EP2019276B1 - Dispositif de congélation - Google Patents

Dispositif de congélation Download PDF

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Publication number
EP2019276B1
EP2019276B1 EP07743278.9A EP07743278A EP2019276B1 EP 2019276 B1 EP2019276 B1 EP 2019276B1 EP 07743278 A EP07743278 A EP 07743278A EP 2019276 B1 EP2019276 B1 EP 2019276B1
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EP
European Patent Office
Prior art keywords
refrigerant
chamber
insulating
box body
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP07743278.9A
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German (de)
English (en)
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EP2019276A1 (fr
EP2019276A4 (fr
Inventor
Satoshi Okuda
Hidetoshi Shinya
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PHC Holdings Corp
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PHC Holdings Corp
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Publication of EP2019276A1 publication Critical patent/EP2019276A1/fr
Publication of EP2019276A4 publication Critical patent/EP2019276A4/fr
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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00General constructional features
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D19/00Arrangement or mounting of refrigeration units with respect to devices or objects to be refrigerated, e.g. infrared detectors
    • F25D19/02Arrangement or mounting of refrigeration units with respect to devices or objects to be refrigerated, e.g. infrared detectors plug-in type
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25BREFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B9/00Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • F25B9/006Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D19/00Arrangement or mounting of refrigeration units with respect to devices or objects to be refrigerated, e.g. infrared detectors
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00General constructional features
    • F25D23/06Walls
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00General constructional features
    • F25D23/06Walls
    • F25D23/065Details
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D29/00Arrangement or mounting of control or safety devices
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2201/00Insulation
    • F25D2201/10Insulation with respect to heat
    • F25D2201/14Insulation with respect to heat using subatmospheric pressure

Definitions

  • the present invention relates to a refrigeration apparatus which includes a refrigeration circuit constituted of a compressor, an evaporator and the like and in which a storage chamber constituted in an insulating box body is cooled to an extremely low temperature by the evaporator.
  • a main body in a refrigeration apparatus which maintains an extremely low in-chamber temperature, a main body has been constituted of an insulating box body constituted by filling a space where an inner box is combined with an outer box with a foam insulating material.
  • an extremely low temperature space at, for example, -80°C or less is formed by the refrigeration apparatus of, for example, a two-dimensional refrigeration system (see Japanese Patent Application Laid-Open No. 62-73046 ).
  • the refrigeration apparatus which keeps the inside of the storage chamber at an extremely low temperature of -80°C or less is constituted of the insulating box body having an opening in the upper surface thereof, and an insulating door which openably closes the upper surface opening, and a mechanical chamber provided with a cooling apparatus of the two-dimensional refrigeration system is arranged by the side of the insulating box body.
  • the insulating box body to decrease the leakage of cold from the inner box, an insulating material having a considerable thickness is interposed between the inner box and the outer box in consideration of a temperature difference between the outside and the inner box.
  • the refrigeration apparatus is used for the storage of a living tissue in a physical and chemical laboratory or the like, and the temperature at which a sample received in the storage chamber is actually stored is sometimes accurately measured, and recorded.
  • a temperature sensor for temperature control provided in the refrigeration apparatus, a temperature sensor for measuring the actual temperature in the storage chamber needs to be especially installed for the sample in the storage chamber or the like, and a measurement hole for introducing the temperature sensor is required.
  • FIG. 10 shows a perspective view of a conventional refrigeration apparatus 100.
  • the refrigeration apparatus 100 has an opening in the upper surface thereof, and is constituted of an insulating box body 101 in which a storage chamber is formed, and a mechanical chamber 102 formed laterally adjacent to this insulating box body 101, and the upper-surface opening of the insulating box body 101 is openably closed with an insulating door 103.
  • a measurement hole 105 is formed in a side surface 101A of this insulating box body 101 on a side opposite to a side on which the mechanical chamber 102 is formed.
  • the temperature sensor can be inserted into the storage chamber through this measurement hole 105, and a wiring line drawn from the temperature sensor is connected to an external recording apparatus main body via the measurement hole 105. Furthermore, a gap between this measurement hole 105 and the wiring line is closed with a plug 106 constituted of a sponge-like deformable special material. It is to be noted that in a state in which the temperature sensor is not attached, the measurement hole 105 is closed by the plug 106 in an insulating manner.
  • the refrigeration apparatus is often installed along a wall or another apparatus in the physical and chemical laboratory or the like. Therefore, when the measurement hole is formed in the back surface of the storage chamber, the temperature sensor for recording is not easily inserted or detached. In consequence, the measurement hole is often formed in the side surface of the insulating box body on the side opposite to the side provided with the mechanical chamber.
  • this refrigeration apparatus maintains the inside of the storage chamber at a predetermined extremely low temperature as described above, the insulating box body provided with the insulating material having a predetermined thickness needs to be used. Therefore, the whole dimension with respect to the volume in the storage chamber increases.
  • the refrigeration apparatus has to be installed with the predetermined dimension being left between the wall of the laboratory or the like or the other apparatus, and hence there is a problem that an area required for installing the refrigeration apparatus increases.
  • a refrigeration apparatus having the features recited in the preamble to claim 1 is known from Figure 10 .
  • the present invention has been developed to solve a conventional technical problem, and an object thereof is to provide a refrigeration apparatus in which a temperature in a storage chamber or the like can be measured using a measurement hole without influencing an installation environment.
  • a refrigeration apparatus is characterised by the features recited in the characterising portion of claim 1.
  • the insulating box body is formed of a composite constitution of vacuum insulating panels and a foam insulating material and the vacuum insulating panels are arranged in front and rear walls of the insulating box body and a side wall of the insulating box body on a side opposite to the mechanical chamber.
  • the mechanical chamber is provided with an openable/closable panel which covers the measurement hole.
  • a top panel of the mechanical chamber is configured to open or close and that the measurement hole is operable in a state in which the top panel is opened.
  • the apparatus of the invention enables a measuring instrument, as the temperature sensor for recording, to be inserted into the measurement hole from the side of the mechanical chamber, whereby the measuring instrument can easily be installed in the storage chamber.
  • the refrigeration apparatus is suitable for determining layout in a laboratory or the like.
  • FIG. 1 is a perspective view of a refrigeration apparatus 1 to which the present invention is applied
  • FIG. 2 is a front view of the refrigeration apparatus 1
  • FIG. 3 is a plan view of the refrigeration apparatus 1
  • FIG. 4 is a side view in a state in which a storage chamber 4 is seen through the refrigeration apparatus 1
  • FIG. 5 is a perspective view of the refrigeration apparatus 1 in a state in which a top panel 5 is opened.
  • the refrigeration apparatus 1 of the present embodiment is suitable for storing, at an extremely low temperature, for example, a living tissue, a specimen or the like to be stored at a low temperature for a long time, and a main body of the apparatus is constituted of an insulating box body 2 which opens in an upper surface, and a mechanical chamber 3 which is positioned by the side of the insulating box body 2 and in which a compressor 10 and the like are installed.
  • This insulating box body 2 is constituted of an outer box 6 made of a steel plate and an inner box 7 made of a satisfactorily thermally conductive metal such as aluminum, the boxes having opened upper surfaces.
  • the insulating box body is also constituted of a breaker 8 connecting the upper ends of both the boxes 6, 7 to each other, and an insulating material 9 with which a space surrounded by the outer box 6, the inner box 7 and the breaker 8 is filled by an on-site foam system and which is made of a polyurethane resin.
  • the inside of the inner box 7 is the storage chamber 4 having an open upper surface.
  • a targeted temperature (hereinafter referred to as the in-chamber temperature) in the storage chamber 4 is set to, for example, -150°C or less. Therefore, the insulating box body 2 which separates the inside of the storage chamber 4 and outside air needs to have large insulating capability against a set low in-chamber temperature around 0°C. Therefore, to secure the insulating capability only by the insulating material 9 made of the polyurethane resin, the material has to be formed to be remarkably thick. There is also a problem that a sufficient storage amount in the storage chamber 4 cannot be secured with a limited main body dimension.
  • vacuum insulating panels 12 made of glass wool are arranged in the inner wall surfaces of a front wall 6A of the outer box 6, a rear wall 6B and a side wall 6C positioned on a side opposite to a side provided with the mechanical chamber 3.
  • the panels are tentatively fixed with an adhesive double coated tape, and then a space between both the boxes 6 and 7 is filled with the insulating material 9 by the on-site foam system.
  • this vacuum insulating panel 12 glass wool having insulating properties is received in a container constituted of a multilayered film made of aluminum, a synthetic resin or the like which does not have any gas permeability. Afterward, air is discharged from the container by predetermined vacuum exhaust means, and an opening of the container is thermally sealed and joined. In consequence, since the vacuum insulating panel 12 has the insulating performance, the thickness dimension of the insulating material 9 is decreased as compared with a conventional example, but the same insulating effect can be obtained.
  • an evaporator (an evaporation pipe) 62 constituting a refrigerant circuit of a cooling apparatus R described later in detail is attached to the peripheral surface of the inner box 7 on the insulating material 9 side in a heat exchange manner.
  • the upper surface of the breaker 8 of the insulating box body 2 having the above constitution is formed in a staircase-like shape, and an insulating door 13 is provided on the surface via a packing (not shown) so that the insulating door is rotatable around one end, that is, the rear end of the door in the present embodiment by pivotable members 14, 14.
  • the upper-surface opening of the storage chamber 4 is provided with an openable/closable inner lid 15 constituted of an insulating material.
  • the lower surface of the insulating door 13 is provided with a pressing portion configured to protrude downwards.
  • the pressing portion of the insulating door 13 presses the inner lid 15 to openably close the upper-surface opening of the storage chamber 4.
  • the other end, that is, the front end of the insulating door 13 in the present embodiment is provided with a handle portion 16, and the handle portion 16 is operated to open or close the insulating door 13.
  • a front panel 3A, a rear panel (not shown) and a side panel 3B constituting a side surface on a side opposite to a side provided with the insulating box body 2 form the mechanical chamber 3.
  • the mechanical chamber 3 according to the present invention is provided with a partition plate 17 which divides the inside of the chamber into upper and lower chambers.
  • the compressor 10, a compressor 20 and the like constituting the cooling apparatus R as described above are received and installed under the partition plate 17, and the front panel 3A and the side panel 3B positioned under the partition plate 17 are provided with slits 3C for ventilation.
  • An upper mechanical chamber 18 having an opened upper surface is constituted above the partition plate 17.
  • the upper-surface opening of the upper mechanical chamber 18 is provided with the top panel 5 so that the panel is rotatable around one end, that is, the rear end of the panel in the present embodiment, whereby the upper mechanical chamber 18 is openably closed.
  • a panel positioned on the front surface of the upper mechanical chamber 18 is an operation panel 21 for operating the refrigeration apparatus 1.
  • a side surface constituting this upper mechanical chamber 18 on the insulating box body 2 side is provided with a measurement hole 19.
  • This measurement hole 19 is extended through the outer box 6, the insulating material 9 and the inner box 7 constituting the insulating box body 2 so as to communicate with the storage chamber 4 formed in the insulating box body 2 provided adjacent to the measurement hole.
  • a temperature sensor can be inserted into the storage chamber 4 from the outside, and a wiring line drawn from the temperature sensor is connected to an external recording apparatus main body through the measurement hole 19.
  • a gap between this measurement hole 19 and the wiring line is closed by a plug 19A constituted of a sponge-like deformable special material having insulating properties. It is to be noted that the measurement hole 19 is closed by the plug 19A in an insulating manner in a state in which the temperature sensor is not attached to the hole.
  • the top panel 5 provided in the mechanical chamber 3 is opened, and the measuring instrument can be inserted into the storage chamber 4 through the measurement hole 19 formed in the side surface of the insulating box body 2 positioned in the upper mechanical chamber 18. This can facilitate an operation of installing the measuring instrument in the storage chamber 4 cooled to a predetermined extremely low temperature.
  • the measurement hole 19 according to the present invention is formed in the side surface of the insulating box body 2 on the mechanical chamber 18 side. Therefore, even when the refrigeration apparatus 1 is installed adjacent to the wall of an installation environment such as the laboratory, or another device, a space necessary for using the measurement hole 19 does not especially have to be disposed. In consequence, an area required for installing the refrigeration apparatus 1 can be decreased, which is suitable for determining the layout of the laboratory or the like.
  • the vacuum insulating panels 12 can be provided in the side surface other than the side surface adjacent to the mechanical chamber 3, that is, the front and rear walls and the side surface of the insulating box body 2 constituted so as to face the outside without influencing the forming position of the measurement hole 19.
  • the wall surface of the insulating box body 2 provided with the measurement hole 19 is provided with an insulating structure 70 in which a cascade heat exchanger 43, an intermediate heat exchanger 48 and the like are integrally formed of the insulating material as described later in detail. Therefore, even when the vacuum insulating panel 12 is not provided, the inside of the storage chamber 4 can effectively be insulated by the insulating structure 70.
  • the insulating performance of the insulating box body 2 itself can be improved, and the dimension of an insulating wall can be decreased.
  • a storage volume in the storage chamber 4 can be increased.
  • the outer dimension can be decreased. Even in this case, the area required for installing the refrigeration apparatus 1 can be decreased.
  • the measurement hole 19 according to the present invention is covered with the top panel 5 which can openably close the upper-surface opening of the upper mechanical chamber 18, whereby the appearance of the apparatus has a constitution in which the measurement hole 19 is not exposed, and the appearance can be improved. Moreover, when the top panel 5 is opened, an operation can easily be performed with respect to the measurement hole 19, and operability can be improved. When the partition plate 17 is removed, another device constituting the cooling apparatus R installed under the partition plate 17 can easily be operated, and the efficiency of a maintenance operation can be improved.
  • the mechanical chamber 18 is closed with the top panel 5 in a case other than the case where the operation is performed with respect to the measurement hole 19, so that the top panel 5 can be used as a side table for an operation, and the panel is convenient for an operation of storing articles such as samples in the storage chamber 4 or taking the articles from the chamber.
  • the measurement hole 19 is covered with the top panel 5 which closes the upper-surface opening of the upper mechanical chamber 18, but this is not restrictive, and a lid member for covering the measurement hole 19 or the like may be provided in the vicinity of the measurement hole 19.
  • the refrigerant circuit of the refrigeration apparatus 1 in the present embodiment is constituted of a two-dimensional two-stage refrigerant circuit, as a multi-dimensional multistage refrigerant circuit, including independent refrigerant circuits of a high-temperature-side refrigerant circuit 25 as a first refrigerant circuit and a low-temperature-side refrigerant circuit 38 as a second refrigerant circuit.
  • the compressor 10 constituting the high-temperature-side refrigerant circuit 25 is an electromotive compressor using a one-phase or three-phase alternating-current power source, and a discharge side pipe 10D of the compressor 10 is connected to an auxiliary condenser 26.
  • this auxiliary condenser 26 is connected to a refrigerant pipe 27 (hereinafter referred to as a frame pipe) arranged on the back side of this opening edge.
  • this frame pipe 27 is connected to an oil cooler 29 of the compressor 10, and then connected to a condenser 28.
  • the refrigerant pipe exiting from the condenser 28 is connected to an oil cooler 30 of the compressor 20 constituting the low-temperature-side refrigerant circuit 38, and is then connected to a condenser 31.
  • the refrigerant pipe exiting from the condenser 31 is connected to an evaporator 34 as an evaporator portion constituting the evaporator successively via a drier 32 and a capillary tube 33 as a pressure reducing unit.
  • An outlet side refrigerant pipe of the evaporator 34 is connected to an accumulator 35 as a refrigerant liquid reservoir, and the refrigerant pipe exiting from the accumulator 35 is connected to a suction side pipe 10S of the compressor 10.
  • the auxiliary condenser 26 and the condensers 28 and 31 in the present embodiment are constituted as an integral condenser, and are cooled by a blower 36 for the condenser.
  • the high-temperature-side refrigerant circuit 25 is filled with a refrigerant constituted of R407D and n-pentane as non-azeotropic refrigerants having different boiling points.
  • R407D is constituted of R32 (difluoromethane: CH 2 F 2 ), R125 (pentafluoroethane: CHF 2 CF 3 ), and R134a (1,1,1,2-tetrafluoroethane: CH 2 FCF 3 ), and a composition includes 15 wt% of R32, 15 wt% of R125 and 70 wt% of R134a.
  • R32 has -51.8°C
  • R125 has -48.57°C
  • R134a has -26.16°C.
  • the boiling point of n-pentane is +36.1°C.
  • the high-temperature gas refrigerant discharged from the compressor 10 is condensed, releases heat and is liquefied by the auxiliary condenser 26, the frame pipe 27, the oil cooler 29, the condenser 28, the oil cooler 30 of the compressor 20 of the low-temperature-side refrigerant circuit 38 and the condenser 31. Afterward, a water content contained in the refrigerant is removed by the drier 32, and the pressure of the refrigerant is reduced by the capillary tube 33. The refrigerants successively flow into the evaporator 34 to evaporate the refrigerants R32, R125 and R134a. Then, vaporization heat is absorbed from a surrounding area to cool the evaporator 34, and the refrigerant returns to the compressor 10 through the accumulator 35 as the refrigerant liquid reservoir.
  • the compressor 10 has a capability of, for example, 1.5 HP, and the final reaching temperature of the evaporator 34 which is being operated is in a range of -27°C to -35°C.
  • the refrigerant does not evaporate in the evaporator 34 and still has a liquid state. Therefore, the refrigerant hardly contributes to cooling, but the refrigerant has a function of feeding the lubricant of the compressor 10 and a mixed water content which cannot completely be absorbed by the drier 32 back to the compressor 10 in a state in which the same is dissolved in the refrigerant.
  • the refrigerant also has a function of lowering the temperature of the compressor 10 by the evaporation of the liquid refrigerant in the compressor 10.
  • the compressor 20 of the low-temperature-side refrigerant circuit 38 is an electromotive compressor using a one-phase or three-phase alternating-current power source in the same manner as in the compressor 10, and a discharge side pipe 20D of the compressor 20 is connected to an oil separator 40 via a radiator 39 constituted of a wire condenser.
  • This oil separator 40 is connected to an oil return tube 41 which returns to the compressor 20.
  • a refrigerant pipe connected to the outlet side of the oil separator 40 is connected to a condensing pipe 42 as a high-pressure-side pipe inserted into the evaporator 34.
  • This condensing pipe 42 constitutes the cascade heat exchanger 43 together with the evaporator 34.
  • a discharge pipe connected to the outlet side of the condensing pipe 42 is connected to a first gas-liquid separator 46 via a drier 44.
  • a gas-phase refrigerant separated by the gas-liquid separator 46 passes through the first intermediate heat exchanger 48 via a gas-phase pipe 47 to flow into a second gas-liquid separator 49.
  • a liquid-phase refrigerant separated by the first gas-liquid separator 46 flows into the first intermediate heat exchanger 48 through a liquid-phase pipe 50, a drier 51 and a capillary tube 52 as a pressure reducing unit to evaporate the gas-phase refrigerant and cool the chamber.
  • the liquid-phase refrigerant separated by the second gas-liquid separator 54 flows into a second intermediate heat exchanger 56 through a liquid-phase pipe 53, a drier 54 and a capillary tube 55 as a pressure reducing unit.
  • the gas-phase refrigerant separated by the second gas-liquid separator 49 is cooled and liquefied while passing through a gas-phase pipe 57, the second intermediate heat exchanger 56 and third and fourth intermediate heat exchangers 58, 59, and the refrigerant flows into a capillary tube 61 as a pressure reducing unit through a pipe 68 and a drier 60.
  • the capillary tube 61 is connected to an evaporation pipe 62 as an evaporator, and the evaporation pipe 62 is connected to the fourth intermediate heat exchanger 59 via a return pipe 69.
  • the fourth intermediate heat exchanger 59 is successively connected to the third, second and first intermediate heat exchangers 58, 56 and 48, and then connected to a suction side pipe 20S of the compressor 20.
  • the suction side pipe 20S is further connected to expansion tanks 65 which store the refrigerant during the stop of the compressor 20 via a capillary tube 66 as a pressure reducing unit.
  • the capillary tube 66 is connected in parallel with a check valve 67 in an expansion tank 65 direction as a forward direction.
  • a non-azeotropic mixed refrigerant including R245fa, R600, R404A, R508, R14, R50 and R740 is introduced as a mixed refrigerant of seven types of refrigerants having different boiling points.
  • R245fa is 1,1,1,-3,3-pentafluoropropane (CF 3 CH 2 CHF 2 ), and R600 is butane (CH 3 CH 2 CH 2 CH 3 ).
  • R245fa has a boiling point of +15.3°C
  • R600 has a boiling point of -0.5°C. Therefore, when these refrigerants are mixed at a predetermined ratio, the mixed refrigerant can be used as a substitute for heretofore used R21 having a boiling point of +8.9°C.
  • R600 is a combustible substance.
  • the refrigerant is introduced as an incombustible refrigerant in the refrigerant circuit 38.
  • R245fa is set to 70 wt% with respect to a total weight of R245fa and R600. Above this value, the refrigerant becomes incombustible. Therefore, the weight percentage may be set to this value or more.
  • R404A is constituted of R125 (pentafluoroethane: CHF 2 CF 3 ), R143a (1,1,1-trifluoroethane: CH 3 CF 3 ) and R134a (1,1,1,2-tetrafluoroethane: CH 2 FCF 3 ), and a composition includes 44 wt% of R125, 52 wt% of R143a and 4 wt% of R134a.
  • the mixed refrigerant has a boiling point of -46.48°C. Therefore, the refrigerant can be used as a substitute for heretofore used R22 having a boiling point of -40.8°C.
  • R508 is constituted of R23 (trifluoromethane: CHF 3 ) and R116 (hexafluoroethane: CF 3 CF 3 ), and a composition includes 39 wt% of R23 and 61 wt% of R116.
  • the mixed refrigerant has a boiling point of -88.64°C.
  • R14 is tetrafluoromethane (carbon tetrafluoride: CF 4 ), R50 is methane (CH 4 ) and R740 is argon (Ar).
  • R14 has a boiling point of -127.9°C
  • R50 has -161.5°C
  • R740 has -185.86°C. It is to be noted that R50 might cause explosion when coupled with oxygen, but when R50 is mixed with R14, the danger of the explosion is eliminated. Therefore, even if a mixed refrigerant leakage accident occurs, any explosion is not generated.
  • R245fa and R600, and R14 and R50 are beforehand mixed once in an incombustible state.
  • the mixed refrigerant of R245fa and R600, R404A, R508A, the mixed refrigerant of R14 and R50, and R740 are beforehand mixed, and introduced into the refrigerant circuit.
  • R245fa and R600, R404A, R5080A, R14 and R50, and R740 are introduced in this order from the refrigerant having the highest boiling point.
  • composition of the refrigerants includes, for example, 10.3 wt% of the mixed refrigerant of R245fa and R600, 28 wt% of R404A, 29.2 wt% of R508A, 26.4 wt% of the mixed refrigerant of R14 and R50 and 5.1 wt% of R740.
  • n-pentane in a range of 0.5 to 2 wt% with respect to the total weight of the non-azeotropic refrigerants
  • R404A 4 wt% of n-pentane (in a range of 0.5 to 2 wt% with respect to the total weight of the non-azeotropic refrigerants) may be added to R404A.
  • the high-temperature high-pressure gas mixed refrigerant discharged from the compressor 20 flows into the radiator 39 via the discharge side pipe 20D, and radiates heat in the radiator. Then, a part of n-pentane or R600 as an oil carrier refrigerant having a high boiling point and a satisfactory oil solubility in the mixed refrigerant is condensed and liquefied.
  • the mixed refrigerant discharged from the radiator 39 flows into the oil separator 40, and a large part of lubricating oil of the compressor 20 mixed with the refrigerant and a part (a part of n-pentane or R600) of the refrigerant condensed and liquefied in the radiator 39 are fed back to the compressor 20 via the oil return tube 41.
  • the refrigerant having higher purity and lower boiling point flows into the refrigerant circuit 38 after the cascade heat exchanger 43, and the extremely low temperature can efficiently be obtained. Therefore, even the compressors 10 and 20 having the same capability can cool the inside of the storage chamber 4 as a cooling target having a larger volume to a predetermined extremely low temperature, and the storage capacity can be increased without enlarging the whole refrigeration apparatus 1.
  • the refrigerant fed into the oil separator 40 is once cooled in the radiator 39, and hence the temperature of the refrigerant flowing into the cascade heat exchanger 43 can be lowered.
  • the temperature of the refrigerant fed into the cascade heat exchanger 43 has heretofore been about +65°C, but the temperature can be lowered to about +45°C in the present embodiment.
  • a load to be applied to the compressor of the high-temperature-side refrigerant circuit 25 for cooling the refrigerant in the low-temperature-side refrigerant circuit 35 can be decreased.
  • the load to be applied to the compressor 20 constituting the low-temperature-side refrigerant circuit 35 can be decreased. In consequence, the operation efficiency of the whole refrigeration apparatus 1 can be improved.
  • Another mixed refrigerant itself is cooled to about -40°C to -30°C by the evaporator 34 in the cascade heat exchanger 43 to condense and liquefy a part of the refrigerants (a part of R245fa, R600, R404A and R508) having the high boiling point in the mixed refrigerant. Then, the mixed refrigerant discharged from the condensing pipe 42 of the cascade heat exchanger 43 flows into the first gas-liquid separator 46 through the drier 44.
  • R14, R50 and R740 in the mixed refrigerant have a remarkably low boiling point, the refrigerants are not condensed yet, and have a gas state, and an only part of R245fa, R600, R404A and R508 is condensed and liquefied. Therefore, R14, R50 and R740 are separated to the gas-phase pipe 47, and R245fa, R600, R404A and R508 are separated to the liquid-phase pipe 50.
  • the refrigerant mixture which has flowed into the gas-phase pipe 47 performs heat exchange between the mixture and the first intermediate heat exchanger 48, is condensed, and then reaches the second gas-liquid separator 49.
  • the low-temperature refrigerant returning from the evaporation pipe 62 flows into the first intermediate heat exchanger 48.
  • the liquid refrigerant which has flowed into the liquid-phase pipe 50 flows through the drier 51 to reach the capillary tube 52 where the pressure of the refrigerant is reduced. Afterward, the refrigerant flows into the first intermediate heat exchanger 48 to evaporate in the exchanger, thereby contributing to the cooling.
  • the first intermediate heat exchanger 48 has an intermediate temperature of about -60°C. Therefore, R508 in the mixed refrigerant which has passed through the gas-phase pipe 47 is completely condensed and liquefied, and branched to the second gas-liquid separator 49.
  • R14, R50 and R740 have a lower boiling point, and hence still have a gas state.
  • the drier 54 removes the water content from R508 branched by the second gas-liquid separator 49, and the pressure of the refrigerant is reduced by the capillary tube 55. Afterward, the refrigerant flows into the second intermediate heat exchanger 56, R14, R50 and R740 in the gas-phase pipe 57 are cooled together with the low-temperature refrigerant returning from the evaporation pipe 62, and R14 having the highest evaporation temperature among these refrigerants is condensed. In consequence, the second intermediate heat exchanger 56 has an intermediate temperature of about -90°C.
  • the gas-phase pipe 57 passing through this second intermediate heat exchanger 56 subsequently passes through the third intermediate heat exchanger 58 and the fourth intermediate heat exchanger 59.
  • the refrigerant immediately discharged from the evaporation pipe 62 is fed back to the fourth intermediate heat exchanger 59.
  • the fourth intermediate heat exchanger 59 reaches a considerably low intermediate temperature of about -130°C.
  • the refrigerants still having a gas phase state are successively condensed in the intermediate heat exchangers 48, 56, 58 and 59 by use of an evaporation temperature difference between the refrigerants in the low-temperature-side refrigerant circuit 38, and an extremely low temperature of -150°C or less can be achieved in the evaporation pipe 42 as a final stage. Therefore, the evaporation pipe 62 is wound along the insulating material 9 side of the inner box 6 in a heat exchange manner, so that an in-chamber temperature of -152°C or less can be realized in the storage chamber 4 of the refrigeration apparatus 1.
  • the refrigerant discharged from the evaporation pipe 62 successively flows into the fourth intermediate heat exchanger 59, the third intermediate heat exchanger 58, the second intermediate heat exchanger 56 and the first intermediate heat exchanger 48, and the refrigerant joins the refrigerants evaporated in the respective heat exchangers, and returns to the compressor 20 via the suction side pipe 20S.
  • a large part of the oil mixed with the refrigerant and discharged from the compressor 20 is separated by the oil separator 40 and returned to the compressor 20.
  • the mist-like oil discharged from the oil separator 40 together with the refrigerant is returned to the compressor 20 in a state in which the oil is dissolved in R600 having high oil solubility. In consequence, the lubricating defect of the compressor 20, or locking can be prevented.
  • R600 returns to the compressor 20 while maintaining the liquid state, and is evaporated in this compressor 20, so that the discharge temperature of the compressor 20 can be lowered.
  • the compressor 20 constituting the low-temperature-side refrigerant circuit 38 having the above constitution is subjected to ON-OFF control by a controller (not shown) based on the in-chamber temperature of the storage chamber 4.
  • a controller not shown
  • the mixed refrigerant in the low-temperature-side refrigerant circuit 38 is collected in the expansion tank 65 via the check valve 67 having the expansion tank 65 direction as the forward direction.
  • the refrigerant in the refrigerant circuit 38 can remarkably quickly be collected in the expansion tank 65 via the check valve 67.
  • the rise of the pressure in the refrigerant circuit 38 can be prevented.
  • the compressor 20 is started by the controller, the refrigerant is gradually returned from the expansion tank 65 to the refrigerant circuit 38 via the capillary tube 66, and the starting load of the compressor 20 can be decreased.
  • the evaporation pipe 62 of the low-temperature-side refrigerant circuit 38 has an extremely low temperature in a range of -160.3°C to -157.3°C, and even the cascade heat exchanger 43 has a low temperature in a range of about -40°C to -30°C.
  • the first intermediate heat exchanger 48 has an extremely low temperature of about -60°C
  • the second intermediate heat exchanger 56 has about -90°C
  • the third and fourth intermediate heat exchangers 58, 59 have about -130°C. Therefore, even the heat exchanger 43 and the like excluding the evaporation pipe 62 arranged in the insulating box body 2 need to be sufficiently insulated.
  • FIG. 7 shows a perspective view of the insulating structure 70
  • FIG. 8 shows a perspective view in a state in which an insulating material of the insulating structure 70 has been removed.
  • the insulating structure 70 is, in addition to the above heat exchangers, the accumulator 35 and the capillary tube 33 constituting the high-temperature-side refrigerant circuit 25, and the drier 44, the gas-liquid separators 46, 49, the driers 51, 54 and the capillary tubes 52, 55 constituting the low-temperature-side refrigerant circuit 38 constitute the insulating structure 70.
  • the cascade heat exchanger 43 is arranged on one end of the insulating structure 70, and the intermediate heat exchangers 48, 56, 58 and 59 are positioned by the side of this cascade heat exchanger 43 and arranged in layers.
  • Each of the intermediate heat exchangers 48, 56, 58 and 59 has a spiral double pipe structure in which an outer pipe having a comparatively large diameter is spirally wound as much as a plurality of stages, the resultant flat pipes are superimposed on one another, and each of the gas-phase pipes 47, 57 passes as an inner pipe on the inner side from the outer pipe with a space being left between the pipes.
  • the exchanges are arranged in order from the exchanger having the lowest temperature, that is, the fourth and third intermediate heat exchangers 58, 59 are arranged in the lowermost layer, the second intermediate heat exchanger 56 is arranged on the exchangers, and the first intermediate heat exchanger 48 is arranged in the uppermost layer.
  • the gas-liquid separators 46, 49 (it is to be noted that the second gas-liquid separator 49 is not shown in FIG. 8 ), the driers 44, 51 and 54 (not shown in FIG. 8 ), the capillary tubes 33, 52 and 55 (not shown) and the accumulator 35 are arranged, a dead space is decreased, and dimensions are decreased.
  • pipes connecting devices arranged in the insulating structure 70 to those arranged outside the insulating structure 70 are arranged so as to face a one-end side surface on a side opposite to a side provided with the cascade heat exchanger 34.
  • the suction side pipes 10S, 20S and the discharge side pipe 20D through which the refrigerant having a comparatively high temperature circulates are bundled and externally arranged toward the mechanical chamber 3 in a state in which the insulating structure 70 is attached to the insulating box body 2 in the present embodiment.
  • the pipe 68 and the return pipe 69 which are connected to the evaporation pipe 62 and through which the extremely low temperature refrigerant circulates are converged and externally arranged toward the insulating box body 2 on a side opposite to the suction side pipe 10S and the like in the state in which the insulating structure 70 is attached to the insulating box body 2 in the present embodiment.
  • the drier 60 and the capillary tube 61 connected to the pipe 68 are arranged outside the insulating structure 70.
  • FIG. 9 shows a back perspective view of the refrigeration apparatus 1.
  • the side wall of the insulating box body 2 positioned on the mechanical chamber 3 side is provided with a rectangular opening 71 extending in a front-to-rear direction and opening rearwards, and the rear part of the side wall on the mechanical chamber 3 side is provided with a cutout 72 corresponding to the opening 71.
  • the insulating structure 70 is inserted into this opening 71 from the backside of the insulating box body 2. At this time, the insulating structure 70 is inserted into the opening 71 from the side provided with the cascade heat exchanger 34.
  • the pipes 10S, 20S, 20D, 68 and 69 arranged so as to extend on one side of the insulating structure 70, and the pipe 10D connected to the capillary tube 33 of the high-temperature-side refrigerant circuit 25 are opposed to the surface in a direction in which the insulating structure 70 is inserted or removed, that is, the back surface of the insulating box body 2 in the present embodiment.
  • the insulating structure 70 is finally inserted into the opening 71.
  • the pipes 68, 69 are connected to the evaporation pipe 62 provided on the insulating box body 2 side, and the pipes 10S, 10D, 20S and 20D are connected to the pipes of the devices on the mechanical chamber 3 side.
  • the devices constituting the insulating structure 70 can easily be connected to the evaporation pipe 62 arranged in the insulating box body 2 and the pipes of devices such as the compressors 10, 20 arranged in the mechanical chamber 3 from the back surface of the insulating box body 2, and piping operation efficiency and assembling operation efficiency can be improved.
  • the insulating structure 70 is drawn in a direction different from a direction in which the insulating box body 2 and the mechanical chamber 3 are constituted, and a maintenance operation can easily be performed.
  • a part of the back surface from which the pipes of the insulating structure 70 extend and the side surface opposed to the mechanical chamber 3 side is closed by a cover member 73 bent so as to form a substantially L-shaped section.
  • an insulating plate (not shown) filled with glass wool may be arranged in a gap formed between the insulating structure 70 and the side surface on the mechanical chamber 3 side.
  • the cascade heat exchanger 43 and the intermediate heat exchangers 48, 56, 58 and 59 are arranged on the side wall of the insulating box body 2 on the mechanical chamber 3 side in a state in which the insulating structure 70 is integrally formed of the insulating material. Therefore, as compared with a case where the insulating structure 70 is installed in the back surface portion of the insulating box body 2 as in the conventional example, the depth dimension of the whole refrigeration apparatus 1 can be decreased.
  • the depth dimension of the whole apparatus 1 increases owing to the presence of a protruding part constituted of the insulating structure 70 for surrounding the cascade heat exchanger 43 and the like.
  • the whole depth dimension can be suppressed to about 765 mm.
  • a disadvantage that the refrigeration apparatus is stuck in a usual carrying entrance in general, about 800 mm
  • the insulating structure 70 can be carried inwards and outwards through the usual carrying entrance in a state in which the structure is attached to the apparatus 1. Therefore, in the installation place, the insulating structure 70 does not have to be disconnected from or connected to the main body, and a laborious operation can be avoided.
  • the refrigeration apparatus 1 can easily be carried inwards or outwards.
  • the insulating structure 70 for surrounding the cascade heat exchanger 43 and the like does not protrude externally from the back surface, and hence the area required for installation can be decreased.
  • the back surface of the insulating box body 2 is not provided with the cascade heat exchanger or the insulating structure for surrounding the periphery of each intermediate heat exchanger. Therefore, as described above, the vacuum insulating panels 12 can be arranged in the front wall 6A and the rear wall 6B of the insulating box body 2 configured to face the outside and the side wall 6C opposite to the mechanical chamber side. Even at an extremely low temperature of, for example, -150°C or less in the storage chamber 4, the insulating performance of the insulating box body 2 itself can be improved. Therefore, even when the dimension can be decreased and the outer dimension is similar to that in the conventional example, the storage volume in the storage chamber 4 can be increased. Alternatively, even with the storage volume similar to that in the conventional example, the outer dimension can be decreased. Even in this case, the area required for installing the refrigeration apparatus 1 can be decreased.
  • the insulating structure 70 can be inserted into or detached from the side wall of the insulating box body 2 from the backside, that is, the back surface of the refrigeration apparatus 1, but this is not restrictive, and the insulating structure may be inserted or detached from the front of the insulating box body 2 or the upside of the insulating box body.
  • the cascade heat exchanger 43, the intermediate heat exchanger 48 and the like integrated as the insulating structure 70 can easily be incorporated in the apparatus 1 main body, and the assembling operation efficiency can be improved.
  • the insulating structure 70 can be drawn to the front or the upside to remove the structure from the apparatus 1 main body, and the maintenance operation of the cascade heat exchanger 43, the intermediate heat exchanger 48 and the like constituting the insulating structure 70 can easily be performed.
  • the cascade heat exchanger 43, the intermediate heat exchanger 48 and the like constituting the refrigeration apparatus 1 are integrally constituted.
  • the only cascade heat exchanger 43, or the only intermediate heat exchanger 48 and the like may integrally be constituted as the insulating structure 70, and may detachably be arranged on the side wall of the insulating box body 2 as in the present embodiment.
  • the refrigeration apparatus 1 of a two-dimensional multistage system has been described.
  • the refrigerant circuit constituting the refrigeration apparatus 1 is constituted of the high-temperature-side refrigerant circuit 25 and the low-temperature-side refrigerant circuit 38 constituting independent refrigerant closed circuits so that the refrigerant discharged from the compressor 10 or 20 is condensed and then evaporated to exert a cooling function.
  • the low-temperature-side refrigerant circuit 38 has the compressor 20, the condensing pipe 42, the evaporation pipe 62, a plurality of, specifically four intermediate heat exchangers 48, 56, 58 and 59 connected in series so that the refrigerant fed back from the evaporation pipe 62 circulates, and a plurality of, specifically three capillary tubes 42, 55 and 61.
  • a plurality of types of non-azeotropic mixed refrigerants are introduced, and the condensed refrigerant in the refrigerants fed through the condensing pipe 42 joins each intermediate heat exchanger via each capillary tube.
  • the non-condensed refrigerant in the refrigerants is cooled by the intermediate heat exchanger to successively condense the refrigerant having a lower boiling point.
  • the refrigerant having the lowest boiling point is allowed to flow into the evaporation pipe 62 through the final-stage capillary tube 61.
  • the evaporator 34 of the high-temperature-side refrigerant circuit 25 and the condensing pipe 42 of the low-temperature-side refrigerant circuit 38 constitute the cascade heat exchanger 43, and the extremely low temperature is obtained in the evaporation pipe 42 of the low-temperature-side refrigerant circuit 38.
  • the present invention is not limited to this apparatus.
  • the cascade heat exchanger 43 may be constituted in the insulating structure 70 as in the present embodiment, and the insulating structure 70 may detachably be inserted into the side surface of the insulating box body 2 on the mechanical chamber 3 side, so that a similar effect can be obtained.
  • the respective intermediate heat exchangers may be constituted in the insulating structure 70 as in the present embodiment, and the insulating

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Devices That Are Associated With Refrigeration Equipment (AREA)
  • Refrigerator Housings (AREA)

Claims (2)

  1. Appareil réfrigérant qui comporte un circuit réfrigérant, un corps de boîtier isolant (2) ayant des parois latérales, un compartiment de stockage (4) ayant une surface supérieure ouverte, dans lequel la surface supérieure ouverte du compartiment de stockage (4) est munie d'un couvercle ouvrable/fermable constitué d'un matériau isolant, un compartiment mécanique (3) qui est constitué sur une desdites parois latérales du corps de boîtier isolant (2), dans lequel le compartiment supérieur (18) du compartiment mécanique (3) comprend une surface supérieure ouverte et un panneau supérieur (5) pour fermer de manière ouvrable la surface supérieure ouverte du compartiment mécanique (3), et un trou de mesure (19) est formé dans la paroi latérale du corps de boîtier isolant (2) sur le côté du compartiment mécanique afin de communiquer avec l'intérieur du compartiment de stockage (4), un bouchon (19A) constitué d'un matériau ayant des propriétés isolantes étant reçu dans ledit trou de mesure (19), et dans lequel le trou de mesure (19) est formé dans ladite paroi latérale du corps de boîtier isolant (2) sur laquelle le compartiment mécanique (3) est constitué de telle façon que ledit trou de mesure (19) débouche dans ledit compartiment supérieur (18) du compartiment mécanique (3) de sorte que, lorsque l'appareil réfrigérant est opérationnel pour refroidir le compartiment de stockage (4) et qu'un instrument de mesure ou d'enregistrement de la température du compartiment de stockage (4) doit être utilisé, le panneau supérieur (5) du compartiment mécanique (3) est ouvert et l'instrument de mesure de la température dans le compartiment de stockage (4) est introduit dans le compartiment de stockage (4) à travers le trou de mesure (19) depuis le côté du compartiment mécanique (3), caractérisé en ce que le circuit réfrigérant est constitué d'un compresseur, d'un évaporateur et similaires, dans lequel le compartiment de stockage (4) est refroidi par l'évaporateur, en ce que le bouchon (19A) est constitué d'un matériau spongieux déformable, et en ce que le compartiment mécanique (3) a une plaque de séparation (17) qui divise le compartiment mécanique (3) en un compartiment supérieur (18) et un compartiment inférieur dans lequel le compresseur et similaires sont installés.
  2. Appareil de réfrigération selon la revendication 1, dans lequel le corps de boîtier isolant (2) est formé d'une constitution composite de panneaux isolants sous vide (12) et d'un matériau isolant alvéolaire (9), et les panneaux isolants sous vide (12) sont disposés dans des parois avant et arrière du corps de boîtier isolant (2) et dans une paroi latérale du corps de boîtier isolant (2) sur un côté opposé au compartiment mécanique (3).
EP07743278.9A 2006-05-15 2007-05-14 Dispositif de congélation Active EP2019276B1 (fr)

Applications Claiming Priority (2)

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JP2006135252A JP2007303791A (ja) 2006-05-15 2006-05-15 冷凍装置
PCT/JP2007/059843 WO2007132802A1 (fr) 2006-05-15 2007-05-14 Mécanisme de congélation

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EP (1) EP2019276B1 (fr)
JP (1) JP2007303791A (fr)
KR (1) KR20090008343A (fr)
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WO (1) WO2007132802A1 (fr)

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JP5906225B2 (ja) * 2013-09-30 2016-04-20 エスペック株式会社 環境試験装置
KR102168586B1 (ko) 2013-11-29 2020-10-22 삼성전자주식회사 냉장고
WO2017033680A1 (fr) * 2015-08-26 2017-03-02 パナソニックヘルスケアホールディングス株式会社 Congélateur pour températures ultrabasses
US10126039B2 (en) 2015-12-29 2018-11-13 Whirlpool Corporation Refrigeration appliance having side air intake vent with sound dampening
EP3428559B1 (fr) * 2016-03-11 2019-12-25 PHC Holdings Corporation Congélateur pour températures ultrabasses
US11125474B2 (en) * 2016-05-26 2021-09-21 Mohammad Sharaz Ahmad Self-ice making / self heating hybrid food and beverage storage chest
KR102588870B1 (ko) * 2016-06-24 2023-10-13 엘지전자 주식회사 초저온 냉장고
JP6994419B2 (ja) * 2018-03-29 2022-01-14 東京エレクトロン株式会社 冷却システム
JP7311483B2 (ja) * 2019-03-04 2023-07-19 東芝ライフスタイル株式会社 冷蔵庫
CN110305631A (zh) * 2019-07-03 2019-10-08 上海沛芾航天科技发展有限公司 一种用于环境试验箱的混合工质制冷剂

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CN101443613B (zh) 2011-09-14
WO2007132802A1 (fr) 2007-11-22
EP2019276A4 (fr) 2013-12-25
JP2007303791A (ja) 2007-11-22
US20090249823A1 (en) 2009-10-08
KR20090008343A (ko) 2009-01-21
CN101443613A (zh) 2009-05-27

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