WO2024057105A1 - Fluide frigorigène à mélange binaire quasi-azéotropique à faible effet de réchauffement planétaire - Google Patents

Fluide frigorigène à mélange binaire quasi-azéotropique à faible effet de réchauffement planétaire Download PDF

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Publication number
WO2024057105A1
WO2024057105A1 PCT/IB2023/057465 IB2023057465W WO2024057105A1 WO 2024057105 A1 WO2024057105 A1 WO 2024057105A1 IB 2023057465 W IB2023057465 W IB 2023057465W WO 2024057105 A1 WO2024057105 A1 WO 2024057105A1
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Prior art keywords
refrigerant
binary blend
refrigerants
blend
binary
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Inventor
Maria Lourdes Vega Fernandez
Ismail Issa Ismail ALKHATIB
Felix Lluis LLOVELL FERRET
Carlos ALBA GARRIGA
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Khalifa University of Science, Technology and Research (KUSTAR)
Universitat Rovira i Virgili URV
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Khalifa University of Science, Technology and Research (KUSTAR)
Universitat Rovira i Virgili URV
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Priority to EP23864860.4A priority Critical patent/EP4587532A1/fr
Publication of WO2024057105A1 publication Critical patent/WO2024057105A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • F25B1/10—Compression machines, plants or systems with non-reversible cycle with multi-stage compression
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B40/00—Subcoolers, desuperheaters or superheaters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • F25B2400/121—Inflammable refrigerants using R1234
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/13—Economisers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/23—Separators
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B41/00—Fluid-circulation arrangements
    • F25B41/30—Expansion means; Dispositions thereof
    • F25B41/39—Dispositions with two or more expansion means arranged in series, i.e. multi-stage expansion, on a refrigerant line leading to the same evaporator
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B6/00—Compression machines, plants or systems, with several condenser circuits
    • F25B6/04—Compression machines, plants or systems, with several condenser circuits arranged in series

Definitions

  • HFCs hydrofluorocarbons
  • GHGs Green House Gases
  • HFCs hydrofluorocarbons
  • the desirable substitute refrigerant should be effective without major engineering changes to the conventional vapor compression technology currently used with existing refrigerants.
  • the desirable properties include: 1) Global warming potential (GWP) less than 150. 2) No Ozone Depletion Potential (ODP). 3) Non-toxic (Class A according to ASHRAE classification). 4) Non-flammable (Class 1) or mildly-flammable (Class 2L according to ASHRAE classification). 5) Pure components or near-azeotropic blends (preferably glide temperature ⁇ 0.1 K, but 5 ⁇ 10 K are acceptable) with similar normal boiling temperature and condensation pressures of the refrigerant to be replaced.
  • Embodiments of the present disclosure provide for near azeotropic, binary blends of more than one of refrigerants R1243zf, R1234ze(E), R1234yf, R152a, R1123, R32, that have low GWP.
  • Embodiments of the present disclosure describe a method of retrofitting an existing heat transfer system that includes an existing refrigerant, wherein the method comprises unsealing the heat transfer system to gain access to the existing refrigerant, removing substantially all of the existing refrigerant from the heat transfer system, replacing the existing refrigerant with a refrigerant that is near-azeotropic and comprises a binary blend of more than one of R1243zf, R1234ze(E), R1234yf, R152a, R1123, R32 refrigerants, and resealing the heat transfer system.
  • Embodiments of the present disclosure describe a heat transfer system comprising a compressor, a condenser, and an evaporator in fluid communication and operating with an evaporator temperature (ET) from about 243 K to about 263 K; condenser temperature (CT) from about 293 K to about 315 K, and a refrigerant in said system, wherein the said refrigerant comprises a binary blend of more than one of R1243zf, R1234ze(E), R1234yf, R152a, R1123, R32 refrigerants.
  • ET evaporator temperature
  • CT condenser temperature
  • FIGS. 1(a-c) illustrate the process flow diagram for the vapor compression refrigeration cycle (VCRC) in existing system (FIG. 1(a)), Pressure-Enthalpy (PH) diagram (FIG.1(b)) and temperature-entropy (TS) diagram (FIG.1(c)) for near-azeotropic blends used in the present disclosure.
  • FIGS. 1(a-c) illustrate the process flow diagram for the vapor compression refrigeration cycle (VCRC) in existing system (FIG. 1(a)), Pressure-Enthalpy (PH) diagram (FIG.1(b)) and temperature-entropy (TS) diagram (FIG.1(c)) for near-azeotropic blends used in the present disclosure.
  • FIGS. 1(a-c) illustrate the process flow diagram for the vapor compression refrigeration cycle (VCRC) in existing system (FIG. 1(a)), Pressure-Enthalpy (PH) diagram (FIG.1(b)) and temperature-entropy (TS) diagram (FIG.
  • FIGS.3(a-f) show the schematics for the advanced refrigeration cycles simulated in the present disclosure with liquid-to-suction line heat exchanger (LL/SL-HX) (FIG. 3(a-c) and two-stage linear compressor systems (TS-VCRC) (FIG. 3(d-f), with their corresponding PH and TS-diagrams.
  • FIGS. 3(a-f) show the schematics for the advanced refrigeration cycles simulated in the present disclosure with liquid-to-suction line heat exchanger (LL/SL-HX) (FIG. 3(a-c) and two-stage linear compressor systems (TS-VCRC) (FIG. 3(d-f), with their corresponding PH and TS-diagrams.
  • FIGS. 3(a-c) show Drop-in KPIs for promising drop-in replacement blends for R134a as a function of different outlet evaporator temperature, as seen from predicted VCC (FIG.2(a)), DLT (FIG.2(b)) and
  • FIGS. 4(a-d) show the Vapor Liquid Equilibria (VLE) of selected refrigerants binary mixtures or blends for those containing a) R32, b) R134a, c) R1234yf and d) R1234ze(E), using polar soft-SAFT (solid lines), compared to experimental data (symbols).
  • FIG. 5 shows the predicted Vapor-Liquid Equilibria (VLE) of the binary blend comprising R1243zf and R1234ze(E).
  • FIGS.7(a-b) present the results of the environmental impact based on the TEWI metric in SS-VCRC cycle.
  • FIG.7(a) shows the different major HFCs producers, and
  • FIG.7(b) shows selected EU-27 countries, sorted by population from left to right.
  • FIGS.8(a-b) show Economic analysis for most promising alternatives for R134a.
  • Fig. 8(a) shows the economic analysis for most promising alternatives for R134a for the different major HFCs producers based on total costs.
  • FIG.8(b) shows Economic analysis for most promising alternatives for R134a for the cycle configurations based on operating costs 4105.090PCT1 (2022-044-02) (left y-axis, darker colors of the bars) and environmental cost (right y-axis, lighter color of the bars) performed under the Spanish regulations, being the most restrictive within the EU-27.
  • FIG. 4105.090PCT1 (2022-044-02)
  • environmental cost right y-axis, lighter color of the bars
  • FIG. 9 shows the predicted Vapor Liquid Equilibria (VLE) of the binary blend comprising R1123 +R32.
  • FIG.10 shows the environmental impact for blend 1 as an alternative to R410A in SS-VCRC cycle, with the bar colors corresponding to the studied benchmark refrigerants and designed blends for different major HFCs producers.
  • FIG.11 shows the economic analysis for most promising alternatives for R410A for the different major HFCs producers based on total costs.
  • the colors represent the different refrigerants and blends, as per the legend inside the figures.
  • the different portions of the bars represent the split of the total annual cost, from bottom to top (darker to lighter colors): CAPEX, OPEX, Enviro, and set-up costs.
  • the present disclosure relates to near azeotropic, binary blends of refrigerants that have low GWP; method of retrofitting an existing heat transfer system with the said refrigerants; heat transfer systems comprising the said refrigerants, and the like.
  • Embodiments of the present disclosure describe a refrigerant that is near azeotropic and comprises a binary blend of more than one of R1243zf, R1234ze(E), R1234yf, R152a, R1123, R32 refrigerants.
  • the present disclosure describes a robust framework for rapidly assessing the feasibility of replacing single-component or binary blends of third generation refrigerants HFCs with low GWP fourth generation refrigerants HFOs and HCFOs, connecting features of their molecular structure to their performance.
  • the framework is built on the use of a molecular-based EoS, namely, polar soft-SAFT, for the holistic thermodynamic characterization of the investigated refrigerants.
  • FIG.1(a) depicts the vapor compression refrigeration cycle.
  • the cooling process as shown in FIG. 1(a), comprises a single-stage compressor, condenser, evaporator, and thermo- static expansion valve (TXV).
  • the cycle starts with the isentropic compression of the refrigerant (1 ⁇ 2), with the superheated vapor flowing through the condenser, and releasing its sensible (2 ⁇ 3) and latent (3 ⁇ 4) heats to surrounding air to reach the saturation temperature at the condenser’s pressure (2 ⁇ 4). Subsequently, the saturated liquid is expanded resulting in two phase vapor ⁇ liquid mixture, with the TXV regulating the refrigerant mass flow rate (4 ⁇ 5), routed to the isobaric evaporator with the refrigerant reaching its saturated vapor phase (5 ⁇ 1).
  • VCC volumetric cooling capacity
  • COP coefficient of performance
  • the computations of these criteria require pressure enthalpy (PH) diagram ((FIG. 1(b)), and temperature-entropy (TS) diagram (FIG.1(c)) and physicochemical properties that were predicted using polar soft-SAFT for all studied refrigerants, under the imposed conditions of the cooling cycle.
  • Refrigerants are deemed compatible if the values of their VCC are similar, denoting equivalent refrigerant volume handled by the compressor without need for compressor retrofitting. Additionally, the replacement refrigerant should possess either a similar or higher COP value compared to the refrigerant to be replaced, denoting either a similar or higher cycle efficiency.
  • NBP normal boiling point
  • P cond condenser pressure
  • ⁇ v suction density
  • cP liquid specific heat
  • RE refrigeration effect
  • the normal boiling point measures the ease of vaporizing the refrigerant upon absorbing heat, which should be minimized for low-medium temperature applications, as high NBP would require operating the compressor at low pressures or even vacuum to facilitate vaporization, at the expense of higher operating costs.
  • the condenser pressure should also be minimized to reduce the compression power and the operating costs, while the suction density relates to the density of the saturated vapor exiting the evaporator, which should be maximized to reduce the size of the compressor and required capital costs.
  • the specific heat of the refrigerant at liquid state represents the amount of heat required to increase the temperature of the refrigerant by one temperature unit (e.g., 1 K), with lower specific heat being preferred as it reduces the amount of heat required to change the temperature of the refrigerant.
  • This is defined as the enthalpy difference of the saturated liquid leaving the condenser at T cond (H cond,out ) and the subcooled liquid leaving the condenser at (Tcond ⁇ 1 K) (Hcond,out ⁇ 1 K ) at isobaric conditions.
  • the refrigeration effect is a measure of the amount of latent heat absorbed in the evaporator, corresponding to the cooling capacity of the refrigerant, which should be maximized to ensure higher extracted heat or lower refrigerant mass flow rates.
  • POE polyol ester
  • PECs pentaerythritol esters
  • thermophysical properties of the selected refrigerants considered in the present disclosure have been modeled using the polar soft-SAFT Equation of State (EoS), an extension of the original soft-SAFT equation.
  • Table 1 summarizes the designation and IUPAC names of the refrigerants related to the present disclosure.
  • 4105.090PCT1 (2022-044-02) [0 ularly refrigerant compositions that are highly advantageous in vapor compression cooling systems, particularly refrigerant systems of the type that have been used with or designed for use with R134a or R410A.
  • the embodiments of the present disclosure relate to compositions, methods, and heat transfer systems having utility particularly in refrigeration applications with particular benefit in low-medium temperature refrigeration application.
  • Certain embodiments of the present disclosure relate in particular aspects to refrigerant compositions useful in systems for replacing the refrigerant R134 or R410A for refrigeration (cooling) applications and to retrofitting low-medium temperature refrigeration systems.
  • the embodiments of the present discosure further include systems designed for use with R134a or R410A, comprising, but not limited to automotive and domestic air conditioning systems or high pressure commercial and industrial refrigeration.
  • the most compatible blends (> 90%) designed in the present disclosure, for replacing R134a include blends 2 – 5, and blends 1’ and 2’, with the highest compatibility seen with blend 3, outperforming the commercial blends R513A and R450A in addition to single- component refrigerants.
  • the only feasible blend for replacing R410A was blend 1, achieving similar compatibility ratio (73%) to R32.
  • the results of the 4105.090PCT1 (2022-044-02) ranking were consistent irrespective of the chosen operating conditions, as seen from predicted VCC (FIG. 2(a)), DLT (FIG. (2b)) and COP (FIG. 2(c)) values as a function of the outlet evaporator temperature in FIGS.2(a-c).
  • Table 2 Short listed refrigerant blends and their compositions based on initial screening criteria Table 2’: Compatibility analysis of promising blends designed for replacing R134a and R410A. Color codes designate null (green), partial (yellow), and complete (red) – retrofitting required. 4105.090PCT1 (2022-044-02) [0029] Following completion of the aforementioned investigation, the binary blend refrigerants comprising more than one of R1243zf, R1234ze(E), R1234yf, R152a, R1123, R32 refrigerants, were of interest.
  • Embodiments of the present disclosure describe azeotropic-like, binary blend refrigerant compositions, that comprise:(a) from about 60% to about 90% by weight of R1243zf (3,3,3-trifluoroprop-1-ene, C 3 F 3 H 3 ) and (b) from about 10% to about 40% by weight of R1234ze(E) (trans-1,3,3,3-tetrafluoroprop-1-ene, C3H2F4).
  • the amount of (a) improves one or more of a global warming potential, capacity, efficiency, discharge temperature, discharge pressure, and/or energy consumption of the composition, particularly in a low or medium temperature refrigeration system and as compared to the refrigerant R134a.
  • Embodiments of the present disclosure also describe near azeotropic, binary blend refrigerant compositions, that comprise: (c) from about 80% to about 90% by weight of R1234yf (2,3,3,3-tetrafluoroprop-1-ene, C3H2F4) and (d) from about 10% to about 20% by weight of R152a (1,1-difluoroethane, C 2 H 4 F 2 ).
  • the amount of (c) improves one or more of a global warming potential, capacity, efficiency, discharge temperature, discharge pressure, and/or energy consumption of the composition, particularly in a low or medium temperature refrigeration system and as compared to the refrigerant R134a.
  • the present disclosure describes near azeotropic, binary blend refrigerant compositions, that comprise: (e) about 90% by weight of R1123 (1,1,2- trifluoroethene, C2HF3) and (f) about 10% by weight of R32 (Difluoromethane).
  • the composition improves one or more of a global warming potential, capacity, efficiency, discharge temperature, discharge pressure, and/or energy consumption of the composition, particularly in a low or medium temperature refrigeration system and as compared to the refrigerant R410A.
  • Applicants have found the combination of components in the present compositions, especially within the preferred ranges specified herein, are capable of at once achieving a combination of important and difficult to achieve refrigerant performance properties that cannot be achieved by any one of the components alone, including particularly low GWP.
  • Table 3 illustrates the substantial improvement in GWP exhibited by certain compositions of the present disclosure in comparison to GWP of R134a and R410A.
  • Objects (1) and (2) in Table 3 can be directly used as replacements for existing vapor compression systems with R134a without any engineering changes to existing systems, and maintaining relatively similar volumetric cooling capacity, discharge line temperature, condenser pressure, but with 4105.090PCT1 (2022-044-02) negligible GWP, and higher flammability than R134a.
  • the flammability rating of Objects (1) and (2) are classified as mild-flammable (rating 2L) according to ASHRAE classification compared to the non-flammable rating of R134a (rating 1).
  • Object (3) in Table 3 can be used for replacing systems with R410A with minimal retrofitting costs, in addition to similar flammability rating to R410A.
  • compositions of binary blend refrigerants and their GWP disclosure tend to exhibit many of the desirable characteristics for R134a (objects 1 and 2) and R410A (Object 3), having a GWP that is substantially lower than that of R134a or R410A while at the same time having a capacity, efficiency, energy consumption, discharge temperature and/or condenser pressure that is substantially similar or substantially matches to R134a or R410A.
  • Certain other preferred compositions of the present disclosure all exhibit a glide temperature close to 0.1 K at variable pressure ranges typical for systems operated with R134a or R410A, ensuring their near-azeotropic behavior. In other words, blends acting as a single pure substance in the refrigeration cycle.
  • a low temperature refrigeration system is used herein to refer to a refrigeration system that utilizes one or more compressors and operates under or within the following conditions: 1. Condenser temperature of about 293 K to about 315 K. 2. Evaporator temperature of about 243 K to about 263 K. 3. Degree of superheating at evaporator outlet of 5 K 4. Degree of subcooling at condenser outlet of 5 K 4105.090PCT1 (2022-044-02)
  • the embodiments can be best represented by the basic vapor compression cooling cycle typically operated in existing systems, showcased in FIGS. 1(a-c). Table 4 below illustrates some key performance characteristics of the present invention compared to existing systems operated with R134a and R410A.
  • VCC volumetric cooling capacity
  • DLT discharge line temperature
  • P cond condenser pressure
  • COP coefficient of performance
  • FIGS.3(a-f) show the schematics for the advanced refrigeration cycles simulated in the present disclosure with LL/SL-HX (FIGS.3(a-c)) and TSVCRC (FIGS.3(d- f)), with their corresponding PH and TS-diagrams.
  • Table 5 shows the key technical 4105.090PCT1 (2022-044-02) performance criteria for evaluating commercial refrigerants, and the embodiments of blends designed (with their ID) in the three refrigeration cycles of the present disclosure.
  • the present disclosure provides retrofitting methods which comprise: unsealing the heat transfer system to gain access to the existing refrigerant (R134a or R410A); removing substantially all of the existing refrigerant from the heat transfer system; replacing the existing refrigerant with a refrigerant that is near-azeotropic and comprises a binary blend of more than one of R1243zf, R1234ze(E), R1234yf, R152a, R1123, 4105.090PCT1 (2022-044-02) R32 refrigerants; and resealing the heat transfer system.
  • the retrofitting methods occur preferably without substantial modification of the systems and even more preferably without any change in major system components, such as compressors, condensers, evaporators, and expansions valves. It is important in certain embodiments that such systems are capable of exhibiting reliable system operating parameters with drop-in refrigerants, such operating parameters include: 1) Volumetric cooling capacity, of about 100% or less for existing systems with R134a or R410A. This is important to allow the use of existing pressure components. (compressor) without major modifications. 2) High pressure side (Condenser pressure) that is within 105% and even preferably within 103% of the high pressure of systems using R134a or R410A. This is important in such embodiments as it allows the use of existing pressure components.
  • Embodiments of the present disclosure describe methods of retrofitting an existing system, wherein the said binary blend has a composition of 60% to about 90% by weight of R1243zf, and a remainder of said refrigerant is R1234ze(E). Yet other embodiments of the present disclosure describe methods, wherein the binary blend has a composition of 80% to about 90% by weight of R1234yf, and a remainder of said refrigerant R152a.
  • Embodiments of the present disclosure describe methods, wherein the binary blend has a composition of 90% by weight of R1123, and a remainder of said refrigerant R32. [0038] Embodiments of the present disclosure describe methods, wherein the binary blend a) has a global warming potential of less than 150, b) has an ozone depletion potential of zero, c) has a safety classification of A2L or A1, d) is non-toxic according to ASHRAE classification. [0039] Embodiments of the present disclosure describe a method as mentioned above, wherein the binary blend has a Glide Temperature of ⁇ 0.1 K.
  • Embodiments of the method described in the present disclosure comprise a system, wherein the degree of superheating at evaporator outlet is about 5 K and the degree of subcooling at the condenser outlet is about 5 K. 4105.090PCT1 (2022-044-02) [0041] Embodiments of the present disclosure describe a method of retrofitting an existing system, wherein the system comprises a low to medium refrigeration system and has cooling applications. [0042] Embodiments of the present disclosure further describe a method, wherein the system comprises a domestic or automotive air conditioning system. In certain embodiments of the present disclosure, the method of retrofitting an existing system comprises high pressure commercial or industrial refrigeration system.
  • Embodiments of the present disclosure also comprises the method, wherein the system comprises one operated with advanced cooling cycles and including liquid-line/suction line heat exchanger (LL/SL HX) cycles. Yet other embodiments describe the method, wherein the system comprises two-stage linear compressor systems.
  • the methods of retrofitting an existing system with the binary blends described in the present disclosure improves one or more of a global warming potential, capacity, efficiency, discharge temperature, discharge pressure, and/or energy consumption of the composition, particularly in a low or medium temperature refrigeration system and as compared to the refrigerant R134a or R410A.
  • Embodiments of the present disclosure describe a heat transfer system comprising a compressor, a condenser, and an evaporator in fluid communication and operating with an evaporator temperature (ET) from about 243 K to about 263 K; condenser temperature (CT) from about 293 K to about 315 K, and a refrigerant in said system, said refrigerant comprises a binary blend of more than one of R1243zf, R1234ze(E), R1234yf, R152a, R1123, R32 refrigerants.
  • ET evaporator temperature
  • CT condenser temperature
  • the embodiment according to the present disclosure comprises a system, wherein the degree of superheating at evaporator outlet is about 5 K and the degree of subcooling at the condenser outlet is about 5 K.
  • Embodiments of the present disclosure describe a retrofitted system, wherein the said binary blend has a composition of 60% to about 90% by weight of R1243zf, and a remainder of said refrigerant is R1234ze(E).
  • Yet other embodiments of the present disclosure describe system, wherein the binary blend has a composition of 80% to about 90% by weight of R1234yf, and a remainder of said refrigerant R152a.
  • Embodiments of the present disclosure describe systems, wherein the binary blend has a composition of 90% by weight of R1123, and a remainder of said refrigerant R32.
  • Embodiments of the present disclosure describe a retrofitted system, wherein the binary blend a) has a global warming potential of less than 150, b) has an ozone depletion 4105.090PCT1 (2022-044-02) potential of zero, c) has a safety classification of A2L or A1, d) is non-toxic according to ASHRAE classification.
  • Embodiments of the present disclosure describe a retrofitted system, wherein the degree of superheating at evaporator outlet is about 5 K and the degree of subcooling at the condenser outlet is about 5 K. [0049] Embodiments of the present disclosure describe a retrofitted system as mentioned above wherein the binary blend has a Glide Temperature of ⁇ 0.1 K. [0050] Embodiments of the present disclosure describe a retrofitted system, wherein the system comprises a low to medium refrigeration system and has cooling applications. [0051] Embodiments of the present disclosure further describe a retrofitted system, wherein the system comprises a domestic or automotive air conditioning system.
  • retrofitting an existing system comprises high pressure commercial or industrial refrigeration system.
  • Embodiments of the present disclosure also comprises retrofitting an existing system, wherein the system comprises one operated with advanced cooling cycles and including liquid-line/suction line heat exchanger cycles.
  • the system comprises two-stage linear compressor systems.
  • the methods of retrofitting an existing system with the binary blends described in the present disclosure improves one or more of a global warming potential, capacity, efficiency, discharge temperature, discharge pressure, and/or energy consumption of the composition, particularly in a low or medium temperature refrigeration system and as compared to the refrigerant R134a or R410A.
  • Embodiments of the present disclosure comprise binary blends that could be used as drop-in replacements in the existing systems containing R134a and/or R410A, with minimal modification to the existing system.
  • the reliability of polar soft-SAFT in modeling the thermodynamic behavior of refrigerant binary blends is validated to ensure high fidelity in model predictions for all thermodynamic state variables used in the subsequent technical evaluation for the suitability of identified promising refrigerant blends.
  • VLE experimental vapor liquid equilibria
  • Example 1 Cooling application of Binary blend comprising R1243zf and R1234ze (E) [0055]
  • These predictions typically serve as another layer of reliability and accuracy testing, especially in the case of first and second order derivative properties, due to their heightened sensitivity to errors in modeling the vapor ⁇ liquid equilibria (VLE) of the pure fluid.
  • FIG. 5 shows the predicted VLE of the blend.
  • FIG. 5 symbols are experimental data and lines are polar soft SAFT calculations.
  • the model performance was obtained for said binary blend, with their polar soft-SAFT computed coexisting densities and vapor pressure included in FIG.5.
  • the additional predicted properties for the modeled refrigerants include enthalpy of vaporization ( ⁇ H vap ), single phase density, isobaric heat capacity (c P ), and speed of sound ( ⁇ ), as provided in FIGS. 6(a-d), for selected fourth generation refrigerants, R1234yf, R1234ze(E), and R1233zd(E).
  • FIGS.6(a-d) show the Thermodynamic properties of low GWP refrigerants, including (a) enthalpy of vaporization, (b) single-phase density, (c) isobaric heat capacity, and (d) speed of sound, for R1234ze(E), R1234yf, and R1233zd(E), with polar soft- SAFT predictions (solid lines) compared to experimental data (symbols).
  • the molecular-based polar soft- SAFT EoS was used as a reliable platform for generating properties needed for the rational design of binary blends.
  • KPI key performance indicators
  • the binary blend of refrigerant comprising R1243zf and R1234ze (E) satisfying the initial screening criteria mentioned in the previous subsection were then evaluated based on their technical compatibility as drop-in replacements for R134a and R410A.
  • the technical evaluation was first carried out simulating a simple single-stage vapor compression refrigeration cycle (SS-VCRC), represented in FIGS.1(a-c).
  • SS-VCRC simple single-stage vapor compression refrigeration cycle
  • the SS-VCRC operates with the isentropic compression of superheated vapor in the single- stage reciprocating air compressor (1 – 2), followed by the isobaric de-superheating of the working fluid in a series of shell-and- tube air-to-refrigerant heat exchangers (2 – 2*). Condensation occurs afterward, releasing both its latent (2* – 3 SAT ) and specific (3 SAT – 3) heats to deliver a subcooled liquid phase working fluid.
  • Tev T1
  • FIGS. 1(b-c) a 5 K superheating and subcooling were applied to the system to lengthen the lifespan of the compressor and EEV, by preventing the formation of droplets in the compressor, while maintaining a liquid phase in the EEV.
  • KPIs key performance indicators for technical evaluation of drop-in replacement blends to R134a and R410A are based on volumetric cooling capacity (VCC), discharge line temperature (DLT), and condenser pressure (P cond ), which should be similar to the replaced refrigerant to ensure high system compatibility and minimal retrofitting.
  • VCC volumetric cooling capacity
  • DLT discharge line temperature
  • P cond condenser pressure
  • thermodynamic properties and performance criteria have also been included to assess the degree of blend compatibility with existing systems using R134a and R410A in SS-VCRC 4105.090PCT1 (2022-044-02) cycles. These include normal boiling point (NBP), pressure ratio (PR), suction density ( ⁇ v), refrigeration effect (RE), power per ton of refrigeration (PPTR) and coefficient of performance (COP), also predicted using the thermodynamic model. These technical criteria are used to determine the compatibility of the short-listed blends in SS-VCRC cycles. Equal weights were given for each metric included in Table 4 for the sake of simplicity, with promising blends selected based on a 90% compatibility ratio, for further evaluation in terms of performance in advanced refrigerant cycles, overall environmental impact, and projected yearly cooling cycle cost rate.
  • Table 5 summarizes the KPIs in liquid-line/suction line heat exchanger cycles and two-stage linear compressor systems.
  • blends 1 – 5, 1’ and 2’ As drop- in replacements in basic SS-VCRC system, representing a benchmark model, was established, the performance of these blends in other advanced refrigeration cycles (i.e., LL/SL-HX and TSVCRC) was examined. The technical performance of the designed blends in these systems was evaluated under the same operating conditions and assumptions.
  • Table 5 summarizes the key performance indicators of the binary blend of R1243zf and R1234ze(E) (ID 5) as compared to commercial refrigerants like R134a and R410A.
  • TEWI total equivalent warming impact
  • AIRAH Australian Institute of Refrigeration, Air conditioning and Heating
  • the environmental assessment of these blends not only accounts for their GWP, but also includes the indirect impact associated with the energy consumption of the VCRC cycle, dependent on the type and efficiency of the cooling system, and the properties of the refrigerant blend, alongside with the level of decarbonization in the energy mix within a specific country also considering the country- dependent indirect emission factor.
  • Table 6 summarizes the environmental evaluation of binary blends comprising different ratios of R1243zf and R1234ze(E).
  • the GWP for this specific blend in the example is less than 1, thus conforming with being near azeotropic, low GWP binary blend that could be used as a drop-in replacement to R134a and R410A.
  • T G Glide 4105.090PCT1 (2022-044-02) Temperature is represented as T G (K).
  • T G blend glide temperature
  • T G blend glide temperature
  • acceptable T G was set to 0.1 K, benchmarked to the TG of the near-azeotropic blend R410A at atmospheric pressure, although this criterion can be less stringent for other cooling applications.
  • Table 6 Environmental evaluation of binary blends comprising different ratios of R1243zf and R1234ze(E) The results of the environmental impact based on the TEWI metric in SS-VCRC cycle are presented in FIGS.7(a-b). The level of direct emissions related to the leakage rate and end-of- life cycle disposal of the working fluids were similar across all examined geographical areas (FIGS.7(a-b), as the parameters concerned there were fixed beforehand. This is simplistic for the sake of convenience. However, it suffices for a comparative analysis. FIGS.
  • FIG. 7(a-b) show TEWI analysis for most promising alternatives for R134a in SS-VCRC cycle, with the bar colors corresponding to the studied benchmark refrigerants and designed blends.
  • FIG. 7(a) shows the different major HFCs producers
  • FIG. 7(b) shows selected EU-27 countries, sorted by population from left to right.
  • the strong color represents direct emissions, while the light-equivalent color stands for indirect emissions.
  • the colors represent the different refrigerants and blends, as per the legend inside the figures.
  • both commercial refrigerants R410A and R134a present the highest direct emissions of 10.46 and 7.07 tCO2-eq, respectively, closely related to their high GWP.
  • the total annualized cost (TAC, ⁇ ) for deploying the promising refrigerants blends in the VCRC cycles examined in the present disclosure includes the capital (CAPEX, ⁇ ⁇ ⁇ ), operating and maintenance (OPEX, ⁇ op), environmental (Enviro ⁇ ⁇ nv ), and set-up ( ⁇ ⁇ et ⁇ ⁇ p ) costs, utilized as monetized KPIs for determining the optimal drop-in refrigerant blend, and they are calculated according to the following equation: T AC ($.y -1 ) ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ (3.a)
  • T AC ($.y -1 ) ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ (3.a)
  • FIG. 8(a) shows the economic analysis 4105.090PCT1 (2022-044-02) for most promising alternatives for R134a for the different major HFCs producers based on total costs.
  • the colors represent the different refrigerants and blends, as per the legend inside the figures.
  • the different portions of the bars represent the split of the total annual cost, from bottom to top (darker to lighter colors): CAPEX, OPEX, Enviro, and set-up costs, calculated from above mentioned Equation, utilized as monetized KPIs for determining the optimal drop- in refrigerant blend.
  • Example 2 Cooling application of Binary blend comprising R1123 and R32 [0064] The strength of using molecular-based EoSs is also validated from the example comprising the binary blend of R1123 and R32.
  • FIG.9 shows the predicted VLE of the blend. In FIG.9, symbols are experimental data and lines are polar soft SAFT calculations.
  • the developed 4E analysis (Energy, Exergy, Environmental, Economic evaluation) approach has been implemented in the present disclosure for identifying low GWP refrigerants as drop-in replacements for R410A in selected refrigeration cycles, based on technical KPIs (Key Performance Indicator), flammability, environmental and economic impact.
  • the molecular-based polar soft- SAFT EoS was used as a reliable platform for generating thermodynamic properties needed for the rational design of binary blends.
  • Technical, Environmental, and Economic evaluation of potential drop-in replacement blends in basic refrigeration cycle based on key performance indicators (KPI) [0066]
  • KPI key performance indicators
  • the binary blend of refrigerant comprising R1132 and R32 satisfying the initial screening criteria mentioned in the previous subsection were then evaluated based on their technical compatibility as drop-in replacement for R410A.
  • the technical evaluation was carried out simulating a simple single-stage vapor compression refrigeration cycle (SS-VCRC), represented in FIGS.1(a-c) under the same operating conditions described in Example 1, based on the same KPIs with their values in Tables 3 – 5.
  • SS-VCRC simple single-stage vapor compression refrigeration cycle
  • Table 7 Environmental evaluation of binary blends comprising different ratios of R1123 and R32 [0068]
  • the results of the environmental impact based on the TEWI metric in SS-VCRC cycle are presented in FIG.10, showing the environmental impact for blend 1 as an alternative to R410A in SS-VCRC cycle, with the bar colors corresponding to the studied benchmark refrigerants and designed blends, for different major HFCs producers.
  • blend 1 has the lowest environmental impact compared to R410A and its alternative R32.
  • the addition of R1123 significantly helped in reducing the GWP of the designed blend, resulting in lower direct emissions (see dark bars in the figure).
  • FIG. 11 shows the economic analysis for most promising alternatives for R410A for the different major HFCs producers based on total costs.
  • the colors represent the different refrigerants and blends, as per the legend inside the figures.
  • the different portions of the bars represent the split of the total annual cost, from bottom to top (darker to lighter colors): CAPEX, OPEX, Enviro, and set-up costs, calculated from above mentioned Equation in [0063], utilized as monetized KPIs for determining the optimal drop-in refrigerant blend.
  • Non-flammable Class 1
  • mildly-flammable Class 2L according to ASHRAE classification
  • Pure components or near-azeotropic blends (Glide temperature ⁇ 0.1 K) with similar normal boiling temperature and condensation pressures of the refrigerant to be replaced.
  • Have similar volumetric cooling capacity i.e., amount of refrigerant to deliver a specific cooling capacity
  • condenser pressure and discharge line temperature than R134a or R410A, depending on the application.
  • 7. Having similar system performance energetic efficiency, and energy consumption.

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Abstract

Des modes de réalisation de la présente divulgation concernent des mélanges binaires quasi-azéotropiques de fluides frigorigènes qui présentent un faible PRP ; un procédé de modernisation d'un système de transfert de chaleur existant avec lesdits fluides frigorigènes ; des systèmes de transfert de chaleur comprenant lesdits fluides frigorigènes et analogues. Des modes de réalisation de la présente divulgation décrivent un fluide frigorigène qui est quasi-azéotropique et qui comprend un mélange binaire de plus d'un fluide frigorigène parmi R1243zf, R1234ze(E), R1234yf, R152a, R1123, R32.
PCT/IB2023/057465 2022-09-13 2023-07-21 Fluide frigorigène à mélange binaire quasi-azéotropique à faible effet de réchauffement planétaire Ceased WO2024057105A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110029416A (ko) * 2009-09-15 2011-03-23 인하대학교 산학협력단 Ｒ1234ｙｆ와 Ｒ152ａ로 구성된 2원 혼합냉매
EP3144601A1 (fr) * 2014-05-12 2017-03-22 Panasonic Intellectual Property Management Co., Ltd. Dispositif à cycle de réfrigération
WO2021131096A1 (fr) * 2019-12-25 2021-07-01 ダイキン工業株式会社 Dispositif à cycle frigorifique, huile pour machine frigorifique et agent de prévention des fuites de fluide frigorigène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110029416A (ko) * 2009-09-15 2011-03-23 인하대학교 산학협력단 Ｒ1234ｙｆ와 Ｒ152ａ로 구성된 2원 혼합냉매
EP3144601A1 (fr) * 2014-05-12 2017-03-22 Panasonic Intellectual Property Management Co., Ltd. Dispositif à cycle de réfrigération
WO2021131096A1 (fr) * 2019-12-25 2021-07-01 ダイキン工業株式会社 Dispositif à cycle frigorifique, huile pour machine frigorifique et agent de prévention des fuites de fluide frigorigène

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* Cited by examiner, † Cited by third party
Title
YANG ZHIQIANG; VALTZ ALAIN; COQUELET CHRISTOPHE; WU JIANGTAO; LU JIAN: "Experimental measurement and modelling of vapor-liquid equilibrium for 3,3,3- Trifluoropropene (R1243zf) and trans-1,3,3,3-Tetrafluoropropene (R1234ze(E)) binary system", INTERNATIONAL JOURNAL OF REFRIGERATION, vol. 120, 25 August 2020 (2020-08-25), AMSTERDAM, NL , pages 137 - 149, XP086340725, ISSN: 0140-7007, DOI: 10.1016/j.ijrefrig.2020.08.016 *

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