WO2012086518A1 - Compresseur de réfrigération et climatisation, et appareil de réfrigération et climatisation - Google Patents

Compresseur de réfrigération et climatisation, et appareil de réfrigération et climatisation Download PDF

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WO2012086518A1
WO2012086518A1 PCT/JP2011/079058 JP2011079058W WO2012086518A1 WO 2012086518 A1 WO2012086518 A1 WO 2012086518A1 JP 2011079058 W JP2011079058 W JP 2011079058W WO 2012086518 A1 WO2012086518 A1 WO 2012086518A1
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oil
compressor
refrigeration
air conditioning
refrigerant
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PCT/JP2011/079058
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English (en)
Japanese (ja)
Inventor
亮 太田
井関　崇
荒木　邦成
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日立アプライアンス株式会社
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Priority to CN201180061046.9A priority Critical patent/CN103261689B/zh
Priority to KR1020137015757A priority patent/KR101505344B1/ko
Priority to JP2012549765A priority patent/JP5466772B2/ja
Publication of WO2012086518A1 publication Critical patent/WO2012086518A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B39/00—Component parts, details, or accessories, of pumps or pumping systems specially adapted for elastic fluids, not otherwise provided for in, or of interest apart from, groups F04B25/00 - F04B37/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B39/00—Component parts, details, or accessories, of pumps or pumping systems specially adapted for elastic fluids, not otherwise provided for in, or of interest apart from, groups F04B25/00 - F04B37/00
    • F04B39/02—Lubrication
    • F04B39/0215—Lubrication characterised by the use of a special lubricant
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C18/00—Rotary-piston pumps specially adapted for elastic fluids
    • F04C18/02—Rotary-piston pumps specially adapted for elastic fluids of arcuate-engagement type, i.e. with circular translatory movement of co-operating members, each member having the same number of teeth or tooth-equivalents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C18/00—Rotary-piston pumps specially adapted for elastic fluids
    • F04C18/02—Rotary-piston pumps specially adapted for elastic fluids of arcuate-engagement type, i.e. with circular translatory movement of co-operating members, each member having the same number of teeth or tooth-equivalents
    • F04C18/0207—Rotary-piston pumps specially adapted for elastic fluids of arcuate-engagement type, i.e. with circular translatory movement of co-operating members, each member having the same number of teeth or tooth-equivalents both members having co-operating elements in spiral form
    • F04C18/0215—Rotary-piston pumps specially adapted for elastic fluids of arcuate-engagement type, i.e. with circular translatory movement of co-operating members, each member having the same number of teeth or tooth-equivalents both members having co-operating elements in spiral form where only one member is moving
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C23/00—Combinations of two or more pumps, each being of rotary-piston or oscillating-piston type, specially adapted for elastic fluids; Pumping installations specially adapted for elastic fluids; Multi-stage pumps specially adapted for elastic fluids
    • F04C23/008—Hermetic pumps
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C29/00—Component parts, details or accessories of pumps or pumping installations, not provided for in groups F04C18/00 - F04C28/00
    • F04C29/02—Lubrication; Lubricant separation
    • 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
    • C09K2205/24—Only one single fluoro component present
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids 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
    • 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
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; 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
    • 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
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C2210/00—Fluid
    • F04C2210/26—Refrigerants with particular properties, e.g. HFC-134a

Definitions

  • the present invention relates to a refrigeration air conditioning compressor and a refrigeration air conditioning apparatus using a heat pump cycle.
  • CFCs and HCFCs that are ozone depleting substances
  • selection of refrigerants and heat insulating materials and development of equipment are promoted with a focus on not depleting the ozone layer, low toxicity and flammability, and ability to ensure efficiency.
  • CFC11 is substituted in order of HCFC141b and cyclopentane, and it is transfering now to combined use with a vacuum heat insulating material.
  • refrigerants include hydrocarbons such as propane and propylene, and low GWP hydrofluorocarbons such as fluoroethane (HFC 161) and difluoroethane (HFC 152a).
  • HFC 161 fluoroethane
  • HFC 152a difluoroethane
  • difluoromethane (HFC 32) is considered in consideration of flammability, air conditioning capacity, reduction of refrigeration air conditioning cycle efficiency due to non-azeotropic refrigerant temperature gradient, ease of handling, refrigerant cost, change of equipment (development), etc. Is most preferred.
  • Refrigerant oil is used in a hermetic electric compressor and plays a role of lubricating, sealing, cooling and the like of the sliding portion thereof.
  • the most important characteristic of the refrigeration air for refrigeration air conditioning is compatibility with the refrigerant, and when two-layer separation of the liquid refrigerant and the refrigerator oil occurs in the compressor disposed in the outdoor unit, the liquid separated in each sliding portion The refrigerant may be supplied, which may cause a lubrication failure.
  • refrigeration oil is in the form of mist due to mechanical action during compressor operation, it is discharged to the refrigeration air conditioning cycle, but if compatibility is poor, refrigeration oil will stagnate in the low temperature part of the refrigeration air conditioning cycle, The amount of oil returned to the compressor decreases.
  • package air conditioners and multi-type air conditioners since the pipes constituting the refrigeration air conditioning cycle are long, it is necessary to use for refrigeration oil which is excellent in compatibility with a refrigerant.
  • the two-layer separation of the refrigerant and the refrigerator oil can be evaluated by a two-layer separation curve according to the refrigerator oil concentration.
  • the two-layer separation on the low temperature side is an upwardly convex curve.
  • the maximum value of this curve is the lower critical solution temperature (UCST), and the lower the temperature, the better the compatibility.
  • a compressor for refrigeration air conditioning using refrigeration oil for refrigeration air conditioning having compatibility a compressor using polyvinyl ether oil polyol ester oil compatible with a hydrofluoroolefin refrigerant described in Patent Document 1 is is there.
  • 2,3,3,3-tetrafluoropropene (HFO 1234yf) represented by hydrofluoroolefins is found to be compatible with these refrigerator oils, on the other hand, the disclosed refrigerator oils are difluoromethane It is known that the compatibility with is poor.
  • Patent Document 2 discloses a refrigerator oil having compatibility with a hydrocarbon-based refrigerant.
  • the hydrocarbon-based refrigerant is also similar to that of Patent Document 1 and has compatibility with various refrigerator oils, but is hardly compatible with difluoromethane.
  • Patent Document 3 discloses a refrigerator using an alkylbenzene oil which does not have compatibility with a refrigerant.
  • a refrigerator oil that is incompatible with the refrigerant it is easy to secure a lubricating oil film in the sliding part of the compressor, but since there is no oil return from the refrigeration air conditioning cycle, it is necessary to newly provide an oil separator There is.
  • the alkyl benzene oil used here is also incompatible with difluoromethane.
  • Patent Document 4 discloses a scroll-type compressor using a mixed oil obtained by mixing a refrigerating machine oil incompatible with a refrigerant and a refrigerating machine oil compatible with a refrigerant, and is compatible with difluoromethane. Refrigeration oil is used. However, long-term reliability and efficiency of the refrigeration air conditioning cycle are still inadequate.
  • the object of the present invention is to improve the long-term reliability by improving the wear resistance of a refrigeration air conditioning compressor using difluoromethane (HFC 32) as a refrigerant, and to use the compressor for a refrigeration air conditioning cycle of a refrigeration air conditioning system. It is about realizing high efficiency.
  • HFC 32 difluoromethane
  • the refrigeration air conditioning compressor according to the present invention is provided with a refrigerant compression unit having a sliding unit, and contains difluoromethane as a refrigerant and refrigeration oil, and the refrigeration oil has a kinematic viscosity at 40 ° C. 30 to 100 mm 2 / s, and the low temperature side critical solution temperature of the refrigerant and the refrigerator oil is + 10 ° C. or less.
  • FIG. 1 is a cross-sectional view showing a scroll-type hermetic compressor for a room air conditioner.
  • the refrigeration air conditioning compressor is provided with a refrigerant compression unit having a sliding unit, and encloses difluoromethane, which is a refrigerant, and refrigeration oil.
  • the refrigeration oil has a dynamic viscosity of 30 to 100 mm 2 / s at 40 ° C., and the low temperature side critical solution temperature of the refrigerant and the refrigeration oil is + 10 ° C. or less.
  • the refrigerant dissolution amount with respect to oil under conditions of 60 ° C. and 2.5 MPa is 17 to 22% by weight, and the oil viscosity at the time of refrigerant dissolution is 3.0 to 5.0 mm 2 / s.
  • the refrigerator oil is a polyol ester oil or a polyvinyl ether oil.
  • the polyol ester oil is a compound represented by the following chemical formulas (1), (2), (3) and (4) (wherein, R 1 to R 11 each have 4 to 6 carbon atoms) And at least one selected from the group consisting of complex ester oils as a base oil.
  • the polyvinyl ether oil is a base oil represented by the following chemical formula (5) (wherein, Q i (i is any of 1 to m and Q 1 to Q m is And the superscript numbers are connected in series in the following numerical order) have a chemical structure represented by the following chemical formula (6), and OR 12 in the following chemical formula (6) is a methyloxy group, an ethyloxy group, OR 12 which is a propyloxy group or a butyloxy group and is included in any one of Q 1 to Q m is a methyloxy group, and m is 5 to 15).
  • the propyloxy group is a term including an isopropyloxy group
  • the butyloxy group is a term including an isobutyloxy group, a sec-butyloxy group and a tert-butyloxy group.
  • the refrigeration air conditioner uses the refrigeration air conditioning compressor.
  • the refrigeration air conditioning compressor is a scroll-type or rotary-type hermetic compressor with a built-in motor, and the kinematic viscosity of the refrigeration oil main agent at 40 ° C. is 30 to 100 mm 2 / s.
  • the refrigeration air conditioner uses the scroll or rotary hermetic compressor.
  • the embodiment discloses a compressor using difluoromethane and a refrigeration air conditioner using the same.
  • the refrigerant of the example is difluoromethane, and the refrigerator oil is a polyol ester oil or a polyvinyl ether oil.
  • the polyol ester oil is obtained by the condensation reaction of a polyhydric alcohol and a monohydric fatty acid.
  • the polyol ester oil is preferably a hindered type excellent in thermal stability, and preferred as the raw material polyhydric alcohol are, for example, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like.
  • n-pentanoic acid As a monovalent fatty acid to be a raw material, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 2-methylpentanoic acid, 2- There are ethyl butanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, iso-octanoic acid, 3,5,5-trimethylhexanoic acid, etc. These may be used alone or in combination of two or more.
  • the complex type polyol ester oil is an ester compound in which a divalent fatty acid and a monovalent fatty acid are bonded to a polyhydric alcohol.
  • preferable polyhydric alcohols as raw materials are, for example, neopentyl glycol, trimethylolpropane and pentaerythritol.
  • a monovalent fatty acid to be a raw material n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2 -Ethylhexanoic acid, isooctanoic acid, 3,5,5-trimethylhexanoic acid, etc., and these are used singly or in combination of two or more.
  • a divalent fatty acid to be a raw material there are propane diacid, butane di acid, pentane di acid, hexane di acid, heptane di acid, octane di acid and the like, and these may be used alone or in combination of two or more Use.
  • a specific example of the complex ester oil is represented by the following chemical formula (7).
  • R 13 and R 15 each represent an alkyl group having 4 to 9 carbon atoms. Further, R 14 represents an alkylene group having 1 to 9 carbon atoms. n is a positive integer.
  • polyvinyl ether oil is a polymer of alkoxyvinyl, and a methyloxy group and an ethyloxy group are preferable because compatibility with difluoromethane is poor when the number of alkyl carbons of the alkoxy group is large.
  • the viscosity grade of the refrigerator oil used for the air conditioner and refrigerator of the embodiment differs depending on the type of compressor, but the dynamic viscosity at 40 ° C. is in the range of 46 to 100 mm 2 / s in the scroll type hermetic compressor. Is preferred.
  • the kinematic viscosity at 40 ° C. is preferably in the range of 30 to 70 mm 2 / s.
  • the heat resistance class of the electrical insulation is defined by the heat resistance class of the electrical insulation system and the thermal durability evaluation JEC-6147-2010 (Standards of Electrical Standards Committee of the Institute of Electrical Engineers of Japan), and is adopted for compressors for refrigeration air conditioners
  • the insulating material is also selected according to the heat resistance class of the above standard.
  • organic insulating materials for refrigeration and air conditioning equipment, it is used in a special environment such as in a refrigerant atmosphere, so that deformation and denaturation due to pressure can be suppressed besides temperature, and polar compounds such as refrigerant and refrigerator oil It is also resistant to solvents, extraction, thermal, chemical and mechanical stability, and refrigerant resistance (crasing (fine bellows-like cracks generated when immersed in refrigerant after stressing the film) ), Blisters (refrigerant absorbed in the film, bubbles of the film caused by temperature rise), etc. must also be considered. Furthermore, the heat resistance of the electrical insulating material is very important because difluoromethane has a large adiabatic index and thus the temperature rise in the compression process is large.
  • PET polyethylene terephthalate
  • PET of a film material is used for coil insulation with the iron core of a distributed winding motor
  • fibrous PET is used for a covering material of a tie yarn of a coil and a lead wire of the motor.
  • Other insulating films include PPS (polyphenylene sulfide), PEN (polyethylene naphthalate), PEEK (polyether ether ketone), PI (polyimide), PA (polyamide) and the like.
  • PPS polyphenylene sulfide
  • PEN polyethylene naphthalate
  • PEEK polyether ether ketone
  • PI polyimide
  • PA polyamide
  • THEIC modified polyester, polyamide, polyamide imide, polyester imide, polyester amide imide, etc. are used as the main insulation coating material of the coil, and double coated copper wire coated with polyester imide-amide imide is preferably used.
  • a lubricity improver an antioxidant, an acid scavenger, an antifoaming agent, a metal deactivator and the like are added to the above-mentioned refrigerator oil.
  • the polyol ester oil causes deterioration due to hydrolysis in the presence of water, so the blending of an antioxidant and an acid scavenger is essential.
  • DBPC 2,6-di-t-butyl-p-cresol which is a phenol type is preferable.
  • an aliphatic epoxy compound or a carbodiimide compound which is a compound having an epoxy ring is generally used.
  • the carbodiimide type compound has extremely high reactivity with fatty acid and captures hydrogen ions dissociated from fatty acid, the effect of suppressing the hydrolysis reaction of the polyol ester oil is very large.
  • carbodiimide compounds include bis (2,6-isopropylphenyl) carbodiimide.
  • the blending amount of the acid scavenger is preferably 0.05 to 1.0% by weight with respect to the refrigerator oil.
  • polyvinyl ether oil is inferior in abrasion resistance, it is desirable to blend a tertiary phosphate typified by tricresyl phosphate as a lubricity improver.
  • a mixture prepared by mixing an arbitrary amount of oil (refrigerant oil) and a refrigerant was sealed in a pressure resistant glass container, and the contents in a state where the temperature was changed were observed. When the contents were cloudy, it was judged to be two-layer separation, and when it was transparent, it was determined to be dissolution.
  • combinations of the above mixtures have a separation zone on the hot side and the cold side.
  • the temperature at which the mixture is subjected to two-phase separation is gradually raised from -60.degree.
  • the temperature at that time was measured as the temperature at which two layers were separated.
  • the data in the case where the temperature at which the two-layer separation is performed is 20 ° C. or higher is not obtained.
  • the oil which separates into two layers at 20 ° C. or more is unsuitable as an oil used for a compressor for refrigeration air conditioning.
  • the temperature at which the refrigerant and the refrigerator oil separate into two layers changes depending on the concentration.
  • the curve is convex upward, the total oil concentration is measured, and the maximum value of the separation curve becomes the low temperature critical solution temperature, which is an important temperature. Since the operating conditions of the compressor of the air conditioner, the outside air temperature at which the outdoor unit and the like are placed, and the concentrations of the refrigerant and the refrigerating machine oil also change variously in the refrigeration cycle, the two-layer separation temperature also changes accordingly. For this reason, with regard to two-phase separation at low temperatures, it is important to measure the two-phase separation temperature for all refrigerants and oil concentrations and to evaluate at the maximum value thereof.
  • the low temperature side critical solution temperature does not appear at a specific concentration. Therefore, measurement of the two-phase separation temperature at a specific concentration does not provide an appropriate evaluation guideline as an oil used in a compressor. For this reason, in the compatibility evaluation of the present example, a graph was created in which the concentration (oil concentration) of the oil mixed with the refrigerant was taken as the abscissa and the two-layer separation temperature was taken as the ordinate. This graph generally indicates the oil concentration dependency of the temperature of separation into two layers, and is an upwardly convex curve having a maximum value. This maximum value was defined as the low temperature side critical solution temperature.
  • the refrigerator oil used is as follows.
  • the viscosity at 40 ° C. is the kinematic viscosity of refrigerator oil at 40 ° C.
  • Hindered-type polyol ester oil H-POE (pentaerythritol-based pentanoic acid / 3,5,5-trimethylhexanoic acid mixed fatty acid ester oil): 40 ° C. viscosity 65.9 mm 2 / s
  • H-POE Hindered-type polyol ester oil
  • Hindered-type polyol ester oil H-POE (a mixed fatty acid ester oil of pentaerythritol type 2-methylhexanoic acid / 3,5,5-trimethylhexanoic acid): 40 ° C. viscosity 60.1 mm 2 / s
  • Hindered type polyol ester oil H-POE (mixed fatty acid ester oil of dipentaerythritol-based pentanoic acid / 2-methylbutanoic acid): 40 ° C.
  • H-POE Hindered type polyol ester oil
  • H-POE Hindered-type polyol ester oil
  • Hindered-type polyol ester oil H-POE (trimethylolpropane / pentaerythritol mixed 2-ethylhexanoic acid / 3,5,5-trimethylhexanoic acid mixed fatty acid ester oil): 40 ° C.
  • Hindered-type polyol ester oil H-POE (mixed fatty acid ester oil of 2-methylhexanoic acid / 2-ethylhexanoic acid of pentaerythritol type): viscosity at 40 ° C.
  • Hindered-type polyol ester oil H-POE (pentaerythritol / fatty acid ester oil of 2-ethylhexanoic acid based on neopentyl glycol): 40 ° C.
  • viscosity 14.9 mm 2 / s O
  • Hindered type polyol ester oil H-POE (fatty acid ester oil of 2-ethylhexanoic acid of neopentyl glycol type): viscosity at 40 ° C.
  • Polyvinyl ether oil (copolymer of alkoxy vinyl, copolymer ether oil wherein alkoxy group is ethyloxy group and isobutyloxy group): 40 ° C. viscosity 64.9 mm 2 / s
  • Polyvinyl ether oil (copolymer of alkoxyvinyl, copolymer ether oil wherein alkoxy group is ethyloxy group and isobutyloxy group): viscosity at 40 ° C. 50.1 mm 2 / s
  • Naphthenic mineral oil viscosity at 40 ° C.
  • H-POE Hindered-type polyol ester oil
  • the low temperature side critical solution temperature which is the degree of compatibility between the refrigerant HFC 32 and the refrigerator oil, largely differs depending on the type of the refrigerator oil. According to this table, refrigeration oil compatible with HFC 32 can be selected.
  • the low temperature side critical solution temperature is + 10 ° C. or less.
  • Comparative Examples 8 and 9 show the evaluation results of compatibility in different oil types, but are difficult to use because the low temperature side critical solution temperature is + 20 ° C. or higher.
  • thermochemical stability is a problem with hydrolyzability, particularly in the case of polyol ester oils.
  • the volume resistivity was measured as electrical insulation.
  • the lubricity was evaluated for wear resistance using a Falex tester. The evaluation method is shown below. ⁇ Hydrolyzability test> The test method of hydrolyzability is as follows.
  • a shield tube test was carried out by sealing a refrigerant (difluoromethane) and a refrigerator oil at 0.5 g / 3 ml in a glass ampoule tube having an outer diameter of 13 mm and an inner diameter of 8 mm.
  • the water content of the oil is adjusted to 1000 ppm, and the catalyst is made of copper, iron and aluminum wire polished with sandpaper, heated at 150 ° C. for 21 days, and the oil is 1/10 N KOH aqueous solution (isopropanol)
  • the total acid number was determined by titration with.
  • Volume resistivity> The volume resistivity measurement of refrigeration oil applies a DC voltage of 250 V to an electrode for 1 minute, and calculates
  • the measurement temperature is 20 ° C.
  • the volume resistivity ( ⁇ ) was calculated by the following equation.
  • the standard value as an electrical insulating oil is 1 ⁇ 10 13 ⁇ ⁇ cm or more.
  • ⁇ 3.6 ⁇ CoR R: Resistance value ( ⁇ )
  • Co Capacitance between electrodes without oil (pF) ⁇ Lubricity>
  • a Falex friction tester was used to evaluate the lubricity. The friction part of the tester is immersed in the oil cup, and the test piece is composed of two V blocks and a pin rotating between them. The rotational speed of the pin is 290 min -1 (slip speed 0.1 m / s). The test pieces were thoroughly washed with toluene and degreased.
  • the material of the pin is SAE3135 (NiCr steel), and the material of the V block is AISI 1137 (sulfur free-cutting steel).
  • the washed test piece was set at a predetermined position, and the wear amount after operating at a temperature of 80 ° C. and a load of 0.45 kN for 3 hours was measured. In addition, while heating up from room temperature to 80 degreeC, the smoothing operation was performed by 0.22 kN for about 10 minutes. The amount of wear here was determined by calculating the total wear depth of the pin and the V block from the scale change of the ratchet.
  • the evaluation results of Examples 15 to 17 and Comparative Examples 12 to 16 are shown in Table 2.
  • the discharge temperature in the compressor rises by about 5 to 15 ° C. because the adiabatic index is large.
  • the stability to heat is much more important than the refrigerator oil used in the air conditioner which adopted R410A refrigerant. It is a general finding that the higher the temperature is, the greater the deterioration to the organic matter. Therefore, the hydrolyzability of the polyol ester oil is also one of the evaluation methods, and there is a concern that the presence of a large amount of fatty acid of the decomposition product may cause clogging of the cycle or corrosion wear of the sliding portion of the compressor. Further, at high temperatures, the adsorption ability of the polyol ester oil itself is reduced, so that the oil effect is reduced, and therefore it is necessary to have excellent lubricity.
  • the compounds shown in Comparative Examples 12 to 14 are excellent in lubricity because they use linear fatty acids, but are inferior in hydrolysis resistance, and furthermore, the volume resistivity does not satisfy the standard value.
  • the comparative examples 15 and 16 using the refrigerator oil excellent in compatibility with the R410A refrigerant are sufficiently satisfactory in hydrolyzability, electrical insulation and lubricity.
  • R410A is used as a refrigerant as in Comparative Example 16
  • the compatibility is excellent, but in Comparative Example 15 where difluoromethane is used as a refrigerant, there is a problem in the compatibility as shown in Table 1.
  • Examples 15 to 17 which are polyol ester oils using branched chain fatty acids, satisfy the compatibility shown in Table 1, and are similarly satisfactory in hydrolyzability, electrical insulation and lubricity. It turned out that I could do it.
  • a polyol ester oil using linear fatty acid is preferably a polyol ester oil using a branched chain fatty acid because hydrolysis resistance and a decrease in volume resistivity are observed. That is, among the polyol ester oils represented by the chemical formulas (1), (2), (3) and (4), polyol ester oils in which R is a branched alkyl group are preferable. Furthermore, the wear amount of Examples 16 and 17 was smaller than that of Example 15, and excellent lubricity was obtained.
  • the compound of Examples 16 and 17 is a mixture of dipentaerythritol and pentaerythritol and contains dipentaerythritol having a large number of adsorption functional groups, and the adsorption ability is large on the metal sliding surface, which is oily. It is because the effect was easy to express and the outstanding lubricity was obtained. In particular, by mixing pentaerythritol with dipentaerythritol having a high adsorption capacity, more excellent thermochemical stability and electrical insulating properties are obtained.
  • dipentaerythritol in order to express the oiliness effect by the adsorption capacity of dipentaerythritol, it is preferable that dipentaerythritol is contained 40 mol% or more.
  • a polyol ester oil comprising a branched fatty acid which is composed of a mixture of dipentaerythritol and pentaerythritol and contains 40 mol% or more of dipentaerythritol is preferable.
  • FIG. 1 shows an outline of a room air conditioner which is also used for heating and cooling, which is used in this embodiment.
  • the room air conditioner 50 is composed of an indoor unit 51 and an outdoor unit 52.
  • the indoor unit 51 incorporates the indoor heat exchanger 5. Further, the outdoor unit 52 incorporates the compressor 1, the four-way valve 2, the outdoor heat exchanger 3 and the expansion means 4 (expansion portion).
  • the compressor 1 is provided with a refrigerant compression unit having a sliding unit.
  • the high-temperature, high-pressure refrigerant gas adiabatically compressed by the compressor 1 passes through the discharge pipe and the four-way valve 2 and is cooled by the outdoor heat exchanger 3 (used as a condensing unit).
  • High pressure liquid refrigerant This refrigerant is expanded by expansion means 4 (for example, a capillary tube, a thermal expansion valve, etc.) and becomes a low-temperature low-pressure liquid containing a slight amount of gas to reach the indoor heat exchanger 5 (used as an evaporation means). Then, heat is obtained from the air in the room, and in the state of a low temperature gas, it passes through the four-way valve 2 to the compressor 1 again. When the room is heated, the flow of the refrigerant is changed in the reverse direction by the four-way valve 2 to cause the reverse action.
  • expansion means 4 for example, a capillary tube, a thermal expansion valve, etc.
  • a scroll-type hermetic compressor was used as the compressor 1.
  • FIG. 2 shows a schematic structure of the above-described scroll-type hermetic compressor.
  • the compressor 100 includes a fixed scroll member 6 having a spiral wrap 8 provided vertically to the end plate 7, a orbiting scroll member 9 having a wrap 10 of substantially the same shape as the stationary scroll member 6, and a orbiting scroll. It includes a frame 14 for supporting the member 9, a crankshaft 11 for pivoting movement of the orbiting scroll member 9, an electric motor 17, and a pressure vessel 15 containing these.
  • the spiral wrap 8 and the wrap 10 face each other and mesh with each other to form a compression mechanism.
  • the orbiting scroll member 9 is positioned on the outermost side among the compression chambers 12 (12a, 12b, etc.) formed between the fixed scroll member 6 and the orbiting scroll member 9 when the orbiting motion is performed by the rotation of the crankshaft 11.
  • the compression chamber 12 moving toward the central portions of the fixed scroll member 6 and the orbiting scroll member 9 while gradually reducing the volume as the orbiting motion progresses.
  • the compression chamber 12 communicates with the discharge port 13, and the compressed gas inside the compression chamber 12 is discharged from the discharge pipe 16 to the outside of the compressor 100. Is discharged.
  • the crankshaft 11 is rotated at a constant speed or at a rotational speed corresponding to a voltage controlled by an inverter (not shown) to perform a compression operation.
  • an oil reservoir 20 is provided below the electric motor 17, and oil in the oil reservoir 20 passes through an oil hole 19 provided in the crankshaft 11 due to a pressure difference, and the orbiting scroll member 9 and The sliding portion with the crankshaft 11, the sliding bearing 18 and the like are lubricated.
  • the oil of the oil retaining portion 20 is always in contact with the refrigerant, and the refrigerant is in a dissolved state. The amount of refrigerant dissolved in the oil in the compressor and the oil viscosity at the time of refrigerant dissolution were measured using this room air conditioner.
  • the model was a 4.0 kW class machine. Since R410A and difluoromethane were different in capacity, tests were carried out so that the capacity was constant by changing the enclosed amount and rotation speed. The amount of the refrigerant charged was 1500 g of difluoromethane. In addition, 500 ml of refrigeration oil was enclosed. The operation with a refrigerant capacity adjusted to 2.0 kW was conducted as a representative test condition. In order to maintain the performance of the air conditioner and to ensure the long-term reliability of the compressor, it is necessary to control the amount of refrigerant dissolved in the oil in the compressor, and accordingly the oil viscosity at the time of refrigerant dissolution is important Parameters.
  • the amount of refrigerant dissolved in oil is 26 to 31 wt%, and the oil viscosity at the time of refrigerant dissolution is 3.0 to 5.0 mm 2 / s under the environment of a temperature of 53 ° C. and a pressure of 2.40 MPa under the above representative conditions. It becomes.
  • the oil viscosity at the time of refrigerant dissolution be 3.0 to 5.0 mm 2 / s even under the environment of a temperature of 60 ° C. and a pressure of 2.50 MPa under the above-mentioned typical conditions.
  • the amount of refrigerant dissolved in oil is 17 to 22% by weight.
  • Examples 18 to 21 and Comparative Examples 17 to 18 are shown in Table 3.
  • the amount of refrigerant dissolved in oil was about 20 wt%, and it could be confirmed that the oil viscosity at the time of appropriate refrigerant dissolution was maintained.
  • Comparative Example 17 since the solubility of difluoromethane and oil is too good, the kinematic viscosity is lowered.
  • Comparative Example 18 the solubility and the kinematic viscosity of difluoromethane and oil are in appropriate ranges, but as shown in Comparative Example 1, application is difficult because the low temperature side critical solution temperature is too high.
  • Example 22 to 27 and Comparative Examples 19 to 23 In Examples 22 to 27 and Comparative Examples 12 to 16, using the room air conditioner shown in FIG. 1, the indoor unit was installed in a constant temperature room (room temperature 35 ° C., humidity 75%) and an actual machine test was performed for 2160 hours of operation. .
  • Heat-resistant PET film (class B 130 ° C) was used to insulate the core of the motor from the coil, and polyesterimide and amidimide were used as the main insulation coating material for the coil, and double coating of polyesterimide-amideimide was applied. A double coated copper wire was used.
  • difluoromethane As a refrigerant, difluoromethane was used.
  • the advantage of difluoromethane is that the refrigeration air conditioning cycle of the current R410A can be used almost as it is.
  • the compatibility between the refrigerant and the refrigerator oil is an important characteristic for securing the oil return amount to the compressor, and it is necessary to circulate the refrigerator oil as well as the refrigerant. If the compatibility is poor, refrigeration oil discharged from the compressor by mechanical action does not circulate, and in particular, oil separated in the low temperature portion is retained, so the amount of oil in the compressor decreases and lubricating oil of the sliding portion Cause problems. For this reason, it is preferable that the refrigerant and the refrigerator oil be compatible with each other in the operating condition temperature range in the refrigeration air conditioning cycle. That is, the state in which the refrigerant and the refrigerator oil are dissolved is preferable.
  • refrigerating machine oils (A), (B), (F), (I), (T) and (V) of which the effects were examined among the examples 1 to 14 having compatibility with difluoromethane. Took up).
  • the compatibility with difluoromethane was evaluated as poor (K) and (P), and the compatibility with low kinematic viscosity (N) was evaluated.
  • comparative evaluation was also performed for (K) and (P) using the current refrigerant R410A.
  • the condition of the compressor considered to be suitable in this test is that the increase in clearance due to wear between the frame and the shaft after the test (sliding bearing clearance increase) is 10 ⁇ m or less, and the amount of residual oil in the compressor is secured. It is
  • Table 4 shows the results of Examples 22 to 27 and Comparative Examples 19 to 23.
  • the refrigeration air conditioners shown in Examples 22 to 27 having compatibility with difluoromethane can significantly reduce the amount of increase in the gap between the frame and the shaft, and the amount of residual refrigeration oil of the compressor can be reduced. Since it can be secured, high reliability can be obtained in the refrigeration air conditioning system.
  • the refrigeration air conditioner of the present invention can suppress the wear of the compressor and can sufficiently ensure long-term insulation reliability.
  • the present invention is applicable to a refrigeration air conditioning compressor and a refrigeration air conditioning apparatus.

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Abstract

La présente invention porte sur la réfrigération et la climatisation. La présente invention vise à améliorer la résistance à l'abrasion d'un compresseur de réfrigération et climatisation qui utilise le difluorométhane (HFC32) comme agent de refroidissement afin d'améliorer par ce moyen la fiabilité à long terme du compresseur et d'améliorer le rendement d'un cycle de réfrigération et climatisation d'un appareil de réfrigération et climatisation grâce à l'utilisation du compresseur. Un compresseur (100) est équipé d'une section de compression de l'agent de refroidissement ayant un élément coulissant et il a du difluorométhane qui joue le rôle d'agent de refroidissement et une huile de machine de réfrigération qui sont tous deux enfermés à l'intérieur, l'huile de machine de réfrigération à utiliser a une viscosité cinématique de 30-100 mm2/s à 40°C et une température de solution critique côté basse température entre l'agent de refroidissement et l'huile de machine de réfrigération est de +10°C ou moins.
PCT/JP2011/079058 2010-12-20 2011-12-15 Compresseur de réfrigération et climatisation, et appareil de réfrigération et climatisation WO2012086518A1 (fr)

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JPWO2012086518A1 (ja) 2014-05-22
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KR20130086248A (ko) 2013-07-31
JP5466772B2 (ja) 2014-04-09
CN103261689B (zh) 2016-05-25
CN105907376A (zh) 2016-08-31
KR101505344B1 (ko) 2015-03-23

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