Patent Grant
9863677
The present disclosure relates to a sublimation defrost system and sublimation defrost method in which frost attached to a heat exchanger pipe disposed in a cooling device is removed through sublimation without melting the frost, the system and the method applied to a refrigeration apparatus in which a CO2 refrigerant is permitted to circulate in the cooling device disposed in a freezer for cooling inside the freezer.
To prevent the ozone layer depletion, global warming, and the like, natural refrigerants such as NH3 or CO2 have been reviewed as a refrigerant in a refrigeration apparatus used for room air conditioning and refrigerating food products. Thus, refrigeration apparatuses using NH3, with high cooling performance and toxicity, as a primary refrigerant and using CO2, with no toxicity or smell, as a secondary refrigerant have been widely used.
In the refrigeration apparatus, a primary refrigerant circuit and a secondary refrigerant circuit are connected to each other through a cascade condenser. Heat exchange between the NH3 refrigerant and the CO2 refrigerant takes place in the cascade condenser. The CO2 refrigerant cooled and liquefied with the NH3 refrigerant is sent to a cooling device disposed in the freezer, and cools air in the freezer through a heat transmitting pipe disposed in the cooling device. The CO2 refrigerant partially vaporized therein returns to the cascade condenser through the secondary refrigerant circuit, to be cooled and liquefied again in the cascade condenser.
Frost attaches to a heat exchanger pipe disposed in the cooling device while the refrigeration apparatus is under operation, and thus the heat transmission efficiency degrades. Thus, the operation of the refrigeration apparatus needs to be periodically stopped, to perform defrosting.
Conventional defrost methods for the heat exchanger pipe disposed in the cooling device include a method of spraying water onto the heat exchanger pipe, a method of heating the heat exchanger pipe with an electric heater, and the like. The defrosting by spraying water ends up producing a new source of frost, and the heating by the electric heater is against an attempt to save power because valuable power is wasted. In particular, the defrosting by spraying water requires a tank with a large capacity and water supply and discharge pipes with a large diameter, and thus increases plant construction cost.
Patent Documents 1 and 2 disclose a defrost system for the refrigeration apparatus described above. A defrost system disclosed in Patent Document 1 is provided with a heat exchanger part unit which vaporizes the CO2 refrigerant with heat produced in the NH3 refrigerant, and achieves the defrosting by permitting CO2 hot gas generated in the heat exchanger part unit to circulate in the heat exchanger pipe in the cooling device.
A defrost system disclosed in Patent Document 2 is provided with a heat exchanger part unit which heats the CO2 refrigerant with cooling water that has absorbed exhaust heat from the NH3 refrigerant, and achieves the defrosting by permitting the heated CO2 refrigerant to circulate in the heat exchanger pipe in the cooling device.
Patent Document 3 discloses a method of providing a heating tube in the cooling device separately and independently from a cooling tube, and melts and removes the frost attached to the cooling tube by permitting warm water or warm brine to flow in the heating tube at the time of a defrosting operation.
One ideal defrost method involves sublimation defrosting. In this method, a surface of the heat exchanger pipe is uniformly heated at a temperature not higher than 0° C., that is, without turning the frost into water, so that the frost is removed from the surface of the heat exchanger pipe through sublimation. This method involves no drainage, and thus requires no drain pan or discharge facility, and thus can largely reduce a facility cost.
The applicants have proposed a method of first cooling the freezer inner air to a temperature at or below 0° C., and removing frost attached to the heat exchanger pipe of the cooling device, in a low water vapor atmosphere achieved by dehumidification, by an adsorption dehumidifier device through sublimation (Patent Document 4).
Each of the defrost systems disclosed in Patent Documents 1 and 2 requires the pipes for the CO2 refrigerant and the NH3 refrigerant in a system different from the cooling system to be constructed at the installation site, and thus might increase the plant construction cost. The heat exchanger part unit is separately installed outside the freezer, and thus an extra space for installing the heat exchanger part unit is required.
In the defrost system in Patent Document 2, a pressurizing/depressurizing adjustment unit is required to prevent thermal shock (sudden heating/cooling) in the heat exchanger pipe. To prevent the heat exchanger part unit, where the cooling water and the CO2 refrigerant exchange heat, from freezing, an operation of discharging the cooling water in the heat exchanger part unit needs to be performed after the defrosting operation is terminated. Thus, there is a problem in that, for example, an operation is complicated.
The defrost unit disclosed in Patent Document 3 has a problem in that the heat transmission efficiency is low because the cooling tube is heated from the outside with plate fins and the like.
Furthermore, in a cascade refrigerating device including: a primary refrigerant circuit in which the NH3 refrigerant circulates and a refrigerating cycle component is provided; and a secondary refrigerant circuit in which the CO2 refrigerant circulates and a refrigerating cycle component is disposed, the secondary refrigerant circuit being connected to the primary refrigerant circuit through a cascade condenser, the secondary refrigerant circuit contains CO2 gas with high temperature and high pressure. Thus, the defrosting can be achieved by permitting the CO2 hot gas to circulate in the heat exchanger pipe in the cooling device. However, the cascade refrigerating device has the following problems. Specifically, the device is complicated and involves high cost because selector valves, branch pipes, and the like are provided. Furthermore, a control system is unstable due to high/low temperature heat balance.
In the sublimation defrosting described above, the frost on the surface of the heat exchanger pipe needs to be uniformly heated at a temperature not higher than 0° C. However, it is difficult to uniformly heat the heat exchanger pipe at a temperature not higher than 0° C. with a general heating method employed in the defrost method disclosed in Patent Document 4. Thus, the sublimation defrosting has not been put into practice.
The present invention is made in view of the problem described above, and an object of the present invention is to achieve reduction of initial and running costs required for a refrigeration apparatus and power saving, by implementing the sublimation defrost method described above.
A defrost system according to at least one embodiment of the present invention is:
(1) A sublimation defrost system for a refrigeration apparatus including: a cooling device which is disposed in a freezer, and includes a casing and a heat exchanger pipe disposed in the casing; a refrigerating device for cooling and liquefying a CO2 refrigerant; and a refrigerant circuit which is connected to the heat exchanger pipe and which is configured to permit the CO2 refrigerant cooled and liquefied in the refrigerating device to circulate to the heat exchanger pipe, the defrost system including:
a dehumidifier device for dehumidifying freezer inner air in the freezer;
a CO2 circulation path which is formed of a circulation path forming path connected to an inlet path and an outlet path of the heat exchanger pipe, and includes the heat exchanger pipe;
an on-off valve disposed in each of the inlet path and the outlet path of the heat exchanger pipe and configured to be closed at a time of defrosting so that the CO2 circulation path becomes a closed circuit;
a circulating unit for CO2 refrigerant, the circulating unit being disposed in the CO2 circulation path;
a first heat exchanger part configured to cause heat exchange between a brine as a first heating medium and the CO2 refrigerant circulating in the CO2 circulation path; and
a pressure adjusting unit which adjusts a pressure of the CO2 refrigerant circulating in the closed circuit at the time of defrosting so that a condensing temperature of the CO2 refrigerant becomes equal to or lower than a freezing point of a water vapor in the freezer inner air in the freezer, in which
the defrosting is able to be achieved without a drain receiving unit.
In the configuration (1), when the defrosting is performed, when the freezer inner air in the freezer has saturated water vapor pressure, the freezer inner air is first dehumidified by the dehumidifier device, so that the water vapor partial pressure is reduced. Then, the on-off valve is closed so that the CO2 circulation path becomes the closed circuit.
Then, the pressure adjusting unit adjusts the pressure of the CO2 refrigerant circulating in the closed circuit so that the condensing temperature of the CO2 refrigerant becomes equal to or lower than a freezing point of the water vapor in the freezer inner air in the freezer. Then, the CO2 refrigerant is permitted to circulate in the closed circuit by the circulating unit.
For example, the circulating unit is a liquid pump disposed in the CO2 circulation path for permitting a liquid CO2 refrigerant to circulate in the closed circuit, and the like. For example, the pressure adjusting unit includes a pressure sensor which detects the pressure of the CO2 refrigerant or a unit which detects the temperature of the CO2 refrigerant and obtains the pressure of the CO2 refrigerant based on the saturated pressure of the CO2 refrigerant corresponding to the temperature detection value.
Then, a warm brine as a heating medium heats the CO2 refrigerant circulating in the closed circuit in the first heat exchanger part, whereby the CO2 refrigerant is vaporized. Then, the vaporized CO2 refrigerant is circulated in the closed circuit. Thus, the frost attached to the outer surface of the heat exchanger pipe is removed through sublimation by the heat of the CO2 refrigerant gas. The CO2 refrigerant that has imparted heat to the frost is liquefied, and then is heated and vaporized again in the first heat exchanger part.
The “freezer” includes a refrigerator and anything that forms other cooling spaces. The inlet path and the outlet path of the heat exchanger pipe are areas of the heat exchanger pipe disposed in the freezer. The areas extend from a range around a partition wall of the casing of the cooling device to the outer side of the casing.
The conditions required for the sublimation of the frost attached to the outer surface of the heat exchanger pipe are (1) the water vapor partial pressure of the freezer inner air is not as high as saturated water vapor pressure, and (2) the temperature of the frost is equal to or lower than the freezing point. As a preferable but not required condition, (3) sublimated water vapor is dissipated by forming airflow on the outer surface of the heat exchanger part. The frost can be sublimated by heating the frost under these conditions.
In the configuration (1), the frost attached to the outer surface of the heat exchanger pipe is heated with the heat of the CO2 refrigerant flowing in the heat exchanger pipe. Thus, the entire area of the heat exchanger pipe can be uniformly heated. The pressure in the closed circuit is adjusted, so that the condensing temperature of the CO2 refrigerant is controlled. Thus, the temperature of the CO2 refrigerant gas flowing in the can be accurately controlled. Thus, the frost can be accurately heated to a temperature at or below the freezing point, whereby the sublimation defrosting can be achieved.
The frost attached to the heat exchanger pipe is not melted but is sublimated, and thus a drain pan and a facility for discharging the drainage accumulated in the drain pan are not required, whereby the cost of the refrigeration apparatus can be largely reduced. The frost attached to the heat exchanger pipe is heated from the inside through a pipe wall of the heat exchanger pipe only. Thus, the heat exchange efficiency can be improved and power saving can be achieved.
The defrosting can be achieved with the CO2 refrigerant in a low pressure state corresponding to the condensing temperature equal to or lower than the freezing point of the water vapor in the freezer. Thus, a pipe system device such as the CO2 circulation path needs not to be pressure resistant, whereby a high cost is not required.
In some embodiments, in the configuration (1),
(2) the circulation path forming path is a defrost circuit branched from the inlet path and the outlet path of the heat exchanger pipe, and
the heat exchanger part is formed in the defrost circuit.
In the configuration (2), the defrost circuit is provided, whereby a portion where the first heat exchanger part is installed can be more freely determined.
In some embodiments, in the configuration (1),
(3) the circulation path forming path is a bypass path disposed between the inlet path and the outlet path of the heat exchanger pipe, and
The first heat exchanger part is formed in a partial area of the heat exchanger pipe.
In the configuration (3), the CO2 circulation path is formed of the heat exchanger pipe only, except for the bypass path. Thus, there is no need to additionally provide new pipes for forming the CO2 circulation path, except for the bypass path, whereby a high cost is not required.
In some embodiments, in any one of configurations (1) to (3),
(4) the CO2 circulation path is formed with a difference in elevation, and the first heat exchanger part is formed in a lower area of the CO2 circulation path, and
the circulating unit is configured to permit the CO2 refrigerant to naturally circulate in the closed circuit at the time of defrosting by a thermosiphon effect.
In the configuration (4), the CO2 refrigerant in the lower area of the heat exchanger pipe is heated by the brine as the heating medium to be vaporized in the first heat exchanger part. The vaporized CO2 refrigerant is permitted to rise in the closed circuit by the thermosiphon effect. The CO2 refrigerant that has rose to the upper area of the closed circuit heats and removes the frost attached to the outer surface of the heat exchanger pipe through sublimation, and then is liquefied. The liquefied CO2 refrigerant descends by the gravity.
In the configuration (4), the CO2 refrigerant can be permitted to naturally circulate in the closed circuit by the thermosiphon effect. Thus, a unit for forcibly circulating the CO2 refrigerant in the closed circuit is not required, and equipment and power for forcing circulation are not required, whereby cost reduction can be achieved.
In some embodiments, any one of the configurations (1) to (4) further includes:
(5) a second heat exchanger part for heating the brine with a second heating medium; and
a brine circuit for permitting the brine heated by the second heating unit to be circulated to the first heating unit, the brine circuit being connected to the first heating unit and the second heating unit.
Any heating medium other than the cooling water can be used as the second heating medium. Such a heating medium includes, for example, refrigerant gas with high temperature and high pressure discharged from the compressor forming the refrigerating device, warm discharge water from a factory, a medium that has absorbed heat emitted from a boiler or potential heat of an oil cooler, and the like.
In the configuration (5), the second heat exchanger part and the brine circuit are provided, whereby the heated brine can be supplied to the first heat exchanger part, and the brine circuit can be disposed in accordance with a disposed position of the first heat exchanger part. Thus, a position where the heat exchanger part is disposed can be more freely determined.
In some embodiments, in the configuration (5),
(6) the heat exchanger pipe is provided with a difference in elevation in the cooling device,
the brine circuit is formed in the cooling device and in a lower area of the heat exchanger pipe, and
the first heat exchanger part is formed between the brine circuit and the lower area of the heat exchanger pipe.
In the configuration (6), the frost attached to the outer surface of the heat exchanger pipe can be removed through sublimation with the CO2 refrigerant vaporized in the lower area of the heat exchanger pipe permitted to naturally circulate by the thermosiphon effect. Thus, no additional pipes other than the heat exchanger pipe are required, and no equipment for forcing circulation of the CO2 refrigerant is required. All things considered, the cost of the cooling device can be reduced.
The brine branch circuit is not disposed in the upper area of the heat exchanger pipe, whereby the power used for the fan for forming airflow in the cooling device can be reduced. The cooling performance of the cooling device can be improved by additionally providing the heat exchanger pipe in a vacant space in the upper area.
In some embodiments, in the configuration (5),
(7) each of the heat exchanging pipe and the brine circuit is provided with a difference in elevation in the cooling device and is configured in such a manner that the brine flows from a lower side to an upper side in the brine circuit, and
a flowrate adjustment valve is disposed at an intermediate position in the brine circuit in an upper and lower direction, and the first heat exchanger part is formed at a portion of the brine circuit on an upstream side of the flowrate adjustment valve.
In the configuration (7), the brine flowrate is regulated by the flowrate adjustment valve, and the flowrate of the brine flowing into the upper area of the brine circuit is regulated. Thus, the first heat exchanger part can be formed only in the lower area of the heat exchanger pipe. Thus, as in the configuration (6), the frost attached can be removed through sublimation with the CO2 refrigerant permitted to naturally circulate by the thermosiphon effect
Thus, the frost attached to the heat exchanger pipe cane be removed through sublimation even in a known cooling device in which a heating tube for circulating the warm brine is disposed across the entire area of the heat exchanger pipe in the upper and lower direction such as the cooing device disclosed in Patent Document 3, with a simple arrangement of adding the flowrate adjustment valve to the heat exchanger pipe
In some embodiments, the configuration (5) further includes:
(8) a first temperature sensor and a second temperature sensor which are respectively disposed at an inlet and an outlet of the brine circuit to detect a temperature of the brine flowing through the inlet and the outlet.
In the configuration (8), a small difference between the detected values of the two temperature sensors indicates that the melted amount of the frost is reduced, and the defrosting is almost completed. The timing at which the defrosting operation is completed can be accurately determined by obtaining the difference between the detected values of the two temperature sensors because sensible heating is performed in the heat exchanger part with the brine.
Thus, excessive heating in the freezer or diffusion of the water vapor due to the excessive heating can be prevented, and further power saving can be achieved. Furthermore, a stable temperature in the freezer can be achieved, whereby the quality of food products frozen in the freezer can be improved.
In some embodiments, in the configuration (1),
(9) the pressure adjusting unit includes:
a pressure sensor for detecting the pressure of the CO2 refrigerant circulating in the closed circuit;
a pressure adjusting valve disposed in the outlet path of the heat exchanger pipe; and
a control device for receiving a detected value from the pressure sensor, and controlling an opening aperture of the pressure adjusting valve in such a manner that the condensing temperature of the CO2 refrigerant circulating in the closed circuit becomes equal to or lower than the freezing point of the water vapor in the freezer inner air in the freezer.
In the configuration (9), the control device can accurately control the pressure of the CO2 refrigerant circulating in the closed circuit.
In some embodiments, in the configuration (1),
(10) the refrigerating device includes:
a primary refrigerant circuit in which NH3 refrigerant circulates and a refrigerating cycle component is disposed;
a secondary refrigerant circuit in which the CO2 refrigerant circulates, the secondary refrigerant circuit led to the cooling device, the secondary refrigerant circuit being connected to the primary refrigerant circuit through a cascade condenser; and
a liquid CO2 receiver for storing the CO2 refrigerant liquefied in the cascade condenser and a liquid CO2 pump for sending the CO2 refrigerant stored in the liquid.
In the configuration (10), in the refrigerating device, natural refrigerants of NH3 and CO2 are used, and thus an attempt to prevent the ozone layer depletion, global warming, and the like is facilitated. Furthermore, the refrigerating device uses NH3, with high cooling performance and toxicity, as a primary refrigerant and uses CO2, with no toxicity or smell, as a secondary refrigerant, and thus can be used for room air conditioning and for refrigerating food products and the like, while maintaining higher cooling performance.
In some embodiments, in the configuration (1),
(11) the refrigerating device is a NH3/CO2 cascade refrigerating device including:
a primary refrigerant circuit in which NH3 refrigerant circulates and a refrigerating cycle component is disposed; and
a secondary refrigerant circuit in which the CO2 refrigerant circulates and a refrigerating cycle component is disposed, the secondary refrigerant circuit led to the cooling device, the secondary refrigerant circuit being connected to the primary refrigerant circuit through a cascade condenser.
In the configuration (11), in the refrigerating device, the natural refrigerant is used, and thus an attempt to prevent the ozone layer depletion, global warming, and the like is facilitated. Furthermore, the refrigerating device uses CO2, with no toxicity or smell, as a secondary refrigerant, and thus can be used for room air conditioning and for refrigerating food products and the like while maintaining high cooling performance. The refrigerating device is a cascade refrigerating device, and thus can have higher COP.
In some embodiments, the configuration (10) or (11) further includes:
a cooling water circuit led to a condenser provided as a part of the refrigerating cycle component disposed in the primary refrigerant circuit, and
the second heat exchanger part is a heat exchanger part to which the cooling water circuit and the brine circuit are led, the heat exchanger part configured to heat the brine circulating in the brine circuit with cooling water heated by the condenser.
In the configuration (12), the brine can be heated with the heated cooling water, and thus no heating source outside the refrigeration apparatus is required.
The temperature of the cooling water can be lowered by the brine during the defrosting operation, whereby the condensing temperature of the NH3 refrigerant during the refrigerating operation can be lowered, and the COP of the refrigerating device can be improved.
In an example embodiment where the cooling water circuit is disposed between the condenser and a cooling tower, the second heat exchanger part can be disposed in the cooling tower. Thus, a space where the device used for the defrosting can be downsized.
In some embodiments the configuration (10) or (11) further includes:
(13) a cooling water circuit led to a condenser provided as a part of the refrigerating cycle component disposed in the primary refrigerant circuit; and
a cooling tower for cooling the cooling water circulating in the cooling water circuit by exchanging heat between the cooling water and spray water, and
the second heat exchanger part includes a heating tower for receiving the spray water and exchanging heat between the brine circulating in the brine circuit and the spray water, the heating tower being integrally formed with the cooling tower.
In the configuration (13), the heating tower is integrally formed with the cooling tower, whereby a space in which the second heat exchanger part is installed can be downsized.
(14) A sublimation defrost method according to at least one embodiment of the present invention includes:
a first step of dehumidifying the freezer inner air in the freezer with the dehumidifier device so that a partial pressure of the water vapor in the freezer inner air does not become a saturated vapor partial pressure;
a second step of closing the on-off valve at the time of defrosting to form the closed circuit;
a third step of adjusting the pressure of the CO2 refrigerant circulating in the closed circuit so that the condensing temperature of the CO2 refrigerant becomes equal to or lower than the freezing point of the water vapor in the freezer inner air in the freezer; and
a fourth step of vaporizing the CO2 refrigerant by exchanging heat between the brine as a heating medium and the CO2 refrigerant circulating in the closed circuit; and
a fifth step of permitting the CO2 refrigerant vaporized in the fourth step to circulate in the closed circuit, and removing frost attached on an outer surface of the heat exchanger pipe by sublimation with heat of the CO2 refrigerant.
In the configuration (14), the frost attached to the outer surface of the heat exchanger pipe is heated by the heat of the CO2 refrigerant flowing in the heat exchanger pipe, and thus the entire area of the heat exchanger pipe can be uniformly heated. The pressure in the closed circuit is adjusted, so that the condensing temperature of the CO2 refrigerant is controlled, whereby the temperature of the CO2 refrigerant gas flowing in the closed circuit can be accurately controlled. Thus, the frost can be accurately heated to a temperature equal to or lower than the freezing point, whereby the sublimation defrosting can be achieved.
As described above, the frost attached to the heat exchanger pipe is not melted but is sublimated, and thus a drain pan and a facility for discharging the drainage accumulated in the drain pan are not required, whereby the cost of the refrigeration apparatus can be largely reduced. The frost attached to the heat exchanger pipe is heated from the inside through a pipe wall of the heat exchanger pipe only. Thus, the heat exchange efficiency can be improved and power saving can be achieved.
In some embodiments, in the configuration (14)
(15) in the fourth step, the brine and the CO2 refrigerant circulating in the closed circuit exchange heat in the lower area of the closed circuit provided with a difference in elevation, and
in the fifth step, the CO2 refrigerant is permitted to naturally circulate in the closed circuit by a thermosiphon effect.
In the configuration (15), the CO2 refrigerant is permitted to naturally circulate in the closed circuit by the thermosiphon effect, whereby a unit for forcing circulation of the CO2 refrigerant is not required, and the cost reduction can be achieved.
According to at least one embodiment of the present invention, sublimation defrosting of the frost attached to the surface of the heat exchanger pipe of the cooling device can be achieved. Thus, the drain pan and a drainage discharge facility are not required. Furthermore, no drain discharging operation is required, whereby initial and running costs required for the defrosting can be reduced, and the power saving can be achieved.
Embodiments of the present invention shown in the accompanying drawings will now be described in detail. It is intended, however, that dimensions, materials, shapes, relative positions, and the like of components described in the embodiments shall be interpreted as illustrative only and not limitative of the scope of the present invention unless otherwise specified.
For example, expressions indicating a relative or absolute arrangement such as “in a certain direction”, “along a certain direction”, “parallel to”, “orthogonal to”, “center of”, “concentric to”, and “coaxially” do not only strictly indicate such arrangements but also indicate a state including a tolerance or a relative displacement within an angle and a distance achieving the same function.
For example, expressions such as “the same”, “equal to”, and “equivalent to” indicating a state where the objects are the same, do not only strictly indicate the same state, but also indicate a state including a tolerance or a difference achieving the same function
For example, expressions indicating shapes such as rectangular and cylindrical do not only indicate the shapes such as rectangular and cylindrical in a geometrically strict sense, but also indicate shapes including recesses/protrusions, chamfered portions, and the like, as long as the same effect can be obtained.
Expressions such as “comprising”, “including”, “includes”, “provided with”, or “having” a certain component are not exclusive expressions that exclude other components.
Refrigeration apparatus 10A to 10D in these embodiments include: cooling devices 33a and 33b respectively disposed in freezers 30a and 30b; refrigerating devices 11A and 11B which cool and liquefy CO2 refrigerant; and a refrigerant circuit (corresponding to secondary refrigerant circuit 14) which permits the CO2 refrigerant cooled and liquefied in the refrigerating devices to circulate to the cooling devices 33a and 33b. The cooling devices 33a and 33b respectively include: casings 34a and 34b; and heat exchanger pipes 42a and 42b disposed in the casings. The internal temperature of the freezers 30a and 30b is kept as low as −25° C., for example in the refrigeration apparatus 10A to 10D shown in
In the exemplary configurations of the embodiments, the heat exchanger pipes 42a and 42b are led into the casings 34a and 34b from the outside of the casings 34a and 34b.
Here, areas of heat exchanger pipes 42a and 42b outside partition walls of the casings 34a and 34b and inside the freezers 30a and 30b are referred to as an inlet tube 42c and an outlet tube 42d.
Dehumidifier devices 38a and 38b for dehumidifying freezer inner air are disposed in the freezers 30a and 30b. The dehumidifier devices 38a and 38b are adsorption dehumidifier devices in some embodiments shown in
A CO2 circulation path is formed of a circulation path forming path connected to the inlet tube 42c and the outlet tube 42d of the heat exchanger pipes 42a and 42b. The circulation path forming path is defrost circuits 50a and 50b connected to the inlet tube and the outlet tube of the heat exchanger pipes 42a and 42b in the embodiments shown in
An on-off valve for making the CO2 circulation path become a closed circuit at the time of defrosting is disposed in each of the inlet tube 42c and the outlet tube 42d of the heat exchanger pipes 42a and 42b. In some embodiments shown in
In the example configurations of the embodiments shown in
Pressure adjusting units 45a and 45b for storage spacing pressure of a CO2 refrigerant circulating in the closed circuit at the time of defrosting are disposed. The pressure of the CO2 refrigerant in the closed circuit is adjusted by the pressure adjusting units 45a and 45b so that the CO2 refrigerant has condensing temperature higher than a freezing point (for example, 0° C.) of the water vapor in freezer inner air in the freezers 30a and 30b, at the time of defrosting.
In the example configurations of some embodiments shown in
In the example configuration of the embodiment, the pressure regulating valves 48a and 48 are disposed in parallel to the solenoid on-off valves 52a and 52b.
The pressure sensors 46a and 46b are disposed in the outlet tube 42d on the upstream side of the pressure regulating valves 48a and 48b. The control devices 47a and 47b controls the opening aperture of the pressure regulating valves 48a and 48b and thus adjusts the pressure of the CO2 refrigerant in accordance with the detected values from the pressure sensors. Thus, the condensing temperature of the CO2 refrigerant circulating in the closed circuit becomes equal to or lower than the freezing point of the water vapor in the freezer inner air in the freezers 30a and 30b.
When the solenoid on-off valves 52a and 52b are closed at the time of defrosting so that the CO2 circulation path becomes a closed circuit, a circulating unit permits the CO2 refrigerant to circulate in the closed circuit. The circulating unit is a liquid pump disposed in the CO2 circulation path for example. Alternatively, the circulating unit may permit the CO2 refrigerant to naturally circulate by a thermosiphon effect as in some embodiments shown in
A brine is used as a heating medium. A first heat exchanger part which heats the CO2 refrigerant circulating in the CO2 circulation path with the brine, and thus vaporizes the refrigerant, is disposed. The first heat exchanger part is heat exchanger parts 70a and 70b to which brine branch circuits 61a and 61b, branched from defrost circuits 50a and 50b and a brine circuit 60, are led, in the embodiments shown in
An aqueous solution such as ethylene glycol or propylene glycol can be used as the brine for example.
In the embodiments shown in
In the embodiments shown in
In the embodiments shown in
More specifically, in the embodiments shown in
In the CO2 circulation path with the difference in elevation, the CO2 refrigerant can be permitted to circulate in the closed circuit formed at the time of defrosting by the thermosiphon effect. More specifically, the CO2 refrigerant gas vaporized by the first heat exchanger part rises due to the thermosiphon effect. The CO2 refrigerant gas that has risen exchange heat with the frost that has attached to an outer surface of the heat exchanger part in the heat exchanger pipes 42a and 42b or an upper area of the heat exchanger pipe, and thus removes the frost through sublimation. The CO2 refrigerant with the potential heat taken away is liquefied. The liquefied CO2 refrigerant descends in the CO2 circulation path with gravity. Thus, a loop thermosiphon effect is obtained, and the CO2 refrigerant is permitted to naturally circulate in the closed circuit.
In some embodiments shown in
In the embodiments shown in
At least one embodiment shown in
The first heat exchanger part is formed between the brine branch circuits 63a and 63b and the lower areas of the heat exchanger pipes 42a and 42b.
In the example configuration of the cooling device 33a shown in
In the example configuration of the cooling device 33a shown in
In at least one embodiment shown in
In this configuration, the opening aperture of the flowrate adjustment valves 82a and 82b is narrowed, whereby the first heat exchanger part can be formed in upstream side areas of the flowrate adjustment valves 82a and 82b, that is, the heat exchanger pipes 42a and 42b on the lower side of the flowrate adjustment valves 82a and 82b.
In some embodiments shown in
In the embodiments shown in
In the embodiment shown in
In some embodiments shown in
The refrigerating cycle component disposed in the primary refrigerant circuit 12 includes a compressor 16, a condenser 18, a NH3 liquid receiver 20, an expansion valve 22, and the cascade condenser 24.
The secondary refrigerant circuit 14 includes a CO2 liquid receiver 36 in which a liquid CO2 refrigerant liquefied by the cascade condenser 24 is temporarily stored, and a CO2 liquid pump 37 that permits the liquid CO2 refrigerant stored in the CO2 liquid receiver 36 to circulate to the heat exchanger pipes 42a and 42b.
A CO2 circulation path 44 is disposed between the cascade condenser 24 and the CO2 liquid receiver 36. The CO2 refrigerant gas introduced into the cascade condenser 24 through the CO2 circulation path 44 from the CO2 liquid receiver 36 is cooled and liquefied by the NH3 refrigerant in the cascade condenser 24, and then returns to the CO2 liquid receiver 36.
In the refrigerating device 11A, natural refrigerants of NH3 and CO2 are used, and thus an attempt to prevent the ozone layer depletion, global warming, and the like is facilitated. Furthermore, the refrigerating device 11A uses NH3, with high cooling performance and toxicity, as a primary refrigerant and uses CO2, with no toxicity or smell, as a secondary refrigerant, and thus can be used for room air conditioning and for refrigerating food products and the like.
In at least one example embodiment shown in
The NH3 refrigerant flowing in the branch path 12a is expanded and cooled in the intermediate expansion valve 86, and then is introduced into the intermediate cooling device 84. In the intermediate cooling device 84, the NH3 refrigerant discharged from the lower stage compressor 16b is cooled with the NH3 refrigerant introduced from the branch path 12a. Providing the intermediate cooling device 84 can improve the COP (coefficient of cooling performance) of the refrigerating device 11B.
The liquid CO2 refrigerant, cooled and liquefied by exchanging heat with the NH3 refrigerant in the cascade condenser 24, is stored in the liquid CO2 receiver 36. Then, the liquid CO2 pump 37 makes the liquid CO2 refrigerant circulate in the cooling device 33 disposed in the freezer 30, from the liquid CO2 receiver 36.
In at least one example embodiment shown in
The refrigerating device 11C is a cascade refrigerating device in which a mechanical compression refrigerating cycle is formed in each of the primary refrigerant circuit 12 and the secondary refrigerant circuit 14, whereby the COP of the refrigerating device can be improved.
In some embodiments shown in
Refrigerant water circulating in the cooling water circuit 28 is heated by the NH3 refrigerant in the condenser 18. The heated cooling water serves as the heating medium to heat the brine circulating in the brine circuit 60 in the heat exchanger part 58, at the time of defrosting.
When the temperature of the cooling water introduced into the heat exchanger part 58 from the cooling water branch circuit 56 is 20 to 30° C. for example, the brine can be heated up to 15 to 20° C. with this cooling water.
In another embodiment, any heating medium other than the cooling water can be used as the second heating medium. Such a heating medium includes NH3 refrigerant gas with high temperature and high pressure discharged from the compressor 16, warm discharge water from a factory, a medium that has absorbed heat emitted from a boiler or potential heat of an oil cooler, and the like.
As an example configuration some embodiments, the cooling water circuit 28 is disposed between the condenser 18 and a closed-type cooling tower 26. The cooling water is circulated in the cooling water circuit 28 by the cooling water pump 29. The cooling water that has absorbed exhaust heat from the NH3 refrigerant in the condenser 18 comes into contact with the outer air in a closed-type cooling tower 26 and is cooled with vaporization latent heat of water.
The closed-type cooling tower 26 includes: a cooling coil 26a connected to the cooling water circuit 28; a fan 26b that blows the outer air a into the cooling coil 26a; and a spray pipe 26c and a pump 26d for spraying the cooling water onto the cooling coil 26a. The cooling water sprayed from the spray pipe 26c partially vaporizes. The cooling water flowing in the cooling coil 26c is cooled with the vaporization latent heat thus produced.
In at least one embodiment shown in
The closed-type heating tower 91 receives spray water used for cooling the cooling water circulating in the cooling water circuit 28 in the closed-type cooling tower 26, and causes heat exchange between the spray water and the brine circulating in the brine circuit 60. The closed-type heating tower 91 includes: a heating coil 91a connected to the brine circuit 60; and a spray pipe 91c and a pump 91d for spraying the cooling water onto the cooling coil 91a. An inside of the closed-type cooling tower 26 communicates with an inside of the closed-type heating tower 91 through a lower portion of a common housing.
The spray water that has absorbed the exhaust heat from the NH3 refrigerant circulating in the primary refrigerant circuit 12 is sprayed onto the cooling coil 91a from the spray pipe 91c, and serves as a heating medium which heats the brine circulating in the cooling coil 91a and the brine circuit 60.
In some embodiments shown in
The brine circuit 60 extending to a portion near the freezers 30a and 30b from the heat exchanger part 58 is branched to brine branch circuits 61a and 61b (illustrated in dashed line) outside the freezers 30a and 30b.
In the refrigeration apparatus 10A shown in
The sublimation defrosting is performed in the refrigeration apparatus 10A as follows. Specifically, when the freezer inner air in the freezers 30a and 30b has saturated water vapor pressure, the dehumidifier devices 38a and 38b are operated for dehumidification to achieve low water vapor partial pressure. Then, the solenoid on-off valves 52a and 52b are closed so that the CO2 circulation path, including the heat exchanger pipe 42a and 42b and the defrost circuits 50a and 50b, becomes the closed circuit.
The detected values of the pressure sensors 46a and 46b are input to the control devices 47a and 47b. The control devices 47a and 47b operates the pressure regulating valves 48a and 48b based on the detected values to adjust the pressure of the CO2 refrigerant circulating in the closed circuit so that the condensing temperature of the CO2 refrigerant becomes equal to or lower than the freezing point (for example, 0° C.) of the water vapor in the freezer inner air. For example, the CO2 refrigerant is boosted to 3.0 MPa (condensing temperature −5° C.).
Then, the CO2 refrigerant is vaporized through the heat exchange between the brine and the CO2 refrigerant in the heat exchanger parts 70a and 70b. Then, the vaporized CO2 refrigerant is circulated in the closed circuit, whereby the frost attached to the outer surface of the heat exchanger pipes 42a and 42b is removed through sublimation with the condensing latent heat (249 kJ/kg at −5° C./3.0 MPa) of the CO2 refrigerant.
The lower limit value of the condensing temperature of the CO2 refrigerant to be adjusted for the sublimation of the frost is a freezer inner temperature (for example, −25° C.). During the refrigerating operation, the CO2 refrigerant at a temperature equal to or lower than the freezer inner temperature (for example, −30° C.) is permitted to circulate in the heat exchanger pipes 42a and 42b for cooling in the freezer. Thus, the temperature of the frost is equal to or lower than the freezer inner temperature (for example, −25° C. to −30° C.), accordingly, sublimation of frost through heating can be achieved when the condensing temperature of the CO2 refrigerant is within a range of the freezer inner temperature and the freezing point of the water vapor in the freezer at the time of sublimation defrosting.
In the present embodiment, the defrost circuits 50a and 50b are disposed below the heat exchanger pipes 42a and 42b, and the CO2 circulation path has the difference in elevation. Thus, the CO2 refrigerant vaporized in the heat exchanger parts 70a and 70b rises to the heat exchanger pipes 42a and 42b due to the thermosiphon effect. Thus, the frost attached to the outer surfaces of the heat exchanger pipes 42a and 42b is sublimated and thus is liquefied by the potential heat of the CO2 refrigerant gas that has risen to the heat exchanger pipes 42a and 42b. The liquefied CO2 refrigerant descends in the defrost circuits 50a and 50b with gravity, and then is vaporized again in the heat exchanger part 70a and 70b.
In the refrigeration apparatus 10B shown in
Bypass tubes 72a and 72b are connected between the inlet tube and the outlet tube of the heat exchanger pipes 42a and 42b outside the casings 34a and 34b. Solenoid on-off valves 74a and 74b are disposed in the bypass tubes 72a and 72b.
In the inlet tube, the solenoid on-off valves 54a and 54b are disposed on the upstream side of the bypass tubes 52a and 52b. In the outlet tube, the solenoid on-off valves 54a and 54b are disposed on the downstream side of the bypass tubes 52a and 52b.
In the refrigeration apparatus 10B, the brine branch circuits 63a and 63b are led to the lower areas of the heat exchanger pipes 42a and 42b. The heat exchanger part is formed of the lower areas of the heat exchanger pipes 42a and 42b and the brine branch circuits 63a and 63b.
In the refrigeration apparatus 10C, the brine branch circuits 80a and 80b are disposed over substantially the entire area of the area where the heat exchanger pipes 42a and 42b are disposed. The flowrate adjustment valves 82a and 82b are disposed at intermediate portions of the brine branch circuits 80a and 80b in the upper and lower direction. The brine branch circuits 80a and 80b form a flow path in which brine b flows to an upper area from a lower area.
In an example configuration of the cooling devices 33a and 33b, for example, as in the cooling device 33a shown in
The heat exchanger pipe 42a includes headers 43a and 43b in the inlet tube 42c and the outlet tube 42d, outside the cooling device 33a. The brine branch circuits 63a and 80a includes headers 78a and 78b at an inlet and an outlet of the cooling device 33a.
A large number of plate fins 76a are disposed in the upper and lower direction in the cooling device 33a. The heat exchanger pipe 42a and the branch circuit 63a or 80a are inserted in a large number of holes formed on the plate fins 76a and thus are supported by the plate fins 76a. With the plate fins 76a, supporting strength for the pipes is increased, and the heat transmission between the heat exchanger pipe 42a and the brine branch circuit 63a or 80a is facilitated.
During the refrigerating operation, the fan 35a diffuses the freezer inner air c cooled in the cooling device 33a into the freezer 32a. Because no dissolved water is produced at the time of defrosting, a drain pan is not disposed below the casing 34a. The configuration of the cooling device 33a described above is the same as that of the cooling device 33b.
In the refrigerating devices 11B and 11C, the inlet tube 42c and the outlet tube 42d of the heat exchanger pipes 42a and 42b are connected to the CO2 branch circuits 40a and 40b through the contact part 41, outside the freezers 30a and 30b. The brine branch circuits 63a, 63b, 80a, and 80b are connected to the brine branch circuits 61a and 61b through the contact part 62, outside the freezers 30a and 30b.
In the refrigeration apparatus 10B, the casings 34a and 34b of the freezers 30a and 30b, the heat exchanger pipes 42a and 42b including the inlet tube 42c and the outlet tube 42d, the brine branch circuits 63a and 63b, and the bypass tubes 72a and 72b form the cooling units 31a and 31b that are integrally formed.
In the refrigeration apparatus 10C, the casings 34a and 34b of the freezers 30a and 30b, the heat exchanger pipes 42a and 42b including the inlet tube 42c and the outlet tube 42d, the brine branch circuits 80a and 80b, and the bypass tubes 72a and 72b form the cooling units 32a and 32b that are integrally formed.
The cooling units 31a and 31b or 32a and 32b are detachably connected to the CO2 branch circuits 40a and 40b and the brine branch circuits 61a and 61b through the contact parts 41 and 62.
In the refrigeration apparatuses 10B and 10C, the solenoid on-off valves 74a and 74b are closed, and the solenoid on-off valves 52a and 52b are opened during the refrigerating operation. The solenoid on-off valves 74a and 74b are opened, and the solenoid on-off valves 52a and 52b are closed at the time of defrosting, whereby the closed circuit including the heat exchanger pipes 42a and 42b and the bypass tubes 72a and 72b is formed.
In the refrigeration apparatus 10B, the CO2 refrigerant is vaporized by the potential heat of the brine flowing in the brine branch circuits 63a and 63b, in the lower areas of the heat exchanger pipes 42a and 42b, at the time of defrosting. The vaporized CO2 refrigerant rises to the upper areas of the heat exchanger pipes 42a and 42b, and removes the frost attached to the outer surfaces of the heat exchanger pipes 42a and 42b in the upper areas, through sublimation. The CO2 refrigerant that has humidified the frost through sublimation is liquefied and descends by gravity, and vaporizes again in the lower area. Thus, the CO2 refrigerant is naturally circulated in the closed circuit by the thermosiphon effect.
In the refrigeration apparatus 10C, at the time of defrosting, the opening apertures of the flowrate adjustment valves 82a and 82b are narrowed so that the flowrate of the brine b is restricted. Thus, the heat exchanger part in which the CO2 refrigerant and the brine exchange heat can be formed only in the upstream area (lower area) of the flowrate adjustment valves 82a and 82b.
Thus, the CO2 refrigerant is naturally circulated by the thermosiphon effect and the frost can be removed through sublimation by the potential heat of the circulating CO2 refrigerant, between the areas of the heat exchanger pipes 42a and 42b corresponding to the upstream and the downstream areas of the flowrate adjustment valves 82a and 82b.
According to some embodiments shown in
The fans 35a and 35b are operated at the time of defrosting, so that the air flow flowing in and out of the casings 34a and 34b is formed, whereby the sublimation can be facilitated.
Thus, the frost attached to the heat exchanger pipes 42a and 42b is not melted but is sublimated, and thus a drain pan and a facility for discharging the drainage accumulated in the drain pan are not required, whereby the cost of the refrigeration apparatus can be largely reduced. The frost attached to the heat exchanger pipes 42a and 42b is heated from the inside through a pipe wall of the heat exchanger pipe only. Thus, the heat exchange efficiency can be improved and power saving can be achieved.
The defrosting can be achieved with the CO2 refrigerant in a low pressure state. Thus, a pipe system device such as the CO2 circulation path needs not to be pressure resistant, whereby a high cost is not required.
Thus, with the sublimation defrosting achieved, a micro channel heat exchanger pipe, which is considered to be difficult to apply to the cooling device for a freezer due to the large performance degradation caused by frost formation and dew condensation, can be employed. This technique can be applied not only to the freezer, but can also be applied to a defrost method for a batch freezing chamber or a freezer requiring continuous non-defrosting operation for a long period of time.
In the refrigeration apparatus 10A shown in
In the refrigeration apparatus 10B shown in
In some embodiments shown in
The brine circuit 60 is provided, and can be disposed in accordance with a disposed position of the heat exchanger part in which the heated brine exchanges heat with the CO2 refrigerant. Thus, a position where the heat exchanger part is disposed can be more freely determined.
In the embodiments shown in
The brine branch circuits 63a and 63b are not disposed in the upper areas of the heat exchanger pipes 42a and 42b, whereby the power used for the fans 35a and 35b for forming airflow in the cooling devices 33a and 33b can be reduced. The cooling performance of the cooling devices 33a and 33b can be improved by additionally providing the heat exchanger pipes 42a and 42b in a vacant space in the upper area.
In the embodiment shown in
In some embodiments shown in
In some embodiments shown in
In some embodiments shown in
The heat exchanger part 58 can be disposed in the closed-type cooling tower 26. Whereby a space where an apparatus used for defrosting is installed can be downsized.
In the embodiments shown in
Furthermore, by using the cooling units 31a, 31b, 32a, and 32b of the configuration described above, the cooling devices 33a and 33b with a defrosting device can be easily attached to the freezers 30a and 30b. When the units are integrally assembled in advance, the attachment to the freezers 30a and 30b is further facilitated.
The freezer 30 and the cargo-handling chamber 100 each incorporate the dehumidifier device 38 such as the desiccant humidifier. The dehumidifier device 38 takes in the outer air a from the outside of the chamber and discharges the water vapor s from the chamber, whereby the cold dry air d is supplied into the chamber.
The temperature in the cargo-handling chamber 100 is kept at +5° C. for example. An electric heat insulating door 102 is disposed at an entrance for going in and out of the freezer 30 from the cargo-handling chamber 100. Thus, the amount of water vapor entering the freezer 30 when the door is opened/closed is minimized.
For example, when the freezer 30 is cooled to have a temperature of −25° C., and has a volume of 7, 500 m3 the absolute humidity is 0.4 g/kg at the relative humidity of 100% and the absolute humidity is 0.1 g/kg at the relative humidity of 25%. Thus, the amount of containable water vapor, obtained by multiplying the difference in the absolute humidity by the volume of the freezer 30, is 2.25 kg. Thus, the sublimation defrosting can be well achieved by setting the relative humidity of the freezer inner air to 25%.
According to the present invention the sublimation defrosting can be achieved, whereby the initial and running costs require for the defrosting in the refrigeration apparatus can be reduced, and the power saving can be achieved
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-259751 | Dec 2013 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2014/081044 | 11/25/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/093235 | 6/25/2015 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3084519 | Hanson et al. | Apr 1963 | A |
| 3228204 | Matthies | Jan 1966 | A |
| 6170270 | Arshansky et al. | Jan 2001 | B1 |
| 7698902 | Kang et al. | Apr 2010 | B2 |
| 7992397 | Nemoto et al. | Aug 2011 | B2 |
| 20060266058 | Nemoto et al. | Nov 2006 | A1 |
| 20070234753 | Nemoto et al. | Oct 2007 | A1 |
| 20090260389 | Dube | Oct 2009 | A1 |
| 20120055182 | Dube | Mar 2012 | A1 |
| 20120055185 | Luo et al. | Mar 2012 | A1 |
| 20130098078 | Contreras Lafaire et al. | Apr 2013 | A1 |
| 20140260361 | Rodier | Sep 2014 | A1 |
| 20140352343 | Hinde et al. | Dec 2014 | A1 |
| 20150204589 | Liu | Jul 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 2662986 | Oct 2009 | CA |
| 2503303 | Aug 1975 | DE |
| 29817062 | Apr 1999 | DE |
| 1630495 | Mar 2006 | EP |
| 5244468 | Mar 1977 | JP |
| 52131652 | Oct 1977 | JP |
| 2001027473 | Jan 2001 | JP |
| 2003021365 | Jan 2003 | JP |
| 2003329334 | Nov 2003 | JP |
| 2004170007 | Jun 2004 | JP |
| 4197562 | Oct 2008 | JP |
| 2010181093 | Aug 2010 | JP |
| 2012072981 | Apr 2012 | JP |
| 2013124812 | Jun 2013 | JP |
| 2013160427 | Aug 2013 | JP |
| 5316973 | Oct 2013 | JP |
| 2019940008247 | Apr 1994 | KR |
| 1020110021128 | Mar 2011 | KR |
| 2006049355 | May 2006 | WO |
| 2008112554 | Sep 2008 | WO |
| 2009034300 | Mar 2009 | WO |
| Entry |
|---|
| U.S. Appl. No. 14/767,635, filed Aug. 13, 2015. |
| U.S. Appl. No. 14/903,870, filed Jan. 8, 2016. |
| International Preliminary Report on Patentability issued in Intl. Appln. No. PCT/JP2014/081042 dated Jun. 21, 2016. English translation provided. |
| International Preliminary Report on Patentability issued in Intl. Appln. No. PCT/JP2014/081043 dated Jun. 21, 2016. English translation provided. |
| International Preliminary Report on Patentability issued in Intl. Appln. No. PCT/JP2014/081044 dated Jun. 21, 2016. English translation provided. |
| Extended European Search Report issued in European Appln. No. 14873060.9, dated Oct. 28, 2016. |
| Extended European Search Report issued in European Appln. No. 14871996.6, dated Oct. 28, 2016. |
| Office Action issued in Korean Appln. No. 10-2016-7019058 dated Apr. 10, 2017. English translation provided. |
| Office Action issued in Korean Appln. No. 10-2016-7019012 dated Apr. 10, 2017. English translation provided. |
| Office Action issued in Korean Appln. No. 10-2016-7018741 dated Apr. 10, 2017. English translation provided. |
| International Search Report issued in PCT/JP2014/081042 dated Feb. 24, 2015. English translation provided. |
| Written Opinion issued in PCT/JP2014/081042 dated Feb. 24, 2015. |
| International Search Report issued in PCT/JP2014/081043, dated Feb. 24, 2015. English translation provided. |
| Written Opinion issued in PCT/JP2014/081043, dated Feb. 24, 2015. |
| Notice of Allowance issued in U.S. Appl. No. 14/903,870 dated Jun. 16, 2017. |
| Scientific & Technical Information Center (STIC) EIC 3700 Search Report—Retrieved Jun. 2017. |
| Intemational Search Report issued in PCT/JP2014/081044, dated Feb. 24, 2015. English translation provided. |
| Written Opinion issued in PCT/JP2014/081044, dated Feb. 24, 2015. |
| Number | Date | Country | |
|---|---|---|---|
| 20160187041 A1 | Jun 2016 | US |
