EP3906289A1 - Stabilized heat transfer compositions, methods and systems - Google Patents
Stabilized heat transfer compositions, methods and systemsInfo
- Publication number
- EP3906289A1 EP3906289A1 EP19907889.0A EP19907889A EP3906289A1 EP 3906289 A1 EP3906289 A1 EP 3906289A1 EP 19907889 A EP19907889 A EP 19907889A EP 3906289 A1 EP3906289 A1 EP 3906289A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat transfer
- lubricant
- weight
- present
- refrigerant
- 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.)
- Pending
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
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
-
- 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
- C09K2205/102—Alcohols
-
- 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
- C09K2205/11—Ethers
-
- 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
- C09K2205/122—Halogenated 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
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/128—Perfluorinated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/042—Epoxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
- C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
- C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
- C10M2211/0225—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- the present invention relates to compositions, methods and systems having utility in heat exchange applications, including in air conditioning and refrigeration applications.
- the invention relates to compositions useful in heat transfer systems of the type in which the refrigerant R-410A would have been used.
- the compositions of the invention are useful in particular as a replacement of the refrigerant R-410A for heating and cooling applications and to retrofitting heat exchange systems, including systems designed for use with R-410A.
- Chlorofluorocarbons were developed in the 1930s as refrigerants for such systems. However, since the 1980s, the effect of CFCs on the stratospheric ozone layer has become the focus of much attention. In 1987, a number of governments signed the Montreal Protocol to protect the global environment, setting forth a timetable for phasing out the CFC products. CFCs were replaced with more environmentally acceptable materials that contain hydrogen, namely the hydrochlorofluorocarbons (HCFCs).
- HCFCs hydrochlorofluorocarbons
- HCFC-22 chlorodifluoromethane
- HFCs hydrofluorocarbons
- R-410A a 50:50 w/w blend of difluoromethane (HFC-32) and pentafluoroethane (HFC-125)
- HFC-32 difluoromethane
- HFC-125 pentafluoroethane
- R-410A is not a drop-in replacement for R-22.
- the replacement of R-22 with R-410A required the redesign of major components within heat exchange systems, including the replacement and redesign of the compressor to accommodate the substantially higher operating pressure and volumetric capacity of R-410A, when compared with R-22.
- R-410A has a more acceptable Ozone Depleting Potential (ODP) than R-22, the continued use of R-410A is problematic since it has a high Global Warming Potential of 2088. There is therefore a need in the art for the replacement of R-410A with a more environmentally acceptable alternative.
- ODP Ozone Depleting Potential
- the EU implemented the F-gas regulation to limit HFCs which can be placed on the market in the EU from 2015 onwards, as shown in Table 1 .
- Table 1 By 2030, only 21 % of the quantity of HFCs that were sold in 201 5 will be available. Therefore, it is desired to limit GWP below 427 as a long term solution.
- *2015 GWP level is based on UNEP 2012 Use Study with no growth rate.
- thermodynamic performance or energy efficiency may result in an increase in fossil fuel usage as a result of the increased demand for electrical energy.
- the use of such a refrigerant will therefore have a negative secondary environmental impact.
- non-flammable refers to compounds or
- compositions which are determined to be non-flammable in accordance with ASTM standard E-681 -2009 Standard Test Method for Concentration Limits of Flammability of Chemicals (Vapors and Gases) at conditions described in ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and described in Appendix B1 to ASHRAE Standard 34-2016, which is incorporated herein by reference and referred to herein for convenience as "Non-Flammability Test”.
- R-410A is currently commonly used with polyol ester (POE) lubricating oil in air conditioning applications, as R-410A is miscible with POE at temperatures experienced during use of such systems.
- POE polyol ester
- R-410A is immiscible with POE at temperatures typically experienced during operation of low temperature refrigeration systems, and heat pump systems. Therefore, unless steps are taken to mitigate against this immiscibility, POE and R-410A cannot be used in low temperature refrigeration or heat pump systems.
- compositions which are capable of being used as a replacement for R-410A in air conditioning applications, and in particular in residential air conditioning and commercial air conditioning applications, which include, rooftop air conditioning, variable refrigerant flow (VRF) air conditioning and chiller air conditioning applications.
- VRF variable refrigerant flow
- Applicants have also come to appreciate that the compositions, methods and systems of the invention have advantage in, for example, heat pump and low temperature refrigeration systems, wherein the drawback of immiscibility with POE at temperatures experienced during operation of these systems is eliminated.
- the present invention provides refrigerant compositions which can be used as a replacements for R-410A and which exhibit in preferred embodiments the desired mosaic of properties of excellent heat transfer properties, chemical stability, low or no toxicity, non flammability, lubricant miscibility and lubricant compatibility in combination with low Global Warming Potential (GWP) and near zero ODP.
- GWP Global Warming Potential
- the present invention includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- HFC-32 difluoromethane
- HFC-125 pentafluoroethane
- said lubricant comprising polyol ester (POE) lubricant and/or polyvinyl ether (PVE) lubricant, and said stabilizer comprising alkylated naphthalene, wherein said alkylated naphthalene is present in the composition in an amount of from 1 % to less than 10% by weight based on the weight of the alkylated naphthalene and the lubricant.
- the heat transfer composition according to this paragraph is sometimes referred to herein for convenience as Heat Transfer Composition 1.
- the term“relative percentage” means the percentage of the identified compound based on the total weight of the listed compounds.
- the term“about” with respect to an amount of an identified component means the amount of the identified component can vary by an amount of +/- 1 % by weight.
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially ofthe following three compounds, with each compound being present in the following relative percentages:
- CF3I trifluoroiodomethane
- said lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant
- said stabilizer comprising alkylated naphthalene, wherein said alkylated naphthalene is present in an amount of from 1 % to 8% by weight based on the weight of the alkylated naphthalene and the lubricant.
- the heat transfer composition according to this paragraph is sometimes referred to herein for convenience as Heat Transfer Composition 2.
- the present invention includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- said lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant
- said stabilizer comprising alkylated naphthalene, wherein said alkylated naphthalene is present in an amount of from 1.5% to 8% by weight based on the weight of the alkylated naphthalene and the lubricant.
- the heat transfer composition according to this paragraph is sometimes referred to herein for convenience as Heat Transfer Composition 3.
- the present invention includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- said lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant
- said stabilizer comprising alkylated naphthalene, wherein said alkylated naphthalene is present in an amount of from 1.5% to 6% by weight based on the weight of the alkylated naphthalene and the lubricant.
- the heat transfer composition according to this paragraph is sometimes referred to herein for convenience as Heat Transfer Composition 4.
- the present invention includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially of of the following three compounds, with each compound being present in the following relative percentages:
- CF 3 I trifluoroiodomethane
- said lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant
- said stabilizer comprising alkylated naphthalene, wherein said alkylated naphthalene is present in an amount of from 1 % to less than 10% by weight based on the weight of the alkylated naphthalene and the lubricant.
- the heat transfer composition according to this paragraph is sometimes referred to herein for convenience as Heat Transfer Composition 5.
- the present invention includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially of of the following three compounds, with each compound being present in the following relative percentages:
- CF 3 I trifluoroiodomethane
- said lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant
- said stabilizer comprising alkylated naphthalene, wherein said alkylated naphthalene is present in an amount of from 1 % to 8% by weight based on the weight of the alkylated naphthalene and the lubricant.
- the heat transfer composition according to this paragraph is sometimes referred to herein for convenience as Heat Transfer Composition 6.
- the present invention includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- the present invention includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentiallyof the following three compounds, with each compound being present in the following relative percentages:
- the present invention also includes any of Heat T ransfer Compositions 1 - 8 wherein said stabilizer is essentially free of an ADM as defined hereinafter.
- the heat transfer composition according to this paragraph is sometimes referred to herein for convenience as Heat Transfer Composition 8A.
- the present invention also includes any of Heat Transfer Compositions 1 - 8 wherein said stabilizer is essentially free of an ADM and wherein said stabilizer further comprises BHT.
- the heat transfer composition according to this paragraph is sometimes referred to herein for convenience as Heat Transfer Composition 8B.
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages: 39 to 45% by weight difluoromethane (HFC-32),
- said lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant, and said stabilizer comprising alkylated naphthalene and an acid depleting moiety.
- PVE polyvinyl ether
- the term“acid depleting moiety” (which is sometimes referred to herein for convenience as“ADM”) means a compound or radical which when present in a heat transfer composition comprising a refrigerant that contains about 10% by weigh or greater of CF3I (said percentage being based in the weight of all the refrigerants in the heat transfer composition), has the effect of substantially reducing the acid moieties that would otherwise be present in the heat transfer composition.
- ADM acid depleting moiety
- substantially reducing as used with respect to the acid moieties in the heat transfer composition means that acid moieties are reduced sufficiently to result in a reduction in TAN value (as defined hereinafter) of at least about 10 relative percent.
- stabilizers which comprise or consist essentially of alkylated naphthalene stabilizer(s).
- certain materials are able to aid in the depletion of acidic moieties in heat transfer compositions containing CF3I, including any heat transfer compositions of the present invention.
- formulating heat transfer compositions to have an ADM provides an unexpected and synergistic enhancement to the stability function of at least the alkylated naphthalene stabilizers according to the present invention.
- the reason for this synergistic effect is not understood with certainty, but without being bound by or to any theory of operation, it is believed that the alkylated naphthalene stabilizers of the present invention function in large part by stabilizing free radicals formed from the CF3I of the present refrigerants, but that this stabilizing effect is at least somewhat diminished in the presence of acid moieties.
- the presence of the ADM of the present invention allows the alkylated naphthalene stabilizers to perform with an unexpected and synergistically enhanced effect.
- the present invention therefore includes stabilizer comprising an alkylated naphthalene and an ADM.
- the stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 1 .
- the present invention also includes stabilizer comprising from about 40% by weight to about 99.9% of alkylated naphthalenes and from 0.05% to about 50% by weight of ADM based on the weight of the stabilizer.
- stabilizer comprising from about 40% by weight to about 99.9% of alkylated naphthalenes and from 0.05% to about 50% by weight of ADM based on the weight of the stabilizer.
- the stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 2.
- the present invention also includes stabilizer comprising from about 50% by weight to about 99.9% of alkylated naphthalenes and an from 0.1 % to about 50% by weight of ADM based on the weight of the stabilizer.
- stabilizer comprising from about 50% by weight to about 99.9% of alkylated naphthalenes and an from 0.1 % to about 50% by weight of ADM based on the weight of the stabilizer.
- the stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 3.
- the present invention also includes stabilizer comprising from about 40% by weight to about 95% of alkylated naphthalenes and an from 5% to about 30% by weight of ADM based on the weight of the alkylated naphthalenes and ADM in the stabilizer.
- stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 4.
- the present invention also includes stabilizer comprising from about 40% by weight to about 95% of alkylated naphthalenes and an from 5% to about 20% by weight of ADM based on the weight of the alkylated naphthalenes and ADM in the stabilizer.
- the stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 5.
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant and Stabilizer 2, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant and Stabilizer 4, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant and Stabilizer 5, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant and Stabilizer 1 , said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant and Stabilizer 2, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant and Stabilizer 3, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant and Stabilizer 4, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages:
- the present invention also includes heat transfer compositions comprising refrigerant, lubricant comprising POE lubricant and/or polyvinyl ether (PVE) lubricant and Stabilizer 5, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages: 41 % ⁇ 1 % by weight difluoromethane (HFC-32),
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant and/or polyvinyl ether (PVE) lubricant; and (b) a stabilizer of the present invention.
- stabilized lubricants comprising: (a) POE lubricant and/or polyvinyl ether (PVE) lubricant; and (b) a stabilizer of the present invention.
- Figure 1 shows the LCCP of one of the refrigerants of the present invention and certain known refrigerants.
- the term“about” in relation to temperatures in degrees centigrade (°C) means that the stated temperature can vary by an amount of +/- 5°C.
- temperature specified as being about is preferably +/- 2°C, more preferably +/- 1 °C, and even more preferably +/- 0.5°C of the identified temperature.
- the term“capacity” is the amount of cooling provided, in BTUs/hr, by the refrigerant in the refrigeration system. This is experimentally determined by multiplying the change in enthalpy in BTU/lb, of the refrigerant as it passes through the evaporator by the mass flow rate of the refrigerant. The enthalpy can be determined from the measurement of the pressure and temperature of the refrigerant.
- the capacity of the refrigeration system relates to the ability to maintain an area to be cooled at a specific temperature.
- the capacity of a refrigerant represents the amount of cooling or heating that it provides and provides some measure of the capability of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity will deliver more cooling or heating power.
- COP coefficient of performance
- thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see for example, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall,
- discharge temperature refers to the temperature of the refrigerant at the outlet of the compressor.
- the advantage of a low discharge temperature is that it permits the use of existing equipment without activation of the thermal protection aspects of the system which are preferably designed to protect compressor components and avoids the use of costly controls such as liquid injection to reduce discharge temperature.
- GWP Global Warming Potential
- LCCP Life Cycle climate Performance
- LCCP includes the direct impacts of refrigerant emissions and the indirect impacts of energy consumption used to operate the system, energy to manufacture the system, and transport and safely dispose of the system.
- the direct impacts of refrigerant emissions are obtained from the refrigerant’s GWP value.
- the measured refrigerant properties are used to obtain the system performance and energy consumption.
- the Direct Emissions as determined by Equation 1 and the Indirect Emissions as determined by Equation 2 are added together to provide the LCCP.
- TMY2 and TMY3 data produced by the National Renewable Laboratory and available in Bin Maker® Pro Version 4 Software is used for the analysis.
- the GWP values reported in the Intergovernmental Panel on climate Change (IPCC)’s Assessment Report 4 (AR4) 2007 are used for the calculations.
- LCCP is expressed as carbon dioxide mass (kg-C0 2eq ) over the lifetime of the air conditioning or refrigeration systems.
- mass flow rate is the mass of refrigerant passing through a conduit per unit of time.
- OEL Occupational Exposure Limit
- “replacement for” with respect to a particular heat transfer composition or refrigerant of the present invention as a“replacement for” a particular prior refrigerant means the use of the indicated composition of the present invention in a heat transfer system that heretofore had been commonly used with that prior refrigerant.
- a refrigerant or heat transfer composition of the present invention is used in a heat transfer system that has heretofore been designed for and/or commonly used with R410A, such as residential air conditioning and commercial air conditioning (including roof top systems, variable refrigerant flow (VRF) systems and chiller systems) then the present refrigerant is a replacement for R410A is such systems.
- VRF variable refrigerant flow
- thermodynamic glide applies to zeotropic refrigerant mixtures that have varying temperatures during phase change processes in the evaporator or condenser at constant pressure.
- thermodynamic glide applies to zeotropic refrigerant mixtures that have varying temperatures during phase change processes in the evaporator or condenser at constant pressure.
- TAN value refers to the total acid number as
- the heat transfer compositions of the present invention are capable of providing exceptionally advantageous properties and in particular stability in use and non flammability, especially with the use of the heat transfer compositions as a replacement for R-410A and especially in prior 410A residential air conditioning systems, and prior R-410A commercial air conditioning systems (including prior R-410A roof top systems, prior R-410A variable refrigerant flow (VRF) systems and prior R-410A chiller systems).
- the reference Heat Transfer Compositions 1 - 17 refers to each of Heat Transfer Compositions 1 through 17, including Heat Transfer Compositions 8A and 8B.
- a particular advantage of the refrigerants included in the heat transfer compositions of the present invention is that they are non-flammable when tested in accordance with the Non-Flammability Test, and as mentioned above there has been a desire in the art to provide refrigerants and heat transfer compositions which can be used as a replacement for R-41 OA in various systems, and which has excellent heat transfer properties, low
- the heat transfer compositions of the present invention include refrigerant in an amount of greater than 40% by weight of the heat transfer composition .
- the heat transfer compositions of the present invention include refrigerant in an amount of greater than 50% by weight, or greater than 70% by weight, or greater than 80% by weight, or greater than 90%, of the heat transfer composition.
- the heat transfer compositions of the present invention including each of Heat T ransfer Compositions 1 - 17, consist essentially of the refrigerant, the lubricant and stabilizer.
- the heat transfer compositions of the invention may include other components for the purpose of enhancing or providing certain functionality to the compositions, preferably without negating the enhanced stability provided in accordance with present invention .
- Such other components or additives may include , dyes, solubilizing agents, compatibilizers, auxiliary stabilizers, antioxidants, corrosion inhibitors, extreme pressure additives and anti wear additives.
- alkylated napthalenes are highly effective as stabilizers for the heat transfer compositions of the present invention.
- alkylated naphthalene refers to compounds having the following structure:
- each Ri - R 8 is independently selected from linear alkyl group, a branched alkyl group and hydrogen.
- the particular length of the alkyl chains and the mixtures or branched and straight chains and hydrogens can vary within the scope of the present invention, and it will be appreciated and understood by those skilled in the art that such variation is reflecteded the physical properties of the alkylated naphthalene, including in particular the viscosity of the alkylated compound, and producers of such materials frequently define the materials by reference to one or more of such properties as an alternative the specification of the particular R groups.
- alkylated naphthalene as a stabilizer according to the present invention having the following properties, and alkylated naphthalene compounds having the indicated properties are referred to for convenience herein as Alkylated Napthalene 1 (or AN1 ) - Alylated Napthalene 5 (or AN5) as indicated respectively in rows 1 - 5 in the Table below:
- the term“about” means +/- 0.4 cSt. As used herein in connection with pour point as measured according to ASTM D97, the term“about” means +/- 5°C.
- alkylated Napthalene 6 or AN6
- Alkylated Napthalene 10 or AN 10
- alkylated napthalyenes within the meaning of Alkylated Naphthalene 1 and Alkylated Naphthalene 6 include those sold by King Industries under the trade designations NA-LUBE KR-007A; KR- 008; KR-009; KR-015; KR-019; KR-005FG; KR- 015FG; and KR-029FG.
- alkylated napthalyenes within the meaning of Alkylated Naphthalene 2 and Alkylated Naphthalene 7 include those sold by King Industries under the trade designations NA-LUBE KR-007A; KR- 008; KR-009; and KR-005FG.
- alkylated napthylene that is within the meaning of Alkylated Naphthalene 5 and Alkylated Naphthalene 10 includes the product sold by King Industries under the trade designation NA-LUBE KR-008.
- the present invention included heat transfer compositions, including each of Heat Transfer Compositions 1 - 17 hereof, wherein the alkylated naphthalene is AN1 , AN2, of AN3, or AN4, or AN5, or AN6, or AN7, or AN8, or AN9 or AN10.
- AD Ms are within the scope hereof.
- epoxides and partculrly alkylated epoxides, are effective at producing the enhanced stability discussed herein when used in combination with alkylated naphthalene stabilizers, and while applicants are not necessarily bound by theory it is believed that this synergistic enhancement stems at least in part due to its effective functioning as an ADM in the heat transfer compositions of the present invention.
- the epoxide is selected from the group consisting of epoxides that undergo ring-opening reactions with acids, thereby depleting the system of acid while not otherwise deleteriously affecting the system.
- Useful epoxides include aromatic epoxides, alkyl epoxides, and alkyenyl epoxides.
- Preferred epoxides include epoxides of the following Formula I:
- Ri - R 4 is selected from a two to fifteen carbon (C2 - C15) acyclic group, a C2 - C15 aliphatic group and a C2 - C15 ethers.
- An epoxide according to Formula 1 is sometimes referred to herein for convenience as ADM1 .
- At least one of R1 - R4 of Formula I is an ether having the following structure:
- An epoxide according to the paragraph is sometimes referred to herein for convenience as ADM2.
- one of Ri - R 4 of Formula I is an ether having the following structure: R.5 — O - Re where each of R 5 and R 6 is independently a C1 - C14 straight chain or branched chain, preferably unsubstituted, alkyl group, and the remaining three of Ri - R are H.
- An epoxide according to the paragraph is sometimes referred to herein for convenience as ADM3.
- the epoxide comprises, conists essentially of or consists of 2-ethylhexyl glycidyl ether.
- An epoxide according to this paragraph is sometimes referred to herein for convenience as ADM4.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17 hereof, wherein the alkylated naphthalene is AN1 and further comprising ADM1 .
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN1 and further comprising ADM1 .
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN1 and further comprising ADM2.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN1 and further comprising ADM3.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN1 and further comprising ADM4.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN5 and further comprising ADM1 .
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN5 and further comprising ADM2.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN5 and further comprising ADM3.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN5 and further comprising ADM4.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN10 and further comprising ADM1 .
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN10 and further comprising ADM2.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN10 and further comprising ADM3.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 8 and 9 - 17, wherein the alkylated naphthalene is AN10 and further comprising ADM4.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN2, or AN3 or AN4 or AN6, or AN7 or AN8 or AN9 and further comprising ADM1 .
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17, wherein the alkylated naphthalene is AN2, or AN3 or AN4 or AN6, or AN7 or AN8 or AN9 and further comprising ADM2.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 8 and 9 - 17, wherein the alkylated naphthalene is AN2, or AN3 or AN4 or AN6, or AN7 or AN8 or AN9 and further comprising ADM3.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 8 and 9 - 17, wherein the alkylated naphthalene is AN2, or AN3 or AN4 or AN6, or AN7 or AN8 or AN9 and further comprising ADM4.
- the alkylated naphthalene is preferably is present in an amount of from 0.01 % to about 10%, or from about 1 .5% to about 4.5%, or from about 2.5% to about 3.5%, where amounts are in percent by weight based on the amount of alkylated naphthalene plus refrigerant in the system.
- the alkylated naphthalene is preferably present in an amount of from 0.1 % to about 20%, or from 1 ,5% to about 10%, or from 1 ,5% to about 8%, where amounts are in percent by weight based on the amount of alkylated naphthalene plus lubricant in the system.
- the ADM can include carbodiimides.
- the carbodiimides include compounds having the following structure:
- stabilizers other than the alkylated naphthalenes and ADM may be included in the heat transfer compositions of the present invention, including each of Heat Transfer Compositions 1 - 17. Examples of such other stabilzers are described hereinafter.
- the stabilizer further includes a phenol based compound.
- the phenol-based compound can be one or more compounds selected from 4,4’- methylenebis(2,6-di-tert-butylphenol); 4,4’-bis(2,6-di-tert-butylphenol); 2,2- or 4,4- biphenyldiols, including 4,4’-bis(2-methyl-6-tert-butylphenol); derivatives of 2,2- or 4,4- biphenyldiols; 2,2’-methylenebis(4-ethyl-6-tertbutylphenol); 2,2’-methylenebis(4-methyl-6- tert-butylphenol); 4,4-butylidenebis(3-methyl-6-tert-butylphenol); 4,4-isopropylidenebis(2,6- di-tert-butylphenol); 2,2’-methylenebis(4-methyl-6-nonylphenol); 2,2’-isobutylidenebis(4,6- dimethylphenol); 2,2’-methylenebis(4-methyl
- the phenol compounds, and in particular BHT can be provided in the heat transfer composition in an amount of greater than 0 and preferably from 0.0001 % by weight to about 5% by weight, preferably 0.001 % by weight to about 2.5% by weight, and more preferably from 0.01 % to about 1 % by weight. In each case, percentage by weight refers to the weight of the heat transfer composition.
- the phenol compounds, and in particular BHT can be provided in the heat transfer composition in an amount of greater than 0 and preferably from 0.0001 % by weight to about 5% by weight, preferably 0.001 % by weight to about 2.5% by weight, and more preferably from 0.01 % to about 1 % by weight.
- percentage by weight refers to the weight based on the weight of the lubricant in the heat transfer composition.
- the present invention also includes stabilizer comprising from about 40% to about 95% by weight of alkylated naphthalenes, including each of AN1 - AN 10, and from 0.1 to about 10% by weight of BHT, based on the weight of the all the stabilizer components in the composition.
- stabilizer comprising from about 40% to about 95% by weight of alkylated naphthalenes, including each of AN1 - AN 10, and from 0.1 to about 10% by weight of BHT, based on the weight of the all the stabilizer components in the composition.
- Stabilizer 6 is sometimes referred to herein for convenience as Stabilizer 6.
- the present invention also includes stabilizer comprising from about 40% to about 95% by weight of alkylated naphthalenes, including each of AN1 - AN 10, from 5% to about 30% by weight of ADM, including each of ADM1 - ADM4, and from 0.1 to about 10% by weight of BHT, based on the weight of the all the stabilizer components in the composition.
- stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 7.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 17 hereof, wherein the heat transfer composition comprises Stablizer 6.
- the present invention includes heat transfer compositions, including each of Heat T ransfer Compositions 1 - 8 and 9 - 26 hereof, wherein the heat transfer compositions comprises Stablizer 7.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 17 hereof, comprising AN1 and BHT.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 17 hereof, comprising AN5 and BHT.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 17 hereof, comprising AN10 and BHT.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17 hereof, comprising of AN5, ADM4 and BHT.
- the present invention includes heat transfer compositions, including each of Heat Transfer Compositions 1 - 8 and 9 - 17 hereof, comprising AN10, ADM4 and BHT.
- the diene-based compounds include C3 to C15 dienes and to compounds formed by reaction of any two or more C3 to C4 dienes.
- the diene based compounds are selected from the group consisting of allyl ethers, propadiene, butadiene, isoprene, and terpenes.
- the diene-based compounds are preferably terpenes, which include but are not limited to terebene, retinal, geraniol, terpinene, delta-3 carene, terpinolene, phellandrene, fenchene, myrcene, farnesene, pinene, nerol, citral, camphor, menthol, limonene, nerolidol, phytol, carnosic acid, and vitamin A1 .
- the stabilizer is farnesene.
- Preferred terpene stabilizers are disclosed in US Provisional Patent Application No. 60/638,003 filed on December 12, 2004, published as US 2006/0167044A1 , which is incorporated herein by reference.
- the diene based compounds can be provided in the heat transfer composition in an amount greater than 0 and preferably from 0.0001 % by weight to about 5% by weight, preferably 0.001 % by weight to about 2.5% by weight, and more preferably from 0.01 % to about 1 % by weight. In each case, percentage by weight refers to the weight of the heat transfer composition.
- the phosphorus compound can be a phosphite or a phosphate compound.
- the phosphite compound can be a diaryl, dialkyl, triaryl and/or trialkyl phosphite, and/or a mixed aryl/alkyl di- or tri-substituted phosphite, in particular one or more compounds selected from hindered phosphites, tris-(di-tert-butylphenyl)phosphite, di-n-octyl phophite, iso-octyl diphenyl phosphite, iso-decyl diphenyl phosphite, tri-iso-decyl phosphate, triphenyl phosphite and diphenyl phosphite, particularly diphenyl phosphite.
- the phosphate compounds can be a triaryl phosphate, trialkyl phosphate, alkyl mono acid phosphate, aryl diacid phosphate, amine phosphate, preferably triaryl phosphate and/or a trialkyl phosphate, particularly tri-n-butyl phosphate.
- the phosphorus compounds can be provided in the heat transfer composition in an amount of greater than 0 and preferably from 0.0001 % by weight to about 5% by weight, preferably 0.001 % by weight to about 2.5% by weight, and more preferably from 0.01 % to about 1 % by weight. In each case, by weight refers to weight of the heat transfer composition.
- the stabilizer when the stabilizer is a nitrogen compound, the stabilizer may comprise an amine based compound such as one or more secondary or tertiary amines selected from diphenylamine, p-phenylenediamine, triethylamine, tributylamine, diisopropylamine, triisopropylamine and triisobutylamine.
- the amine based compound can be an amine antioxidant such as a substituted piperidine compound, i.e.
- amine antioxidants selected from 2,2,6,6-tetramethyl-4-piperidone, 2,2,6,6-tetramethyl-4- piperidinol; bis-(1 ,2,2,6,6-pentamethylpiperidyl)sebacate; di(2,2,6,6-tetramethyl-4- piperidyl)sebacate, poly(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate; alkylated paraphenylenediamines such as N-phenyl-N’-(1 ,3-dimethyl-butyl)-p- phenylenediamine or N,N’-di-sec-butyl-p-phenylenediamine and hydroxylamines such as tallow amines, methyl bis tallow amine and bis tallow
- the amine based compound also can be an alkyldiphenyl amine such as bis (nonylphenyl amine), dialkylamine such as (N-(1 - methylethyl)-2-propylamine, or one or more of phenyl-alpha-naphthyl amine (PANA), alkyl- phenyl-alpha-naphthyl-amine (APANA), and bis (nonylphenyl) amine.
- alkyldiphenyl amine such as bis (nonylphenyl amine), dialkylamine such as (N-(1 - methylethyl)-2-propylamine, or one or more of phenyl-alpha-naphthyl amine (PANA), alkyl- phenyl-alpha-naphthyl-amine (APANA), and bis (nonylphenyl) amine.
- the amine based compound is one or more of phenyl-alpha-naphthyl amine (PANA), alkyl-phenyl- alpha-naphthyl-amine (APANA) and bis (nonylphenyl) amine, amd more preferably phenyl- alpha-naphthyl amine (PANA).
- PANA phenyl-alpha-naphthyl amine
- APANA alkyl-phenyl- alpha-naphthyl-amine
- PANA bis (nonylphenyl) amine
- one or more compounds selected from dinitrobenzene, nitrobenzene, nitromethane, nitrosobenzene, and TEMPO may be used as the stabilizer.
- the nitrogen compounds can be provided in the heat transfer composition in an amount of greater than 0 and from 0.0001 % by weight to about 5% by weight, preferably 0.001 % by weight to about 2.5% by weight, and more preferably from 0.01 % to about 1 % by weight. In each case, percentage by weight refers to the weight of the heat transfer composition.
- Isobutylene may also be used as a stablilizer according to the present invention.
- the present invention also provides stabilizer comprising alkylated naphthalene, including each of AN1 - AN10 and an ADM, including each of ADM1 - ADM4 and a phenol.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as
- the present invention also provides a stabilizer consisting essentially of alkylated naphthalene, including each of AN1 - AN10 and an ADM, including each of ADM1 - ADM4 and a phosphate.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 9.
- the present invention also provides stabilizer comprising alkylated naphthalene, including each of AN1 - AN10 and an ADM, including each of ADM1 - ADM4 and a combination of a phosphate and a phenol.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 10.
- the present invention also provides a stabilizer comprising alkylated naphthalene, including each of AN1 - AN10, in an amount of from about 40% by weight to about 95% by weight, an ADM, including each of ADM1 - ADM4, in an amount of from about 0.5% by weight to about 25% by weight, and an additional stabilizer selected from a phosphate, a phenol and combinations of thesein an amount of from about 0.1 % by weight to about 50% by weight, wherein said weight percentages are based on the total weight of the stabilizer.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 11 .
- the present invention also provides a stabilizer comprising alkylated naphthalene, including each of AN1 - AN10, in an amount of from about 70% by weight to about 95% by weight, an ADM, including each of ADM1 - ADM4, in an amount of from about 0.5% by weight to about 15% by weight, and an additional stabilizer selected from a phosphate, a phenol and combinations of these in an amount of from about 0.1 % by weight to about 25% by weight, wherein said weight percentages are based on the total weight of the stabilizer.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 12.
- the present invention also provides a stabilizer consisting essentially of alkylated naphthalene, including each of AN1 - AN10 and an ADM, including each of ADM1 - ADM4 and BHT.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 13.
- the present invention also provides a stabilizer consisting of alkylated naphthalene, including each of AN1 - AN10 and an ADM, including each of ADM1 - ADM4 and BHTI.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as
- the present invention also provides a stabilizer consisting essentially of alkylated naphthalene, including each of AN1 - AN10 and an ADM, including each of ADM1 - ADM4, BHT and a phosphate.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 15.
- the present invention also provides a stabilizer consisting of alkylated naphthalene, including each of AN1 - AN10 and an ADM, including each of ADM1 - ADM4, BHT and a phosphate.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 16.
- the present invention also provides a stabilizer comprising alkylated naphthalene, including each of AN1 - AN10, in an amount of from about 40% by weight to about 95% by weight, an ADM, including each of ADM1 - ADM4, in an amount of from about 0.5% by weight to about 10% by weight, and BHT, in an amount of from about 0.1 % by weight to about 50% by weight, wherein said weight percentages are based on the total weight of the stabilizer.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 17.
- the present invention also provides a stabilizer comprising alkylated naphthalene, including each of AN1 - AN10, in an amount of from about 70% by weight to about 95% by weight, an ADM, including each of ADM1 - ADM4, in an amount of from about 0.5% by weight to about 10% by weight, and BHT, in an amount of from about 0.1 % by weight to about 25% by weight, wherein said weight percentages are based on the total weight of the stabilizer.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 18.
- the present invention also provides a stabilizer comprising alkylated naphthalene, including each of AN1 - AN10, in an amount of from about 40% by weight to about 95% by weight, an ADM, including each of ADM1 - ADM4, in an amount of from about 5% by weight to about 25% by weight, and a third stabilizer compound selected from BHT, a phosphate and combinations of these in an amount of from 1 % by weight to about 55% by weight, wherein said weight percentages are based on the total weight of the stabilizer.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 19.
- the present invention also provides a stabilizer comprising alkylated naphthalene, including each of AN1 - AN10, in an amount of from about 40% by weight to about 95% by weight, an ADM, including each of ADM1 - ADM4, in an amount of from about 5% by weight to about 25% by weight, and BHT, in an amount of from about 0.1 % by weight to about 5% by weight, wherein said weight percentages are based on the total weight of the stabilizer.
- a stabilizer according to this paragraph is sometimes referred to herein for convenience as Stabilizer 20.
- the stabilizers of the present invention can be used in any of the heat transfer compositions of the present invention, including any of Heat Transfer compositions 1 - 8 and 9 - 17
- the stabilizers of the present invention including each of Stabilizers 1 - 6, can also be used in any of Heat Transfer compositions 8A and 8B.
- the heat transfer composition of the present invention comprises a POE lubricant and/or a PVE lubricant wherein the lubricant is preferably present in amounts preferably of from about 0.1 % by weight to about 5%, or from 0.1 % by weight to about 1 % by weight, or from 0.1 % by weight to about 0.5% by weight, based on the weigth of the heat transfer composition .
- the POE lubricant of the present invention includes in preferred embodiments a neopentyl POE lubricant.
- neopentyl POE lubricant refers to polyol esters (POEs) derived from a reaction between a neopentyl polyol (preferably
- pentaerythritol trimethylolpropane, or neopentyl glycol, and in embodiments where higher viscosities are preferred, dipentaerythritol) and a linear or branched carboxylic acid.
- Emkarate RL32-3MAF and Emkarate RL68H are preferred neopently POE lubricants having the properties identified below:
- esters include phosphate esters, di-basic acid esters and fluoro esters.
- a lubricant consisting essentially of a POE having a viscosity at 40°C measured in accordance with ASTM D445 of from about 30 cSt to about 70 cSt and a viscosity Measured @ 100°C in accordance with ASTM D445 of from about 5 cSt to about 10 cSt is referred to herein as Lubricant 1 .
- a lubricant consisting essentially of a neopentyl POE having a viscosity at 40°C measured in accordance with ASTM D445 of from about 30 cSt to about 70 cSt is referred to for convenience as Lubricant 2.
- the present invention also provides heat transfer compositons, including each of Heat Transfer Compositions 1 - 17, comprising a POE lubricant.
- the present Heat Transfer Compositions including each of Heat T ransfer Compositions 1 - 17, comprise lubricant consisting essentially of a POE lubricant.
- the present Heat Transfer Compositions including each of Heat T ransfer Compositions 1 - 17, comprise lubricant consisting of a POE lubricant.
- the present invention also provides heat transfer compositons, including each of Heat T ransfer Compositions 1 - 17, wherein the lubricant is Lubricant 1 and/or Lubricant 2.
- the lubricant of the present invention can include PVE lubricants generally.
- the PVE lubricant is as PVE according to Formula II below:
- R 2 and R 3 are each independently C1 - C10 hydrocarbons, preferably C2 - C8 hydrocarbons, and Ri and R are each independently alkyl, alkylene glycol, or polyoxyalkylene glycol units and n and m are selected preferably according to the needs of those skilled in the art to obtain a lubricant with the desired properties, and preferable n and m are selected to obtain a lubricant with a viscosity at 40°C measured in accordance with ASTM D445 of from about 30 to about 70 cSt.
- a PVE lubricant according to the description immediately above is referred to for convenience as Lubricant 3.
- Commercially available polyvinyl ethers include those lubricants sold under the trade designations FVC32D and FVC68D, from Idemitsu.
- the present Heat Transfer Compositions including each of Heat Transfer Compositions 1 - 17, comprise a PVE lubricant.
- the present Heat Transfer Compositions including each of Heat T ransfer Compositions 1 - 17, comprise lubricant consist essentially of a PVE lubricant.
- the present Heat Transfer Compositions including each of Heat T ransfer Compositions 1 - 17, comprise lubricant consisting of a PVE lubricant.
- the PVE in the present Heat Transfer Compositions is a PVE according to Formula II.
- the present invention also provides heat transfer compositons, including each of Heat T ransfer Compositions 1 - 17, comprising Lubricant 1 , or Lubricant 2 or Lubricant 3.
- the present invention also provides stabilized lubricants comprising: (a) POE lubricant; and (b) a stabilizer of the present invention, including each of Stabilizers 1 - 20.
- the stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 1 .
- the present invention also provides stabilized lubricants comprising: (a) neo pentyl POE lubricant; and (b) a stabilizer of the present invention, including each of Stabilizers 1 - 20.
- the stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 2.
- the present invention also provides stabilized lubricants comprising: (a) Lubricant 1 ; and (b) a stabilizer of the present invention, including each of Stabilizers 1 - 20.
- the stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 3.
- the present invention also provides stabilized lubricants comprising: (a) Lubricant 2; and (b) a stabilizer of the present invention, including each of Stabilizers 1 - 20.
- the stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 4.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 1.
- PVE polyvinyl ether
- Stabilizer 1 The stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 5.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 2.
- PVE polyvinyl ether
- Stabilizer 2 The stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 6.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 3.
- PVE polyvinyl ether
- Stabilizer 3 The stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 7.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 4.
- PVE polyvinyl ether
- Stabilizer 4 The stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 8.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant and/or polyvinyl ether (PVE) lubricant; and (b) Stabilizer 5.
- PVE polyvinyl ether
- Stabilizer 5 The stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 9.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant; and (b) from 1 % to less than 10% by weight of alkylated naphthalene based on the weight of the lubricant and alkylated naphthalene.
- stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 10.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant; and (b) from 1 % to 8% by weight of alkylated naphthalene based on the weight of the lubricant and alkylated naphthalene.
- stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 11.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant; and (b) from 1 .5% to 8% by weight of alkylated naphthalene based on the weight of the lubricant and alkylated naphthalene.
- stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 12.
- the present invention also includes stabilized lubricants comprising: (a) POE lubricant; and (b) from 1 .5% to 6% by weight of alkylated naphthalene based on the weight of the lubricant and alkylated naphthalene.
- stabilized lubricant according to this paragraph is sometimes referred to herein for convenience as Stabilized Lubricant 13.
- the present invention includes heat transfer compositions of the invention, including each of Heat Transfer Compositions 1 - 17, in which the lubricant and stabilizer are a stabilized lubricant of the present invention, including each of Stabilized Lubricants 1 - 13.
- the heat transfer compositions disclosed herein are provided for use in heat transfer applications, including air conditioning applications, with highly preferred air conditioning applications including residential air conditioning, commercial air conditioning applications (such as roof top applications, VRF applications and chillers.
- the present invention also includes methods for providing heat transfer including methods of air conditioning, with highly preferred air conditioning methods including providing residential air conditioning, providing commercial air conditioning (such as methods of providing roof top air conditioning, methods of providing VRF air conditioning and methods of providing air conditioning using chillers.
- the present invention also includes heat transfer systems, including air conditioning systems, with highly preferred air conditioning systems including residential air conditioning, commercial air conditioning systems (such as roof top air conditioning systems, VRF air conditioning systems and air conditioning chiller systems).
- air conditioning systems with highly preferred air conditioning systems including residential air conditioning, commercial air conditioning systems (such as roof top air conditioning systems, VRF air conditioning systems and air conditioning chiller systems).
- the invention also provides uses of the heat transfer compositions, methods using the heat transfer compositions and systems containing the heat transfer compostions in connection with refrigeration, heat pumps and chillers (including portable water chillers and central water chillers).
- the heat transfer composition of the invention refers to each and any of the heat transfer compositions as described herein.
- the heat transfer composition may comprise or consist essentially of any of Heat Transfer Compositions 1 - 17.
- the system can comprises a loading of refrigerant and lubricant such that the lubricant loading in the system is from about 5% to 60% by weight, or from about 10% to about 60% by weight, or from about 20% to about 50% by weight, or from about 20% to about 40% by weight, or from about 20% to about 30% by weight, or from about 30% to about 50% by weight, or from about 30% to about 40% by weight.
- the term“lubricant loading” refers to the total weight of lubricant contained in the system as a percentage of total of lubricant and refrigerant contained in the system.
- Such systems may also include a lubricant loading of from about 5% to about 10% by weight, or about 8 % by weight of the heat transfer composition.
- the heat transfer systems according to the present invention can comprise a compressor, an evaporator, a condenser and an expansion device, in fluid communication with each other, a Heat Transfer Compositions 1 - 17 and a sequestration material in the system, wherein said sequestration material preferably comprises: i. copper or a copper alloy, or ii. activated alumina, or iii. a zeolite molecular sieve comprising copper, silver, lead or a combination thereof, or iv. an anion exchange resin, or v. a moisture-removing material, preferably a moisture-removing molecular sieve, or vi.a combination of two or more of the above.
- said sequestration material preferably comprises: i. copper or a copper alloy, or ii. activated alumina, or iii. a zeolite molecular sieve comprising copper, silver, lead or a combination thereof, or iv. an anion exchange resin, or v. a moisture-removing material
- the present invention also includes methods for transferring heat of the type comprising evaporating refrigerant liquid to produce a refrigerant vapor,
- residential air conditioning systems and methods have refrigerant evaporating temperatures in the range of from about 0°C to about 10°C and the condensing temperature is in the range of about 40°C to about 70°C.
- residential air conditioning systems and methods used in a heating mode have refrigerant evaporating temperatures in the range of from about -20°C to about 3°C and the condensing temperature is in the range of about 35°C to about 50°C.
- commercial air conditioning systems and methods have refrigerant evaporating temperatures in the range of from about 0°C to about 10°C and the condensing temperature is in the range of about 40°C to about 70°C.
- hydronic system systems and methods have refrigerant evaporating temperatures in the range of from about -20°C to about 3°C and the condensing temperature is in the range of about 50°C to about 90°C.
- medium temperature systems and methods have refrigerant evaporating temperatures in the range of from about -12°C to about 0°C and the condensing temperature is in the range of about 40°C to about 70°C.
- low temperature systems and methods have refrigerant evaporating temperatures in the range of from about -40°C to about -12°C and the condensing temperature is in the range of about 40°C to about 70°C
- rooftop air conditioning systems and methods have refrigerant evaporating temperatures in the range of from about 0°C to about 10°C and the condensing temperature is in the range of about 40°C to about 70°C.
- VRF systems and methods have refrigerant evaporating temperatures in the range of from about 0°C to about 10°C and the condensing
- temperature is in the range of about 40°C to about 70°C.
- the present invention includes the use of heat transfer compositions of the present invention, including each of Heat Transfer Compositions 1 - 17, in a residential air conditioning system.
- the present invention includes the use of heat transfer compositions of the present invention, including each of Heat Transfer Compositions 1 - 17, in a chiller system.
- compressors for the purposes of this invention include reciprocating, rotary (including rolling piston and rotary vane), scroll, screw, and centrifugal compressors.
- the present invention provides each and any of the refrigerants and/or heat transfer compositions as described herein for use in a heat transfer system comprising a reciprocating, rotary (including rolling piston and rotary vane), scroll, screw, or centrifugal compressor.
- Examples of commonly used expansion devices for the purposes of this invention include a capillary tube, a fixed orifice, a thermal expansion valve and an electronic expansion valve.
- the present invention provides each and any of the refrigerants and/or heat transfer compositions as described herein for use in a heat transfer system comprising a capillary tube, a fixed orifice, a thermal expansion valve or an electronic expansion valve.
- the evaporator and the condenser can each be in the form a heat exchanger, preferably selected from a finned tube heat exchanger, a microchannel heat exchanger, a shell and tube, a plate heat exchanger, and a tube-in-tube heat exchanger.
- the present invention provides each and any of the refrigerants and/or heat transfer compositions as described herein for use in a heat transfer system wherein the evaporator and condenser together form a finned tube heat exchanger, a microchannel heat exchanger, a shell and tube, a plate heat exchanger, or a tube-in-tube heat exchanger.
- the systems of the present invention thus preferably include a sequestration material in contact with at least a portion of a refrigerant and/or at least a portion of a the lubricant according to the present invention wherein the temperature of said sequestration material and/or the temperature of said refrigerant and/or the temperature of said lubricant when in said contact are at a temperature that is preferably at least about 10C wherein the sequestration material preferably comprises a combination of: an anion exchange resin, activated alumina, a zeolite molecular sieve comprising silver, and a moisture-removing material, preferably a moisture-removing molecular sieve.
- each type or specific sequestration material is: (i) located physically together with each other type or specific material, if present; (ii) is located physically separate from each other type or specific material, if present, and (iii) combinations in which two or more materials are physically together and at least one sequestration material is physically separate from at least one other sequestration material.
- the heat transfer composition of the invention can be used in heating and cooling applications.
- the heat transfer composition can be used in a method of cooling comprising condensing a heat transfer composition and subsequently evaporating said composition in the vicinity of an article or body to be cooled.
- the invention relates to a method of cooling in a heat transfer system comprising an evaporator, a condenser and a compressor, the process comprising i) condensing a heat transfer composition as described herein; and
- the evaporator temperature of the heat transfer system is in the range of from about -40°C to about +10°C.
- the heat transfer composition can be used in a method of heating comprising condensing the heat transfer composition in the vicinity of an article or body to be heated and subsequently evaporating said composition.
- the invention relates to a method of heating in a heat transfer system comprising an evaporator, a condenser and a compressor, the process comprising i) condensing a heat transfer composition as described herein, in the vicinity of a body or article to be heated and
- evaporator temperature of the heat transfer system is in the range of about -30°C to about 5°C.
- the heat transfer composition of the invention is provided for use in air conditioning applications including both transport and stationary air conditioning applications.
- any of the heat transfer compositions described herein can be used in any one of:
- an air conditioning application including mobile air conditioning, particularly in trains and buses conditioning,
- a mobile heat pump particularly an electric vehicle heat pump
- chiller particularly a positive displacement chiller, more particularly an air cooled or water cooled direct expansion chiller, which is either modular or conventionally singularly packaged,
- a residential air conditioning system particularly a ducted split or a ductless split air conditioning system
- VRF variable refrigerant flow
- the heat transfer composition of the invention is provided for use in a refrigeration system.
- the term“refrigeration system” refers to any system or apparatus or any part or portion of such a system or apparatus which employs a refrigerant to provide cooling.
- any of the heat transfer compositions described herein can be used in any one of:
- Each of the heat transfer compositions described herein, including Heat Transfer Compositions 1 - 17, is particularly provided for use in a residential air- conditioning system (with an evaporator temperature in the range of about 0 to about 10°C, particularly about 7°C for cooling and/or in the range of about -20 to about 3°C, particularly about 0.5°C for heating).
- each of the heat transfer compositions described herein, including each of Heat T ransfer Compositions 1 - 17, is particularly provided for use in a residential air conditioning system with a reciprocating, rotary (rolling-piston or rotary vane) or scroll
- Each of the heat transfer compositions described, including Heat Transfer Compositions 1 - 17, is particularly provided for use in an air cooled chiller (with an evaporator temperature in the range of about 0 to about 10°C, particularly about 4.5°C), particularly an air cooled chiller with a positive displacement compressor, more particular an air cooled chiller with a reciprocating scroll compressor.
- Each of the heat transfer compositions described herein, including Heat Transfer Compositions 1 - 17, is particularly provided for use in a residential air to water heat pump hydronic system (with an evaporator temperature in the range of about -20 to about 3°C, particularly about 0.5°C or with an evaporator temperature in the range of about -30 to about 5°C, particularly about 0.5°C).
- Each of the heat transfer compositions described herein, including Heat Transfer Compositions 1 - 17, is particularly provided for use in a medium temperature refrigeration system (with an evaporator temperature in the range of about -12 to about 0°C, particularly about -8°C).
- Each of the heat transfer compositions described herein, including Heat Transfer Compositions 1 - 17, is particularly provided for use in a low temperature refrigeration system (with an evaporator temperature in the range of about -40 to about -12°C, particularly about from about -40oC to about -23°C or preferably about -32°C).
- the heat transfer composition of the invention including Heat Transfer Compositions 1 - 17, is provided for use in a residential air conditioning system, wherein the residential air-conditioning system is used to supply cool air (said air having a temperature of for example, about 10°C to about 17°C, particularly about 12°C) to buildings for example, in the summer.
- cool air said air having a temperature of for example, about 10°C to about 17°C, particularly about 12°C
- the heat transfer composition of the invention including Heat Transfer Compositions 1 - 17, is thus provided for use in a split residential air conditioning system, wherein the residential air-conditioning system is used to supply cool air (said air having a temperature of for example, about 10°C to about 17°C, particularly about 12°C).
- the heat transfer composition of the invention including Heat Transfer Compositions 1 - 17, is thus provided for use in a ducted split residential air conditioning system, wherein the residential air-conditioning system is used to supply cool air (said air having a temperature of for example, about 10°C to about 17°C, particularly about 12°C).
- the heat transfer composition of the invention including Heat Transfer Compositions 1 - 17, is thus provided for use in a window residential air conditioning system, wherein the residential air-conditioning system is used to supply cool air (said air having a temperature of for example, about 10°C to about 17°C, particularly about 12°C).
- the heat transfer composition of the invention, including Heat Transfer Compositions 1 - 17 is thus provided for use in a portable residential air
- the residential air-conditioning system is used to supply cool air (said air having a temperature of for example, about 10°C to about 17°C, particularly about 12°C).
- the residential air conditions systems as described herein, including in the immediately preceeding paragraphs, preferably have an air-to-refrigerant evaporator (indoor coil), a compressor, an air-to-refrigerant condenser (outdoor coil), and an expansion valve.
- the evaporator and condenser can be round tube plate fin, a finned tube or microchannel heat exchanger.
- the compressor can be a reciprocating or rotary (rolling-piston or rotary vane) or scroll compressor.
- the expansion valve can be a capillary tube, thermal or electronic expansion valve.
- the refrigerant evaporating temperature is preferably in the range of 0 °C to 10°C.
- the condensing temperature is preferably in the range of 40 °C to 70 °C.
- the heat transfer composition of the invention including Heat Transfer Compositions 1 - 17, is provided for use in a residential heat pump system, wherein the residential heat pump system is used to supply warm air (said air having a temperature of for example, about 18°C to about 24°C, particularly about 21 °C) to buildings in the winter. It can be the same system as the residential air-conditioning system, while in the heat pump mode the refrigerant flow is reversed and the indoor coil becomes condenser and the outdoor coil becomes evaporator. Typical system types are split and mini-split heat pump system.
- the evaporator and condenser are usually a round tube plate fin, a finned or microchannel heat exchanger.
- the compressor is usually a reciprocating or rotary (rolling-piston or rotary vane) or scroll compressor.
- the expansion valve is usually a thermal or electronic expansion valve.
- the refrigerant evaporating temperature is preferably in the range of about -20 to about 3°C or about -30 °C to about 5°C.
- the condensing temperature is preferably in the range of about 35 °C to about 50 °C.
- the heat transfer composition of the invention is provided for use in a commercial air-conditioning system wherein the commercial air conditioning system can be a chiller which is used to supply chilled water (said water having a temperature of for example about 7°C) to large buildings such as offices and hospitals, etc. Depending on the application, the chiller system may be running all year long.
- the chiller system may be air-cooled or water-cooled.
- the air-cooled chiller usually has a plate, tube-in-tube or shell-and- tube evaporator to supply chilled water, a reciprocating or scroll compressor, a round tube plate fin, a finned tube or microchannel condenser to exchange heat with ambient air, and a thermal or electronic expansion valve.
- the water-cooled system usually has a shell-and-tube evaporator to supply chilled water, a reciprocating, scroll, screw or centrifugal compressor, a shell-and-tube condenser to exchange heat with water from cooling tower or lake, sea and other natural recourses, and a thermal or electronic expansion valve.
- the refrigerant evaporating temperature is preferably in the range of about 0 °C to about 10°C.
- the condensing temperature is preferably in the range of about 40 °C to about 70 °C.
- the heat transfer composition of the invention including Heat Transfer Compositions 1 - 17, is provided for use in a residential air-to-water heat pump hydronic system, wherein the residential air-to-water heat pump hydronic system is used to supply hot water (said water having a temperature of for example about 50°C or about 55°C) to buildings for floor heating or similar applications in the winter.
- the hydronic system usually has a round tube plate fin, a finned tube or microchannel evaporator to exchange heat with ambient air, a reciprocating, scroll or rotary compressor, a plate, tube-in-tube or shell-in-tube condenser to heat the water, and a thermal or electronic expansion valve.
- the condensing temperature is preferably in the range of about 50 °C to about 90 °C.
- the heat transfer composition of the invention including Heat Transfer Compositions 1 - 17, is provided for use in a medium temperature refrigeration system, wherein the refrigerant has and evaporating temperature preferably in the range of about -12 °C to about 0°C, and in such systems the refrigerant has a condensing temperature preferably in the range of about 40 °C to about 70 °C, or about 20 °C to about 70 °C.
- the present invenition thus provides a medium temperature refrigeration system used to chill food or beverages, such as in a refrigerator or a bottle cooler, wherein the refrigerant has an evaporating temperature preferably in the range of about -12 °C to about 0°C, and in such systems the refrigerant has a condensing temperature preferably in the range of about 40 °C to about 70 °C, or about 20 °C to about 70 °C.
- the medium temperature systems of the present invention preferably have an air-to-refrigerant evaporator to provide chilling, for example to the food or beverage contained therein, a reciprocating, scroll or screw or rotary compressor, an air-to- refrigerant condenser to exchange heat with the ambient air, and a thermal or electronic expansion valve.
- the heat transfer composition of the invention including Heat T ransfer Compositions 1 - 17, is provided for use in a low temperature refrigeration system, wherein the refrigerant has an evaporating temperature that is preferably in the range of about -40 °C to about -12°C and the refrigerant has a condensing temperature that is preferably in the range of about 40 °C to about 70 °C, or about 20 °C to about 70 °C.
- the present invenition thus provides a low temperature refrigeration system used to provide cooling in a freezer wherein the refrigerant has an evaporating temperature that is preferably in the range of about -40 °C to about -12°C and the refrigerant has a condensing temperature that is preferably in the range of about 40 °C to about 70 °C, or about 20 to about 70 °C.
- the present invenition thus also provides a low temperature refrigeration system used to provide cooling in an cream machine refrigerant has an evaporating temperature that is preferably in the range of about -40 °C to about -12°C and the refrigerant has a condensing temperature that is preferably in the range of about 40 °C to about 70 °C, or about 20 °C to about 70 °C.
- the low temperature systems of the present invention preferably have an air-to- refrigerant evaporator to chill the food or beverage, a reciprocating, scroll or rotary compressor, an air-to-refrigerant condenser to exchange heat with the ambient air, and a thermal or electronic expansion valve.
- the present invention therefore provides the use in a chiller of a heat transfer compositon of the present invention, including each of Heat Transfer Compositions 1 - 17 wherein said alkylated naphthalene is AN5wherein said heat transfer composition further comprises BHT, wherein the AN 5 is provided in an amount of from about 0.001 % by weight to about 5% by weight based on the weight of the lubricant and the BHT is provided in an amount of from about 0.001 % by weight to about 5 % by weight based on the weight of the lubricant.
- the present invention therefore provides the use use in a chiller of a heat transfer compositon of the present invention, including each of Heat Transfer Compositions 1 - 17 wherein said heat transfer composition further comprises BHT, wherein the AN5 is present in an amount of from about 0.001 % by weight to about 5% by weight based on the weight of the heat transfer composition and the BHT is present in an amount of from about 0.001 % by weight to about 5 % by weight based on the weight of heat transfer composition.
- each heat transfer composition in accordance with the present invention including each of Heat Transfer Compositions 1 - 17, is provided for use in a chiller with an evaporating temperature in the range of about 0 °C to about 10°C and a condensing temperature in the range of about 40 °C to about 70 °C.
- the chiller is provided for use in air conditioning or refrigeration, and preferably for commercial air conditioning.
- the chiller is preferably a positive displacement chiller, more particularly an air cooled or water cooled direct expansion chiller, which is either modular or conventionally singularly packaged.
- the present invention therefore provides the use of each heat transfer composition in accordance with the present invention, including each of Heat Transfer Compositions 1 - 26, in stationary air conditioning, particularly residential air conditioning, industrial air conditioning or commercial air conditioning.
- the present invention therefore provides the use in stationary air conditioning, particularly residential air conditioning, industrial air conditioning or commercial air conditioning ,of a heat transfer compositon of the present invention, including each of Heat Transfer Compositions 1 - 17 wherein said alkylated naphthalene is AN5 and wherein said heat transfer composition further comprises BHT, wherein the AN5 is present in an amount of from about 0.001 % by weight to about 5% by weight based on the weight of the lubricant and the BHT is present in an amount of from about 0.001 % by weight to about 5 % by weight based on the weight of the lubricant .
- the present invention therefore provides the use in stationary air conditioning, particularly residential air conditioning, industrial air conditioning or commercial air conditioning ,of a heat transfer compositon of the present invention, including each of Heat Transfer Compositions 1 - 17 wherein said alkylated naphthalene is AN5 and wherein said heat transfer composition further comprises BHT, wherein the AN5 is present in an amount of from about 0.001 % by weight to about 5% by weight based on the weight of the heat transfer composition and the BHT is present in an amount of from about 0.001 % by weight to about 5 % by weight based on the weight of heat transfer composition.
- Each heat transfer composition in accordance with the present invention including each of Heat Transfer Compositions 1 - 17, is provided as a low Global Warming (GWP) replacement for the refrigerant R-410A.
- GWP Global Warming
- Each heat transfer composition in accordance with the present invention including each of Heat T ransfer Compositions 1 - 17, is provided as a low Global Warming (GWP) retrofit for the refrigerant R-410A. .
- GWP Global Warming
- the present invention thus includes methods of retrofitting existing heat transfer system designed for and containing R-410A refrigerant, without requiring substantial engineering modification of the existing system, particularly without modification of the condenser, the evaporator and/or the expansion valve.
- the present invention thus also includes methods of using a refrigerant or heat transfer composition of the present invention as a replacement for R-410A, and in particular as a replacement for R-410A in residential air conditioning refrigerant, without requiring substantial engineering modification of the existing system, particularly without modification of the condenser, the evaporator and/or the expansion valve.
- the present invention thus also includes methods of using a refrigerant or heat transfer composition of the present invention as a replacement for R-410A, and in particular as a replacement for R-410A in a residential air conditioning system.
- the present invention thus also includes methods of using a refrigerant or heat transfer composition of the present invention as a replacement for R-410A, and in particular as a replacement for R-410A in a chiller system.
- the step of replacing preferably comprises removing at least a substantial portion of, and preferably substantially all of, the existing refrigerant (which can be but is not limited to R-410A) and introducing a heat transfer composition , including each of Heat Transfer Composiitons 1 - 17, without any substantial modification of the system to accommodate the refrigerant of the present invention.
- the method comprises removing at least about 5%, about 10%, about 25%, about 50%, or about 75% by weight of the R-410A from the system and replacing it with the heat transfer compositions of the invention.
- the heat transfer composition can be used in a method of retrofitting an existing heat transfer system designed to contain or containing R410A refrigerant, wherein the system is modified for use with a Heat Transfer Composition of the present invention.
- the heat transfer composition can be used as a replacement in a heat transfer system which is designed to contain or is suitable for use with R-410A refrigerant.
- the invention encompasses the use of the heat transfer compositions of the invention, including each of Heat Transfer Compositions 1 - 17, as a low Global Warming replacement for R-410A or is used in a method of retrofitting an existing heat transfer system or is used in a heat transfer system which is suitable for use with R-410A refrigerant as described herein.
- the method preferably comprises removing at least a portion of the existing R-410A refrigerant from the system.
- the method comprises removing at least about 5%, about 10%, about 25%, about 50% or about 75% by weight of the R-410A from the system and replacing it with the heat transfer compositions of the invention, including each of Heat Transfer Compositions 1 - 17.
- the heat transfer compositions of the invention may be employed as a replacement in systems which are used or are suitable for use with R-410A refrigerant, such as existing or new heat transfer systems.
- compositions of the present invention exhibit many of the desirable properties
- R-410A characteristics of R-410A but have a GWP that is substantially lower than that of R-410A while at the same time having operating characteristics i.e. capacity and/or efficiency (COP) that are substantially similar to or substantially match, and preferably are as high as or higher than R-410A.
- COP capacity and/or efficiency
- the heat transfer compositions of the invention therefore preferably exhibits operating characteristics compared with R-410A wherein the efficiency (COP) of the composition is greater than 90% of the efficiency of R-41 OA in the heat transfer system.
- the heat transfer composition of the invention therefore preferably exhibits operating characteristics compared with R-410A wherein the capacity is from 95 to 105% of the capacity of R-410A in the heat transfer system.
- R-410A is an azeotrope-like composition.
- the any of the refrigerants included in the heat transfer compositions of the invention, including each of Heat Transfer Compositions 1 - 17, desirably show a low level of glide.
- the refrigerants included in the heat transfer compositions of the invention, including each of Heat Transfer Compositions 1 - 17, according to invention as described herein may provide an evaporator glide of less than 2°C, preferably less than 1.5 °C.
- the heat transfer composition of the invention therefore preferably exhibits operating characteristics compared with R-410A wherein the efficiency (COP) of the composition is from 100 to 102% of the efficiency of R-410A in the heat transfer system and wherein the capacity is from 92 to 102% of the capacity of R-410A in the heat transfer system.
- the efficiency (COP) of the composition is from 100 to 102% of the efficiency of R-410A in the heat transfer system and wherein the capacity is from 92 to 102% of the capacity of R-410A in the heat transfer system.
- the heat transfer composition of the invention preferably exhibit operating characteristics compared with R-410A wherein:
- the efficiency (COP) of the composition is from 100 to 105% of the efficiency of R- 410A;
- the capacity is from 92 to 102% of the capacity of R-410A
- compositions of the invention are to replace the R- 410A refrigerant.
- the heat transfer composition of the invention further exhibit the following characteristics compared with R-410A:
- the discharge temperature is not greater than 10°C higher than that of R-410A;
- the compressor pressure ratio is from 98 to 102% of the compressor pressure ratio of R-410A in heat transfer systems, in which the composition of the invention is used to replace the R- 410A refrigerant.
- the existing heat transfer compositions used to replace R-410A are preferably used in air conditioning heat transfer systems including both mobile and stationary air conditioning systems.
- mobile air conditioning systems means mobile, non passenger car air conditioning systems, such as air conditioning systems in trucks, buses and trains.
- each of the heat transfer compositions as described herein, including each of Heat Transfer Compositions 1 - 17, can be used to replace R-410A in any one of: an air conditioning system including a mobile air conditioning system, particularly air conditioning systems in trucks, buses and trains,
- a mobile heat pump particularly an electric vehicle heat pump
- a chiller particularly a positive displacement chiller, more particularly an air cooled or water cooled direct expansion chiller, which is either modular or conventionally singularly packaged,
- a residential air conditioning system particularly a ducted split or a ductless split air conditioning system
- VRF variable refrigerant flow
- each of the heat transfer compositions as described herein, including each of Heat Transfer Compositions 1 - 17, can be used to replace R10A in in any one of:
- Each of the heat transfer compositions described herein is particularly provided to replace R-410A in a residential air- conditioning system (with an evaporator temperature in the range of about 0 °C to about 10°C, particularly about 7°C for cooling and/or in the range of about -20 °C to about 3°C or 30 to about 5°C, particularly about 0.5°C for heating).
- a residential air- conditioning system with an evaporator temperature in the range of about 0 °C to about 10°C, particularly about 7°C for cooling and/or in the range of about -20 °C to about 3°C or 30 to about 5°C, particularly about 0.5°C for heating.
- Compositions 1 - 17, is particularly provided to replace R-410A in a residential air conditioning system with a reciprocating, rotary (rolling-piston or rotary vane) or scroll compressor.
- Each of the heat transfer compositions described herein is particularly provided to replace R-410A in an air cooled chiller (with an evaporator temperature in the range of about 0 °C to about 10°C, particularly about 4.5°C), particularly an air cooled chiller with a positive displacement compressor, more particular an air cooled chiller with a reciprocating scroll compressor.
- Each of the heat transfer compositions described herein, including each of Heat Transfer Compositions 1 - 17, is particularly provided to replace R-410A in a residential air to water heat pump hydronic system (with an evaporator temperature in the range of about - 20 °C to about 3°C or about -30 °C to about 5°C, particularly about 0.5°C).
- Each of the heat transfer compositions described herein including each of Heat Transfer Compositions 1 - 17, is particularly provided to replace R-410A in a medium temperature refrigeration system (with an evaporator temperature in the range of about -12 °C to about 0°C, particularly about -8°C).
- Each of the heat transfer compositions described herein including each of Heat Transfer Compositions 1 - 17, is particularly provided to replace R-410A in a low
- temperature refrigeration system (with an evaporator temperature in the range of about -40 °C to about -12°C, particularly from about -40°C to about -23°C or preferably about -32°C).
- the invention further provides a heat transfer system comprising a compressor, a condenser and an evaporator in fluid communication, and a heat transfer composition in said system, said heat transfer composition according to the present invention, including each of Heat T ransfer Compositions 1 - 17.
- the heat transfer system is a residential air-conditioning system (with an evaporator temperature in the range of about 0 °C to about 10°C, particularly about 7°C for cooling and/or in the range of about -20 °C to about 3°C or about -30 °C to about 5°C, particularly about 0.5°C for heating).
- the heat transfer system is an air cooled chiller (with an evaporator temperature in the range of about 0 °C to about 10°C, particularly about 4.5°C), particularly an air cooled chiller with a positive displacement compressor, more particular an air cooled chiller with a reciprocating or scroll compressor.
- the heat transfer system is a residential air to water heat pump hydronic system (with an evaporator temperature in the range of about -20 °C to about 3°C or about - 30 °C to about 5°C, particularly about 0.5°C).
- the heat transfer system can be a refrigeration system, such as a low temperature refrigeration system, a medium temperature refrigeration system, a commercial refrigerator, a commercial freezer, an ice machine, a vending machine, a transport refrigeration system, a domestic freezer, a domestic refrigerator, an industrial freezer, an industrial refrigerator and a chiller.
- a refrigeration system such as a low temperature refrigeration system, a medium temperature refrigeration system, a commercial refrigerator, a commercial freezer, an ice machine, a vending machine, a transport refrigeration system, a domestic freezer, a domestic refrigerator, an industrial freezer, an industrial refrigerator and a chiller.
- refrigerant compositions identified in Table 2 below as Refrigerants A1 , A2 and A3 are refrigerants within the scope of the present invention as described herein.
- Each of the refrigerants was subjected to thermodynamic analysis to determine its ability to match the operating characteristics of R-4104A in various refrigeration systems. The analysis was performed using experimental data collected for properties of various binary pairs of components used in the composition. The vapor/liquid equilibrium behavior of CF 3 I was determined and studied in a series of binary pairs with each of HFC-32 and R125. The composition of each binary pair was varied over a series of relative percentages in the experimental evaluation and the mixture parameters for each binary par were regressed to the experimentally obtained data.
- Vapor/liquid equilibrium behavior data for the binary pair HFC-32 and HFC-125 available in the National Institute of Science and Technology (N IST) Reference Fluid Thermodynamic and Transport Properties Database software (Refprop 9.1 NIST Standard Database 2013) were used for the Examples.
- the parameters selected for conducting the analysis were: same compressor displacement for all refrigerants, same operating conditions for all refrigerants, same compressor isentropic and volumetric efficiency for all refrigerants.
- simulations were conducted using the measured vapor liquid equilibrium data. The simulation results are reported for each Example.
- Refrigerant A1 comprises 100% by weight of the three compounds listed in Table 2 in their relative percentages and is non-flammable.
- Refrigerant A1 consists of the three compounds listed in Table 2 in their relative percentages and is non-flammable.
- Refrigerant A2 comprises 100% by weight of the three compounds listed in Table 2 in their relative percentages and is non-flammable.
- Refrigerant A2 consists of the three compounds listed in Table 2 in their relative percentages and is non-flammable.
- Refrigerant A3 comprises 100% by weight of the fhree compounds listed in Table 2 in their relative percentages and is non-flammable. Refrigerant A3 consists of the three compounds listed in Table 2 in their relative percentages and is non-flammable.
- LCCP was determined for R410, other known refrigerants, and a refrigerant of the present invention and reported in Table 3.
- the refrigerant having a GWP of 400 is a refrigerant of the present invention.
- Known refrigerants were used for the GWPs of 1 , 1 50, 250, 750, and 2088.
- the known refrigerant having a GWP of 2088 is R41 0A.
- Table 3 shows LCCP results in four regions: USA, EU, China and Brazil. As GWP decreases, the direct emissions are lower. However, system efficiency is lower so it consumes more energy and increases the indirect emissions. Therefore, the total emissions (kg-C0 2eq ) first decreases and then increases as GWP decreases.
- the different energy structures in these regions show values of the optimum GWP that has the lowest total emissions.
- the number of AC units is also different among these regions: USA and EU have more AC units than China and Brazil.
- Figure 1 and the last column of Table 3 shows the total emissions considering all four regions and number of AC units.
- GWP decreases, the total emissions decrease until reaching the lowest value for a refrigerant of the present invention having a GWP of 400.
- the total emissions are very similar.
- total emission significantly increases when GWP is lower than 150 because the indirect emissions increase significantly. So the present invention demonstrates a surprising and unexpected result.
- Table 4 shows the thermodynamic performance of a residential air-conditioning system compared to R410A system.
- Refrigerants A1 to A3 show 92% or higher capacity and higher efficiency than R410A. It indicates the system performance is similar to R410A.
- Refrigerants A1 to A3 show 100% pressure ratio compared to R410A. It indicates the compressor efficiencies are similar to R410A, and no changes on R410A compressor are needed.
- Example 2B - Residential Air-Conditioning System (Cooling)
- a residential air-conditioning system configured to supply cool air in accordance with Example 2A in which POE lubricant is included in the system and is stabilized with alkylated naphthalene according to the present invention (AN4 in an amount of from about 6% to about 10% based on the weight of the lubricant) and ADM according to the present invention (ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant).
- AN4 alkylated naphthalene according to the present invention
- ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant
- Refrigerant A1 compared to R410A system.
- the capacity of Refrigerant A1 can be recovered with a larger compressor.
- Refrigerants A2 and A3 show 90% or higher capacity and higher efficiency than R410A. It indicates the system performance is similar to R410A.
- Refrigerants A1 to A3 show 100% pressure ratio compared to R410A. It indicates the compressor efficiencies are similar to R410A, and no changes on R410A compressor are needed.
- Example 3B Residential Heat Pump System (Heating)
- a heat pump system is configured in accordance with Example 3A in which POE lubricant was included in the system and which iss stabilized with alkylated naphthalene according to the present invention (AN4 in an amount of from about 6% to about 10% based on the weight of the lubricant) and ADM according to the present invention (ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant).
- AN4 alkylated naphthalene according to the present invention
- ADM4 ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant
- Example 4A Commercial Air-Conditioning System - Chiller
- Table 6 shows the thermodynamic performance of a commercial air-conditioning system compared to R410A system.
- Refrigerants A1 to A3 show 92% or higher capacity and higher efficiency than R410A. It indicates the system performance is similar to R410A.
- Refrigerants A1 to A3 show 100% pressure ratio compared to R410A. It indicates the compressor efficiencies are similar to R410A, and no changes on R410A compressor are needed.
- Example 4B Commercial Air-Conditioning System - Chiller
- a commercial air conditioning is configured in accordance with Example 4A in which POE lubricant is included in the system and is stabilized with alkylated naphthalene according to the present invention (AN4 in an amount of from about 6% to about 10% based on the weight of the lubricant) and ADM according to the present invention (ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant).
- AN4 alkylated naphthalene according to the present invention
- ADM4 ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant.
- Refrigerants A1 to A3 show 93% or higher capacity and higher efficiency than R410A. It indicates the system performance is similar to R410A.
- Refrigerants A1 to A2 show 100% pressure ratio compared to R410A. It indicates the compressor efficiencies are similar to R410A, and no changes on R410A compressor are needed.
- Example 5B - Residential Air-to-Water Heat Pump Hvdronic System
- a residential air-to-water heat pump hydronic system is configured in accordance with Example 5A in which POE lubricant is included in the system and is stabilized with alkylated naphthalene according to the present invention (AN4 in an amount of from about 6% to about 10% based on the weight of the lubricant) and ADM according to the present invention (ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant).
- AN4 alkylated naphthalene according to the present invention
- ADM4 ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant
- Example 6A Medium Temperature Refrigeration System
- Medium temperature refrigeration system is used to chill the food or beverage such as in refrigerator and bottle cooler.
- Refrigerants A1 , A2, and A3 were used in a simulation of a medium temperature refrigeration system as described above and the performance results are in Table 8 below.
- Table 8 shows the thermodynamic performance of a medium temperature refrigeration system compared to R410A system.
- Refrigerants A1 to A3 show 94% or higher capacity and higher efficiency than R410A. It indicates the system performance is similar to R410A.
- Refrigerants A1 to A2 show 100% pressure ratio compared to R410A. It indicates the compressor efficiencies are similar to R410A, and no changes on R410A compressor are needed.
- Example 6B Medium Temperature Refrigeration System
- a medium temperature refrigeration system is configured to chill food or beverages such as in a refrigerator and bottle cooler is configured in accordance with Example 6A in which POE lubricant is included in the system and is stabilized with alkylated naphthalene according to the present invention (AN4 in an amount of from about 6% to about 10% based on the weight of the lubricant) and ADM according to the present invention (ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant).
- AN4 alkylated naphthalene according to the present invention
- ADM4 ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant
- Example 7A Low Temperature Refrigeration System
- Low temperature refrigeration system is used to freeze the food such as in ice cream machine and freezer.
- Refrigerants A1 , A2, and A3 were used in a simulation of a low temperature refrigeration system as described above and the performance results are in Table 9 below.
- Table 9 shows the thermodynamic performance of a low temperature refrigeration system compared to R410A system.
- Refrigerants A1 to A3 show 96% or higher capacity and higher efficiency than R410A. It indicates the system performance is similar to R410A.
- Refrigerants A1 to A3 show 99% or 100% pressure ratio compared to R410A. It indicates the compressor efficiencies are similar to R410A, and no changes on R410A compressor are needed.
- Example 7B Low Temperature Refrigeration System
- a low temperature refrigeration system is configured to freeze food such as in an ice cream machine and a freezer is configured in accordance with Example 7A in which POE lubricant is included in the system and is stabilized with alkylated naphthalene according to the present invention (AN4 in an amount of from about 6% to about 10% based on the weight of the lubricant) and ADM according to the present invention (ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant).
- AN4 alkylated naphthalene according to the present invention
- ADM4 ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant
- Example 8A Commercial Air-Conditioning System - Packaged Rooftops
- a packaged rooftop commercial air conditioning system configured to supply cooled or heated air to buildings is tested.
- the experimental system includes a packaged rooftop air-conditioning/heat pump systems and has an air-to-refrigerant evaporator (indoor coil), a compressor, an air-to-refrigerant condenser (outdoor coil), and an expansion valve.
- the testing described herein is representative of the results from such systems.
- the operating conditions for the test are:
- Example 8A Commercial Air-Conditioning System - Packaged Rooftops
- a packaged rooftop commercial air conditioning system is configured to supply cooled or heated air to buildings in accordance with Example 8A in which POE lubricant is included in the system and is stabilized with alkylated naphthalene according to the present invention (AN4 in an amount of from about 6% to about 10% based on the weight of the lubricant) and ADM according to the present invention (ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant).
- AN4 alkylated naphthalene according to the present invention
- ADM4 ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant
- Example 9A Commercial Air-Conditioning System - Variable Refrigerant Flow Systems
- a commercial air-conditioning system with vaiable refrigerant flow is configured to supply cooled or heated air to buildings is tested.
- the experimental system includes multiple (4 or more) air-to-refrigerant evaporators (indoor coils), a compressor, an air-to- refrigerant condenser (outdoor coil), and an expansion valve.
- the testing described herein is representative of the results from such systems.
- the operating conditions for the test are:
- A1 - A3 is found to be acceptable.
- Example 9B Commercial Air-Conditioning System - Variable Flow Refrigerant
- a commercial air-conditioning system with vaiable refrigerant flow is configured to supply cooled or heated air to buildings is configured in accordance with Example 9A in which POE lubricant is included in the system and is stabilized with alkylated naphthalene according to the present invention (AN4 in an amount of from about 6% to about 10% based on the weight of the lubricant) and ADM according to the present invention (ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant).
- AN4 alkylated naphthalene according to the present invention
- ADM4 ADM4 in an amount of about 0.05 - 0.5 % by weight based on the weight of the lubricant
- a heat transfer compositions of the present invention is tested in accordance with ASHRAE Standard 97 - "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems" to simulate long-term stability of the heat transfer compositions by accelerated aging.
- the tested refrigerant consists of 41 % by weight R-32, 3.5% by weight of R-125 and 55.5% by weight of CF3I), with 1 .7 volume % air in the refrigerant.
- the POE lubricant tested was an ISO 32 POE having a viscosity at 40°C of about 32 cSt and having a moisture content of 300 ppm or less (Lubricant A).
- TAN total acid number
- the experiment is carried out by preparing sealed tubes containing 50% by weight of the R-466a refrigerant and 50% by weight of the indicated lubricant, each of which has been degassed. Each tube contains a coupon of steel, copper, aluminum and bronze. The stability is tested by placing the sealed tube in an oven maintained at about 175°C for 14 days. The results were as follows:
- Example 10 Stabilizers for Heat Transfer Compositions Comprising Refrigerant and Lubricant
- Comparative Example 1 (designated CE1 ).
- the refrigerant/lubricant fluid without the alkylate naphthalene stabilizer according to the present invention exhibits a less than ideal visual appearance, and relatively high TAN and R-23 values. This results are achieved notwithstanding that BHT stabilizer is included.
- the addition of 2% alkylated naphthalene according to the present invention produces a dramatic and unexpected improvement in all tested stability results, including a dramatic, order of magnitude improvement in both TAN and R-23 concentration.
- Example 10 The test of Example 10 is repeated except that 4% by weight of alkylated naphthalene (AN4) based on the weight of the lubricant is added. The results are similar to the results of Example 10.
- AN4 alkylated naphthalene
- Example 12 Stabilizers for Heat T ransfer Compositions Comprising Refrigerant and Lubricant
- Example 10 The test of Example 10 is repeated except that 6% by weight of alkylated naphthalene (AN4) based on the weight of the lubricant is added. The results are similar to Example 10.
- AN4 alkylated naphthalene
- Example 13 Stabilizers for Heat T ransfer Compositions Comprising Refrigerant and Lubricant
- Example 10 The test of Example 10 is repeated except that 8% by weight of alkylated naphthalene (AN4) based on the weight of the lubricant is added. The results are similar to the results of Example 10.
- AN4 alkylated naphthalene
- Example 14 Stabilizers for Heat Transfer Compositions Comprising Refrigerant and Lubricant
- Example 1 Comparative Example 1 (designated CE1 ) and Example 10 (designated E10).
- the refrigerant/lubricant fluid with 10% alkylated naphthalene stabilizer unexpectedly exhibits a substantial deterioration in stabilizing performance for each criteria tested compared to the fluid with the AN level of 2%.
- Example 14 The test of Example 14 is repeated except that in addition to the 10% by weight of alkylated naphthalene (AN4) based on the weight of the lubricant being added, 1000 ppm by weight (0.1 % by weight) of ADM (ADM4) is also added.
- the results (designated E15) are reported in Table 12 below, together with the results from Comparative Example 1
- Example 10 designated E10
- Example 14 designated E14
- the refrigerant/lubricant fluid with 10% alkylated naphthalene stabilizer and 0.1 % by weight (1000 ppm) ADM unexpectedly exhibits the best performance, with an R-23 value that is even better than the excellent results from Example 10.
- Example 16 Stabilizers for Heat Transfer Compositions Comprising Refrigerant and Lubricant
- Example 15 The test of Example 15 is repeated except that the lubricant was an ISO 74 POE having a viscosity at 40°C of about 74 cSt and having a moisture content of 300 ppm or less (Lubricant B). The results were as follows:
- Example 17 Stabilizers for Heat T ransfer Compositions Comprising Refrigerant and Lubricant
- the test of Example 15 is repeated except that the lubricant is an ISO 68 PVE having a viscosity at 40°C of about 68 cSt and having a moisture content of 300 ppm or less (Lubricant c).
- the results were as follows:
- Example 18 Stabilizers for Heat Transfer Compositions Comprising Refrigerant and Lubricant
- Example 15 The test of Example 15 is repeated except that the lubricant was an ISO 32 PVE having a viscosity at 40°C of about 32 cSt and having a moisture content of 300 ppm or less (Lubricant c). The results were similar to the results from Example 17.
- R-410A is immiscible with POE oil below about -22 °C, and R-410A cannot therefore be used in low temperature refrigeration applications without make provisions to overcomve the accumulation of POE oil in the evaporator. Furthermore, R-410A is immiscible with POE oil above 50°C, which will cause problems in the condenser and liquid line (e.g. the separated POE oil will be trapped and accumulated) when R-410A is used in high ambient conditions. Conversely, applicants have surprisingly and unexpectedly found that refrigerants of the present invention are fully miscible with POE oil across a temperature range of -40°C to 80°C, thus providing a substantial and unexpected advantage when used in such systems.
- a heat transfer compositions comprising refrigerant, lubricant and stabilizer, said refrigerant consisting essentially of the following three compounds, with each compound being present in the following relative percentages: 39 to 45% by weight difluoromethane (HFC-32), 1 to 4% by weight pentafluoroethane (HFC-125), and 51 to 57% by weight trifluoroiodomethane (CF3I), said lubricant comprising polyol ester (POE) lubricant and/or polyvinyl ether (PVE) lubricant, and said stabilizer comprising alkylated naphthalene.
- HFC-32 difluoromethane
- HFC-125 pentafluoroethane
- CF3I trifluoroiodomethane
- said lubricant comprising polyol ester (POE) lubricant and/or polyvinyl ether (PVE) lubricant
- PVE polyvinyl
- Numbered Embodiment 8 A heat transfer composition according to any of Number Embodiments 1 - 7 wherein said alkylated naphthalene is selected from AN1 , or AN2, or AN3, or AN4, or AN5, or AN6, or AN7, or AN8, or AN9 or AN10.
- a heat transfer composition according to any of Number Embodiments 1 - 9 wherein said stabilizer is selected from Stablizer 1 , Stablilizer 2, Stablizer 3, Stablilizer 4, Stablizer 5, Stablilizer 6, Stablizer 7, Stablilizer 8, Stablizer 9, Stablilizer 10, Stablizer 1 1 , Stablilizer 12, Stablizer 13, Stablilizer 14, Stablizer 15, Stablilizer 16, Stablilizer 17, Stablizer 18, Stablilizer 19, Stablizer 20.
- Numbered Embodiment 20 A heat transfer composition according to any of Number Embodiments 1 - 19 wherein said lubricant comprises POE.
- Numbered Embodiment 22 A heat transfer composition according to any of Number Embodiments 1 - 19 wherein said lubricant consists of POE.
- Numbered Embodiment 23 A heat transfer composition according to any of Number Embodiments 1 - 22 wherein said lubricant comprises Lubricant 1 .
- Numbered Embodiment 32 The heat transfer composition of any one of Numbered Embodiments 1 to 8 and 15 to 31 , wherein the alkylated naphthalene is one or more of NA- LUBE KR-007A;KR- 008, KR-009; KR-0105, KR-019 and KR-005FG.
- Numbered Embodiment 33 The heat transfer composition of any one of Numbered Embodiments 1 to 8 and 15 - 31 , wherein the alkylated naphthalene is one or more of NA- LUBE KR-007A, KR-008, KR-009 and KR-005FG.
- Numbered Embodiment 34 The heat transfer composition of any one of Numbered Embodiments 1 to 33 wherein the alkylated naphthalene is NA-LUBE KR-008.
- Numbered Embodiment 35 The heat transfer composition of any one of Numbered Embodiments 1 - 34, wherein the stabilizer comprises a phenol based compound selected from 4,4’-methylenebis(2,6-di-tert-butylphenol); 4,4’-bis(2,6-di-tert-butylphenol); 2,2- or 4,4- biphenyldiols, including 4,4’-bis(2-methyl-6-tert-butylphenol); derivatives of 2,2- or 4,4- biphenyldiols; 2,2’-methylenebis(4-ethyl-6-tertbutylphenol); 2,2’-methylenebis(4-methyl-6- tert-butylphenol); 4,4-butylidenebis(3-methyl-6-tert-butylphenol); 4,4-isopropylidenebis(2,6- di-tert-butylphenol); 2,2’-methylenebis(4-methyl-6-nonylphenol); 2,2’
- Numbered Embodiment 36 The heat transfer composition of any one of Numbered Embodiments 30 to 34, wherein the stabilizer comprises BHT.
- Numbered Embodiment 37 The heat transfer composition of any one of Numbered Embodiments 30 to 34, wherein the phenol consists essentially of BHT.
- Numbered Embodiment 38 The heat transfer composition of any one of Numbered Embodiments 30 to 34, wherein the phenol consists of BHT.
- Numbered Embodiment 39 The heat transfer composition of Numbered Embodiment 30 to 35 wherein said phenol is present in the heat transfer composition in an amount of greater than 0 and preferably from 0.0001 % by weight to about 5% by weight, preferably 0.001 % by weight to about 2.5% by weight, and more preferably from 0.01 % to about 1 % by weight, where percentage by weight refers to the weight of the heat transfer composition.
- Numbered Embodiment 40 The heat transfer composition of Numbered Embodiment 30 to 35 wherein said phenol is present in the heat transfer composition in an amount of greater than 0 and preferably from 0.0001 % by weight to about 5% by weight, preferably 0.001 % by weight to about 2.5% by weight, and more preferably from 0.01 % to about 1 % by weight, where percentage by weight refers to the weight of the heat transfer composition.
- Numbered Embodiment 40 The heat transfer composition of Numbered Embodiment 30 to 35 wherein said phenol is present in the
- a heat transfer system comprising a compressor, an evaporator, a condenser and an expansion device, in fluid communication with each other, and a heat transfer composition as defined in any one of Numbered Embodiments 1 to 40.
- a heat transfer system according to Number Embodiment 41 and further comprising a sequestration material, wherein said sequestration material comprises: i. copper or a copper alloy, or ii. activated alumina, or iii. a zeolite molecular sieve comprising copper, silver, lead or a combination thereof, or iv. an anion exchange resin, or v. a moisture-removing material, preferably a moisture-removing molecular sieve, or vi. a combination of two or more of the above.
- Numbered Embodiment 43 The heat transfer system as defined in any one of Numbered Embodiments 41 and 42, wherein said system is a residential air conditioning system, or an industrial air conditioning system, or a commercial air conditioning system.
- a method of cooling in a heat transfer system comprising an evaporator, a condenser and a compressor, the process comprising i) condensing a refrigerant as required the heat transfer composition of any of Nu bered Embodiments 1 - 33; and
- evaporator temperature of the heat transfer system is in the range of from about
- a method of cooling in a heat transfer system comprising an evaporator, a condenser and a compressor, the process comprising i) condensing a refrigerant as required the heat transfer composition of any of Numbered Embodiments 1 - 33; and
- evaporator temperature of the heat transfer system is in the range of about - 30°C to about 5°C.
- Numbered Embodiment 46 wherein said use in air conditioning is selected from use in a residential air conditioning system, an industrial air conditioning system, or a commercial air conditioning system, or a commercial air conditioning system that is a roof top system, or a commercial air conditioning system that is a variable refrigerant flow system, or a commercial air conditioning system that is a chiller system, or a transport air conditioning system, or a stationary air conditioning.
- Numbered Embodiment 48 The use of a heat transfer composition as defined in any one of as required the heat transfer composition of any of Numbered Embodiments 1 - 33 for use in a mobile heat pump, or a positive displacement chiller, or in an air cooled or water cooled direct expansion chiller, or in a residential heat pump, a residential air to water heat pump/hydronic system, or a commercial air source, water source or ground source heat pump system, or in a a refrigeration system, low temperature refrigeration system, or in a medium temperature refrigeration system, or in a commercial refrigerator, or in a commercial freezer, or in an ice machine, or in a transport refrigeration system, or a domestic freezer, or in a domestic refrigerator, or in an industrial freezer, or in an industrial refrigerator, or in a chiller.
- Numbered Embodiment 46 wherein said use in air conditioning is selected from use in a residential air conditioning system with a reciprocating, rotary (rolling-piston or rotary vane) or scroll compressor, or a split residential air conditioning system, or a ducted residential air conditioning system, or a window residential air conditioning system, or a portable residential air conditioning system, or a medium temperature refrigeration system.
- Numbered Embodiment 50 The use of a heat transfer composition as required by any one of Numbered Embodiments 1 to 33, for use as a replacement for R410A.
- Numbered Embodiment 51 A method of retrofitting an existing heat transfer system designed to contain or containing R-410A refrigerant or which is suitable for use with R- 410A refrigerant, said method comprising replacing at least a portion of the existing R-410A refrigerant with a heat transfer composition as defined in Numbered Embodiments 1 - 33.
- Numbered Embodiment 52 The method of Numbered Embodiment 51 , wherein the use of the heat transfer composition as defined in Numbered Embodiments 1 to 33 to replace R410A does not require modification of the condenser, the evaporator and/or the expansion valve in the heat transfer system.
- Numbered Embodiment 53 The method of Numbered Embodiment 51 , wherein the use of the heat transfer composition as defined in Numbered Embodiments 1 to 33 is provided as a replacement for R-410A in a chiller system, or a residential air conditioning system, or a industrial air conditioning system, or in commercial air conditioning system, or commercial air conditioning system is a roof top system, or commercial air conditioning system that is a variable refrigerant flow system, or in a commercial air conditioning system that is a chiller system.
- Numbered Embodiment 54 The method of Numbered Embodiments 51 to 53 comprising removing at least about 5%, by weight of the R-410A from the system and replacing it with the heat transfer composition as defined in Numbered Embodiments 1 to 33.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201862786826P | 2018-12-31 | 2018-12-31 | |
PCT/US2019/068935 WO2020142428A1 (en) | 2018-12-31 | 2019-12-30 | Stabilized heat transfer compositions, methods and systems |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3906289A1 true EP3906289A1 (en) | 2021-11-10 |
EP3906289A4 EP3906289A4 (en) | 2022-09-28 |
Family
ID=71406808
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19907889.0A Pending EP3906289A4 (en) | 2018-12-31 | 2019-12-30 | Stabilized heat transfer compositions, methods and systems |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP3906289A4 (en) |
JP (2) | JP2022516877A (en) |
KR (1) | KR20210099181A (en) |
CN (2) | CN118048126A (en) |
CA (1) | CA3125194A1 (en) |
MX (1) | MX2021007918A (en) |
WO (1) | WO2020142428A1 (en) |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5198134A (en) * | 1991-05-07 | 1993-03-30 | Ciba-Geigy Corporation | Substituted naphthalenediamine stabilizers |
JPH04359997A (en) * | 1991-06-07 | 1992-12-14 | Showa Shell Sekiyu Kk | Hydrocarbon fluid composition |
JP4092780B2 (en) * | 1997-10-17 | 2008-05-28 | ダイキン工業株式会社 | Refrigeration and air conditioning equipment |
US7592495B2 (en) * | 2000-07-11 | 2009-09-22 | King Industries | Compositions of Group II and/or Group III base oils and alkylated fused and/or polyfused aromatic compounds |
US20040018944A1 (en) * | 2001-11-29 | 2004-01-29 | Wu Margaret May-Som | Alkylated naphthalenes as synthetic lubricant base stocks |
US20050023363A1 (en) * | 2003-05-29 | 2005-02-03 | Sharma Ratnesh K. | CRAC unit control based on re-circulation index |
CA2564023C (en) * | 2004-04-16 | 2012-07-17 | Honeywell International Inc. | Azeotrope-like compositions of tetrafluoropropene and trifluoroiodomethane |
JP2005330328A (en) * | 2004-05-18 | 2005-12-02 | Osamu Ogata | Method of improving oil performance |
US20080111100A1 (en) * | 2006-11-14 | 2008-05-15 | Thomas Raymond H | Use of low gwp refrigerants comprising cf3i with stable lubricants |
JP5107666B2 (en) * | 2007-10-25 | 2012-12-26 | 出光興産株式会社 | Lubricating oil composition for refrigerator and lubricating method using the composition |
US10246621B2 (en) * | 2007-11-16 | 2019-04-02 | Honeywell International Inc. | Heat transfer methods, systems and compositions |
WO2009124128A1 (en) * | 2008-04-01 | 2009-10-08 | Honeywell International, Inc. | Method for selecting lubricants for heat pumps |
BR112012018498A2 (en) * | 2010-01-25 | 2018-06-05 | Arkema Inc | heat transfer composition of oxygenated lubricant with hydrofluoroolefin and hydrochlorofluoroolefin refrigerants |
GB2481443B (en) * | 2010-06-25 | 2012-10-17 | Mexichem Amanco Holding Sa | Heat transfer compositions |
US9150812B2 (en) * | 2012-03-22 | 2015-10-06 | Exxonmobil Research And Engineering Company | Antioxidant combination and synthetic base oils containing the same |
JP5986778B2 (en) * | 2012-03-30 | 2016-09-06 | 出光興産株式会社 | Refrigerant composition and method for inhibiting decomposition of fluorinated hydrocarbon |
BR112018067402A2 (en) * | 2016-02-29 | 2019-01-22 | Chemours Co Fc Llc | composition, processes for generating cooling and heating, replacement methods, air conditioning or heat pump system and cooling system |
CN109689832B (en) * | 2016-07-29 | 2021-12-28 | 霍尼韦尔国际公司 | Heat transfer compositions, methods, and systems |
RU2742988C1 (en) * | 2016-07-29 | 2021-02-12 | Ханивелл Интернэшнл Инк. | Compositions, methods and systems of heat transfer |
MX2019001102A (en) * | 2016-07-29 | 2019-06-12 | Honeywell Int Inc | Heat transfer compositions, methods and systems. |
MX2020007762A (en) * | 2018-01-30 | 2020-09-24 | Honeywell Int Inc | Heat transfer compositions, methods, and systems. |
-
2019
- 2019-12-30 EP EP19907889.0A patent/EP3906289A4/en active Pending
- 2019-12-30 CN CN202410180896.XA patent/CN118048126A/en active Pending
- 2019-12-30 KR KR1020217024309A patent/KR20210099181A/en not_active Application Discontinuation
- 2019-12-30 MX MX2021007918A patent/MX2021007918A/en unknown
- 2019-12-30 JP JP2021538105A patent/JP2022516877A/en not_active Ceased
- 2019-12-30 CA CA3125194A patent/CA3125194A1/en active Pending
- 2019-12-30 CN CN201980090010.XA patent/CN113330091B/en active Active
- 2019-12-30 WO PCT/US2019/068935 patent/WO2020142428A1/en unknown
-
2023
- 2023-11-01 JP JP2023187474A patent/JP2024016136A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
CN113330091B (en) | 2024-03-08 |
KR20210099181A (en) | 2021-08-11 |
EP3906289A4 (en) | 2022-09-28 |
WO2020142428A1 (en) | 2020-07-09 |
CA3125194A1 (en) | 2020-07-09 |
CN113330091A (en) | 2021-08-31 |
JP2022516877A (en) | 2022-03-03 |
MX2021007918A (en) | 2021-09-10 |
JP2024016136A (en) | 2024-02-06 |
CN118048126A (en) | 2024-05-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3365408B1 (en) | Heat transfer compositions, methods and systems | |
US11732170B2 (en) | Stabilized heat transfer compositions, methods and systems | |
WO2018022949A2 (en) | Heat transfer compositions, methods and systems | |
US11261360B2 (en) | Stabilized heat transfer compositions, methods and systems | |
US20220177760A1 (en) | Heat transfer compositions, methods, and systems | |
JP7446313B2 (en) | Stabilized heat transfer compositions, methods, and systems | |
US20220112415A1 (en) | Stabilized heat transfer compositions, methods and systems | |
JP2024063145A (en) | Stabilized heat transfer compositions, methods, and systems | |
WO2020142428A1 (en) | Stabilized heat transfer compositions, methods and systems | |
WO2023137025A1 (en) | Stabilized heat transfer compositions, methods and systems | |
WO2022271925A1 (en) | Stabilizer compositions and stabilized heat transfer compositions, methods and systems | |
WO2024050411A1 (en) | Stabilized heat transfer compositions, methods and systems |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20210625 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20220825 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C10M 171/00 20060101ALI20220819BHEP Ipc: C09K 5/04 20060101AFI20220819BHEP |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230414 |