EP2972014A1 - Compositions caloporteuses à faible gwp - Google Patents

Compositions caloporteuses à faible gwp

Info

Publication number
EP2972014A1
EP2972014A1 EP14769131.5A EP14769131A EP2972014A1 EP 2972014 A1 EP2972014 A1 EP 2972014A1 EP 14769131 A EP14769131 A EP 14769131A EP 2972014 A1 EP2972014 A1 EP 2972014A1
Authority
EP
European Patent Office
Prior art keywords
weight
hfc
compositions
heat transfer
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14769131.5A
Other languages
German (de)
English (en)
Other versions
EP2972014A4 (fr
Inventor
Samuel F. Yana Motta
Mark W. Spatz
Ryan Hulse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
Honeywell International Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/209,040 external-priority patent/US20140191153A1/en
Application filed by Honeywell International Inc filed Critical Honeywell International Inc
Publication of EP2972014A1 publication Critical patent/EP2972014A1/fr
Publication of EP2972014A4 publication Critical patent/EP2972014A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/20—Ternary blends of expanding agents
    • C08J2203/202—Ternary blends of expanding agents of physical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00—Foams characterised by their intended use
    • C08J2207/04—Aerosol, e.g. polyurethane foam spray
    • 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—Component parts or details not otherwise provided for in this subclass
    • F25B2400/12—Inflammable refrigerants
    • F25B2400/121—Inflammable refrigerants using R1234

Definitions

  • This invention relates to compositions, methods and systems having utility particularly in refrigeration applications, and in particular aspects to refrigerant compositions particularly useful in systems that have heretofore typically utilized the refrigerant HFC ⁇ 404A ' for heating and cooling applications.
  • R-404A the combination of HFC-125:HFC-143a:HFC ⁇ 134a in an approximate 44:52:4 weight ratio is referred to in the art as R-404A
  • R-404A has an estimated Global Warming Potential (GWP) of 3922, which is considerably higher than is desired and/or required.
  • GWP Global Warming Potential
  • thermodynamic performance or energy efficiency may have secondary environmental impacts through increased fossil fuel usage arising from an increased demand for electricai energy.
  • CFG and/or HFC refrigerant substitutes it is generally considered desirable for CFG and/or HFC refrigerant substitutes to be effective without major engineering changes to conventional vapor compression technology currently used with CFC and/or HFC refrigerants.
  • Flammability is another important property for many applications. That is, it is considered either important or essential in many applications, including particularly in heat transfer applications, to use compositions vvhich are non-flammable or have only mild flammability. Thus, it is frequently beneficial to use in such compositions
  • mildly flammable refers to compounds or compositions which are classified as being 21 in accordance with ASHRAE standard 34 dated 2010, incorporated herein by reference.
  • HFC-152a the fluoroalkane dif!uoroethane
  • compositions, methods, uses and systems which comprise or utilize a mufti-component mixture comprising: (a) from 0% to about 50% by weight of HFC-32; (b) from about 50% to about 90% by weight of a compound selected from unsaturated, -CF3 terminated propenes, unsaturated, -GF3 terminated butenes, and combinations of these, and (c) from 0% to about 25% by weight of HFC-152a, provided that the combination of components (a) and (c) together comprise at !east about 10% by weight of the composition.
  • % by weight refers to the weight percent based on the total of the components (a) ⁇ (c) in the composition
  • compositions, methods, uses and systems which comprise or utilize a multi-component mixture comprising: (a) from about 10% to about 50% by weight of HFC-32; and (b) from about 50% to about 90% by weight of a compound selected from unsaturated, -CF3 terminated propenes, unsaturated, -CF3 terminated butenes, and combinations of these, preferably a compound selected from HFO ⁇ 1234ze, HFO ⁇ 1234yf and combinations of these.
  • the compositions of this embodiment further comprise: ⁇ c ⁇ from greater than 0% to about 25% b weight of HFC-152a.
  • compositions include from 25 to 55% by weight of 2,3,3,3-tetrafluoropropene, from 5 to 20% by weight of HFC-152a and from 30 to 55% by weight of HFC-32. In further aspects, they include from 30 to 45% by weight of HFC-32, from 30 to 53% by weight of 2,3,3,3-tetraf!uoropropene and from 10 to 20% by weight of HFC ⁇ 152a. in even further aspects, they consist of 2,3,3,3- tetrafluoropropene, HFC- 152a, and HFC-32. In certain non-limiting aspects, such composiiions may be used as a heat transfer fluid, such as in a compression system for air conditioning and heating, as a blowing agent, a solvent, or an aerosol.
  • a heat transfer fluid such as in a compression system for air conditioning and heating, as a blowing agent, a solvent, or an aerosol.
  • the present invention provides also methods, uses and systems which utilize the compositions of the present invention, including methods, uses and systems for heat transfer and for retrofitting existing heat transfer systems.
  • Certain preferred method aspects of the present invention relate to methods of providing relatively Sow temperature cooling, such as in low temperature refrigeration systems.
  • Other method aspects of the present invention provide methods of retrofitting an existing Sow
  • temperature refrigeration system designed to contain or containing R-404A refrigerant comprising withdrawing R-404A from the system and/or introducing a composition of the present invention into the system without substantial engineering modification of said existing refrigeration system.
  • HFO-1234ze is used herein genehcaily to refer to 1 ,1,1 ,3- tetrafiuoropropene, independent of whether it is the cis- or trans- form.
  • HFO-1234ze !! therefore includes within its scope cisHFO-1234ze, transHFO-1234ze, and ail combinations and mixtures of these.
  • component (b) of the present invention comprises trans-HFO-1234ze (also referred to as HFO-1234ze(E)), HFO-1234yf and combinations of these.
  • trans-HFO-1234ze also referred to as HFO-1234ze(E)
  • HFO-1234yf and combinations of these.
  • FIG. 1 illustrates the burning velocity of mixtures of HFC-152a and HFO ⁇ 1234yf.
  • FIG. 2 illustrates the burning velocity of mixtures of HFC-152a and HFO-
  • FIG. 3 illustrates the burning velocity of mixtures of HFC-32 and HFO- 1234yf.
  • FIG. 4 illustrates the burning velocity of mixtures of HFC-32 and HFO-
  • FIG. 5 illustrates the burning velocity of a mixture of 40 w ⁇ % HFC-32, 20 t% HFO ⁇ 1234yf, 30 wt% HFO-1234ze(E) and 10 wt% HFC-152a.
  • Low temperature refrigeration systems are important in many applications, such as to the food manufacture, distribution and retail industries. Such systems play a vita! role in ensuring that food which reaches the consumer is both fresh and fit to eat,
  • HFC-404A which has an estimated Global Warming Potential (GWP) of 3922, which is much higher than is desired or required.
  • GWP Global Warming Potential
  • the present compositions provide alternatives and/o replacements for refrigerants currently used in Sow temperature applications, particuiariy and preferably HFC-404A, that at once have Sower GWP values and provid a refrigerant composition that has a degree of f!ammability that is mildly flammable or even iess flammable than mildly flammable, and which have desirably low toxicity, and preferably also have a close match in cooling capacity to HFC-404A in such systems,
  • compositions of the present invention are generally adaptable for use in heat transfer applications, that is, as a heating and/or cooling medium, but are particularly well adapted for use, as mentioned above, in low temperature refrigeration systems that have heretofor used HFC-404A and/or systems that have heretofor used R-22.
  • component (a) of the present invention comprises transHFO-1234ze ! HFO-1234yf or combinations of these, it may sometimes be referred to herein as the "tetrafiuoropropene component" or "TFC.”
  • the HFC-32 is present in the HFC-32
  • compositions of the invention in an amount of from about 25% to about 45% by weight of the compositions, tn further embodiments, HFC-32 is present in the compositions of the invention in an amount from about 30 to about 55% by weight, and in certain embodiments from about 30 to about 45% by weight of the composition,
  • unsaturated -CF3 terminated propenes unsaturated -CF3 terminated butenes, and combinations of these comprises HFQ ⁇ 1234ze, HFQ ⁇ 1234yf ! and combinations of these, preferably where such compounds are present in the compositions in amounts of from about 50% to about 80% by weight, and even more preferably from about 50% to about 80% by weight.
  • the compositions in amounts of from about 50% to about 80% by weight, and even more preferably from about 50% to about 80% by weight.
  • compound comprises HFQ ⁇ 1234yf in an amount from about 25 to about 55 % by weight, in certain embodiments, from about 30 to about 53% by weight of the composition.
  • the compositions comprise HFC-152a in an amount from about 5% to about 20% by weight. In further embodiments, HFC- 152a is present in the compositions of the invention in an amount from about 10 to about 20% by weight of the composition.
  • the multi-component mixture is a mixture of
  • HFC-32 comprises; (a) from about 10% to about 50% by weight of HFC-32; and (b) from about 50% to about 90% by weight of a compound selected from 1 ,1 ,1-irifSuoropropene (HFO- 1243zf), HFO-1234ze, HFO ⁇ 1234yf, 1 ,1 ,1 ,3,3,3-hexafluorobutene (HFO ⁇ 1336mzz) and combinations of these, with the amount of HFO-1243zf preferably comprising not greater than 80% by weight and even more preferably less than about 20% of the composition.
  • HFO- 1243zf 1 ,1 ,1-irifSuoropropene
  • HFO-1234ze HFO ⁇ 1234yf
  • HFO ⁇ 1336mzz 1-hexafluorobutene
  • HFO-1243zf preferably is present in the composition in amount of from about 5% to about 80% by weight, and more preferably from about 5% by weight to about 20% of the composition.
  • the compositions further preferably comprise: (c) greater than 0% and up to about 25% by weight of HFC ⁇ 152a.
  • the multi-component mixture [00293 to certain preferred embodiments, the multi-component mixture
  • component (b) is a compound selected from HFO-1234ze, HFO- 1234yf and combinations of these.
  • compositions include from 25 to 55% by weight of 2,3,3,3-tetrafluoropropene, from 5 to 20% by weight of HFC-152a and from 30 to 55% by weight of HFC-32. In further aspects, they include from 30 to 45% by weight of HFC-32, from 30 to 53% by weight of 2,3,3,3-tetrafluoropropene and from 10 to 20% by weight of HFC-152a, In even further aspects, they consist of 2,3,3,3- tetrafluoropropene, HFC- 152a, and HFC-32. In certain non-limiting aspects, such compositions may be used as a heat transfer fluid, such as in a compression system for air conditioning and heating, as a blowing agent, a solvent, or an aerosol.
  • a heat transfer fluid such as in a compression system for air conditioning and heating, as a blowing agent, a solvent, or an aerosol.
  • compositions of the present invention are capable of achieving a difficult combination of properties, including particularly Sow GWP.
  • Table A illustrates the substantial GWP superiority of certain compositions of the present invention, which are described in parenthesis in terms of weight fraction of each component, in comparison to the GWP of HFC-404A, which has a GWP of 3922.
  • component (a) is HFC-32
  • component (b) is seiected from HFO- 1234ze, HFO-1234yf and combinations of these
  • component (c) is selected from HFO-1243zf, HFC-152a and combinations of these
  • BVcomp is the burning velocity of the composition
  • i is summed for each of components (a) through (c) in the composition, and preferably the amounts of each of the components (a) through (c) is selected to ensure that BVcomp based on the finding of this unexpected formula is less than about 10, more preferably less than about 9 and even more preferably less than about 8, while at the same time the GWP of the composition is less than about 400, more preferably less than about 300 and even more preferably Sess than about 250.
  • component (a) is HFC-32
  • (b) is selected from HFQ-1234ze, HFO-1234yf and combinations of these
  • component (c) is HFC-152a
  • the burning velocity of the present compositions is substantially linearly reiated to the weight averaged burning velocity of the components (a) - (c) according to the Formula i:
  • BVcomp is the burning velocity of the compositions
  • i represents each of components (a) through (c) in the composition, and preferably the amounts of each of the components (a) through (c) is selected to ensure that BVcomp based on the finding of this unexpected formula is less than about 10, more preferably less than about 9 and even more preferably less than about 8, while at the same time the G P of the composition is preferably less than about 400, more preferabl less than about 300, and even more preferably less than about 250.
  • compositions of the present invention may include other components for the purpose of enhancing or providing certain functionality to the composition, or in some cases to reduce the cost of the composition.
  • refrigerant for the purpose of enhancing or providing certain functionality to the composition, or in some cases to reduce the cost of the composition.
  • compositions according to the present invention especially those used in vapor compression systems, include a lubricant, generally in amounts of from about 30 to about 50 percent by weight of the composition, and in some case potentially in amount greater than about 50 percent and other cases In amounts as low as about 5 percent.
  • hydrofluorocarbon (HFC) refrigerants may be used with the refrigerant compositions of the present invention.
  • Commercially available mineral oils include Witco LP 250 (registered trademark) from Witco, Zero! 300 (registered trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet.
  • Commercialiy available alkyi benzene lubricants include Zerol 150 (registered trademark).
  • esters include neoperityi glycoi dipeiargonate, which is available as Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark).
  • Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters.
  • hydrocarbon based oils have sufficient solubility with the refrigerant that Is comprised of an iodocarbon, wherein the combination of the iodocarbon and the hydrocarbon oil are more stable than other types of lubricant. Such combinations are therefore be advantageous.
  • Preferred lubricants include polyalkylene glycols and esters, Polyalkylene glycols are highly preferred in certain embodiments because they are currently in use in particular applications such as mobile air-conditioning. Of course, different mixtures of different types of lubricants may be used.
  • compositions of the present invention are used in refrigeration systems originally designed for use with an HFC refrigerant, such as, for example, R-404A.
  • HFC refrigerant such as, for example, R-404A.
  • the preferred compositions of the present invention tend to exhibit many of the desirable characteristics of R-4G4A but have a GWP that is substantially lower than that of R-404A while at the same time having a capacity that is substantially similar to or substantially matches, and preferably is as high as or higher than R-404A.
  • GWPs global warming potentials
  • GWPs global warming potentials
  • the present compositions are used in refrigeration systems originally designed for use with R ⁇ 404A.
  • Preferred refrigeration compositions of the present invention may be used in refrigeration systems containing a lubricant used conventionally with R-404A, such as poiyoieste oils, and the like, or may be used with other lubricants traditionally used with HFC refrigerants.
  • a lubricant used conventionally with R-404A such as poiyoieste oils, and the like
  • other lubricants traditionally used with HFC refrigerants As used herein the term "refrigeration system” refers generally to any system or apparatus, or an part or portion of such a system or apparatus, which employs a refrigerant to provide cooling.
  • Such refrigeration systems include, for example, air conditioners, electric refrigerators, chillers, and the like.
  • low temperature refrigeration system refers to vapor compression refrigeration systems whic utilize one or more compressors and a condenser temperature of from about 35 e C to about 45°C
  • the systems have an evaporator temperature of from about -25°C to about -35°C, with an evaporator temperature preferably of about ⁇ 32°C.
  • the systems have a degree of superheat at evaporator outlet of from about 0°C to about 10°C, with a degree of superheat at evaporator outlet preferably of from about 4°C to about 8°C.
  • the systems have a degree of superheat in the suction line of from about 5°C to about 15°C, with a degree of superheat in the suction line preferabiy of from about 5°C to about 10°C.
  • FIG. 1 -2 Burning velocity (BV) measurements for certain HFC-152a/HFO-1234yf and HFC-152a/HFO-1234ze ⁇ E) blends are shown in Figures 1 -2.
  • the burning velocity measurements were performed using the vertical tube method described in iSO standard 817 and ASHRAE standard 34, Figures 1-2 also show the GWP of the mixtures.
  • the results in Figures 1-2 illustrate applicants' unexpected finding that the maximum burning velocity can closely be approximated by a linear relationship with wt% of the components. According to certain preferred embodiments, therefore, the amount of the components of the present invention is selected according to the
  • compositions comprise up to about 30 wt% of HFC-152a s more preferably up to 20% of HFC- 52a, while still exhibiting a burning velocity of the blend that is below about 10 cm/s and thus constituting a 21 refrigerant.
  • FIG. 3-4 Burning velocity (8V) measurements of the HFC-32/HFO-1234yf and HFC-32/HFO ⁇ 1234ze(E) blends are shown in Figures 3-4.
  • the burning velocity measurements were performed using the vertical tube method described in ISO standard 817 and ASHRAE standard 34.
  • Figures 3-4 also show the GWP of the mixtures.
  • the results in Figures 3-4 confirm: that the maximum burning velocity can closely be approximated by a linear relationship with wt% of the components.
  • EXAMPLE 3 FSammabt!ity of multi-component mixtures.
  • EXAMPLE 4 Burning velocity of mixtures.
  • the burning velocities of common pure component refrigerants are given in the following Table 1. It has been discovered as described above that the burning velocity of mixtures according to the present invention can be calculated from the wt% times the pure component burning velocity as described in Formula 1 above. The burning velocities of all the mixtures in Table A were calculated and are shown below in Table 2. All of the mixtures with the exception of A3 have a burning velocity of less than 10 cm/s and therefore would be expected to be classified as A2L refrigerants. Table 1; Burning velocities of pure components
  • a low temperature refrigeration system is provided.
  • the condenser temperature is set to 40.55*0, which generally corresponds to an outdoor temperature of about 35°C
  • the degree of subcooling at the expansion device inlet is set to 5.55°C.
  • the evaporating temperature is set to -31.6°C, which corresponds to a box temperature of about ⁇ 26°C
  • the degree of superheat at evaporator outlet is set to 5.55*0.
  • the degree of superheat in the suction line is set to 10°C, and the compressor efficiency is set to 65%.
  • the pressure drop and heat transfer in the connecting lines are considered negligible, and heat leakage through the compressor shell is ignored.
  • compositions A1 - A3, B1 - B3, 01 , C5 identified in Table A above in accordance with the present invention are reported in Table 3 be low, based upon HFC-404A having a COP value of 1.00, a capacity value of 1 .00 and a discharge temperature of 87, ⁇ ⁇ ⁇ ,
  • the replacement should not require substantial redesign of the system and no major item of equipment needs to be replaced in order to accommodate the refrigerant of the present invention.
  • the replacement preferably fulfills one or more of, and preferably all, of the following requirements:
  • High-Side Pressure that is within about 105%, and even more preferably within about 103% of the high side pressure of the same system using R404A. This parameter can be important in such embodiments because it can enhance the ability to use existing pressure components in such systems.
  • Discharge Temperature that is preferably Sower than about 130°C
  • Cooling capacity that is within +6%, and even more preferable within ⁇ 3% of the cooling capacity of the same sysiem using R404A.
  • This paramete is potentially important in certain embodiments because it can help to ensure adequate cooling of the product being refrigerated. It should also be noted that excess capacity can cause overload of the electric motor therefore they should be also avoided.
  • Efficiency (COP) that is superior to R404A without incurring ion excess capacity as noted above.
  • Evaporator glide preferably is below about 6.6 C (12 * F) to avoid excessive
  • the blend is a 2L class refrigerant.
  • compositions of the present invention are capable of at once achieving many of the important refrigeration system performance parameters close to the parameters for R- 404A, and in particular sufficiently close to permit such compositions to be used as replacement for R-404A in low temperature refrigeration systems and/or for use in such existing systems with only minor system modification.
  • compositions A1 - A3 exhibit capacities in this low temperature refrigeration system that are within about 6% of the capacity in such system of 404A.
  • he compositions of the present invention comprise ternary blends of HFC-32, HFO-1234yf and HFO ⁇ 1234ze(E).
  • the three blends (B1, B2, B3) exhibit acceptable performance with B2 being the preferred due to the fulfillment of al! requirements including the glide being lower than the maximum advisable (6.6'C).
  • compositions comprise additionally HFC- 152a.
  • Such blends are preferred in many embodiments because of the superior efficiency, good capacity and low discharge temperature, while also fulfilling the requirement of BV below 10 cm/s to remain a 2L refrigerant.
  • compositions are capable of providing substantial advantage for use in new or newly designed refrigeration systems, including preferably, Sow temperature refrigeration systems.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne des compositions caloporteuses et des procédés, les compositions ayant une vitesse de combustion (BV) inférieure à environ 10 et un potentiel de réchauffement de la planète (GWP) inférieur à environ 400, comprenant : (a) d'environ 0 à environ 50% en poids de HFC-32 ; (b) d'environ 50% à environ 90% en poids d'un composé choisi dans le groupe constitué de propènes insaturés à terminaison -CF3, de butènes insaturés à terminaison -GF3 et de combinaisons de ceux-ci ; et (c) d'environ 0 à environ 25% en poids d'un composé choisi dans le groupe constitué de NFO~1243zf, HFC-152a et de combinaisons de ceux-ci, à condition que la combinaison des composants (a) et (c) réunis comprenne au moins environ 10% en poids de la composition et à condition en outre que la quantité de chacun des composants (a), (b) et (c) soit choisie pour garantir que la BV de la composition est inférieure à environ 10 et le GWP de la composition est inférieur à environ 400.
EP14769131.5A 2013-03-15 2014-03-14 Compositions caloporteuses à faible gwp Withdrawn EP2972014A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201361802349P 2013-03-15 2013-03-15
US14/209,040 US20140191153A1 (en) 2010-11-12 2014-03-13 Low gwp heat transfer compositions
PCT/US2014/027681 WO2014152740A1 (fr) 2013-03-15 2014-03-14 Compositions caloporteuses à faible gwp

Publications (2)

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EP2972014A1 true EP2972014A1 (fr) 2016-01-20
EP2972014A4 EP2972014A4 (fr) 2016-10-26

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EP14769131.5A Withdrawn EP2972014A4 (fr) 2013-03-15 2014-03-14 Compositions caloporteuses à faible gwp

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JP (1) JP2016513749A (fr)
WO (1) WO2014152740A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2009047542A1 (fr) * 2007-10-12 2009-04-16 Ineos Fluor Holdings Limited Compositions de transfert de chaleur
FR2932493B1 (fr) * 2008-06-11 2010-07-30 Arkema France Compositions a base d'hydrofluoroolefines
KR20100013288A (ko) * 2008-07-30 2010-02-09 허니웰 인터내셔널 인코포레이티드 디플루오로메탄 및 플루오르 치환된 올레핀을 함유하는 조성물
FR2936806B1 (fr) * 2008-10-08 2012-08-31 Arkema France Fluide refrigerant
JP5452138B2 (ja) * 2009-09-01 2014-03-26 三菱電機株式会社 冷凍空調装置
FR2950067B1 (fr) * 2009-09-11 2011-10-28 Arkema France Fluide de transfert de chaleur en remplacement du r-410a
FR2950068B1 (fr) * 2009-09-11 2012-05-18 Arkema France Procede de transfert de chaleur
JP5730900B2 (ja) * 2009-12-21 2015-06-10 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ テトラフルオロプロペンおよびジフルオロメタンを含む組成物ならびにその使用
US20120119136A1 (en) * 2010-11-12 2012-05-17 Honeywell International Inc. Low gwp heat transfer compositions
TWI585065B (zh) * 2011-08-26 2017-06-01 杜邦股份有限公司 含四氟丙烯之組成物及其使用方法

Also Published As

Publication number Publication date
EP2972014A4 (fr) 2016-10-26
WO2014152740A1 (fr) 2014-09-25
JP2016513749A (ja) 2016-05-16

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