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    • 专利摘要:
    HEAT TRANSFER COMPOSITION, COOLING SYSTEM, METHOD FOR REPLACING AN EXISTING HEAT TRANSFER, CONTAINED IN THE HEAT TRANSFER SYSTEM, AND HEAT TRANSFER SYSTEM. These are heat transfer systems, methods and compositions, which use a heat transfer fluid, comprising: (a) from about 30% to about 65% by weight of HFC-134a, (b) about from 0% to about 70% by weight of HFO1234ze; and (c) from about 0% to about 70% by weight of HFO-1234yf, provided that the amount of HFO-1234ze and HFO-1234yf in the composition together is at least about 35% by weight, with the weight percentage being based on the total of components (a) - (c) in the composition.
    公开号:BR112012028419B1
    申请号:R112012028419-3
    申请日:2011-05-05
    公开日:2020-10-27
    发明作者:Samuel F. Yana Motta；Mark W. Spatz；Rajiv Ratna Singh；Robert Gerard Richard；Elizabet del Carmen Vera Becerra；Daniel Burger
    申请人:Honeywell International Inc.；
    IPC主号:
    专利说明:

    Field of the Invention
    [0001] This invention relates to compositions, methods and systems having utility in many applications, including domestic and small refrigeration and / or air conditioning applications and / or heat pump applications and, in particular aspects, compositions refrigeration system to replace HFC 134a refrigerant for heating and / or cooling applications and for reforming refrigerant and / or air conditioner systems, including systems designed for use with HFC-134a. Fundamentals of the Invention
    [0002] Mechanical refrigeration systems, and related heat transfer devices, such as heat pumps and air conditioners, using coolants, are well known in the art for industrial, commercial and domestic uses. Fluorocarbon-based fluids have found wide use in many residential, commercial and industrial applications, including as a working fluid in systems such as air conditioning, heat pump and cooling systems, including relatively small systems, such as those used for refrigerators and domestic and automotive air conditioner freezers. Due to certain suspicious environmental problems, including the relatively high global warming potentials associated with the use of some of the compositions, which have been used up to now in these applications, it has become increasingly desirable to use fluids, which have low or even no ozone depletion potential, such as hydrofluorocarbons ("HFCs"). For example, a number of governments have signed the Kyoto Protocol, to protect the global environment and establish a reduction in emissions of CCç (global warming). Thus, there is a need for a low or no inflammation, non-toxic alternative to replace some of the high global warming HFCs.
    [0003] An important type of refrigeration system is known as "small refrigeration" or "domestic refrigeration" systems, which include systems, which are normally used in homes, apartments and the like for use by consumers in refrigerators, freezers, and the like. Also often included in this group are vending machines and the like. Another important refrigeration system comprises automotive air conditioning systems. In such refrigeration systems, a widely used liquid refrigerant has been HFC-134a, also known as R-134a.
    [0004] There has thus been an increasing need for new fluorocarbon and hydrofluorocarbon compounds and compositions, which are attractive alternatives to the compositions used so far in these and other applications. For example, it becomes desirable to reform chlorine-containing refrigeration systems, replacing chlorine-containing refrigerants with non-chlorine-containing refrigerant compounds, which do not destroy the ozone layer, such as hydrofluorocarbons (HFCs). The industry in general, and the heat transfer industry in particular, are continually looking for new fluorocarbon-based blends that offer alternatives, and are considered environmentally safer substitutes for CFCs and HCFCs. It is generally considered important, however, at least with regard to heat transfer fluids, that any potential substitute must also have these properties present in many of the most widely used fluids, such as excellent heat transfer properties, chemical stability , low or no toxicity, non-flammability and / or lubricant compatibility, among others.
    [0005] Regarding the efficiency of use, it is important to note that a loss of energy efficiency or thermodynamic performance of refrigerant can have secondary environmental impacts, through high use of fossil fuels resulting from a high demand for electricity.
    [0006] Furthermore, it is generally considered desirable for CFG refrigerant substitutes to be effective, without major engineering changes to the conventional vapor compression technology currently used in CFC refrigerants.
    [0007] Flammability is another important property for many applications. That is, it is considered important or essential in many applications, including, in particular in heat transfer applications, the use of non-flammable compositions. Thus, it is often beneficial to use non-flammable compounds in such compositions. As used herein, the term "non-flammable" refers to compounds or compositions, which are determined to be in Class 1, as determined in accordance with ASHRAE Standard 34-2007, including the ANSI / ASHRI Addendum, which is incorporated herein by reference. Unfortunately, many HFCs, which might otherwise be desirable for use in refrigeration compositions, are flammable and / or not Class 1. For example, difluorethane fluoralkane (HFC-152a) and 1,1,1-fluoralkene trifluorpropene (HFO-1243zf) are each flammable and therefore not feasible for use in many applications.
    [0008] Applicants therefore realized the need for compositions, systems, and methods and, in particular, heat transfer compositions, which would be highly advantageous in steam compression heating and cooling systems and methods, in particular , refrigeration and heat pump systems of the type, which have so far been used, or designed for use, with HFC-134a. summary
    [0009] Applicants have found that the aforementioned need, and other needs, can be satisfied by compositions, methods and systems, which comprise, or use, a multicomponent mixture, comprising HFC-134a and at least one selected fluorinated olefin. of the group consisting of HFO-1234ze and HFO-1234yf.
    [00010] In preferred embodiments, the compositions of the present invention comprise: (a) from about 30% to about 65% by weight of HFC-134a; (b) from about 0% to about 70% by weight of HFO-1234ze, preferably trans-HFO-1234ze; and (c) from about 0% to about 70% by weight of HFO-1234yf, provided that the amount of HFO-1234ze plus HFO-1234yf in the composition is at least about 35% by weight, with the percentage by weight being based on the total of components (a) - (c) in the composition. Applicants have unexpectedly discovered the combination of components in the present compositions especially within the preferred ranges specified here, being able to achieve, at the same time, a combination of important refrigerant performance properties, difficult to achieve, that cannot be achieved by anyone components separately. For example, the preferred compositions of the present invention are, at the same time, Class 1 with respect to flammability and have a desirably low GWP.
    [00011] If the amount of HFC-134 is greater than the preferred range identified above, for example, the composition will not meet the environmental requirements for many applications. On the other hand, if fluorinated olefins are used in greater quantities than those mentioned above, the composition will not be Class 1 and / or will not behave in an acceptable manner in terms of capacity and / or efficiency.
    [00012] In certain preferred embodiments, the compositions comprise a mixture of multiple components, comprising: (a) from about 35% to about 55% by weight of HFC-134a; (b) from about 30% to about 60% by weight of HFO-1234ze, preferably trans-HFO-1234ze; and (c) from about 5% to about 30% by weight of HFO-1234yf, with the weight percentage being based on the total of components (a) - (c) in the composition.
    [00013] In certain preferred embodiments particularly for use in connection with systems, which have so far used HFC-134a as the refrigerant, the present compositions comprise a mixture of multiple components comprising: (a) from about 35% to about 50% by weight of HFC-134a; (b) from about 30% to about 55% by weight of HFO-1234ze, preferably trans-HFO-1234ze; and (c) from about 5% to about 25% by weight of HFO-1234yf, with the percentage by weight being based on the total of components (a) - (c) in the composition. In even more preferred embodiments, the compositions comprise a multi-component mixture, comprising: (a) from about 40% to about 45% by weight of HFC-134a; (b) from about 35% to about 50% by weight of HFO-1234ze, preferably trans-HFO-1234ze; and (c) from about 10% to about 20% by weight of HFO-1234yf, with the percentage by weight being based on the total of components (a) - (c) in the composition. Applicants have found that such preferred compositions are highly desirable, as they are not only low GWP and Class 1 compositions, but they are also capable of exhibiting, in many refrigeration applications, energy consumption properties, which are equal to or greater than the energy consumption of HFC-134a, preferably as measured according to the American National Standard "Energy Performance and Capacity of Home Refrigerators, Coolers / Freezers and Freezers (ANSI / AHAM HRF- 1-2007) , which is incorporated into this document by reference.
    [00014] In certain preferred embodiments, the present compositions can also include HFO-1233, preferably in amounts of up to about 5% by weight of the composition.
    [00015] The present invention also provides methods and systems, which use the compositions of the present invention, including methods and systems for heat transfer and for reforming existing heat transfer systems. Certain aspects of the preferred method of the present invention concern methods of providing cooling in small refrigeration systems. Other aspects of the method of the present invention provide methods of reforming an existing small refrigeration system, designed to contain, or containing, refrigerant R-134a, which comprises introducing a composition of the present invention into the system, without substantially modifying the engineering of the said existing cooling system.
    [00016] The term "HFO-1234" is used here to refer to all tetrafluorpropenes. Tetrafluorpropenes include tetrafluorpropene 1,1,1,2- (HFO-1234yf) and cis- and trans-1, 1, 1, 3-tetrafluorpropene (HFO-1234ze). The term HFO-1234ze is used generically here to refer to 1, 1, 1, 3-tetrafluorpropene, regardless of whether it is in cis- or trans- form. The terms "cisHFO-1234ze" and "transHFO-1234ze" are used herein to describe, respectively, the cis- and trans- forms of 1, 1, 1, 3-tetrafluorpropene. The term "HFO-1234ze" therefore includes, within its scope, cisHFO-1234ze, transHFO-1234ze, and all combinations and mixtures thereof.
    [00017] The term "HFO-1233" is used here to refer to all trifluoro, monochloropropenes. Among the trifluoro, monochloropropenes are included 1,1,1, -trifluor-2, chlorine propene (HFCO-1233xf), cis- and trans-1,1, 1, l-trifluoro-3, chlororopropene (HFCO-1233zd). The term HFCO-1233zd is used here generically, to refer to 1,1, 1-trifluoro-3, chloro-propene, regardless of whether it is in cis- or trans- form. The terms "cisHFCO-1233zd" and "transHFCO-1233zd" are used herein to describe, respectively, the cis- and trans- forms of 1,1,1,1-trifluoro, 3-chlororopropene. The term "HFCO-1233zd" therefore includes, within its scope, cisHFCO-1233zd, transHFCO-1233zd, and all combinations and mixtures thereof.
    [00018] The term "HFC-134a" is used herein to refer to 1,1,1,2-tetrafluoroethane. Brief Description of Drawings
    [00019] Figure 1 is a schematic representation of a simple heat transfer cycle by vapor compression.
    [00020] Figure 2 is a schematic representation of a heat transfer cycle by vapor compression, which has a heat exchanger in the liquid line / suction line. Detailed Description of the Preferred Embodiments
    [00021] Small refrigeration systems are important in many applications, as mentioned above. In such systems, one of the coolants, which has been commonly used, has been HFC-134a, which has an estimated high Global Warming Potential (GWP) of 1430. Applicants have found that the compositions of the present invention are exceptional and unexpected, the need for alternatives and / or substitutions of refrigerants in such applications, in particular and preferably, of HFC-134a. At the same time, the preferred compositions have lower GWP values, and provide non-flammable and non-toxic fluids, which have a close match in cooling capacity with HFC-134a in such systems.
    [00022] In certain preferred embodiments, compositions of the present invention have a Global Warming Potential (GWP) of not more than about 1000, more preferably, not more than about 700, and even more preferably, about 600 or any less. As used herein, "GWP" is measured against that of carbon dioxide and over a 100-year time horizon, as defined in the "Scientific Assessment of Ozone Destruction, 2002, a report by the Monitoring and Research Project Global Ozorological Association Ozone depletion ", which is hereby incorporated by reference.
    [00023] In certain preferred embodiments, the present compositions also preferably have an Ozone Destruction Potential (ODP) of not more than 0.05, more preferably, not more than 0.02 and, even more preferably, of about zero. As used herein, "ODP" is as defined in the "Scientific Assessment of Ozone Destruction, 2002, a report by the World Meteorological Association's Global Ozone Monitoring and Research Project", which is incorporated herein by reference. Heat Transfer Compositions
    [00024] The compositions of the present invention are generally adaptable for use in heat transfer applications, that is, as a means of heating and / or cooling, but are particularly well adapted for use, as mentioned above, in heating systems. small refrigeration, which until now have used HFC-134a.
    [00025] Applicants have found that the use of the components of the present invention, within the broad and preferred ranges described herein, is important to obtain the combinations of properties, difficult to achieve, exhibited by the compositions of the present invention, in particular in the systems and methods preferred, and that the use of those same components, but substantially outside the identified ranges, can have a deleterious effect on one or more of the important properties of the compositions of the present invention. In highly preferred embodiments, highly preferred combinations of properties are obtained for compositions having a weight ratio of HFC-134a: HFC-1234ze and, preferably, transHFC-1234ze, from about 0.6: 1 to about 1: 0.9, with a ratio of about 0.65: 1 to about 1: 1 being preferred in certain embodiments. Applicants have found that highly preferred combinations of properties are also achieved for compositions with a weight ratio of HFO-1234ze: HFO-1234yf from about 6: 1 to about 3: 1, with a ratio of about 5: 1 to about 4: 1 being preferred in certain embodiments.
    [00026] For convenience, the combination HFO-1234ze and HFO-1234yf is referred to herein as the "tetrafluorpropene component" or "TFC" and, in certain embodiments, highly preferred combinations of properties can be achieved for a composition , which comprises a weight ratio of HFC-134a: TFC from about 0.6: 1 to about 1: 0.9, with a ratio of about 0.65: 1 to about 1: 1 being preferred over certain embodiments.
    [00027] While it is contemplated that any HFO-1234ze isomer can be used to advantage in certain aspects of the present invention, applicants have found it preferable, in certain embodiments, that HFO-1234ze comprises transHFO-1234ze and preferably comprises , transHFO-1234ze in greater proportion and, in certain embodiments, consists essentially of transHFO-1234ze.
    [00028] As mentioned above, applicants have found that the compositions of the present invention are capable of achieving a difficult combination of properties, including particularly low GWP. By way of non-limiting example, the following Table A illustrates the substantial improvement in GWP of certain compositions of the present invention, compared to the global warming potential (GWP) of HFC-134a, which has a GWP of 1430. Table A

    [00029] The compositions of the present invention may include other components, in order to improve or provide certain functionality to the composition, or, in some cases, to reduce the cost of the composition. For example, the present compositions can include co-refrigerants, lubricants, stabilizers, metal passivators, corrosion inhibitors, flammability suppressants, and other compounds and / or components, and the presence of all such compounds and components is within the broader scope of invention.
    [00030] In certain preferred embodiments, the refrigeration compositions according to the present invention, especially those used in steam compression systems, include a lubricant, generally in amounts of about 30 to about 50 percent in weight of the composition and, in some cases, potentially in an amount greater than about 50 percent and, in other cases, in amounts as low as about 5 percent. In addition, the compositions of the present invention may also include a compatibilizer, such as propane, for the purpose of assisting lubricant compatibility and / or solubility. Such compatibilizers, including propane, butanes and pentanes, are preferably present in amounts of about 0.5 to about 5 weight percent of the composition. Combinations of surfactants and solubilizing agents can also be added to the compositions of the present invention to assist oil solubility, as disclosed by U.S. Patent No. 6,516,837, the disclosure of which is incorporated herein by reference. Commonly used refrigeration lubricants, such as polyol esters (POEs) and poly alkylene glycols (PAGs), PAG oils, silicone oil, mineral oil, alkyl benzenes (ABs) and poly (alpha-olefins) (PAG), which are used in refrigeration systems with hydrofluorocarbon (HFC) refrigerants, can be used with refrigerant compositions of the present invention. Commercially available mineral oils include Witco LP 250 (trademark) from Witco, Zerol 300 (trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R 015 from Calumet. Commercially available alkyl benzene lubricants include Zerol 150 (trademark). Commercially available esters include dipelargonate neopentyl glycol, which is available as Emery 2917 (trademark) and Hatcol 2370 (trademark). Other useful esters include phosphate esters, dibasic acid esters, and fluoresters. In some cases, hydrocarbon-based oils have sufficient solubility with the refrigerant, which is composed of an iodocarbon, the combination of the iodocarbon and the hydrocarbon oil may be more stable than other types of lubricant. Such a combination can therefore be advantageous. Preferred lubricants include polyalkylene esters and glycols. Polyalkylene glycols are highly preferred in certain embodiments, because they are currently used in particular applications, such as mobile air conditioners. Of course, different mixtures of different types of lubricants can be used.
    [00031] In certain preferred embodiments, the compositions of the present invention include, in addition to the compounds described above, one or more of the following, as refrigerant co-agents: Trichlorofluoromethane (CFC-11) Dichlorodifluoromethane (CFC-12) Difluoromethane (HFC -32) Pentafluoroethane (HFC-125) 1,1,2,2-tetrafluoroethane (HFC-134) Difluoroethane (HFC-152a) 1,1,1,2,3,3,3-heptafluorpropane (HFC-227ea) 1 , 1,1,3,3,3-hexafluorpropane (HFC-236fa) 1,1,1,3,3-pentafluorpropane (HFC-245fa) 1,1,1,3,3-pentafluorbutane (HFC-365mfc) water CO2
    [00032] Of course, other cooling co-agents can be used, in addition to, or instead of, any one or more of the above examples. Heat Transfer Methods and Systems
    [00033] Preferred heat transfer methods generally comprise providing a composition of the present invention, and making heat transfer to, or from, the composition, or by sensitive heat transfer, heat transfer by phase change, or a combination of these. For example, in certain preferred embodiments, the methods of the present invention provide refrigeration systems, which comprise a refrigerant of the present invention, and methods for producing heating or cooling, by condensing and / or evaporating a composition of the present invention. In certain preferred embodiments, systems and methods for heating and / or cooling, including cooling another fluid, directly or indirectly, or a body, directly or indirectly, comprise the compression of a refrigerant composition of the present invention and, in then, evaporation of said refrigerant composition in the vicinity of the article to be cooled. As used herein, the term "body" is intended to refer not only to inanimate objects, but also to living tissue, including animal tissue in general and human tissue in particular. For example, certain aspects of the present invention involve applying the composition of the present invention to human tissue, for one or more therapeutic purposes, such as a pain-neutralizing technique, as a preparation anesthetic, or as part of a therapy, which involves reducing the body temperature to be treated. In certain embodiments, application to the body comprises providing the present compositions in liquid form under pressure, preferably in a pressurized container having a unidirectional nozzle and / or discharge valve, and releasing the liquid from the container under pressure, by spraying , or other form of application, of the composition on the body. As the liquid evaporates from the surface being sprayed, the surface cools.
    [00034] Certain preferred methods for heating a fluid or body comprise condensing a refrigerant composition, comprising a composition of the present invention, in the vicinity of the fluid or body to be heated and then evaporating said refrigerant composition. In the light of the present disclosure, those skilled in the art will readily be able to heat and cool articles in accordance with the present invention without undue experimentation.
    [00035] In certain embodiments, the present invention provides cooling, by absorbing heat from a fluid or body, preferably by evaporating the current refrigerant composition in the vicinity of the body or fluid to be cooled, to produce steam, comprising the composition of the present invention. Certain aspects of the method and system of the present invention can be illustrated with respect to the simplified flow diagram, provided in Figure 1. In such preferred methods / systems, refrigeration systems / methods comprise the introduction of a refrigerant of the present invention, preferably by means of a suction line 1, in order to compress the refrigerant vapor, usually with a compressor or similar equipment, to produce steam of the present composition at a relatively high pressure in a discharge line 2. Generally, the compression step of the steam results in the addition of heat to the steam, thus causing an increase in the temperature of the relatively high pressure steam. Preferably, in such embodiments, the methods of the present invention include removing, at relatively high temperature and pressure, that steam at least part of the heat added by the evaporation and / or compression steps. The heat removal step preferably includes condensation of the steam at high temperature and pressure, preferably via a discharge line from the compressor 2 into a condenser, while the steam is in relatively high pressure conditions, with the result the production of a liquid with relatively high pressure, which comprises a composition of the present invention. That liquid with relatively high pressure, preferably then undergoes a nominally isentalpic pressure reduction, to produce a liquid with relatively low temperature and pressure. In the embodiment illustrated in Figure 1, this is achieved by introducing the condenser liquid, through the condenser discharge line 3, into the expansion device, such as an expansion valve. In such embodiments, it is that refrigerant with reduced pressure / temperature, which is then vaporized by the heat transferred from the body or the fluid to be cooled. For example, in the embodiment illustrated in Figure 1, liquid with low temperature and pressure, from the expansion device, is introduced, through the discharge line 4, into an evaporator, in which heat is transferred from the fluid or body to be cooled, for the refrigerant. The cycle is then repeated when the evaporator discharge is fed back into the compressor.
    [00036] Another preferred embodiment of the present invention involves a variation of the basic type of system / method described in connection with Figure 1. This preferred embodiment incorporates an additional heat exchange unit, which is generally known as an exchanger between the suction line / liquid line, also known as an "SL-LL heat exchanger". A simplified flow diagram, schematically illustrating methods / systems, which use such an arrangement, is shown in Figure 2. Such preferred systems / methods work, using substantially the same components, as described above, with the exception that an exchange unit additional heat is included in the system, between the evaporator and the compressor, through which at least a portion of the liquid discharged from the condenser, for example, in the discharge line 3, is diverted to be further cooled by absorbing heat from from at least part of the evaporator discharge. Applicants have found that the compositions of the present invention produce unexpected advantages and surprisingly beneficial results when used in connection with heat transfer systems containing an SL-LL heat exchanger. In certain embodiments, said advantages and benefits occur in connection with the improved capacity and efficiency of the system, and beneficial lowering of the compressor discharge temperature.
    [00037] In another embodiment of the process of the invention, the compositions of the present invention can be used in a method for the production of heat, which comprises the condensation of a refrigerant fluid, which comprises the compositions in the vicinity of a liquid or body to be heated. These methods, as previously mentioned, are often reverse cycles for the refrigeration cycle described above. An example of such an embodiment, which can be used to produce heat and / or cooling, are certain types of devices known as heat pumps. Although such devices are available for use, and have been used, to heat and / or cool many types of fluids or other materials, in certain preferred embodiments, the heat pumps of the present invention are used for heating and / or cooling water and preferably drinking water.
    [00038] The present methods, systems and compositions are therefore adaptable for use in connection with a wide variety of heat transfer systems, in general, and cooling systems, in particular, such as air conditioning systems (including air conditioning systems). air conditioners, fixed and mobile), refrigeration, heat pumps, and the like. In certain preferred embodiments, the compositions of the present invention are used in refrigeration systems originally designed for use with an HFC refrigerant, such as, for example, R-134a. Preferred compositions of the present invention tend to have many of the desirable characteristics of R-134a, but having a GWP, which is substantially lower than that of R-134a, while at the same time having a capacity, which is substantially similar or corresponds substantially and is preferably as high or higher than R-134a. In particular, applicants have recognized that certain preferred embodiments of the compositions of the present invention tend to have relatively low global warming potentials ("GWPs"), preferably less than about 1500, more preferably, less than about 1000 and, even more preferably, no more than about 650.
    [00039] In certain other preferred embodiments, the compositions of the present invention are used in refrigeration systems originally designed for use with R-134a. Applicants have found that, in the systems and methods of the present invention, many of the important performance parameters of the refrigeration system are relatively close, and, in certain important cases, unexpectedly superior to the parameters of R-134a. Since many existing refrigeration systems have been designed for R-134a, or for other refrigerants with properties similar to R-134a, those skilled in the art will realize the substantial advantage of a refrigerant with low GWP and / or low ozone depletion , which can be used as a substitute for R-134a or similar refrigerants, with relatively minor modifications to the system. It is contemplated that, in certain embodiments, the present invention provides reform methods, which include replacing the heat transfer fluid (such as a refrigerant) in an existing system with a composition of the present invention, without substantially modifying the system. In certain preferred embodiments, the replacement step is a substitute, in the sense that no substantial redesign of the system is necessary, and no major items of equipment need to be replaced in order to accommodate the composition of the present invention, such as fluid heat transfer.
    [00040] In certain preferred embodiments, the methods comprise a substitute, wherein the energy consumption of the system is at least about 1% less, and even more preferably at least about 2% less than the operation of the same system using HFC-134a.
    [00041] Preferred refrigeration compositions of the present invention can be used in refrigeration systems, which contain a lubricant conventionally used with R-134a, such as mineral oils, polyalkyl benzene oils, polyalkylene glycol, and the like, or can be used with others lubricants traditionally used with HFC refrigerants. As used herein, the term "refrigeration system" generally refers to any system or apparatus, or any part or portion of such a system or apparatus, which uses a refrigerant to provide cooling. Such refrigeration systems include, for example, air conditioners, electric refrigerators, freezers, (including freezers using centrifugal compressors), and the like.
    [00042] As mentioned above, the compositions, systems and methods of the present invention are generally adaptable for use in connection with all types and varieties of heat exchange equipment, and all such compositions, methods and systems are within the scope of the present invention. In certain preferred embodiments, however, the compositions of the present invention are particularly advantageous for use in connection with certain vapor compression heat exchange systems, which are sometimes referred to as "small refrigeration systems". For the purposes of this disclosure, it is preferable that such "small refrigeration systems" refer to vapor compression refrigeration systems, which use one or more compressors and operate at external ambient temperatures ranging from 20 ° C to about 65 ° C. In preferred embodiments of such systems, the systems have a refrigerated room temperature of about -30 ° C to about 5 ° C. Examples
    [00043] The following examples are provided for the purpose of illustrating the present invention, but without limiting its scope. Example 1 - Small Refrigeration System
    [00044] Energy consumption (EC) is an acceptable measure of refrigerant performance for small refrigeration systems. CE represents the amount of energy consumed by the system during a predetermined period of time and for specific operating conditions. One way to estimate a refrigerant's EC under specific operating conditions is through ANSI / AHAM HRF-1-2007, which is mentioned above and incorporated by reference.
    [00045] A small cooling system is provided. An example of such a system includes a household refrigerator, as illustrated in that Example. The outdoor ambient temperature is about 32.2 ° C (+/- 1 ° C). The freezer temperature is about -17 ° C. The test procedure is as follows: • The integral refrigerator is allowed to have an equilibrium temperature of 32.2 ° C for at least 24 hours prior to the test. • The refrigerator doors are closed and the system is started. • Data is collected over a period of at least 48 hours, which is known as the "pull-down" period, which lasts until the desired freezing temperature is reached. These 48 hours also cover a period, during which the cooling system is put into circulation. • Energy consumption, freezer and cabinet temperatures (fresh food compartment), as well as outside ambient temperatures, are recorded.
    [00046] Several operational parameters are determined for the Al - A2 compositions identified in Table A above, according to this test, and these operating parameters are presented in Table 1 below, based on HFC-134a having a consumption value 100% energy. TABLE 1

    [00047] As can be seen in Table 1 above, applicants have found that the compositions of the present invention are able to achieve, at the same time, many of the important performance parameters of the refrigeration system, close to the parameters of R-134a and, in particular, close enough to allow such compositions to be used as a substitute for R-134a in small refrigeration systems and / or for use in such existing systems, with minor modifications to the system. For example, composition A2 exhibits a CE, which is about 2% lower than the R-134a CE in this system, which is a very significant improvement in energy consumption. Such EC reductions are environmentally significant for household refrigerators, vending machines and automotive air conditioners, due to their widespread use. In addition, each of the A1 and A2 compositions is a Class 1 composition and is therefore highly desirable from the point of view of non-flammability. Example 2 - Air Conditioner
    [00048] The performance coefficient (COP) is a universally accepted measure of refrigerant performance, especially useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle, which involves evaporation or condensation of the refrigerant. In refrigeration engineering, this term expresses the relationship between useful refrigeration and energy applied by the compressor, in the compression of steam. The capacity of a refrigerant represents the amount of cooling or heating it provides, and provides a measure of the capacity of a compressor to pump quantities of heat for a given volume flow of refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity will deliver more cooling or heating power. A means of estimating a refrigerant's COP under specific operating conditions is from the refrigerant's thermodynamic properties, using standard refrigeration cycle analysis techniques (see, for example, RC Downing, Fluorocarbon Refrigerant Handbook, Chapter 3, Prentice -Hall, 1988).
    [00049] An air conditioning cycle system is provided, where the condenser temperature is about 45 ° C, and the evaporator temperature is about 7 ° C, under 70% isentropic compression efficiency and 100% volumetric efficiency. The degree of overheating is about 5 ° C, and the degree of undercooling is about 5 ° C. COP is determined for Al - A3 compositions of the present invention, shown in Table 2 below, based on HFC-134a having a COP value of 100%, a capacity value of 100%, and a relative discharge temperature compared to R134a . Table 2
    Example 3 - HFC-134a Substitutes - Medium Temperature, Automotive Air Conditioner, Freezer Systems and Heat Pump
    [00050] This example illustrates the performance of an embodiment of the present invention, in which the refrigerant composition is indicated as Al - A3 in Table A, and is used as a substitute for HFC-134a, in four systems. The first system is one having an evaporator temperature (TE) of about -7 ° C and a condenser temperature (TC) of about 54 ° C (Example 3A). For convenience, such heat transfer systems, i.e. systems having a TE of about -18 ° C to about 2 ° C and a TC of about 27 ° C to about 66 ° C, are here referred to as "medium temperature" systems. The second system is that having a TE of about 2 ° C and a CT of about 66 ° C (Example 3B). For convenience, such heat transfer systems, that is, systems having an evaporator temperature of about 1 ° C to about 16 ° C and a TC of about 32 ° C to about 93 ° C, are referred to herein as "automotive AC" systems. The third system is that having a TE of about 4 ° C and a CT of about 16 ° C (Example 3C). For convenience, such heat transfer systems, that is, systems having an evaporator temperature of about 2 ° C to about 10 ° C and a TC of about 27 ° C to about 149 ° C, are referred to herein as "freezer" or "AC freezer" systems. The fourth system is one having a TE of about 0 ° C, a source temperature (SRT) of about 5 ° C, a TC of about 60 ° C, and a heatsink temperature (SKT) of about 55 ° C (Example 3D). For convenience, such heat transfer systems, that is, systems having a TE of about -5 ° C to about 5 ° C, an SRT of about 0 ° C to about 10 ° C, a TC from about 50 ° C to about 70 ° C, and an SKT from about 45 ° C to about 65 ° C, are referred to herein as "potable water heater heat pump" systems. The operation of each of these systems, which use R-134a and the composition of the designated refrigerant of the present invention, is reported in Tables 3A - 3D below: Table 3A - Temp, Medium, -6, 66 ° C Conditions TE and 54.44 ° C TC

    [00051] As can be seen from the table above, the compositions of the present invention, particularly A3, exhibit a good match of capacity and efficiency with HFC-134a, in such systems. In addition, the superheat level is about the same level as for the HFC-134a, indicating that a change in the expansion device is not necessary. Similar pressures and mass flow allow the use of the same compressor. A lower discharge temperature allows the use of the SL-LL heat exchanger, which will further improve capacity and efficiency. TABLE 3B - Temp Conditions. Auto AC, 2 ° C TE and 5.55 ° C TC

    [00052] As can be seen from the table above, the compositions of the present invention, particularly A3, exhibit a good match of capacity and efficiency with HFC-134a, in such systems. In addition, the superheat level is about the same level as for the HFC-134a, indicating that a change in the expansion device is not necessary. Similar pressures and mass flow allow the use of the same compressor. A lower discharge temperature allows the use of the SL-LL heat exchanger, which will further improve capacity and efficiency. Table 3C - Freezer Temp Conditions, 4.44 ° C TE and 35 ° F TC

    [00053] As can be seen from the table above, the compositions of the present invention, particularly A3, exhibit a good match of capacity and efficiency with HFC-134a, in such systems. In addition, the superheat level is about the same level as for the HFC-134a, indicating that a change in the expansion device is not necessary. Similar pressures and mass flow allow the use of the same compressor. A lower discharge temperature allows the use of the SL-LL heat exchanger, which will further improve capacity and efficiency. 3D TABLE - Heat Pump Temp Conditions, 0 ° C TE (Source at 5 ° C) and 60 ° C TC (Heatsink at 55 ° C)

    [00054] The table above illustrates a common heat pump potable water heater (HPWH) system, which until now has frequently used R-134a as a refrigerant. The table above shows the performance of a typical HPWH, using a temperature difference of 5 ° C (TD) between the source and the evaporation heatsink, and the condensation temperatures, respectively. As can be seen from the table above, the compositions of the present invention, particularly A3, exhibit a good match of capacity and efficiency with HFC-134a, in such systems. In addition, the superheat level is about the same level as for the HFC-134a, indicating that a change in the expansion device is not necessary. Similar pressures and mass flow allow the use of the same compressor. A lower discharge temperature allows the use of the SL-LL heat exchanger, which will further improve capacity and efficiency. Example 4 - Methods and Systems Using SL-LL Heat Exchanger
    [00055] This example illustrates the behavior of three embodiments of the present invention, in which the refrigerant composition is indicated as Al, A2 and A3 in Table A, and compared with the use of three refrigerants, namely, HFC-134a , HFO-1234yf and HFO-1234ze. The system is a vapor compression refrigeration system, which has a compressor, evaporator, condenser, isentalpic expansion device, and a heat exchanger between liquid line / suction line. The system is in the form of a domestic refrigerator, with a volume of about 363.4 liters, and has an air-cooled condenser and a forced convection evaporator. The compressor is a 7.5 cm3 displacement compressor. The system uses an SL-LL heat exchanger with capillary tube, which exchanges heat with the compressor suction line. Substantially stable operating conditions are tested, with an ambient temperature of about 32.2 ° C and a relative humidity of about 50%. The freezer temperature is about -15 ° C. The suction temperature of the compressor is about 32.2 ° C. The overheating of the evaporator is about 5 ° C, and the undercooling of the condenser is about 2 ° C. GWP, capacity (relative to HFC-134a), efficiency (relative to HFC-134a), mass flow (relative to HFC-134a), relationship between suction pressure and discharge pressure (relative to HFC-134a), and discharge temperature (in relation to HFC-134a) are observed and reported in Table 4 below: [TABLE 4]

    [00056] Based on the table above, 1234yf separately is a relatively close match to HFC-134a in terms of capacity and efficiency, in addition to producing an excellent GWP value. However, applicants note that, in such systems, the mass flow is substantially greater, indicating that changes are likely to need to be made to the SL-LL heat exchanger, and / or the expansion device and / or the compressor. With respect to HFO-1234ze, this fluid results in a capacity, which is only 70% of the capacity of HFC-134a under downward conditions. This means that the system has to be modified to use a compressor having a displacement of about 55% greater, and the substantial reduction in mass flow indicates that substantial modifications to the capillary tube heat exchanger are necessary. In addition, neither HFO-1234ze nor HFO-1234yf are Class 1 materials. In contrast, compositions A1, A2 and A3, according to the present invention, are at the same time Class 1 materials, despite HFO -1234yf and HFO-1234ze are included, and each of them is also an excellent match with R-134a in the parameters of capacity, mass flow and efficiency. In addition, each of the compositions of the present invention provides a reduced compression ratio and a reduced discharge temperature, as well as slightly better efficiency than R134a.
    [00057] As can be seen, in general, from the above description, many of the important performance parameters of the refrigeration system compositions of the present invention are relatively close to the parameters for R-134a. Since many existing refrigeration systems have been designed for R-134a, or for other refrigerants with properties similar to R-134a, those skilled in the art will realize the substantial advantage of a refrigerant with a low GWP and / or low depletion ozone and / or Class 1, which can be used as a substitute for R-134a or similar refrigerants with relatively minimal modifications, or no substantial modifications, to the system. It is contemplated that, in certain embodiments, the present invention provides reform methods, which include replacing the refrigerant of an existing system with a composition of the present invention, without substantial modification and / or replacing any of the main equipment of the system . In certain preferred embodiments, the replacement step is a substitute, in the sense that no substantial redesign of the system is required, and no major item of equipment needs to be replaced in order to accommodate the refrigerant of the present invention.
    权利要求:
    Claims (10)
    [0001]
    1. USE OF A COMPOSITION, characterized in that the composition comprises 42% by weight of HFC-134a and 58% by weight of HFO-1234ze in a medium temperature cooling system having an evaporator temperature of from -18 ° C to 2oC, and a condenser temperature from 20 ° C to 66 ° C, in which said HFO-1234ze consists of trans-HFO-1234ze.
    [0002]
    Use according to claim 1, characterized in that the evaporator temperature is -7 ° C, and the condenser temperature is 54 ° C.
    [0003]
    Use according to claims 1 and 2, characterized in that the system comprises a heat exchanger between the suction line and the liquid line.
    [0004]
    4. HEAT TRANSFER SYSTEM, characterized by comprising a heat exchanger between the suction line and the liquid line and a composition comprising: (a) 42% by weight of HFC-134a and (b) 58% by weight of HFO-1234ze, in which said HFO-1234ze consists of trans-HFO-1234ze.
    [0005]
    System according to claim 4, characterized in that said system comprises an evaporator, a condenser, a compressor, and an expansion device.
    [0006]
    System according to any one of claims 6 and 7, characterized in that said heat transfer system is a system selected from the group consisting of air conditioner, heat pump systems, and the like.
    [0007]
    7. COOLING SYSTEM, characterized by comprising a suction line, characterized by the fact that it comprises a heat exchanger between the suction line and the liquid line, and a composition comprising: (a) 42% by weight of HFC-134a and (b) 58% by weight of HFO-1234ze, said cooling system being selected from the group consisting of stationary air conditioner, automotive air conditioner, domestic refrigerator / freezer, freezer, heat pump, and vending machine. , in which said HFO-1234ze consists of trans-HFO-1234ze.
    [0008]
    8. HEAT TRANSFER COMPOSITION, characterized by comprising: (a) from about 30% to about 65% by weight of HFC-134a; (b) from about 35% to about 70% by weight of HFO-1234yf.
    [0009]
    9. COOLING SYSTEM, comprising the heat transfer composition of claim 8, characterized in that said cooling system is in a unit selected from the group consisting of stationary air conditioner, automotive air conditioner, domestic refrigerator / freezer, freezer, pump heat, and vending machine.
    [0010]
    10. COOLING SYSTEM, according to claim 9, characterized by comprising a heat exchanger between the suction line and the liquid line.
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    同族专利:
    公开号 | 公开日
    EP2566930A4|2014-11-05|
    EP3255114A9|2018-04-04|
    JP6093387B2|2017-03-08|
    PL2566930T3|2018-01-31|
    ES2765413T3|2020-06-09|
    MX2012012886A|2012-12-17|
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    ES2640316T3|2017-11-02|
    CN105754553B|2020-08-14|
    WO2011140289A2|2011-11-10|
    JP5806294B2|2015-11-10|
    PT2566930T|2017-09-11|
    US20150144306A1|2015-05-28|
    WO2011140289A3|2012-04-05|
    AU2011248123A1|2012-12-20|
    EP3255114B1|2019-11-27|
    US9994749B2|2018-06-12|
    EP3680307A1|2020-07-15|
    JP2015131966A|2015-07-23|
    KR101818636B1|2018-01-15|
    KR20130103338A|2013-09-23|
    CA2798620C|2020-03-10|
    BR112012028419A2|2016-11-16|
    CN102971394B|2016-04-20|
    JP2013530265A|2013-07-25|
    PL3255114T3|2020-05-18|
    EP2566930B1|2017-08-02|
    EP2566930A2|2013-03-13|
    US8974688B2|2015-03-10|
    CN105754553A|2016-07-13|
    AU2011248123B2|2015-01-22|
    EP3255114A1|2017-12-13|
    CA2798620A1|2011-11-10|
    US20110023507A1|2011-02-03|
    JP2017133010A|2017-08-03|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-26| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-12-10| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-05-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/05/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/776,320|US8974688B2|2009-07-29|2010-05-07|Compositions and methods for refrigeration|
    US12/776,320|2010-05-07|
    PCT/US2011/035283|WO2011140289A2|2010-05-07|2011-05-05|Compositions and methods for refrigeration|
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