US20120096878A1 - Refrigeration Circuit and Method for Improving Same - Google Patents

Refrigeration Circuit and Method for Improving Same Download PDF

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Publication number
US20120096878A1
US20120096878A1 US13/379,316 US201013379316A US2012096878A1 US 20120096878 A1 US20120096878 A1 US 20120096878A1 US 201013379316 A US201013379316 A US 201013379316A US 2012096878 A1 US2012096878 A1 US 2012096878A1
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lubricant
refrigeration circuit
circuit according
refrigerant
type component
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Hiromitsu Kamishima
Tomoaki Matsuzaki
Yuuichi Matsumoto
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Sanden Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • 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
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • 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
    • 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2500/00—Problems to be solved
    • F25B2500/04—Clogging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the present invention relates to a refrigeration circuit in which refrigerant containing unsaturated fluorinated hydrocarbon compound typified by HFO-1234yf as a part or the whole thereof is used, and also relates to a method for improving the refrigeration circuit.
  • HFC134a which is a kind of fluorocarbons is currently used as a typical refrigerant and polyalkylene glycol (PAG) is currently used as a typical refrigerating machine oil.
  • PAG polyalkylene glycol
  • refrigerant manufacturers, refrigerating machine oil manufacturers and air conditioning system manufacturers are carrying out research and development of a new refrigerant and a refrigerating machine oil for the new refrigerant with the aim of further reducing and improving global warming potential (GWP) while maintaining its safety.
  • GWP global warming potential
  • various unsaturated fluorinated hydrocarbon refrigerants having an evaporation temperature in a range of ⁇ 50 to ⁇ 10° C. are being developed by introducing an unsaturated bond into a molecule thereof so as to lower its GWP so as to achieve next-generation refrigerants.
  • the unsaturated fluorinated hydrocarbon refrigerant has low GWP value as one of its features, it has high reactivity, low thermal stability and low chemical stability relative to a conventional saturated fluorinated hydrocarbon refrigerant such as HFC134a since it has an unsaturated bond in a molecule.
  • Inventors of the present invention carried out an experiment for studying the thermal and chemical stability of the refrigerant in an actual refrigeration circuit, and confirmed a fact that, in a refrigeration circuit of an experimental system using a scroll compressor as a compressor, HFO1234yf as refrigerant and polyalkylene glycol as a refrigerating machine oil, a wax-like solid is generated in the compressor especially under high-speed and heavy load conditions.
  • an object of the present invention is to prevent a wax-like solid, which can be a cause of clogging of the refrigeration circuit and degradation in refrigeration performance, from being generated in a refrigeration circuit provided with a scroll compressor as a compressor, an unsaturated fluorinated hydrocarbon refrigerant and an ether-based lubricant such as polyalkylene glycol as refrigeration machine oil.
  • the inventors of the present invention carried out a chemical analysis of the wax-like solid, and confirmed that this solid is a polymerized paraffin with a low molecular mass having a melting point in a range of approximately 50 to 72° C. According to the result of the analysis, the inventors assume a generation mechanism for the wax-like solid as described below. Namely, in a scroll compressor, a refrigerating machine oil used is required to have high lubricating performance because a scroll member of a movable scroll and a scroll member of a fixed scroll come into sliding contact with each other in a state of being pressed strongly by each other in order to oppose the action of high-temperature and high-pressure refrigerant gas concurrently with a rotational movement of the movable scroll.
  • an ether-based lubricant such as polyalkylene glycol to a refrigerant having an unsaturated bond such as HFO1234yf is not quite enough for the scroll compressor.
  • active metal surface is liable to be exposed locally at the sliding contact surface of the compression mechanism part as accompanying with the rotational movement of the movable scroll.
  • an unsaturated fluorinated hydrocarbon refrigerant has high reactivity, low thermal stability and low chemical stability.
  • the exposed active metal surface acts as a reaction catalyst and induces a reaction between the unsaturated fluorinated hydrocarbon refrigerant and a polyoxyalkylene structure of the ether-based lubricant under an atmosphere of high-temperature and high-pressure refrigerant gas in the compression mechanism part of the scroll compressor, and accordingly, decomposition of the unsaturated fluorinated hydrocarbon refrigerant and generation of a polymerizable olefin which is a decomposed ingredient thereof occur, and further, this polymerizable olefin polymerizes to form a polymerized paraffin by the polymerization catalytic activity of the active metal surface under pressure and heat in the compressor.
  • a refrigeration circuit is a refrigeration circuit provided with a scroll compressor for compressing a refrigerant, characterized in that the refrigerant contains an unsaturated fluorinated hydrocarbon refrigerant as a part or the whole thereof, a refrigeration machine oil comprises an ether-based lubricant having a polyoxyalkylene structure, and the ether-based lubricant contains one or more selected from a lubricant type component having no polyoxyalkylene structure and a metal deactivation agent.
  • the lubricant-type component and the metal deactivating agent function as a polymerized paraffin inhibitor preventing decomposition of unsaturated fluorinated hydrocarbon refrigerant caused by operation of the compressor and generation of polymerized paraffin originating from polymerization of a polymerizable decomposed substance.
  • a method for improving a refrigeration circuit is a method for improving a refrigeration circuit provided with a scroll compressor as a compressor for compressing a refrigerant, characterized in that, by a condition where the refrigerant contains an unsaturated fluorinated hydrocarbon refrigerant as a part or the whole thereof, a refrigeration machine oil comprises an ether-based lubricant having a polyoxyalkylene structure, and the ether-based lubricant contains one or more selected from a lubricant type component having no polyoxyalkylene structure and a metal deactivation agent, decomposition of the unsaturated fluorinated hydrocarbon refrigerant caused by operation of the compressor and generation of a polymerized paraffin originating from polymerization of a polymerizable decomposed substance are prevented.
  • chemical structure of the ether-based lubricant can be a polyether structure which has not been denatured, and can also be a polyether structure that a terminal structure of either one end or both ends thereof has been denatured by an ether group, an ester group, etc.
  • An ester-based lubricant such as polyol ester, an alcohol-based friction modifier such as an aliphatic polyol having a carbon number in a range of 2 to 25, an olefin-based friction modifier such as an olefin having a carbon number in a range of 10 to 18, a polyolefin-based lubricant comprising poly- ⁇ -olefin, alkyl aromatic lubricant such as alkylbenzene and alkylnaphthalene, and a silicone-based lubricant are preferred as a lubricant-type component having no polyoxyalkylene structure.
  • Benzotriazole is preferred as a metal deactivating agent.
  • an acid capturing agent for capturing hydrogen fluoride generated by decomposition of the unsaturated fluorinated hydrocarbon refrigerant is used together in the above-described configuration, the polymerized paraffin can be prevented from generating further effectively.
  • Epoxy-alkane having a carbon number in a range of 8 to 25 is preferred as an acid capturing agent.
  • the refrigeration circuit and the method for improving the refrigeration circuit of the present invention can be applied to any refrigeration circuit used in the area of home electronics, residential air conditioning system, distribution system, etc., and is suitable for a refrigeration circuit for an automotive air conditioning system in particular.
  • a refrigeration circuit for an automotive air conditioning system it is possible to realize a refrigeration circuit wherein the environmental load is reduced by using unsaturated fluorinated hydrocarbon refrigerant such as HFO1234yf and the comparable operational stability as before can be achieved.
  • an unsaturated fluorinated hydrocarbon refrigerant as refrigerant and an ether-based lubricant having a polyoxyalkylene structure as lubricant by compensating for shortage in lubricating performance of the ether-based lubricant by combined use of another lubricating component having no polyoxyalkylene structure, exposure of active metal surface accompanying a sliding movement of a compression mechanism part is prevented, and therefore it is possible to prevent the unsaturated fluorinated hydrocarbon refrigerant and the polyoxyalkylene structure of the ether-based lubricant from reacting through catalytic activity of the exposed active metal surface under an atmosphere of high-temperature and high-pressure refrigerant gas in the compression mechanism part. As a result, it is possible to prevent the generation of polymerized paraffin which becomes a cause of clogging in the refrigeration circuit and degradation of refrigeration performance.
  • FIG. 1 is a schematic framework showing an example of a basic equipment layout of a refrigeration cycle as an object of the present invention.
  • FIG. 1 shows a basic configuration of a refrigeration circuit used in an air conditioning system for vehicles, etc.
  • refrigeration circuit 1 has compressor 2 for compressing refrigerant, condenser 3 for condensing compressed refrigerant, expansion valve 4 as a pressure reduction and expansion means for reducing in pressure and expanding condensed refrigerant, and evaporator 5 for evaporating pressure-reduced and expanded refrigerant, where the refrigerant is circulated in refrigeration circuit 1 as changing its state.
  • the scroll compressor used in the present invention is not particularly limited.
  • a configuration material for the compressor not only an Fe-based material but also a light metal-based material such as aluminum, magnesium or an alloy thereof can be used.
  • the light metal-based material such as aluminum, magnesium or an alloy thereof, which has a lighter specific gravity than the Fe-based material, is used in many cases in order to reduce an inertial force.
  • these Fe-based material and light metal-based material have high reactivity in a state of pure metal material, their surfaces are generally covered with an oxidized coating layer, and further, by performing surface treatment for the purpose of improvement of lubricity and protection, their surfaces are in a state where activity of the metal material is suppressed.
  • the active metal surface will be exposed because the oxidized coating layer is lost due to friction, etc. caused by a rotational movement of a rotational scroll.
  • the active metal surface exhibits extremely high catalytic activity because of the high reactivity of the metal material thereof.
  • an ether-based lubricant and an unsaturated fluorinated hydrocarbon refrigerant come into contact with the active metal surface under an atmosphere of high-temperature high-pressure refrigerant, the unsaturated fluorinated hydrocarbon refrigerant reacts with a polyoxyalkylene structure of the ether-based lubricant by the catalytic activity of the active metal surface.
  • the ether-based lubricant contains a lubricant type component having no polyoxyalkylene structure and the lubricant type component does not react with the unsaturated fluorinated hydrocarbon refrigerant even under the atmosphere of high-temperature and high-pressure refrigerant gas, the exhibition of the active metal surface is prevented by compensating for a shortage of lubricating performance of the ether-based lubricant, and thereby preventing decomposition of the unsaturated fluorinated hydrocarbon refrigerant, generation of the polymerizable olefin as the decomposed substance, and generation of the polymerized paraffin originating from polymerization of the polymerizable olefin.
  • a hydrofluoropropene such as 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC-1243zf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243ye); 1,3,3-trifluoro-1-propene (HFC-1243zf); 1,1,2-trifluoro-1-propene (HFC-1243yc);
  • the above-described compounds are used as a single one or a mixture of two or more.
  • the above-described compounds can also be used in combination with a saturated halogenated hydrocarbon refrigerant or hydrocarbon-based refrigerant.
  • a saturated halogenated hydrocarbon refrigerant and hydrocarbon-based refrigerant for example, 1,1,1,2-tetrafluoroethane (R134a), 1,1,2-difluoroethane (R152a), difluoromethane (R32), pentafluoroethane (R125), 1,1,1-trifluoroethane (R143a), 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (R43-10mee), 1,1,1,3,3-pentafluorobutane (R365mfc), 2,2-dichloro-1,1,1-trifluoroethane (R123),
  • hydrocarbon refrigerant for example, propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, 2-methylbutane (isopentane), cyclobutane, cyclopentane, 2,2-dimethylpropane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2,3-dimethylpentane, 2-methylhexane, 3-methylhexane, 2-methylpentane, 3-ethylpentane, 3-methylpentane, cyclohexane, n-heptane, methylcyclopentane, and n-hexane can be exemplified.
  • the lubricant type component having no polyoxyalkylene structure used as a polymerized paraffin inhibitor in the present invention for example, an alcohol-based friction modifier; an olefin-based friction modifier; an ester-based lubricant such as a diester, a polyol ester, etc.; an alkyl aromatic lubricant such as alkylbenzene and alkylnaphthalene, etc.; and a silicone-based lubricant can be exemplified, and particularly, the alcohol-based friction modifier, the olefin-based friction modifier and the ester-based lubricant are preferred due to their significant effect on preventing a polymerized paraffin.
  • the ester-based lubricant is preferred in particular.
  • a higher alcohol having a carbon number in a range of 6 to 20 such as an octyl alcohol, a decyl alcohol, myristyl alcohol, lauryl alcohol, lauryl alcohol, myristyl alcohol, a dodecyl alcohol, cetyl alcohol, palmityl alcohol, oleyl alcohol, stearyl alcohol, linoleyl alcohol, etc.; a dihydric alcohol having a carbon number in a range of 2 to 25 such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propane
  • the aliphatic polyol having a carbon number in a range of 2 to 25 is preferred.
  • An amount of addition of the alcohol-based friction modifier to the ether-based lubricant is preferably in a range of 0.1 to 10 wt. %, and the amount of addition thereof to an amount of refrigerant enclosed is preferably in a range of 0.02 to 2 wt. %.
  • olefin-based friction modifier used as a polymerized paraffin inhibitor in the present invention for example, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, a linear ⁇ -olefin; a branched ⁇ -olefin such as 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene, etc.
  • a linear ⁇ -olefin having a carbon number in a range of 10 to 16 is preferred.
  • An amount of addition of the olefin-based friction modifier to an ether-based lubricant is preferably in a range of 0.5 to 10 wt. %, and the amount of addition thereof to an amount of refrigerant enclosed is preferably in a range of 0.1 to 2 wt. %.
  • ester-based lubricant used as a polymerized paraffin inhibitor in the present invention for example, a diester derived from an aliphatic diacid and monohydric alcohols, and a polyol ester derived from a polyol having a valence number of three or more and monovalent aliphatic acids can be exemplified.
  • an aliphatic diacid having a carbon number in a range of 5 to 10 such as glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexane dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc.
  • the monohydric alcohol for example, a monohydric alcohol having a carbon number in a range of 4 to 18 such as butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc. can be exemplified.
  • a monohydric alcohol having a carbon number in a range of 4 to 18 such as butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc.
  • the polyol which can be a raw material of the polyol ester for example, a dihydric alcohol having a carbon number in a range of 2 to 15 such as ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecan
  • a hindered alcohol such as neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol propane, trimethylol butane, pentaerythritol is preferred.
  • an aliphatic acid having a carbon number in a range of 5 to 20 such as pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid, etc.
  • pentadecanoic acid hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid, etc.
  • the polyol ester may have two or more ester groups, may be a partial ester in which some of the hydroxyl groups of a polyol remain unesterified, or may be a total ester in which all the hydroxyl groups are esterified.
  • An amount of content of the ester-based lubricant to the ether-based lubricant is preferably in a range of 1 to 99 wt. %.
  • An amount of addition of the ester-based lubricant to an amount of refrigerant enclosed is preferably in a range of 0.2 to 20 wt. %.
  • polyolefin-based lubricant used as a polymerized paraffin inhibitor in the present invention for example, an oligomer or co-oligomer of ⁇ -olefin having a carbon number in a range of 2 to 16 such as an octene oligomer, a decene oligomer, an ethylene-propylene co-oligomer, etc. can be exemplified.
  • An amount of addition of the olefin-based lubricant to the ether-based lubricant is preferably in a range of 0.1 to 3 wt. %, and the amount of addition thereof to an amount of refrigerant enclosed is preferably in a range of 0.02 to 0.6 wt. %.
  • alkyl aromatic lubricant used as a polymerized paraffin inhibitor in the present invention for example, an alkylbenzene, which has 1 to 4 alkyl groups having a carbon number in a range of 1 to 15 and in which the total carbon number of these alkyl groups is in a range of 9 to 15, can be exemplified.
  • alkyl group for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc.
  • methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, etc. can be exemplified.
  • an alkylnaphthalene such as a n-propyl naphthalene, an isopropyl naphthalene, a butyl naphthalene, a pentyl naphthalene, an ethyl-propyl naphthalene, a methyl-pentyl naphthalene, an ethyl-butyl naphthalene, a dimethyl-butyl naphthalene, a methyl-hexyl naphthalene, an ethyl-pentyl naphthalene, a propyl-butyl naphthalene, a dimethyl-pentyl naphthalene, a methyl-heptyl naphthalene, an ethyl-hexyl naphthalene, a propyl-pentyl na
  • an amount of addition of the alkyl aromatic lubricant to the ether-based lubricant is in a range of 0.5 to 10 wt. %, and it is preferred that the amount of addition thereof to the refrigerant enclosed is in a range of 0.1 to 2 wt. %.
  • a triazole derivative such as triazole and N,N-dialkyl-triazole-alkylamine
  • a benzotriazole derivative such as benzotriazole and N,N-dialkyl-benzotriazole-methylamine
  • a thiadiazole derivative such as thiadiazole, benzotriazole thiadiazole and 2,5-dialkylmercapto-1,3,4-thiadiazole
  • a benzimidazole derivative such as benzimidazole and 2-alkyldithio-benzimidazole can be exemplified.
  • benzotriazole and its derivatives are preferred.
  • An amount of addition of the metal deactivation agent to the ether-based lubricant is preferably in a range of 0.5 to 10 wt. %, and the amount of addition thereof to an amount of refrigerant enclosed is preferably in a range of 0.1 to 2 wt. %.
  • This acid capturing agent may be added individually to the refrigeration circuit apart from refrigerant and refrigeration machine oil, or may be added at an appropriate amount as a preparative mixture with refrigerant or in combination with various additive agents, which are typically contained in refrigeration machine oil, such as an antioxidant and an extreme pressure agent.
  • the acid capturing agent can also contribute to prevention of corrosion and deterioration of a compressor and pipe of the refrigeration circuit.
  • an epoxy compound such as an epoxide alkane, an aliphatic acid glycidyl ester, an aromatic carboxylic acid glycidyl ester; an orthoester; an oxirane compound; acetals; a carbodiimide can be exemplified.
  • a glycidyl ester of an aliphatic monocarboxylic acid having a carbon number in a range of 6 to 16 such as 2-ethylhexanoic acid glycidyl ester, 3,5,5-trimethylhexanoic acid glycidyl acid, capric acid glycidyl ester, lauric acid glycidyl ester, versatic acid glycidyl ester, myristic acid glycidyl ester, etc.
  • the epoxy alkane having a carbon number in a range of 8 to 25 such as 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxynonadecane, etc. is preferred in particular.
  • An amount of addition of the acid capturing agent to the ether-based lubricant is preferably in a range of 0.5 to 15 wt. %, and the amount of addition thereof to an amount of refrigerant enclosed is preferably in a range of 0.1 to 3 wt. %.
  • the effect of prevention of generation of polymerized paraffin by the present invention can be confirmed by the following practical examples and comparative examples.
  • the refrigeration circuit shown in FIG. 1 is used.
  • a scroll compressor in the refrigeration circuit has a movable scroll made of an aluminum alloy and a fixed scroll anodized with an aluminum alloy.
  • the refrigeration circuit is filled with a specific amount of HFO1234yf refrigerant, and the scroll compressor is filled with a specific amount of a mixture whose prescription is described in Table 1.
  • tricresyl phosphate as the extreme pressure agent is added to the ether-based lubricant at 1.0% thereto.
  • the rotational speed of the scroll compressor is set at 6,000 rpm, and the refrigeration circuit is operated continuously for 400 hours at this rotational speed. After the operation is finished, the inside of the compressor and the inside of the pipe of the refrigeration circuit are inspected in order to confirm the presence or absence of generation of a wax-like solid (a polymerized paraffin). By this confirmation examination, the result described in Table 1 is obtained.
  • the criteria in the column of effect in Table 1 are as follows.
  • PPG means a polyalkylene glycol that a polypropylene glycol as a main structure is denatured with an ether at an end of the molecule, and % means wt. % to an amount of refrigerant enclosed.
  • the present invention can be applied to any refrigeration circuit used in the area of home electronics, air conditioning systems for housing, logistics, etc., and specifically, in a refrigeration circuit for an air conditioning system for vehicles, it is possible to realize a refrigeration circuit which reduces the environmental load by using an unsaturated fluorinated hydrocarbon refrigerant such as HFO1234yf and which achieves a conventional operation stability.

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  • 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)
US13/379,316 2009-06-17 2010-06-16 Refrigeration Circuit and Method for Improving Same Abandoned US20120096878A1 (en)

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JP2009-144077 2009-06-17
JP2009144077 2009-06-17
JP2009210258A JP2011021870A (ja) 2009-06-17 2009-09-11 冷凍回路及びその改良法
JP2009-210258 2009-09-11
PCT/JP2010/003980 WO2010146841A1 (fr) 2009-06-17 2010-06-16 Circuit de refrigeration et procede pour son amelioration

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130200294A1 (en) * 2012-02-08 2013-08-08 Chemtura Corporation Refrigeration Oil and Compositions with Hydrocarbon Refrigerants
US20140165631A1 (en) * 2012-12-14 2014-06-19 GM Global Technology Operations LLC Refrigeration Compositions, Refrigeration Systems and Methods of Making, Operating and Using the Same
US20140352537A1 (en) * 2012-02-29 2014-12-04 Arkema France Air purification system for a vehicle
CN107062679A (zh) * 2017-04-27 2017-08-18 广东美的制冷设备有限公司 空调系统及其控制方法
US20190218439A1 (en) * 2013-01-25 2019-07-18 Trane International Inc. Refrigerant additives and compositions
US10904633B2 (en) 2016-12-19 2021-01-26 Samsung Electronics Co., Ltd. Display device for displaying user interface controlling channel based on user input and controlling method thereof
CN114149790A (zh) * 2021-11-10 2022-03-08 浙江巨化新材料研究院有限公司 一种共沸或类共沸组合物及其制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010024410A (ja) * 2008-07-24 2010-02-04 Sanden Corp 冷凍回路
JP2012012532A (ja) * 2010-07-02 2012-01-19 Panasonic Corp 圧縮機及びそれを用いた冷凍サイクル装置
JP2014172917A (ja) * 2013-03-06 2014-09-22 Ihi Corp 潤滑油および潤滑油の酸化物析出低減方法
JP6763511B2 (ja) 2015-11-19 2020-09-30 出光興産株式会社 冷凍機用潤滑油組成物、冷凍機用組成物、潤滑方法及び冷凍機
JP6717446B2 (ja) * 2016-02-29 2020-07-01 出光興産株式会社 冷凍機油、及び冷凍機用組成物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5895793A (en) * 1996-09-09 1999-04-20 Asahi Glass Company Ltd. Fluorine-containing hydrocarbon composition
US6261474B1 (en) * 1996-02-05 2001-07-17 Idemitsu Kosan Co., Ltd. Lubricating oil for compression-type refrigerators containing pentafluoroethane and a polyvinyl ether
US20030166477A1 (en) * 2002-02-15 2003-09-04 The Lubrizol Corporation Molybdenum, sulfur and boron containing lubricating oil composition
US20060025313A1 (en) * 2004-07-29 2006-02-02 Chevron Oronite Company Llc Lubricating oil composition for internal combustion engines
US20070027028A1 (en) * 2003-08-14 2007-02-01 Pears David A Microencapsulated catalyst-ligand system, methods of preparation and methods of use thereof
US20070257229A1 (en) * 2004-03-04 2007-11-08 Kazuo Tagawa Refrigerating Machine Oil Composition
US20080139696A1 (en) * 2006-12-08 2008-06-12 Bucher Brad A Drag reducing compositions and methods of manufacture and use
US20080234153A1 (en) * 2007-03-19 2008-09-25 Shigeki Matsui Lubricating oil composition
US20080242564A1 (en) * 2007-03-30 2008-10-02 Chinn Kevin A Method for improving the cooling efficiency of a functional fluid

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2074584T3 (es) * 1989-12-14 1995-09-16 Idemitsu Kosan Co Uso de una composicion de aceite de refrigerador para refrigerante de hidrofluorocarbono.
CN1074452C (zh) * 1995-12-28 2001-11-07 大金工业株式会社 制冷机油以及使用该制冷机油的制冷机
US6127324A (en) * 1999-02-19 2000-10-03 The Lubrizol Corporation Lubricating composition containing a blend of a polyalkylene glycol and an alkyl aromatic and process of lubricating
US20080157023A1 (en) * 2006-11-14 2008-07-03 Samuels George J Fluorocarbon stabilizers
JP2010534743A (ja) * 2007-07-27 2010-11-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロオレフィンを含む組成物およびそれらの使用
CA2703921C (fr) * 2007-10-29 2016-05-03 Nippon Oil Corporation Huile de refrigeration et composition de fluide de travail pour machine de refrigeration comprenant un polyalkylene-glycol et un refrigerant a base de fluoropropene
KR101519690B1 (ko) * 2007-11-22 2015-05-12 이데미쓰 고산 가부시키가이샤 냉동기용 윤활유 조성물 및 이것을 사용한 압축기
WO2009066722A1 (fr) * 2007-11-22 2009-05-28 Idemitsu Kosan Co., Ltd. Composition d'huile lubrifiante pour machine réfrigérante

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6261474B1 (en) * 1996-02-05 2001-07-17 Idemitsu Kosan Co., Ltd. Lubricating oil for compression-type refrigerators containing pentafluoroethane and a polyvinyl ether
US5895793A (en) * 1996-09-09 1999-04-20 Asahi Glass Company Ltd. Fluorine-containing hydrocarbon composition
US20030166477A1 (en) * 2002-02-15 2003-09-04 The Lubrizol Corporation Molybdenum, sulfur and boron containing lubricating oil composition
US20070027028A1 (en) * 2003-08-14 2007-02-01 Pears David A Microencapsulated catalyst-ligand system, methods of preparation and methods of use thereof
US20070257229A1 (en) * 2004-03-04 2007-11-08 Kazuo Tagawa Refrigerating Machine Oil Composition
US20060025313A1 (en) * 2004-07-29 2006-02-02 Chevron Oronite Company Llc Lubricating oil composition for internal combustion engines
US20080139696A1 (en) * 2006-12-08 2008-06-12 Bucher Brad A Drag reducing compositions and methods of manufacture and use
US20080234153A1 (en) * 2007-03-19 2008-09-25 Shigeki Matsui Lubricating oil composition
US20080242564A1 (en) * 2007-03-30 2008-10-02 Chinn Kevin A Method for improving the cooling efficiency of a functional fluid

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130200294A1 (en) * 2012-02-08 2013-08-08 Chemtura Corporation Refrigeration Oil and Compositions with Hydrocarbon Refrigerants
US8685271B2 (en) * 2012-02-08 2014-04-01 Chemtura Corporation Refrigeration oil and compositions with hydrocarbon refrigerants
US20140352537A1 (en) * 2012-02-29 2014-12-04 Arkema France Air purification system for a vehicle
US20140165631A1 (en) * 2012-12-14 2014-06-19 GM Global Technology Operations LLC Refrigeration Compositions, Refrigeration Systems and Methods of Making, Operating and Using the Same
US20190218439A1 (en) * 2013-01-25 2019-07-18 Trane International Inc. Refrigerant additives and compositions
US10988651B2 (en) * 2013-01-25 2021-04-27 Trane International Inc. Refrigerant additives and compositions
US11976234B2 (en) 2013-01-25 2024-05-07 Trane International Inc. Refrigerant additives and compositions
US10904633B2 (en) 2016-12-19 2021-01-26 Samsung Electronics Co., Ltd. Display device for displaying user interface controlling channel based on user input and controlling method thereof
CN107062679A (zh) * 2017-04-27 2017-08-18 广东美的制冷设备有限公司 空调系统及其控制方法
CN114149790A (zh) * 2021-11-10 2022-03-08 浙江巨化新材料研究院有限公司 一种共沸或类共沸组合物及其制备方法

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EP2444469A1 (fr) 2012-04-25
WO2010146841A1 (fr) 2010-12-23
JP2011021870A (ja) 2011-02-03

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