WO2018110454A1 - 熱搬送装置及びそれを用いた熱搬送方法 - Google Patents

熱搬送装置及びそれを用いた熱搬送方法 Download PDF

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Publication number
WO2018110454A1
WO2018110454A1 PCT/JP2017/044207 JP2017044207W WO2018110454A1 WO 2018110454 A1 WO2018110454 A1 WO 2018110454A1 JP 2017044207 W JP2017044207 W JP 2017044207W WO 2018110454 A1 WO2018110454 A1 WO 2018110454A1
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Prior art keywords
heat transfer
refrigerant
transfer device
circulation path
oxygen
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Ceased
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PCT/JP2017/044207
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English (en)
French (fr)
Japanese (ja)
Inventor
土屋　立美
浩平 木場
田中　勝
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to AU2017378601A priority Critical patent/AU2017378601B2/en
Priority to US16/468,040 priority patent/US11377578B2/en
Priority to EP17882212.8A priority patent/EP3557158A4/en
Priority to CA3046290A priority patent/CA3046290C/en
Priority to CN201780077022.XA priority patent/CN110073153A/zh
Publication of WO2018110454A1 publication Critical patent/WO2018110454A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
    • F25B43/003—Filters
    • 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
    • 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
    • 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
    • F25B13/00—Compression machines, plants or systems, with reversible cycle

Definitions

  • the present invention relates to a heat transfer device and a heat transfer method using the same.
  • Hydrofluorocarbons “HFC” such as HFC-125 and HFC-32 are widely used as important substitutes to replace chlorofluorocarbon “CFC”, hydrochlorofluorocarbon “HCFC”, etc., which are known to destroy the ozone layer.
  • R-410A which is a mixture of HFC-32 and HFC-125
  • R-404A which is a mixture of HFC-125, HFC-134a and HFC-143a, etc. are known. ing.
  • the above alternative substances are used in various applications such as a heat medium, a refrigerant, a foaming agent, a solvent, a cleaning agent, a propellant, a fire extinguishing agent, and the consumption is large.
  • a heat medium such as a heat medium, a refrigerant, a foaming agent, a solvent, a cleaning agent, a propellant, a fire extinguishing agent, and the consumption is large.
  • GWP global warming potential
  • Hydrohaloolefin is a general term for unsaturated hydrocarbons including hydrogen and halogen (fluorine, chlorine, etc.), and includes, for example, substances represented by the following chemical formula.
  • halogen fluorine, chlorine, etc.
  • the number in parentheses after the chemical formula indicates a refrigerant number widely used in the refrigerant field (including geometric isomers).
  • fluoropropene is a promising substance as a low GWP refrigerant and a heat medium candidate, but it may be gradually decomposed over time and cannot be said to be a
  • the amount of refrigeration oil used for 100 parts by weight of the refrigerant is used.
  • a so-called oil-free device in which the amount is limited to 5 parts by weight or less has also been developed. According to this, the cost and maintenance load related to the replacement of the refrigerating machine oil can be reduced, and the release of the refrigerant dissolved in the refrigerating machine oil to the atmosphere can be avoided.
  • the hydrohaloolefin may be gradually decomposed when air (oxygen) is mixed into the refrigerant.
  • the present invention is a heat transfer device in which a refrigerant containing a hydrohaloolefin is sealed in a circulation path, and can suppress the influence of oxygen mixed in the circulation path, and a heat transfer method using the heat transfer apparatus The purpose is to provide.
  • the present inventors have found that the above object can be achieved by a heat transfer device including an oxygen adsorber in a specific region in the refrigerant circulation path. It came to complete.
  • the present invention relates to the following heat transfer device and a heat transfer method using the same.
  • a heat transfer device in which a refrigerant containing at least one selected from the group consisting of hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO) and hydrochloroolefin (HCO) is enclosed in a circulation path, An oxygen adsorber is provided between the evaporator and the compressor present in the circulation path, A heat transfer device.
  • HFO hydrofluoroolefin
  • HCFO hydrochlorofluoroolefin
  • HCO hydrochloroolefin
  • a heat transfer device in which a refrigerant containing at least one selected from the group consisting of hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO) and hydrochloroolefin (HCO) is enclosed in a circulation path,
  • the apparatus includes an oxygen adsorber in a region of a pressure of 1.0 MPa or less in the circulation path.
  • a heat transfer device. 3. Item 3. The heat transfer device according to Item 1 or 2, wherein the oxygen adsorber contains at least one of a metal oxide oxygen adsorbent and an organic (sugar) oxygen adsorbent. 4).
  • Item 4 The heat transfer device according to any one of Items 1 to 3, wherein the oxygen content in the circulation path is 0.1% by volume or less.
  • the heat transfer device and the heat transfer method using the heat transfer device of the present invention use a heat transfer device having an oxygen adsorber in a specific region in the refrigerant circulation path, thereby removing oxygen mixed in the circulation path with the oxygen adsorber. Therefore, the influence of oxygen on the refrigerant can be suppressed.
  • FIG. 1 shows an air conditioning apparatus
  • FIG. 2 shows a turbo refrigerator
  • the heat transfer device of the present invention is particularly a hydrofluoroolefin (hereinafter also referred to as “HFO”), hydrochlorofluoroolefin (hereinafter also referred to as “HCFO”), and hydrochloroolefin (
  • HFO hydrofluoroolefin
  • HCFO hydrochlorofluoroolefin
  • HCO hydrochloroolefin
  • Embodiment 1 A heat transfer device in which a refrigerant containing at least one selected from the group consisting of hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO) and hydrochloroolefin (HCO) is sealed in a circulation path There, An oxygen adsorber is provided between the evaporator and the compressor present in the circulation path, A heat transfer device.
  • HFO hydrofluoroolefin
  • HCFO hydrochlorofluoroolefin
  • HCO hydrochloroolefin
  • Embodiment 2 A heat transfer device in which a refrigerant containing at least one selected from the group consisting of hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO) and hydrochloroolefin (HCO) is sealed in a circulation path There,
  • the apparatus includes an oxygen adsorber in a region of a pressure of 1.0 MPa or less in the circulation path.
  • a heat transfer device is a refrigerant containing at least one selected from the group consisting of hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO) and hydrochloroolefin (HCO) is sealed in a circulation path There,
  • the apparatus includes an oxygen adsorber in a region of a pressure of 1.0 MPa or less in the circulation path.
  • the heat transfer device of the first embodiment is a heat transfer device in which a refrigerant containing at least one selected from the group consisting of HFO, HCFO, and HCO is sealed in a circulation path, An oxygen adsorber is provided between the evaporator and the compressor present in the circulation path, It is characterized by that.
  • the refrigerant may contain at least one selected from the group consisting of HFO, HCFO and HCO.
  • HFO include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3 , 3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3-tetrafluoropropene (HFO-1234ye), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 1, 2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 3,3,3-trifluoropropene (HFO-1243zf) 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 1,1,1,2, , 4,5,5,5-nonafluorobutyl pentene (HFO-1429myz), and the like.
  • HCFO examples include 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 1-chloro-3,3 , 3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 1 , 2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 1,2,3-trichloro-3,3-difluoropropene (HCFO-1222xd), 2,3,3-trichloro-3 -Fluoropropene (HCFO-1231xf) and the like.
  • HCO examples include 1,3,3,3-tetrachloropropene (HCO-1230zd), 1,1,2,3-tetrachloropropene (HCO-1230xa), 1,1,3,3-tetrachloro.
  • HCO-1230za propene
  • HCO-1230xf 2,3,3,3-tetrachloropropene
  • HFO, HCFO and HCO can be used alone or in admixture of two or more.
  • HFO, HCFC, and HCO other refrigerants can be mixed.
  • the total amount of HFO, HCFO, and HCO in the refrigerant mixture can be set to 50% by weight or more. preferable.
  • refrigerants include, for example, HFC-32, HFC-41, HFC-125, HFC-134, HFC-143, HFC-152, HFC-227, HFC-236, HFC245, HFC-338, HFC-347, HFC-356, HFC-365, HFC-449, HFC-43-10, HFE-125, HFE-134, HFE-143, HFE-152, HFE-236, HFE-245, HFE-254, HFE-338, HFE-347, HFE-356, HFE-365, HFE-449, and the like.
  • those having isomers include isomers.
  • hydrocarbons having 1 to 5 carbon atoms (including those having an isomer are also included), CO 2 and the like can be mentioned.
  • These other refrigerants may include one kind or two or more kinds.
  • Examples of the mixture of at least one selected from the group consisting of HFO, HCFO, and HCO and other refrigerants include R-444A, R-444B, R-445A, R-446A, R-447A, R-448A, R-449A, R-449B, -450A, -451a, R-451B, R-451A, R-454A, R-454B, R-455A, R-513A, R-513B and the like.
  • the refrigerant (or refrigerant mixture) enclosed in the circulation path may be composed of at least one selected from the group consisting of HFO, HCFO, and HCO.
  • a refrigerant containing at least one of the above HFO, HCFO and HCO (hereinafter also abbreviated as “refrigerant” in the case of a refrigerant mixture) is enclosed in a refrigerant circulation path in the apparatus, Heat transfer is performed by passing through each device arranged in the path.
  • the use of the heat transfer device of the present invention is not limited.
  • an air conditioner mobile air conditioner, home air conditioner, commercial air conditioner
  • refrigerator refrigerator, cooler (chiller), container refrigerator, hot water supply Equipment related to heat transfer such as a vessel
  • container refrigerator hot water supply Equipment related to heat transfer such as a vessel
  • an air conditioner see FIG. 1
  • turbo refrigerator see FIG. 2
  • FIG. 1 is a diagram showing an embodiment of a refrigerant circulation path in a heat transfer device (in the following description, an air conditioner) of the present invention.
  • the air conditioner 1 mainly includes a compressor 2, a four-way switching valve 3, an outdoor heat exchanger 4, an expansion mechanism 5, and an indoor heat exchanger 6.
  • a solid line arrow represents the refrigerant circulation direction during the cooling operation
  • a dotted line arrow represents the refrigerant circulation direction during the heating operation.
  • the circulation direction of the refrigerant can be controlled by selecting the refrigerant discharged from the compressor 2 in either the outdoor heat exchanger 4 or the indoor heat exchanger 6 by operating the four-way switching valve 3.
  • the refrigeration cycle of the air conditioner 1 during the cooling operation will be described.
  • the compressor 2 compresses the low-pressure gas refrigerant and discharges the high-pressure gas refrigerant.
  • the refrigerant discharged from the compressor 2 passes through the four-way switching valve 3 and is supplied to the outdoor heat exchanger 4.
  • the outdoor heat exchanger 4 condenses the high-pressure gas refrigerant and discharges the high-pressure liquid refrigerant.
  • the refrigerant discharged from the outdoor heat exchanger 4 passes through the expansion valve of the expansion mechanism 5, becomes a low-pressure gas-liquid mixed refrigerant, and is supplied to the indoor heat exchanger 6.
  • the indoor heat exchanger 6 evaporates the low-pressure gas-liquid mixed refrigerant and discharges the low-pressure gas refrigerant.
  • the low-pressure gas refrigerant discharged from the indoor heat exchanger 6 is supplied to the compressor 2. With this refrigeration cycle, the room can be cooled.
  • the outdoor heat exchanger 4 functions as a condenser
  • the indoor heat exchanger 6 functions as an evaporator. That is, the room is cooled by the latent heat of vaporization of the refrigerant generated in the indoor heat exchanger 6.
  • the outdoor heat exchanger 4 functions as an evaporator
  • the indoor heat exchanger 6 functions as a condenser by switching the four-way switching valve 3. That is, the room is heated by the latent heat of condensation of the refrigerant generated in the outdoor heat exchanger 4.
  • FIG. 2 is a diagram showing an embodiment of a refrigerant circulation path in the heat transfer device (in the following description, a turbo refrigerator) of the present invention.
  • the turbo refrigerator 1 ′ is mainly composed of a compressor 2 ′, a condenser 4 ′, an expansion mechanism 5 ′, and an evaporator 6 ′.
  • the solid line arrows indicate the circulation direction of the refrigerant.
  • the compressor 2 ' compresses the low-pressure gas refrigerant and discharges the high-pressure gas refrigerant.
  • the refrigerant discharged from the compressor 2 ' is supplied to the condenser 4'.
  • the condenser 4 ′ condenses the high-pressure gas refrigerant and discharges the high-pressure liquid refrigerant.
  • the refrigerant discharged from the condenser 4 'passes through the expansion valve of the expansion mechanism 5' becomes a low-pressure gas-liquid mixed refrigerant, and is supplied to the evaporator 6 '.
  • the evaporator 6 ' evaporates the low-pressure gas-liquid mixed refrigerant and discharges the low-pressure gas refrigerant.
  • the low-pressure gas refrigerant discharged from the evaporator 6 ' is supplied to the compressor 2'.
  • cold air made from cold water obtained by the function of the evaporator 6 ' is used for cooling a large-scale space.
  • the heat transfer device of the present invention includes an oxygen adsorber between the evaporator and the compressor that exist in the refrigerant circulation path.
  • the outdoor heat exchanger 4 functions as a condenser
  • the indoor heat exchanger 6 functions as an evaporator. Therefore, an oxygen adsorber 7 is provided between the evaporator 6 and the compressor 2.
  • the outdoor heat exchanger 4 functions as an evaporator and the indoor heat exchanger 6 functions as a condenser. Therefore, an oxygen adsorber 8 is provided between the evaporator 4 and the compressor 2. .
  • the heat transfer device of the present invention adsorbs oxygen in the oxygen adsorber by providing valves (not shown) before and after the oxygen adsorber and making the oxygen adsorber detachable from the circulation path. It is possible to easily remove or replace the oxygen adsorbent.
  • the “valve” only needs to be provided so as to be able to control the flow of refrigerant into and out of the oxygen adsorber in the circulation path, and may be manual or electric. For example, a manual or electric valve is also included.
  • the oxygen adsorber is filled with an oxygen adsorbent, and is selectively adsorbed (absorbed) and removed from the gas refrigerant when oxygen passes through the oxygen adsorber together with the gas refrigerant.
  • an oxygen adsorbent may be any material that can selectively adsorb oxygen, and examples thereof include metal oxide-based oxygen adsorbents and organic (sugar-based) oxygen adsorbents. These oxygen adsorbents can be used alone or in combination of two or more, but metal oxide-based oxygen adsorbents are preferred from the viewpoint of a high oxygen adsorption rate.
  • the shape of the oxygen adsorbing material only needs to be able to permeate the gas refrigerant, and examples thereof include powders and pellets. Moreover, it can also be used in the form of a film or filter in which an oxygen adsorbent is adhered or impregnated.
  • the oxygen content in the circulation path can be preferably maintained at 0.1% by volume or less, thereby at least one of HFO, HCFO and HCO. It is possible to suppress the decomposition over time due to oxygen in the refrigerant containing.
  • the metal oxide-based oxygen adsorbent is an adsorbent that adsorbs oxygen by an oxidation reaction (exotherm).
  • an oxidation reaction for example, metal (Fe and / or Ce) oxidation
  • a physical oxygen adsorbent can be preferably used.
  • this metal oxide-based oxygen adsorbent conventionally known materials can be widely used.
  • the organic (sugar-based) oxygen adsorbent is an adsorbent that removes oxygen from the gas refrigerant by an oxidation reaction (CO 2 release).
  • This organic (sugar) oxygen adsorbent conventionally known materials can be widely used.
  • the oxygen adsorber used in the present invention may be a dedicated member filled with the oxygen adsorbent, and also serves as a dryer (so-called dryer) installed in a refrigerant circulation path in a known heat transfer device.
  • An oxygen adsorber may be used. In this case, by filling the dryer with the oxygen adsorbent together with the desiccant, it can be used as a member for simultaneously removing moisture and oxygen mixed in the gas refrigerant.
  • the heat transfer device of the present invention employs a magnetic bearing, a ceramic bearing, or an air bearing as a bearing that supports a rotating shaft of a motor that drives a compression unit that compresses a refrigerant in a compressor, thereby refrigerating machine oil with respect to 100 parts by weight of the refrigerant. It may be a so-called oil-free heat transfer device in which the amount used is limited to 5 parts by weight or less.
  • oil such as grease
  • 5 parts by weight or less is preferable.
  • the heat transfer device of the second embodiment is a heat transfer device in which a refrigerant containing at least one of hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), and hydrochloroolefin (HCO) is sealed in a circulation path.
  • the apparatus includes an oxygen adsorber in a region of a pressure of 1.0 MPa or less in the circulation path. It is characterized by that.
  • the heat transfer device of the second embodiment is not particularly limited except that an oxygen adsorber is provided in a low pressure region having a pressure of 1.0 MPa or less in the refrigerant circulation path, and the other configuration is the same as that of the heat transfer device of the first embodiment. be able to.
  • the low-pressure region with a pressure of 1.0 MPa or less has a higher risk of sucking outside air than other regions (regions with a pressure exceeding 1.0 MPa), and oxygen may easily enter the circulation route. Therefore, by providing an oxygen adsorber in such a low pressure region, there is an advantage that the influence due to oxygen mixing can be efficiently avoided.
  • the maximum pressure in the entire refrigerant circuit is not limited, it is usually about 3.0 MPa.
  • the heat transfer device includes an oxygen adsorber in the refrigerant circulation path, and the place of the oxygen adsorber is not limited as long as it is in a low pressure region having a pressure of 1.0 MPa or less, but the refrigerant and oxygen exist in a gas state As in the case of the heat transfer device of the first embodiment, oxygen can be efficiently adsorbed between the evaporator and the compressor and in a low pressure region having a pressure of 1.0 MPa or less. A mode provided with an adsorber is preferred.
  • the oxygen content in the circulation path can be preferably maintained at 0.1% by volume or less, thereby at least one of HFO, HCFO, and HCO. It is possible to suppress the decomposition over time due to oxygen in the refrigerant containing.
  • the heat transfer method of the present invention can be implemented by circulating the refrigerant in the refrigerant circulation path in the heat transfer device of the present invention. Specifically, the circulation of the refrigerant is as described above with reference to an example of the air conditioner (see FIG. 1) and the turbo refrigerator (see FIG. 2).
  • Heat transfer device in Fig. 1, air conditioner
  • Compressor Four-way switching valve Outdoor heat exchanger (condenser during cooling operation, evaporator during heating operation) 5). Expansion mechanism6. Indoor heat exchanger (evaporator during cooling operation, condenser during heating operation) 7). Oxygen adsorber (during cooling operation) 8). Oxygen absorber (during heating operation) 1 '. Heat transfer device (turbo refrigerator in Fig. 2) 2 '. Compressor 4 '. Condenser 5 '. Expansion mechanism 6 '. Evaporator 7 '. Oxygen adsorber

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PCT/JP2017/044207 2016-12-13 2017-12-08 熱搬送装置及びそれを用いた熱搬送方法 Ceased WO2018110454A1 (ja)

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Application Number Priority Date Filing Date Title
AU2017378601A AU2017378601B2 (en) 2016-12-13 2017-12-08 Heat transfer device and heat transfer method using same
US16/468,040 US11377578B2 (en) 2016-12-13 2017-12-08 Heat transfer device and heat transfer method using same
EP17882212.8A EP3557158A4 (en) 2016-12-13 2017-12-08 HEAT TRANSFER DEVICE AND HEAT TRANSFER METHOD USING IT
CA3046290A CA3046290C (en) 2016-12-13 2017-12-08 Heat transfer device and heat transfer method using same
CN201780077022.XA CN110073153A (zh) 2016-12-13 2017-12-08 热传送装置和使用其的热传送方法

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JP2016241257 2016-12-13
JP2016-241257 2016-12-13

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CN110440487A (zh) * 2019-07-29 2019-11-12 黄石东贝电器股份有限公司 一种去除制冷系统中残余空气的方法
US20230272255A1 (en) * 2020-11-10 2023-08-31 Daikin Industries, Ltd. Refrigerant-containing composition, use thereof, refrigerator having said composition, and operating method for refrigerator

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CN112154175B (zh) 2018-05-18 2023-01-17 国立大学法人大阪大学 表面处理聚合物的制造方法、聚合物、金属镀覆聚合物及粘接层叠体、以及它们的制造方法
JP7155804B2 (ja) * 2018-09-21 2022-10-19 株式会社富士通ゼネラル 圧縮機及び冷凍サイクル装置
WO2020223196A1 (en) * 2019-04-29 2020-11-05 The Chemours Company Fc, Llc Refrigerant blends in flooded systems

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