巴西专利BR112020002175A2 compositions, device for heat transfer and for generating mechanical energy, use of a composition, m

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专利摘要:
The present invention provides a composition comprising 1,1-difluoroethene (R-1132a), difluoromethane (R-32), 2,3,3,3-tetrafluoropropene (R-1234yf), optionally, carbon dioxide (CO2, R -744) and, optionally, 1,1,2-trifluoroethene (R-1123).
公开号:BR112020002175A2
申请号:R112020002175-0
申请日:2018-08-06
公开日:2020-07-28
发明作者:Robert E. Low
申请人:Mexichem Fluor S.A. De C.V.；
IPC主号:

专利说明:

[001] [001] The invention relates to compositions, preferably to heat transfer compositions and which may be suitable as substitutes for existing refrigerants, such as R-410A.
[002] [002] The listing or discussion of a previously published document or any background in the specification should not necessarily be interpreted as an acknowledgment that a document or background is part of the state of the art or is commonly known.
[003] [003] Mechanical cooling systems and related heat transfer devices, such as heat pumps and air conditioning systems, are well known. In these systems, a coolant evaporates at low pressure, drawing heat from the surrounding area. The resulting steam is then compressed and passes to a condenser, in which it condenses and releases heat to a second zone, with the condensate returning through an expansion valve to the evaporator, thus completing the cycle. The mechanical energy needed to compress the vapor and pump the liquid is supplied, for example, by an electric motor or an internal combustion engine.
[004] [004] Residential and commercial light air conditioning and heat pump units are commonly charged with the non-flammable refrigerant R-410A, a mixture of R-32 (difluoromethane) and R-125 (pentafluoroethane). Although the use of this refrigerant results in high system efficiency and therefore low energy consumption, the R-410A's greenhouse (or global) warming potential (GWP) is high (2100, using the IPCC data set AR4).
[005] [005] R-32 (difluoromethane) has been proposed as an alternative to R-410A. R-32 is classified as mildly flammable (“2L” using the ASHRAE classification system). It offers energy efficiency comparable to that of the R-410A in properly designed equipment and has a GWP of 675.
[006] [006] However, the R-32 has several disadvantages: its compressor discharge temperatures are significantly higher than the R-410A and its operating pressures can also be higher than in the R-410A. It is possible to compensate for these higher discharge temperatures, for example, with the use of “cooling on demand” or liquid injection technologies. However, they can reduce the system's capacity and energy efficiency. Another disadvantage of R-32 is that its GWP (675) is still high when compared to the GWPs of hydrofluoro-olefin refrigerants, such as tetrafluoropropenes or hydrocarbons, such as propane.
[007] [007] Binary mixtures of R-32 with R-1234yf (2,3,3,3-tetrafluoropropene) or R-1234ze (E) (E-1,3,3,3-tetrafluoropropene) and ternary mixtures of R- 32, tetrafluoropropenes (R-1234ze (E) or R-1234yf) and a third component have also been proposed as alternative fluids. Examples of such fluids include R-454B, which is a binary mixture of R-32 / R-1234yf (68.9% / 31.1%) with a GWP of 466 and R-452B, a ternary mixture of R-32 / R-125 / R-1234yf (67% / 7% / 26%) with a GWP of 698. These fluids reduced GWP compared to R-410A and can
[008] [008] When looking for alternative low-temperature refrigerants, several other factors must also be considered. First, if the fluid is used as a rework or conversion fluid for existing equipment or as an “inlet” for new equipment (for example, using an essentially unchanged R-410A system design), then non-flammability is highly desired, as the existing project will have been based on the use of non-flammable fluid.
[009] [009] If an alternative fluid is used in an entirely new system design, a degree of flammability may be tolerable, but the use of highly flammable fluids may impose cost and performance penalties to mitigate risks. The acceptable size of the charge (refrigerant mass) in a system is also controlled by the fluid's flammability rating, with class 3 fluids such as ethane being the most strictly limited. In this case, a weaker flammability characteristic is highly desirable as it can allow for higher system loads.
[0010] [0010] Third, the typical application of such fluids is in residential or commercial air conditioning units and heat pumps, which are usually located in buildings. It is also advantageous to have an acceptably low toxicity as a characteristic of the fluid.
[0011] [0011] In addition, volumetric capacity (a measure of the cooling power that can be achieved by a given compressor size) and energy efficiency are important
[0012] [0012] Thus, there is a need to provide alternative refrigerants that have improved properties, such as low GWP, (in order to
[0013] [0013] More specifically, it would be advantageous to find refrigerant mixtures with comparable performance (capacity and energy efficiency, expressed in COP) to R-410A with compressor discharge temperature comparable to that of R-452B or R-454A, but with a GWP significantly lower than that of R-32. Since R-32 and R-454B are both considered to be weakly flammable mixtures (flammability class “2L” according to ASHRAE 34), it would also be desirable for these mixtures with the lowest GWP to be flammability class 2L.
[0014] [0014] The present invention addresses the above deficiencies, among others, as well as the above needs, by providing a composition comprising 1,1-difluoroethene (R-1132a), difluoromethane (R-32), 2,3,3 , 3-tetrafluoropropene (R-1234yf), optionally, carbon dioxide (CO2, R-744) and, optionally, 1,1,2-trifluoroethene (R-1123). Such compositions are hereinafter referred to as compositions of the invention.
[0015] [0015] The compositions of the invention typically contain from about 1 or 2 or 3 or 4 to about 60% by weight of R-1132a. Advantageously, such compositions comprise from about 1 or 2 or 3 or 4 to about 50% by weight of R-1132a, as from about 1 or 2 or 3 or 4 to about 40% by weight of R-1132a, for example, from about 1 or 2 or 3 or 4 to about 30% by weight of R-1132a. Conveniently, the compositions of the invention comprise from about 1 or 2 or 3 or 4 to about 25% by weight of R-1132a, for example, from 2 to about 20% by weight of R-1132a, for example, of 3 or 4 to about 20% by weight R-1132a. Preferably, these
[0016] [0016] The compositions of the invention typically contain from about 1 to about 99% by weight of R-32 or from about 2 to about 98% by weight of R-32. Advantageously, such compositions comprise from about 2 to about 95% by weight of R-32, for example, from about 3 to about 95% by weight of R-32. The compositions of the invention can comprise from about 5 to about 90% by weight of R-32, for example, from about 5 to about 85% by weight of R-32, from about 10 to about 80% by weight of R-32. Preferably, these compositions comprise from about 15 to about 75% by weight of R-32, for example, from about 15 to about 70% by weight of R-
[0017] [0017] The compositions of the invention typically contain from about 1 to about 99% by weight of R-1234yf or from about 2 to about 98% by weight of R-1234yf. Advantageously, such compositions comprise from about 2 to about 90% by weight of R-1234yf, for example, from 5 to about 90% by weight of R-1234yf. Conveniently, the compositions of the invention comprise from about 7 to about 85% by weight of R-1234yf, for example, from about 8 to about 80% by weight of R-1234yf. Preferably, the compositions comprise from about 10 to about 75% by weight of R-1234yf, for example, from about 10 to about 70% by weight of R-1234yf, or, for example, about 10 to about 65% by weight of R-1234yf.
[0018] [0018] Conventionally, the compositions of the invention comprise from about 1 to about 60% by weight of R-1132a, from about 1 to about 99% by weight of R-32 and from about 1 to about 99 % by weight of R-1234yf. Such compositions typically contain from about 1 to about 50% by weight of R-1132a, from about 2 to about 97% by weight of R-32 and from about 2 to about 97% by weight of R- 1234yf.
[0019] [0019] Conventionally, the compositions of the invention
[0020] [0020] Advantageously, the compositions of the invention comprise from about 1 to about 40% by weight of R-1132a, from about 5 to about 90% by weight of R-32 and from about 5 to about 90 % by weight of R-1234yf; or from about 2 to about 40% by weight R-1132a, from about 5 to about 90% by weight R-32 and from about 5 to about 90% by weight R-1234yf; or from about 2 to about 40% by weight R-1132a, from about 4 to about 94% by weight R-32 and from about 4 to about 94% by weight R-1234yf.
[0021] [0021] Preferably, the compositions of the invention comprise from about 3 to about 20% by weight of R-1132a, from about 10 to about 80% by weight of R-32 and from about 10 to about 75% by weight of R-1234yf; or from about 3 to about 30% by weight R-1132a, from about 10 to about 91% by weight R-32 and from about 6 to about 87% by weight R-1234yf.
[0022] [0022] Conveniently, the compositions of the invention comprise from about 5 to about 20% by weight of R-1132a, from about 20 to about 70% by weight of R-32 and from about 10 to about 65 % by weight of R-1234yf; or from about 4 to about 25% by weight of R-1132a, from about 15 to about 88% by weight of R-32 and from about 8 to about 81% by weight of R-1234yf.
[0023] [0023] Any of the compositions described above may additionally contain carbon dioxide (R-744, CO2). The addition of R-744 has the advantage of reducing R-1132a in the vapor phase and therefore reducing the potential flammability of the vapor phase, but tends to increase the compressor discharge temperature and the temperature drop.
[0024] [0024] When present, the compositions of the invention contain
[0025] [0025] Any of the compositions described above may additionally contain 1,1,2-trifluoroethene (R-1123). An advantage of using R-1123 in the compositions of the invention is that it provides similar capacity to R-32, but has negligible GWP. By incorporating a proportion of R-1123, the overall GWP of a composition with similar capacity to R-410A can then be reduced compared to an equivalent ternary composition R-1132a / R-32 / R-1234yf in proportions of R-1132a and R-1234yf constant. R-1123 can only be used safely as a diluted component in the compositions of the invention. The proportion of R-1123 in the compositions is such that the maximum molar concentration of R-1123 in the composition of the invention as formulated or, in the worst case, in fractionated compositions (as defined in Appendix B of ASHRAE Standard 34) must be lower to 40%.
[0026] [0026] When present, compositions of the invention typically contain from about 1 to about 30% by weight of R-1123; or from about 5 to about 30% by weight of R-1123. Preferably, these compositions contain from about 5 to about 20% by weight of R-1123, such as about 5 to about 15% by weight, for example, from about 5 to about 10% by weight of R -1123.
[0027] Alternatively, the compositions of the invention may contain less than about 8%, or about 7%, or about 6%, or about 5% by weight of R-1123, for example, less than about 4 % or about 3% by weight of R-1132a, for example, less than about 2% or about 1% in
[0028] [0028] Any of the compositions described above can still contain a hydrocarbon. Advantageously, the hydrocarbon is one or more compounds selected from the group consisting of ethane, propane, propene, isobutane, n-butane, n-pentane, isopentane and mixtures thereof. Without being limited by theory, it is believed that, when present, the inclusion of ethane and / or an additional hydrocarbon compound can improve the miscibility, solubility and / or return characteristics of the oil. Typically, the compositions of the invention contain from about 1 to about 20% by weight of hydrocarbon component, for example, from about 1 to about 10% by weight, for example, from about 1 to about 5% in weight.
[0029] [0029] In one embodiment, the compositions may consist essentially of the indicated components. The term "consist essentially of" means that the compositions of the invention contain substantially no other components, particularly no other (hydro) (fluoro) compounds (for example, (hydro) (fluoro) alkanes or (hydro) (fluoro) alkenes) known to be used in heat transfer compositions. The term "to consist of" means "to consist essentially of".
[0030] [0030] In one embodiment, the compositions of the invention are substantially free of any component that has heat transfer properties (in addition to the specified components). For example, the compositions of the invention can be substantially free of any other hydrofluorocarbon compound.
[0031] [0031] The terms "substantially none" and "substantially free" mean that the compositions of the invention contain 0.5% by weight or less of the indicated component, preferably 0.4%, 0.3%, 0, 2% or
[0032] [0032] All chemicals described here are commercially available. For example, fluorochemicals can be obtained from Apollo Scientific (UK) and carbon dioxide can be obtained from suppliers of liquefied gas, such as Linde AG.
[0033] [0033] As used herein, all percentage amounts mentioned in compositions herein, including in the claims, are by weight based on the total weight of the compositions, unless otherwise indicated.
[0034] [0034] The term "about", as used in connection with numerical values of component amounts in% by weight, means ± 0.5% by weight, for example, ± 0.5% by weight.
[0035] [0035] For the avoidance of doubt, it will be understood that the upper and lower values indicated for ranges of component quantities in the compositions of the invention described in this document can be interchanged in any way, as long as the resulting ranges fall within the broader scope of the invention.
[0036] [0036] The compositions of the invention have zero ozone depletion potential.
[0037] [0037] Typically, the compositions of the invention have a GWP of less than about 650, for example, less than about 600, for example, less than about 500. Preferably, the compositions of the invention have a GWP of less than about 480, for example, less than about 450, for example, less than about 400.
[0038] [0038] Typically, the compositions of the present invention are at reduced risk of flammability when compared to R-1132a.
[0039] [0039] Flammability can be determined in accordance with ASHRAE Standard 34 by incorporating ASTM Standard E-681 with test methodology in accordance with 2004 Addendum 34p, the content of which
[0040] [0040] In some embodiments, the compositions have one or more of (a) a higher lower flammable limit; (b) higher ignition energy (sometimes called auto-ignition or pyrolysis energy); or (c) a lower flame speed compared to R-1132a alone. Preferably, the compositions of the invention are less flammable compared to R-1132a in one or more of the following aspects: flammable limit below 23 ° C; flammable limit below 60 ° C; flammable range amplitude at 23 ° C or 60 ° C; auto-ignition temperature (thermal decomposition temperature); minimum ignition energy in dry air or flame speed. Flammable limits are determined according to the specified methods of ASHRAE-34 and the auto-ignition temperature is determined in a 500 ml glass flask by the method of ASTM E659-
[0041] [0041] In a preferred embodiment, the compositions of the invention are not flammable. For example, the compositions of the invention are not flammable at a test temperature of 60 ° C using the ASHRAE-34 methodology. Advantageously, steam mixtures that exist in equilibrium with the compositions of the invention at any temperature between about -20 ° C and 60 ° C are also non-flammable.
[0042] [0042] In some applications, it may not be necessary for the formulation to be classified as non-flammable by the ASHRAE-34 methodology. It is possible to develop fluids whose flammability limits will be sufficiently reduced in the air to make them safe for use in the application, for example, if it is not physically possible to make a flammable mixture by leaking the refrigeration equipment charge into the environment.
[0043] [0043] In one embodiment, the compositions of the invention have flammability classifiable as 1 or 2L according to the method of
[0044] [0044] A composition of the invention preferably has a temperature drop in an evaporator or condenser less than about 10 K, more preferably, less than about 5 K, for example, less than about 1 K.
[0045] [0045] It is believed that the compositions of the invention exhibit a completely unexpected combination of low / non-flammability, low GWP, better lubricant miscibility and better cooling performance properties. Some of these cooling performance properties are explained in more detail below.
[0046] [0046] The compositions of the invention typically have a volumetric cooling capacity that is at least 80% that of R-410A, for example, at least 85% that of R-410A. Preferably, the compositions of the invention have a volumetric cooling capacity that is at least 90% that of R-410A, for example, from about 95% to about 130% of that of R-410A.
[0047] [0047] In one embodiment, the cycle efficiency (Performance Coefficient, COP) of the compositions of the invention is within about 7% of R-410A, for example, within 5% of R-410A. Preferably, the cycle efficiency is equivalent to or greater than R-410A.
[0048] [0048] Conveniently, the compressor discharge temperature of the compositions of the invention is within about 15 K of the existing refrigerant they are replacing (for example, R-410A or R-32), preferably about 10 K or even about 5 K. Advantageously, the compressor discharge temperature of the compositions of the invention is lower than that of R-32.
[0049] [0049] Conveniently, the operating pressure in a condenser
[0050] [0050] The compositions of the invention are typically suitable for use in existing equipment designs, for example, low temperature refrigeration equipment, and are compatible with all classes of lubricants currently used with established HFC refrigerants. They can be optionally stabilized or made compatible with mineral oils by using appropriate additives.
[0051] [0051] Preferably, when used in heat transfer equipment, the composition of the invention is combined with a lubricant.
[0052] [0052] Conveniently, the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkylbenzenes (PABs), polyolesters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinations thereof. PAGs and POEs (particularly the latter) are currently the preferred lubricants for the compositions of the invention.
[0053] [0053] Advantageously, the lubricant further comprises a stabilizer.
[0054] [0054] Preferably, the stabilizer is selected from the group consisting of compounds based on diene, phosphates, phenolic compounds and epoxides and mixtures thereof.
[0055] [0055] Conveniently, the composition of the invention can be combined with a flame retardant.
[0056] [0056] Advantageously, the flame retardant is selected from the group consisting of tri- (2-chloroethyl) -phosphate, (chloropropyl) phosphate, tri- (2,3-dibromopropyl) -phosphate, tri- (1,3- dichloropropyl) -phosphate, diamonium phosphate, various halogenated aromatics, antimony oxide, tri-aluminum
[0057] [0057] In one embodiment, the invention provides a heat transfer device that comprises a composition of the invention. Preferably, the heat transfer device is a cooling device.
[0058] [0058] Conveniently, the heat transfer device is a residential or commercial air conditioning system, a heat pump or a commercial or industrial refrigeration system.
[0059] [0059] The invention also provides for the use of a composition of the invention in a heat transfer device as described herein.
[0060] [0060] According to another aspect of the invention, a sprayable composition is provided which comprises a material to be sprayed and a propellant which comprises a composition of the invention.
[0061] [0061] According to a further aspect of the invention, a method is provided for cooling an article which comprises condensing a composition of the invention and, after that, evaporating said composition next to the article to be cooled.
[0062] [0062] According to another aspect of the invention, a method is provided for heating an article which comprises condensing a composition of the invention next to the article to be heated and, after that, evaporating said composition.
[0063] [0063] In accordance with a further aspect of the invention, a method is provided for extracting a biomass substance which comprises bringing the biomass into contact with a solvent comprising a composition of the invention and separating the substance from the solvent.
[0064] [0064] In accordance with another aspect of the invention, a method of cleaning an article is provided which comprises placing the article in contact
[0065] [0065] According to a further aspect of the invention, a method is provided for extracting a material from an aqueous solution which comprises bringing the aqueous solution into contact with a solvent comprising a composition of the invention and separating the material from the solvent.
[0066] [0066] In accordance with another aspect of the invention, a method is provided for extracting a material from a particulate solid matrix which comprises bringing the particulate solid matrix into contact with a solvent comprising a composition of the invention and separating the material from the solvent.
[0067] [0067] In accordance with a further aspect of the invention, a mechanical energy generating device is provided which contains a composition of the invention.
[0068] [0068] Preferably, the mechanical power generation device is adapted to use a Rankine cycle or a modification of it to generate work from heat.
[0069] [0069] In accordance with another aspect of the invention, a method of refurbishing a heat transfer device is provided which comprises the step of removing an existing heat transfer fluid and introducing a composition of the invention. Preferably, the heat transfer device is a cooling device, such as an ultra low temperature cooling system. Advantageously, the method further comprises the step of obtaining a greenhouse gas emission credit allocation (for example, carbon dioxide).
[0070] [0070] According to the reconditioning method described above, an existing heat transfer fluid can be completely removed from the heat transfer device before introducing a composition of the invention. An existing heat transfer fluid can also be partially removed from a transfer device
[0071] [0071] The compositions of the invention can also be prepared simply by mixing R-1132a, R-32, R-1234yf (and optional components like R-744, R-1123, hydrocarbons, a lubricant, a stabilizer or a retardant) additional flame) in the desired proportions. The compositions can then be added to a heat transfer device (or used in any other way as defined herein).
[0072] [0072] In a further aspect of the invention, a method is provided to reduce the environmental impact arising from the operation of a product comprising an existing compound or composition, the method comprising replacing, at least partially, the compound or the existing composition by a composition of the invention.
[0073] [0073] For environmental impact, we include the generation and emission of greenhouse heating gases through the operation of the product.
[0074] [0074] As mentioned above, this environmental impact can be considered to include not only those emissions of compounds or compositions that have a significant environmental impact from leaks or other losses, but also include the emission of carbon dioxide from the energy consumed by device during your working life. This environmental impact can be quantified by the measure known as Total Equivalent Heating Impact (TEWI). This measure is used to quantify the environmental impact of certain refrigeration equipment and stationary air conditioning, including, for example, supermarket refrigeration systems.
[0075] [0075] The environmental impact can also be considered as including the emissions of greenhouse gases that arise from the synthesis and manufacture of compounds or compositions. In that case, manufacturing emissions are added to energy consumption and the effects of loss
[0076] [0076] In a preferred embodiment, the use of the composition of the invention results in equipment that has a lower total equivalent heating impact and / or a lower life cycle carbon production than would be achieved by using the compound or the existing composition.
[0077] [0077] These methods can be performed on any suitable product, for example, in the fields of air conditioning, refrigeration (for example, low and medium temperature refrigeration), heat transfer, gaseous dielectrics, flame suppression, solvents (for example, carriers, for flavorings and fragrances), cleaning products, topical anesthetics and expansion applications. Preferably, the field is refrigeration.
[0078] [0078] Examples of suitable products include heat transfer devices, solvents and mechanical power generation devices. In a preferred embodiment, the product is a heat transfer device, such as a cooling device or an ultra-low temperature cooling system.
[0079] [0079] The existing compound or composition has an environmental impact measured by GWP and / or TEWI and / or LCCP that is higher than the composition of the invention that they replace. The existing compound or composition can comprise a fluorocarbon compound, such as a perfluorocarbon, hydrofluorocarbon, chlorofluorocarbon or hydrochlorofluorocarbon compound or can comprise a fluorinated olefin.
[0080] [0080] Preferably, the existing compound or composition is a heat transfer compound or composition, such as a refrigerant. Examples of refrigerants that can be replaced include
[0081] [0081] Any amount of the existing compound or composition can be replaced, in order to reduce the environmental impact. This may depend on the environmental impact of the existing compound or composition being replaced and the environmental impact of the replacement composition of the invention. Preferably, the compound or composition in the product is completely replaced by the composition of the invention.
[0082] [0082] The present invention is illustrated by the following non-limiting examples.
[0083] [0083] A thermodynamic model was built to allow estimating the performance of compositions comprising R-1132a or CO2 in a refrigeration cycle by vapor compression or air conditioning. The critical temperature of R-1132a is about 30 ° C and that of CO2 is about 31 ° C; both of which are lower than the condensation temperatures experienced in many R-410A applications, which can vary from 30 to 60 ° C. Therefore, a thermodynamic model was developed capable of predicting the vapor and liquid balance of mixtures at temperatures above the critical temperature of some components of the mixture.
[0084] [0084] The chosen model used the Peng-Robinson equation of state to calculate the thermodynamic properties of the mixtures. The vapor and liquid balance (AVA) of the mixtures was correlated with the use of the Peng-Robinson equation of state coupled with the mixing rules of Wong and Sandler, as described in Orbey, H., & Sandler, S. (1998), Modeling Vapor-Liquid Equilibria: Cubic Equations of State and their Mixing Rules, Cambridge: Cambridge University Press, hereby incorporated by reference. This type of thermodynamic model was successfully used to model the AVA of refrigerant mixtures (Shiflett, M., & Sandler, S.
[0085] [0085] In this work, the Wong-Sandler mixing rules were used with the non-random two-liquid model (NRTL) to represent the free energy of the liquid phase. The parameters of the Peng-Robinson equation for each component of the mixture were modified to use the temperature correlation of Mathias and Copeman, in order to accurately represent the vapor pressures of the components.
[0086] [0086] The interaction parameters of the Wong-Sandler / NRTL model were regressed for experimental measurements of liquid and vapor balance for binary mixtures of R-1132a with CO2, R-32 and R-1234yf. The experimental measurement temperature range used ranged from -55 to +10 ° C for mixtures of R-1132a / CO2 and R-1132a / R-32, to -40 to +40 ° C for mixtures of R- 1132a / R -1234yf. The data for these mixtures and for the binary mixtures of R1234yf with R-32 and CO2 were measured using a static and synthetic equilibrium cell.
[0087] [0087] Literature data were also available for AVA
[0088] [0088] The modeling of the cycle was performed using the state points of the modeling matrix proposed by the AHRI low GWP alternative refrigerants evaluation program. The conditions used are presented in Table 1 below: TABLE 1: CYCLE CONDITIONS FOR MODELING OF R-1132a / R-32 / R-124yf TERNARY SYSTEM Modeling conditions for R410A Average condenser temperature ° C 37.8 Average temperature evaporator temperature ° C 4.4 Condenser subcooling K 5.6 Evaporator overheating K 5.6 Evaporator pressure drop bar 0.00 Suction line pressure drop bar 0.00 Condenser pressure drop bar 0 .00 K compressor suction superheat 0.00 Isentropic efficiency 70.0%
[0089] [0089] To validate that the thermodynamic model provided reasonable results, a comparison was made using the industry standard NIST REFPROP9.1 program to simulate the performance of the R-410A cycle. Mexichem's thermodynamic model was then used to calculate the performance of the cycle. The results of these tests are shown in Table 2
[0090] [0090] The comparative calculations of the performance of the R-32 and R-454B were performed for the first time using the model. The results of these tests are shown in Table 3 below. TABLE 3: REFRIGERATION PERFORMANCE MODELING DATA FOR R-32 AND R-454B IN RELATION TO R-410A Parameter Units R410A R32 R-454B Performance Coefficient (COP) 4.85 4.89 5.06 Volumetric cooling capacity kJ / m3 5,996 6,490 5,823 Discharge temperature ° C 69.3 88.6 74.9 Condenser pressure bar 22.9 23.5 21.1 Evaporator pressure bar 9.3 9.4 8.6 Pressure ratio 2 , 45 2.51 2.46 Drop of condenser K 0.2 0.0 1.4 Drop of evaporator K 0.1 0.0 1.5 COP in relation to the reference 100% 101% 104% COP in relation to the reference 100% 108% 97% Discharge temperature difference from 0 19.4 5.7 reference GWP 2,100 675 466
[0091] [0091] Next, a series of R-1132a / R-32 / R-1234yf compositions ranging from 5 to 20% R-1132a and 20 to 70% R-32 were analyzed. The results of these tests are shown in Tables 4 to 7 below. The compositions of each component are given in percentages by weight in these tables.
[0092] [0092] Surprisingly, the results show that it is possible to formulate ternary mixtures of R-1132a / R-32 / R-1234yf that provide acceptable performance when compared to R-410A, while achieving GWP lower than R-32 or R- 454B.
[0093] [0093] Especially preferred compositions will be those that can be classified as having "2L" flammability and that can be used on an "incoming" or "or almost incoming" basis in systems designed for the R-410A. It is believed that these compositions must meet the following criteria: • Capacity of at least about 90% of the R-410A • COP equivalent to or greater than that of R-410A • Operating pressure in the condenser equal to or less than that of R-32 Discharge temperature of the compressor lower than that of the R-32 • “Drop” of temperature in the evaporator and condenser below 10K • Burning speed of the composition in the worst case less than 10 cm / s, according to ASHRAE standard 34
[0094] [0094] Other compositions that offer acceptable operating pressure and flammability, but that do not meet all of these criteria, can also provide acceptable performance in properly designed new equipment. For example, mixtures with a volumetric capacity less than 90% of that of the R-410A could be used to increase the displacement or speed of the compressor. Mixtures with a temperature drop greater than 10K can be used employing condenser and / or evaporator counterflow heat exchanger designs.
[0095] [0095] Mixtures with good performance characteristics, but which
[0096] [0096] The invention is defined by the following claims.

权利要求:
Claims (66)
[1]
1. Composition, characterized by the fact that it comprises: (i) 1,1-difluoroethene (vinylidene fluoride, R-1132a); (ii) difluoromethane (R-32); and (iii) 2,3,3,3-tetrafluoropropene (R-1234yf).
[2]
Composition according to claim 1, characterized in that it comprises from about 1 to about 50% by weight of R-1132a.
[3]
Composition according to claim 2, characterized in that it comprises from about 2 to about 50% by weight of R-1132a.
[4]
Composition according to claim 2, characterized in that it comprises from about 1 to about 40% by weight of R-1132a.
[5]
Composition according to claim 3 or 4, characterized in that it comprises from about 2 to about 40% by weight of R-1132a.
[6]
Composition according to claim 4, characterized in that it comprises from about 1 to about 30% by weight of R-1132a.
[7]
Composition according to claim 5 or 6, characterized in that it comprises from about 2 to about 30% by weight of R-1132a.
[8]
Composition according to claim 6 or 7, characterized in that it comprises from about 3 to about 20% by weight of R-1132a.
[9]
Composition according to claim 8, characterized in that it comprises from about 5 to about 20% by weight of R-1132a.
[10]
Composition according to any one of the preceding claims, characterized in that it comprises from about 1 to about 99% by weight of R-32.
[11]
Composition according to claim 10, characterized in that it comprises from about 2 to about 98% by weight of R-32.
[12]
Composition according to claim 10 or 11, characterized in that it comprises from about 5 to about 90% by weight of R-32.
[13]
Composition according to claim 12, characterized in that it comprises from about 10 to about 80% by weight of R-32.
[14]
Composition according to claim 13, characterized in that it comprises from about 15 to about 70% by weight of R-32.
[15]
Composition according to any one of the preceding claims, characterized in that it comprises from about 1 to about 99% by weight of R-1234yf.
[16]
16. Composition according to claim 15, characterized in that it comprises from about 2 to about 98% by weight of R-1234yf.
[17]
17. Composition according to claim 15 or 16, characterized in that it comprises from about 5 to about 90% by weight of R-1234yf.
[18]
18. Composition according to claim 17, characterized in that it comprises from about 10 to about 75% by weight of R-1234yf.
[19]
19. Composition according to claim 18, characterized in that it comprises from about 10 to about 65% by weight of R-1234yf.
[20]
20. Composition according to claim 1, characterized in that it comprises from about 1 to about 50% by weight of R-1132a, from about 2 to about 97% by weight of R-32 and about from 2 to about 97% by weight of R-1234yf.
[21]
21. Composition according to claim 20, characterized in that it comprises from about 2 to about 40% by weight of R-1132a, from about 4 to about 94% by weight of R-32 and about from 4 to about 94% by weight of R-1234yf.
[22]
22. Composition according to claim 21, characterized in that it comprises from about 3 to about 30% by weight of R-1132a, from about 10 to about 91% by weight of R-32 and about from 6 to about 87% by weight of R-1234yf.
[23]
23. Composition according to claim 22, characterized in that it comprises from about 4 to about 25% by weight of R-1132a, from about 15 to about 88% by weight of R-32 and about from 8 to about 81% by weight of R-1234yf.
[24]
24. Composition according to any one of the preceding claims, characterized in that it additionally comprises carbon dioxide (CO2, R-744), optionally, in which the CO2 is present in an amount of about 1 to about 30% by weight, for example, from about 2 to about 20% by weight.
[25]
25. Composition according to claim 24, characterized in that R-1132a and CO2 are present in a combined amount of about 2 to about 50% by weight, for example, from about 2 to about 40% by weight, for example, from about 4 to about 30% by weight, for example, from about 5 to about 20% by weight.
[26]
26. Composition according to any one of the preceding claims, characterized in that it additionally comprises 1,1,2-trifluoroethene (R-1123), optionally, in which R-1123 is present in an amount of about 1 to about 30% by weight, for example, from about 5 to about 20% by weight.
[27]
27. Composition according to any one of claims 1 to 25, characterized in that the composition is substantially free of 1,1,2-trifluoroethene (R-1123).
[28]
28. Composition according to claim 27, characterized in that the composition does not contain 1,1,2-trifluoroethane (R-1123).
[29]
29. Composition according to any one of the preceding claims, characterized by the fact that it consists essentially of the components indicated.
[30]
30. Composition according to any one of the preceding claims, the composition being characterized by the fact that it is less flammable than R-1132a alone.
[31]
31. Composition according to claim 30, the composition of which is characterized by the fact that it has: a. a higher flammable limit; B. higher ignition energy; and / or c. a lower flame speed compared to R-1132a alone.
[32]
32. Composition according to any one of the preceding claims, the composition being characterized by the fact that it is not flammable.
[33]
33. Composition according to claim 32, the composition being characterized by the fact that it is not flammable at room temperature, preferably, the composition being non-flammable at 60 ° C.
[34]
34. Composition according to any one of the preceding claims, the composition of which is characterized by the fact that it has a volumetric cooling capacity that is at least 90% of that of R-410A.
[35]
35. Composition according to any one of the preceding claims, the composition of which is characterized by the fact that it has a performance coefficient (COP) equivalent to or greater than that of R-410A.
[36]
36. Composition according to any one of the preceding claims, the composition being characterized by the fact that it has an operating pressure in a capacitor equal to or less than that of R-32.
[37]
37. Composition according to any one of the preceding claims, the composition being characterized by the fact that it has a compressor discharge temperature lower than that of the R-32.
[38]
38. Composition according to any one of the preceding claims, the composition being characterized by the fact that it has a temperature drop in an evaporator or in a condenser less than about 10 K, preferably less than about 5 K.
[39]
39. Composition according to any one of the preceding claims, the composition of which is characterized by the fact that it has a burning speed of less than about 10 cm / s, as measured by the ASHRAE 34 standard.
[40]
40. Composition, characterized by the fact that it comprises a lubricant and a composition according to any one of the preceding claims.
[41]
41. Composition according to claim 40, characterized by the fact that the lubricant is selected from mineral oil, silicone oil, polyalkylbenzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (esters of PAG), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinations of them, and, preferably, the lubricant is selected from among PAGs or POEs.
[42]
42. Composition, characterized by the fact that it comprises a stabilizer and a composition according to any one of the preceding claims.
[43]
43. Composition according to claim 42, characterized by the fact that the stabilizer is selected from compounds based on diene, phosphates, phenolic compounds and epoxides and mixtures thereof.
[44]
44. Composition, characterized by the fact that it comprises a flame retardant and a composition according to any one of the preceding claims.
[45]
45. Composition according to claim 44, characterized by the fact that the flame retardant is selected from the group consisting of tri- (2-chloroethyl) -phosphate, (chloropropyl) phosphate, tri- (2,3-dibromopropyl ) -phosphate, tri- (1,3-dichloropropyl) -phosphate, diamonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoroiodomethane, perfluoroalkylam bromo-fluoroalkylamines and mixtures thereof.
[46]
46. Heat transfer device, characterized in that it contains a composition as defined according to any one of claims 1 to 45.
[47]
47. Heat transfer device according to claim 46, the heat transfer device being characterized by the fact that it is a cooling device.
[48]
48. Heat transfer device according to claims 46 or 47, the heat transfer device being characterized by the fact that it comprises a residential or commercial air conditioning system, a heat pump or a heating system. commercial or industrial refrigeration.
[49]
49. Use of a composition, characterized in that it is as defined according to any one of claims 1 to 45 in a heat transfer device, preferably in a refrigeration device.
[50]
50. Sprayable composition, characterized in that it comprises a material to be sprayed and a propellant that comprises a composition according to any one of claims 1 to 45.
[51]
51. Method for cooling an article, characterized in that it comprises condensing a composition according to any one of claims 1 to 45, and, after that, evaporating the composition next to the article to be cooled.
[52]
52. Method for heating an article, characterized in that it comprises condensing a composition according to any one of claims 1 to 45, next to the article to be heated and, after that, evaporating the composition.
[53]
53. Method for extracting a biomass substance, characterized in that it comprises putting the biomass in contact with a solvent comprising a composition, as defined according to any one of claims 1 to 45, and separating the substance from the solvent.
[54]
54. Method for cleaning an article, characterized in that it comprises putting the article in contact with a solvent comprising a composition as defined according to any one of claims 1 to 45.
[55]
55. Method for extracting a material from an aqueous solution or a particulate solid matrix, characterized by the fact that it comprises placing the aqueous solution or particulate solid matrix in contact with a solvent comprising a composition, as defined according to any one claims 1 to 45, and separate the material from the solvent.
[56]
56. Device for generating mechanical energy, characterized in that it contains a composition as defined according to any one of claims 1 to 45.
[57]
57. Mechanical energy generating device according to claim 56, characterized by the fact that it is adapted to use a Rankine cycle, or a modification thereof, to generate work from heat.
[58]
58. Method for reconditioning a heat transfer device, characterized in that it comprises the step of removing an existing heat transfer composition and introducing a composition as defined according to any one of claims 1 to 45.
[59]
59. The method of claim 58, characterized in that the heat transfer device is a commercial or industrial refrigeration device, a heat pump or a residential or commercial air conditioning system.
[60]
60. Method to reduce the environmental impact arising from the operation of a product that comprises an existing compound or composition, the method being characterized by the fact that it comprises replacing, at least partially, the existing compound or composition with an existing one. composition as defined according to any one of claims 1 to 45.
[61]
61. Method according to claim 60, characterized in that the use of the composition of the invention results in a lower total equivalent heating impact and / or in a production of carbon with a lower life cycle than is obtained by use of the existing compound or composition.
[62]
62. Method according to claim 60 or 61, characterized in that it is carried out in a product from the fields of conditioning, refrigeration, heat transfer, aerosol or spray propagators, gaseous dielectrics, flame suppression, solvents, cleaning products, topical anesthetics and expansion applications.
[63]
63. Method according to claim 60 or 61, characterized in that the product is selected from a heat transfer device, a sprayable composition, a solvent or a mechanical dust generating device, preferably a device for heat transfer.
[64]
64. Method according to claim 63, characterized in that the product is a heat transfer device, preferably a residential or commercial air conditioning system, a heat pump or a commercial or industrial refrigeration system .
[65]
65. The method of any one of claims 58 to 64, characterized in that the existing compound or composition is a heat transfer composition, the heat transfer composition being preferably a refrigerant selected from among R-410A, R-454B, R-452B and R-32.
[66]
66. Any innovative heat transfer composition, characterized by the fact that it is substantially as defined in any of the preceding claims, optionally in relation to the examples.

类似技术:

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BR112020002175A2|2020-07-28|compositions, device for heat transfer and for generating mechanical energy, use of a composition, methods for cooling an article, for heating an article, for cleaning an article, for extracting a biomass substance, for extracting a material from an aqueous solution or a particulate solid matrix, to recondition a heat transfer device and to reduce the environmental impact that comes from operating a product, and any innovative heat transfer composition.

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同族专利:

公开号 | 公开日

US20210395590A1|2021-12-23|

EP3665237A1|2020-06-17|

AU2018315022A1|2020-02-20|

KR20200037799A|2020-04-09|

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US20200224071A1|2020-07-16|

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法律状态:
2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

申请号 | 申请日 | 专利标题

GBGB1712813.3A|GB201712813D0|2017-08-10|2017-08-10|Compositions|

GB1712813.3|2017-08-10|

PCT/GB2018/052243|WO2019030508A1|2017-08-10|2018-08-06|Compositions|

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