycle system equipment. The method comprises replacing HCFC-22 that is leaking or otherwise lost with at least one refrigerant selected from the group consisting of HFC-143a, HFC-125, and optionally HCFC-22.

In one embodiment, a method of producing cooling in a refrigeration, air conditioning or heat pump apparatus suitable for use of HCFC-22 as a refrigerant is provided. The method comprises utilizing a combination of HCFC-22 and at least one refrigerant selected from the group consisting of HFC-143a, HFC-125 and optionally HCFC-22 in the apparatus to produce cooling as a refrigerant.

In one embodiment, a refrigeration apparatus, an air conditioning apparatus, a heat pump apparatus, or a power circulation apparatus including a refrigerant composition and suitable for use of HCFC-22 as a refrigerant is provided. The apparatus is characterized by comprising a refrigerant composition of the present invention consisting of or consisting essentially of: HCFC-22 and at least one selected from the group consisting of HFC-143a, HFC-125 and E-HFO-1234ze. Group of refrigerants.

In one embodiment, disclosed herein is a method of producing a cooling comprising condensing a refrigerant composition of the present invention consisting of or consisting essentially of: HCFC-22 and at least one selected from the group consisting of HFC- The refrigerant of the group consisting of 143a and HFC-125, and then evaporating the refrigerant in the vicinity of the object to be cooled.

An object to be cooled can be defined as any space, location, object, vapor, or object from which heat is to be removed. Examples include spaces that need to be frozen or cooled (open or closed), such as a freezer or freezer in a supermarket.

In one embodiment, disclosed herein is a method of producing heat comprising vaporizing a refrigerant composition of the present invention consisting of or consisting essentially of: HCFC-22 and at least one selected from the group consisting of HFC- The refrigerant of the group consisting of 143a and HFC-125, and then compressing and condensing the refrigerant in the vicinity of the object to be heated.

An object to be heated can be defined as any space, location, object, vapor, or body to which it is intended to provide heat. Examples include spaces that need to be heated (open or closed), such as single family homes, urban houses, or multiple apartment buildings or public buildings.

The method of generating cooling in the vicinity means that the evaporator of the system containing the refrigerant mixture is placed inside or adjacent to the body to be cooled, thus moving through The air of the evaporator will move into or around the body to be cooled. The method of generating heat in the vicinity means that the condenser of the system containing the refrigerant mixture is placed inside or adjacent to the body to be heated, so that the air moving through the condenser will move to the body to be heated or Around.

In certain embodiments, the refrigerant mixture disclosed herein can be used in refrigeration applications, particularly including moderate temperature freezing. The medium temperature refrigeration system includes supermarkets and convenience store freezer for beverage, dairy, fresh food transportation and other items that require refrigeration. Other specific uses are commercial, industrial refrigerators and freezers, supermarket display racks and distribution systems, walk-in and pick-and-place refrigerators and freezers, and combination systems.

In certain embodiments, the compositions of the present invention are useful in air conditioning applications. The air conditioning unit can be a chiller, heat pump, domestic, commercial or industrial air conditioning system and includes ductless, ducted, terminal units, chillers, and those externally connected to the building, such as roof systems. .

In particular, the method of the present invention for substituting R22 or refilling or replenishing a system containing R22 is particularly useful for large equipment requiring significant investment in replacement, such as large submerged evaporator coolers and heat pumps. The use of the method of the present invention will allow existing equipment to continue to operate when R22 is limited, can only be obtained in limited quantities, is expensive, or is no longer available for replenishment or refilling of the system.

In another embodiment, there is provided a method of refilling a refrigeration system, an air conditioning system, a heat pump system or a power cycle system comprising a refrigerant and a lubricant to be replaced, the method comprising from the refrigeration system or an air conditioning system or a heat pump system or The power circulation system removes the refrigerant to be replaced while retaining the main part of the lubricant in the system and guiding One of the compositions of the present invention and additional lubricant to the refrigeration system, air conditioning system, heat pump system or power cycle system.

In another embodiment, a refrigeration system, an air conditioning system, a heat pump system, or a power cycle system comprising the compositions disclosed herein is provided. The system may include a condensing unit, a household air conditioner, a domestic heat pump, a centrifugal or screw cooler, a commercial centrifugal or screw heat pump, and a Rankine cycle systems.

In one embodiment, a freezer or air conditioning device containing the compositions disclosed herein is provided. In another embodiment, a freezer comprising the composition disclosed herein is disclosed. In another embodiment, an air conditioning unit containing the compositions disclosed herein is disclosed. In another embodiment, a heat pump device incorporating the compositions disclosed herein is disclosed. The apparatus typically includes an evaporator, a compressor, a condenser, and an expansion device.

In another embodiment, a power cycle system device is disclosed. The apparatus typically includes an evaporator, an expander, a condenser, and a liquid pump.

In one embodiment, a refrigeration system, an air conditioning system, a heat pump system, or a power cycle system including a cooler is provided. In another embodiment, the cooler is a centrifugal cooler.

In one embodiment, a refrigeration system, an air conditioning system, a heat pump system, or a power cycle system including a heat pump is provided. In another embodiment, the heat pump is a centrifugal heat pump.

In one embodiment, a refrigeration system, an air conditioning system, a heat pump system, or a power cycle system including an organic Rankine cycle system is provided.

In one embodiment, a method is provided comprising refilling a refrigerant composition containing a HCFC-22, an air conditioning system, a heat pump system, or a power cycle system, the refrigerant composition comprising at least one selected from the group consisting of HFC-143a , HFC-125 and, depending on the situation, the refrigerant of the group consisting of HCFC-22.

In another embodiment, a method is provided comprising replacing HCFC-22 in a refrigeration system, an air conditioning system, a heat pump system, or a power cycle system with a refrigerant composition comprising at least one member selected from the group consisting of HFC-143a , HFC-125 and, depending on the situation, the refrigerant of the group consisting of HCFC-22. In another embodiment of the replacement method, the refrigeration system, air conditioning system, heat pump system or power cycle system comprises a centrifugal compressor. In another embodiment of the replacement method, the impeller tip rate of the centrifugal compressor is maintained within 10 percent of the impeller tip rate of the centrifugal compressor operating the system when filled with HCFC-22.

Instance

The concepts disclosed herein are further illustrated by the following examples which do not limit the scope of the invention described in the claims.

Example 1 Make up a HCFC-22 centrifugal cooler with HFC-143a (small amount of filling loss; T _evap = 4.44 ° C)

A relatively small amount of working fluid is lost throughout the year from a well-maintained centrifugal chiller, typically within 1-2 weight percent of the fluid fill per year. With HFC-143a The supplemental loss of HCFC-22 fill will restore the thermodynamic performance of the HCFC-22 cooler to nearly full HCFC-22 performance. The amount of HFC-143a added to achieve optimum cooler performance will (generally) correspond to the amount of HCFC-22 lost. Table 1 compares the chiller performance with HCFC-22-filled chiller performance after HFC-143a supplementation of HCFC-22 fill loss (recovered fill contains up to 20 weight percent HCFC-143a).

For example, in the case of HCFC-22/HFC-143a filled with 20% by weight of HFC-143a, the condenser pressure will be only 3.83 percent higher than the pure HCFC-22, ie the pressure is still a large number of centrifugal coolers. The working pressure is low; the volume cooling capacity will be 0.55% higher than that of pure HCFC-22 (ie, equivalent), and it will continue to meet the cooling load of the cooler; the evaporator and condenser slip will be equivalent to 0.16 ° C, ie For the acceptable performance of even a submerged heat exchanger, it is small enough; and the impeller tip rate required to raise the fluid from the thermodynamic state of the evaporator to the thermodynamic state of the condenser, and the use of pure HCFC The required rate of -22 is almost the same (within 0.5%), so no large-scale impeller modification is required. A slight increase in energy consumption (nearly 1.48 percent) occurs in the case of HCFC-22-filled conditions. HCFC-22/HFC-143a blends containing up to 20 weight percent HCFC-143a are likely to be non-flammable and compatible with mineral oil based coolant lubricants. The addition of a small proportion of a three carbon atom to the HCFC-22/HFC-143a blend will increase the compatibility of the blend with the mineral oil lubricant.

The results in Table 1 show that the annual loss of HCFC-22 by HFC-143a is as high as 2% by weight of the filling, which extends the service life of the centrifugal cooler for at least 10 years without significant performance degradation. Even at higher replenishment rates, the chiller performance of HCFC-22/HFC-143a blends is sufficient in many cases, which is beneficial to solve the problem of HCFC-22 filling loss by replenishing losses with HFC-143a. And thus extending the life of the cooler is even more an alternative (for example: retrofitting the cooler with a different working fluid or replacing the cooler).

Example 2 Complementing HCFC-22 centrifugal cooler with HFC-143a (a large amount of filling loss; T _Evap =4.44°C)

While doing its utmost to prevent a reduction in filling losses, in some cases the rate of loss from the cooler can be significantly higher than the rate of Example 1. Furthermore, it is also possible to catastrophically lose the total amount of fluid filling. Table 2 compares the chiller performance after the HCFC-22 fill loss with HFC-143a (the recovered fill contains more than 20 weight percent HCFC-143a), and the chiller performance filled with HCFC-22. Mixtures with sufficiently high levels of HFC-143a are likely to be flammable and require some means of mitigating the associated flammability risk. Furthermore, blends having a sufficiently high HFC-143a content need to ensure a sufficient compatibility with the mineral oil lubricant (eg, adding a small proportion of hydrocarbons to the blend) or using an alternative lubricant (eg : POE type lubricant).

Table 2 shows that the maximum condenser pressure of 1.74 megapascals (in the case of HFC-143a completely replacing HCFC-22) is lower than the maximum design working pressure of most centrifugal chillers. Again, the volumetric cooling capacity of any blended HCFC-143a content (the required impeller tip rate and evaporator and condenser slip are listed in Table 2) is significantly similar to the value of using pure HCFC-22. Thus, even after supplementing more than about 30 weight percent of HCFC-22 with HFC-143a, the cooler originally designed to operate with pure HCFC-22 can maintain its cooling load without major modifications. However, the energy consumption of the cooler is relatively high, and the HFC-143a content in the cooler fluid filling is high, and the energy consumption is higher.

Example 3 Complementing HCFC-22 centrifugal cooler with HFC-143a/HFC-125 blend (a large amount of filling loss; T _Evap =4.44°C)

If some HCFC-22 cooler applications are unable to accept flammable working fluids, the HFC-143a/HFC-125 blend may be used to supplement the HCFC-22 fill loss so that the recovered fluid fill contains a sufficient proportion of HCFC-22 and HFC -125 instead of Flammable. Table 3 compares the chiller performance and the HCFC-22-filled chiller performance after the HCFC-22 fill loss is supplemented with HFC-143a/HFC-125 blends of different compositions. The blends having a sufficiently high HFC-143a/HFC-125 content in Table 3 are required to ensure adequate compatibility with mineral oil lubricants (eg, adding a small proportion of hydrocarbons to the blend) or using alternatives Lubricant (for example: POE type lubricant).

Table 3 indicates that the addition of HFC-125 to HFC-143a to HCFC-22 to ensure the non-flammability of the working fluid blend results in a better performance for the use of pure HCFC-22 than the addition of HFC-143a alone. Large cooler performance deviates. The condenser pressure remains below the maximum design working pressure of most centrifugal coolers. The evaporator and condenser slips are kept low enough to be acceptable in many cases. The cooler volume cooling capacity increases as the content of HFC-125 increases. In cases where certain working fluids contain a relatively large proportion of HFC-125, it may be advantageous to adjust the impeller tip rate to be more consistent with the cooler operating specifications.

Table 3 (end)

Example 4 Add HFC-143a/HFC-125 (60/40 weight percent) blend to complement HCFC-22 Centrifugal cooler (large filling loss; T _Evap =4.44°C)

HFC-143a/HFC-125 blends containing at least 40 weight percent HFC-125 are non-flammable according to U.S. Patent No. 5,211,867, issued to Jan. Table 4 compares the HCFC-22 filling loss with HFC-143a/HFC-125 blend containing 40% by weight of HFC-125 Subsequent cooler performance and cooler performance filled with HCFC-22. The chiller performance in Table 4 is sufficient in many cases to facilitate the problem of HCFC-22 filling loss by replenishing losses with HFC-143a/HFC-125 blends containing 40 weight percent HFC-125. And thus extending the life of the cooler is an even more alternative (for example: retrofitting the cooler with a different working fluid or replacing the cooler).

Example 5 Replenishing R22 refrigerant filling with other HFC refrigerants

The present invention provides a method of reducing and restoring performance of HCFC-22 by supplementing a chiller or other device with the addition of a composition of the present invention. Tables 5, 6 and 7 show the performance achievable when using HFC-134, HFC-134a or HFC-32 as a make-up refrigerant to make up the refrigerant charge in equipment containing R22.

The data shown in Tables 5, 6 and 7 show that certain amounts of HFC-134, HFC-134a or HFC-32 can be used to complement the R22 filling in the cooling system without substantial loss of performance. Add HFC-134 to HCFC-22 to form up to about 15 weight percent The blend of HFC-134 limits the loss of volume cooling capacity to less than about 6.5 percent relative to pure HCFC-22 (see Table 5). The condenser and evaporator slip will remain below about 1 °C. The addition of HFC-134a to HCFC-22 to form a blend having up to about 30 weight percent HFC-134a can limit the loss of volume cooling capacity to less than about 10 percent relative to pure HCFC-22 (see Table 6). The condenser and evaporator slip will remain below about 1 °C. The addition of HFC-32 to HCFC-22 to form a blend with up to about 10 weight percent HFC-134a enhanced the volume cooling capacity to relatively pure HCFC-22 to about 9% (see Table 7). The condenser and evaporator slip will remain below about 1.3 °C.

Selected embodiment

Embodiment A1: A method comprising adding a second refrigerant to a refrigeration system, an air conditioning system, a heat pump system or a power cycle system containing HCFC-22 as a first refrigerant, wherein the second refrigerant comprises at least one selected from the group consisting of HFC- A second refrigerant of the group consisting of 143a, HFC-125, and mixtures thereof, and optionally HCFC-22, produces a refrigerant composition comprising the first refrigerant and the second refrigerant.

Embodiment A2. The method of Embodiment A1 wherein the second refrigerant comprises HFC-143a.

Embodiment A3. The method of Embodiment A2 wherein the second refrigerant further comprises HCFC-22.

The method of any one of embodiments A2-A3, wherein the second refrigerant further comprises HFC-125.

The method of any one of embodiments A1 to A4, wherein the second refrigerant comprises a HFC-143a and a non-flammable refrigerant selected from the group consisting of HCFC-22, HFC-125, and mixtures thereof Refrigerant mixture.

The method of any one of embodiments A2-A5, wherein the second refrigerant mixture comprises at least about 40 weight percent of HCFC-22, HFC-125, or a mixture thereof.

The method of any one of embodiments A2-A5, wherein the second refrigerant mixture comprises from about 40 weight percent to about 99 weight percent of HCFC-22, HFC-125, or a mixture thereof.

The method of any one of embodiments A1 to A6, wherein the refrigeration system, the air conditioning system, the heat pump system or the power cycle system comprises a centrifugal compressor, and the centrifugal compressor comprises an impeller.

The method of any one of embodiments A1 to A7, wherein the refrigeration system, air conditioning system, heat pump system, or power cycle system comprises a submerged evaporator, a submerged condenser, or a combination thereof.

The method of any one of embodiments A1 to A8, wherein the average temperature slip is maintained below 1 °C.

The method of any one of embodiments A1 to A8, wherein the average temperature slip is maintained below 0.5 °C.

The method of any one of embodiments A1 to A8, wherein the average temperature slip is maintained below 0.25 °C. Example A10: as in Example A1 The method of any of A9, wherein the cooling capacity of the system after the addition of the second refrigerant is maintained within 10 percent of the cooling capacity of the system operating with HCFC-22.

The method of any one of embodiments A1 to A9, wherein the cooling capacity of the system after the addition of the second refrigerant is maintained within 7 percent of the cooling capacity of the system operating when filled with HCFC-22.

The method of any one of embodiments A1 to A9, wherein the cooling capacity of the system after the addition of the second refrigerant is maintained within 5 percent of the cooling capacity of the system operating when filled with HCFC-22.

The method of any one of embodiments A1 to A9, wherein the cooling capacity of the system after the addition of the second refrigerant is maintained within 3 percent of the cooling capacity of the system operating when filled with HCFC-22.

The method of any one of embodiments A1 to A9, wherein the cooling capacity of the system after the addition of the second refrigerant is maintained within 2% of the cooling capacity of the system operating when filled with HCFC-22.

The method of any one of embodiments A1 to A10, wherein the impeller tip speed of the centrifugal compressor is maintained at an impeller tip rate of the centrifugal compressor operating in the system when filled with HCFC-22. Within 10 percentages.

The method of any one of embodiments A1 to A10, wherein the impeller tip speed of the centrifugal compressor is maintained at an impeller tip rate of the centrifugal compressor operating in the system when filled with HCFC-22. Within 7 percentages.

The method of any one of embodiments A1 to A10, wherein the impeller tip speed of the centrifugal compressor is maintained at an impeller tip rate of the centrifugal compressor operating in the system when filled with HCFC-22. Within 5 percentages.

The method of any one of embodiments A1 to A10, wherein the impeller tip speed of the centrifugal compressor is maintained at an impeller tip rate of the centrifugal compressor operating in the system when filled with HCFC-22. Within 3 percentages.

The method of any one of embodiments A1 to A10, wherein the impeller tip speed of the centrifugal compressor is maintained at an impeller tip rate of the centrifugal compressor operating in the system when filled with HCFC-22. Within 2 percentages.

The method of any one of embodiments A1 to A11, further comprising adding at least one lubricant.

The method of any one of embodiments A1 to A12, wherein the refrigeration system, the air conditioning system, the heat pump system or the power cycle system also contains a first lubricant, the method further comprising replacing at least a portion with the second lubricant The first lubricant.

The method of any one of embodiments A1 to A13, wherein the at least one lubricant is selected from the group consisting of polyol esters, polyvinyl ethers, mineral oils, or mixtures thereof.

The method of any one of embodiments A1 to A14, wherein the second lubricant is selected from the group consisting of polyol esters, polyvinyl ethers, mineral oils, or mixtures thereof.

The method of any one of embodiments A1 to A15, wherein the refrigeration system, the air conditioning system, the heat pump system or the power cycle system comprises a refrigerant group The composition comprises HCFC-22 in an amount ranging from greater than 0 weight percent to less than 100 weight percent and the second refrigerant in an amount greater than 0 weight percent to less than 100 weight percent.

The method of any one of embodiments A1 to A16, wherein the refrigeration system, air conditioning system, heat pump system or power cycle system comprises a refrigerant composition comprising a content of from about 40 weight percent to less than 100 weight percent The range of HCFC-22 and the amount of the second refrigerant is from greater than about 0 weight percent to about 60 weight percent.

The method of any one of embodiments A1 to A17, wherein the refrigeration system, air conditioning system, heat pump system or power cycle system comprises a cooler.

The method of any one of embodiments A1 to A18, wherein the refrigeration system, air conditioning system, heat pump system or power cycle system comprises a centrifugal cooler.

The method of any one of embodiments A1 to A19, wherein the refrigeration system, air conditioning system, heat pump system or power cycle system comprises a heat pump.

The method of any one of embodiments A1 to A20, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system comprises a centrifugal heat pump.

The method of any one of embodiments A1 to A21, wherein the refrigeration system, air conditioning system, heat pump system or power cycle system comprises an organic Rankine cycle system.

Embodiment B1: A method comprising refilling a refrigeration system containing HCFC-22, an air conditioning system, a heat pump system or a power circulation system with a refrigerant composition, the refrigerant composition comprising at least one selected from the group consisting of HFC-143a, HFC-125 And a mixture of refrigerants of the mixture, and optionally HCFC-22.

Embodiment B2: The method of Embodiment B1, comprising refilling a refrigeration system containing HCFC-22, an air conditioning system, a heat pump system or a power circulation system with a refrigerant composition, the refrigerant composition comprising at least one selected from the group consisting of HFC-143a a refrigerant composed of a group of HFC-125 and a mixture thereof.

Embodiment C1: A method comprising replacing HCFC-22 in a refrigeration system, an air conditioning system, a heat pump system, or a power cycle system with a refrigerant composition, the refrigerant composition comprising at least one selected from the group consisting of HFC-143a, HFC-125, and The mixture consists of a mixture of refrigerants, and optionally HCFC-22.

Embodiment C2: The method of Embodiment C1, comprising replacing HCFC-22 in a refrigeration system, an air conditioning system, a heat pump system, or a power cycle system with a refrigerant composition, the refrigerant composition comprising at least one selected from the group consisting of HFC-143a, A refrigerant consisting of a group of HFC-125 and mixtures thereof.

The method of any one of embodiments C1 to C2, wherein the refrigeration system, the air conditioning system, the heat pump system or the power cycle system comprises a centrifugal compressor, and the centrifugal compressor comprises an impeller.

The method of any one of embodiments C1 to C3, wherein the impeller tip rate of the centrifugal compressor is maintained at an impeller tip rate of the centrifugal compressor operating in the system when filled with HCFC-22. Within 10 percentages.

Claims (26)

A method comprising: adding a second refrigerant to a refrigeration system, an air conditioning system, a heat pump system or a power cycle system containing HCFC-22 as a first refrigerant, wherein the second refrigerant comprises at least one selected from the group consisting of HFC-143a, HFC The refrigerant of the group consisting of -125 and its mixture, and optionally HCFC-22, produces a refrigerant composition comprising the first refrigerant and the second refrigerant. The method of claim 1, wherein the second refrigerant comprises HFC-143a. The method of claim 2, wherein the second refrigerant further comprises HCFC-22. The method of claim 2, wherein the second refrigerant further comprises HFC-125. The method of claim 2, wherein the second refrigerant comprises an HFC-143a and a non-flammable refrigerant mixture selected from the group consisting of HCFC-22, HFC-125, and mixtures thereof. The method of claim 5, wherein the second refrigerant mixture comprises at least about 40 weight percent of HCFC-22, HFC-125, or a mixture thereof. The method of claim 1, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system comprises a centrifugal compressor, and the centrifugal compressor includes an impeller. The method of claim 1, wherein the refrigeration system, air conditioning system, heat pump system, or power cycle system comprises a submerged evaporator, a submerged condenser, or a combination thereof. The method of claim 1 wherein the average temperature slip is maintained at less than 1 °C. The method of claim 1, wherein the cooling capacity of the system after the addition of the second refrigerant is maintained within 10 percent of the cooling capacity of the system operating when filled with HCFC-22. The method of claim 7, wherein the impeller tip speed of the centrifugal compressor is maintained within 10 percent of the impeller tip rate of the centrifugal compressor operating the system when filled with HCFC-22. The method of claim 1, further comprising adding at least one lubricant. The method of claim 1, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system also contains a first lubricant, the method further comprising replacing at least a portion of the first lubricant with the second lubricant. The method of claim 12, wherein the at least one lubricant is selected from the group consisting of polyol esters, polyvinyl ethers, mineral oils, or mixtures thereof. The method of claim 13, wherein the second lubricant is selected from the group consisting of polyol esters, polyvinyl ethers, mineral oils, or mixtures thereof. The method of claim 1, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power circulation system comprises a refrigerant composition comprising HCFC-22 in an amount ranging from greater than 0 weight percent to less than 100 weight percent and a content of More than 0 weight percent to less than 100 weight percent of the second refrigerant. The method of claim 10, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system comprises a refrigerant composition comprising HCFC-22 in an amount ranging from about 40 weight percent to less than 100 weight percent and a content of More than 0 weight percent to about 60 weight percent of the second refrigerant. The method of claim 1, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system includes a cooler. The method of claim 18, wherein the refrigeration system, air conditioning system, heat pump system, or power cycle system comprises a centrifugal cooler. The method of claim 1, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system comprises a heat pump. The method of claim 20, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system comprises a centrifugal heat pump. The method of claim 1, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system is an organic Rankine cycle system. A method comprising: refilling a refrigerant composition containing HCFC-22, an air conditioning system, a heat pump system, or a power cycle system, the refrigerant composition comprising one less selected from the group consisting of HFC-143a, HFC-125, and mixtures thereof The group of refrigerants, and optionally HCFC-22. A method comprising: replacing a refrigerant system, an air conditioning system, a heat pump system, or a HCFC-22 in a power cycle system with a refrigerant composition comprising at least one member selected from the group consisting of HFC-143a, HFC-125, and mixtures thereof The group of refrigerants, and optionally HCFC-22. The method of claim 24, wherein the refrigeration system, the air conditioning system, the heat pump system, or the power cycle system comprises a centrifugal compressor, and the centrifugal compressor includes an impeller. The method of claim 25, wherein the impeller tip speed of the centrifugal compressor is maintained within 10 percent of the impeller tip rate of the centrifugal compressor operating the system when filled with HCFC-22.