JPWO2017122517A1 - Refrigeration cycle apparatus and thermal cycle system - Google Patents

Abstract

A compressor (10), a condenser (20), a decompression mechanism (30) and an evaporator (40) are connected by piping to constitute a refrigeration cycle, and a refrigeration cycle apparatus using a working medium containing HFO, A deoxygenation part (50) for bringing the refrigerant into contact with a desiccant or a deoxidant is provided at any location in the refrigeration cycle.

Description

  The present invention relates to a refrigeration cycle apparatus and a thermal cycle system.

  Conventionally, a cooling compressor filled with refrigeration oil, a first heat exchanger, a refrigerant flow control unit such as a capillary tube and an expansion valve, and a second heat installed in a space where refrigeration air conditioning is performed. A refrigeration cycle is configured by connecting an exchanger and an accumulator with piping, and a single working medium of hydrofluoroolefin (HFO) or a mixed working medium mainly composed of hydrofluoroolefin is enclosed in a refrigerant cycle, and a cooling cycle There is known a cooling cycle device including an adsorber filled with an adsorbent that adsorbs a substance mainly containing hydrofluoric acid (see, for example, Patent Document 1).

  Similarly, it is a refrigeration system that circulates a working medium mixed with hydrofluorocarbon (HFC) that does not have a double bond, with hydrofluoroolefin having a double bond between carbon as a base component, condensed from the compressor A working medium circulation path through which the working medium circulates, and a hydrogen fluoride scavenging section that is disposed in the working medium circulation path and contains a hydrogen fluoride scavenger. The thing provided with the structure provided is known (for example, refer patent document 2).

  In the configurations described in Patent Documents 1 and 2, hydrofluoroolefin is used as the working medium. When hydrofluoroolefin decomposes under the influence of water or oxygen, hydrofluoric acid is generated during the cooling cycle or refrigeration cycle, and hydrofluoric acid degrades the parts used. In Patent Documents 1 and 2, the generated hydrofluoric acid is removed. This prevents the deterioration of the parts used in the cooling cycle or the refrigeration cycle.

International Publication No. 2010/047116 Japanese Unexamined Patent Publication No. 2010-270957

  However, HFO has the property of self-decomposing when there is an ignition source at high temperature or high pressure.

  Although the use of a working medium containing HFO as a working medium for the refrigeration cycle and the heat cycle has been studied, HFO is responsive to the reactivity of the apparatus, for example, the temperature of the environment of use, oxygen, etc. Countermeasures need to be taken because there is a risk of reaction depending on conditions and the presence of ignition sources.

  In the configurations of Patent Documents 1 and 2, although hydrofluoric acid finally generated in the cycle is removed, the presence of water and oxygen in the cycle is allowed. HFO decomposes under the influence of water and oxygen in a high temperature atmosphere, and the possibility of generating an acid increases. The acid generated by the decomposition of HFO corrodes the metal parts in the cycle and becomes an inorganic sludge of a metal salt, which itself becomes a catalyst for promoting the decomposition of HFO.

  When sludge is generated in the refrigeration cycle, there is a problem that the refrigerant flow rate control unit is clogged and the reliability of the compressor is significantly impaired.

  Therefore, the present invention is a refrigeration cycle apparatus and thermal cycle system using HFO as a working medium, even when HFO is used by removing water and oxygen from the cycle and suppressing the generation of sludge. The purpose is to provide a heat cycle system that can be operated safely.

In order to achieve the above object, a refrigeration cycle apparatus according to an aspect of the present invention uses a working medium containing HFO to form a refrigeration cycle by connecting a compressor, a condenser, a decompression mechanism, and an evaporator with piping. A refrigeration cycle apparatus,
A deoxygenation part for bringing the refrigerant into contact with a desiccant or a deoxidant is provided at any location in the refrigeration cycle.

  The thermal cycle system according to another aspect of the present invention is equipped with the refrigeration cycle apparatus.

  According to the present invention, generation of sludge in the refrigeration cycle is suppressed, and even when a working medium containing HFO is used, it can be safely operated.

1 is an overall configuration diagram illustrating an example of a refrigeration cycle apparatus according to an embodiment of the present invention. It is the figure which showed an example of the deoxidation part of the refrigerating-cycle apparatus which concerns on embodiment of this invention. It is the figure which showed an example of the deoxidation part of a structure different from FIG. It is the figure which showed an example of the deoxidation part of a structure different from FIG.2 and FIG.3. It is the figure which showed the air conditioning apparatus which is an example of the thermal cycle system which concerns on embodiment of this invention.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.

  FIG. 1 is an overall configuration diagram illustrating an example of a refrigeration cycle apparatus according to an embodiment of the present invention. As shown in FIG. 1, the refrigeration cycle apparatus according to the present embodiment includes a compressor 10, a condenser 20, a decompression mechanism 30, an evaporator 40, a deoxygenation unit 50, and a pipe 60. The compressor 10, the condenser 20, the pressure reduction mechanism 30, the evaporator 40, and the deoxygenation part 50 are connected cyclically | annularly by the piping 60, and comprise the refrigerating cycle as a whole. In the refrigeration cycle apparatus according to the present embodiment, a working medium containing HFO is used as the working medium. Although details of the working medium will be described later, HFO is easily decomposed when water or oxygen is contained in the refrigeration cycle, and there is a possibility of generating sludge. The refrigeration cycle apparatus according to the present embodiment has a configuration that suppresses the generation of such sludge. The specific contents will be described below.

  The compressor 10 compresses a low-temperature, low-pressure gaseous working medium to serve as a high-temperature, high-pressure gaseous working medium. The gaseous working medium that has reached a high temperature and a high pressure is sent to the condenser 20.

  The condenser 20 condenses the high-temperature and high-pressure gaseous working medium sent from the compressor 10 and plays a role as a liquid working medium. The liquid working medium is sent to the deoxygenation unit 50. In the condenser 20, the heat of the gaseous working medium is radiated into the air.

The deoxygenation unit 50 serves to remove oxygen from the working medium. Here, oxygen means an oxygen component, that is, an O component, and includes oxygen component O contained in water H ₂ O in addition to oxygen O ₂ . The deoxygenation part 50 has a desiccant or a deoxygenating agent inside, makes the working medium which passes the inside of the deoxygenating part 50 contact a desiccant or a deoxidizing agent, and removes an oxygen component from a working medium. Thereby, it can suppress that sludge generate | occur | produces in a refrigerating cycle.

  The deoxygenation unit 50 may be provided at any location in the refrigeration cycle. This is because it is possible to remove the oxygen component from the working medium at any location. However, in consideration of the efficiency of oxygen removal, it is preferably provided between the condenser 20 and the decompression mechanism 30. This is because the working medium is in the state of a liquid working medium between the condenser 20 and the pressure reducing mechanism 30, and the working medium can be efficiently brought into contact with the desiccant or oxygen scavenger. That is, in the state of the gaseous working medium, since the working medium is diffused, even if a desiccant or a deoxygenating agent is provided in the deoxidizing part 50, the working medium reliably contacts the desiccant or the deoxidizing agent. However, in the state of the liquid working medium, if a desiccant or oxygen scavenger is provided in the flow path, there is a high possibility that the working medium will reliably contact the desiccant or oxygen scavenger. .

  A specific configuration of the deoxygenation unit 50 will be described later.

  The decompression mechanism 30 serves to convert the liquid refrigerant sent directly from the condenser 20 through the deoxygenation unit 50 into low-temperature, low-pressure wet steam. As a result, the liquid working medium is converted back into a gaseous working medium. The decompression mechanism 30 may be called the expansion mechanism 30 because the working medium is expanded by reducing the pressure.

  The evaporator 40 plays a role of evaporating the low-temperature, low-pressure wet steam refrigerant gas sent from the decompression mechanism 30 to form a low-temperature, low-pressure gaseous working medium. Note that the gaseous working medium is evaporated by absorbing heat from the surroundings in the evaporator 40.

  The low-temperature and low-pressure gaseous working medium sent from the evaporator 40 is sucked into the compressor 10 and compressed to become a high-temperature and high-pressure gaseous working medium again.

  Hereinafter, the refrigeration cycle from the compressor 10 described above is repeated, and the release of heat from the working medium and the absorption of heat by the refrigerant are repeated.

  Note that the basic refrigeration cycle is performed by circulating refrigerant through the compressor 10, the condenser 20, the decompression mechanism 30, and the evaporator 40, and the deoxygenation unit 50 removes oxygen components generated in the refrigeration cycle. It plays the role of removing and suppressing the generation of sludge in the refrigeration cycle. Therefore, the deoxygenation unit 50 can be installed at any location in the refrigeration cycle.

  Next, the configuration of an example of the oxygen removal unit 50 will be described with reference to FIG. FIG. 2 is a diagram showing an example of the configuration of the deoxygenation unit 50 of the refrigeration cycle apparatus according to the embodiment of the present invention.

  As shown in FIG. 2, the oxygen absorber 50 includes a tubular member 51, an inlet 52, an outlet 53, an inlet-side flow surface 54, an outlet-side flow surface 55, and an oxygen scavenger holding unit 56. And an oxygen scavenger 57.

  The tubular member 51 is a tubular member that forms the outer shape of the deoxidation unit 50, and is connected to the pipe 60 and is configured to form a part of the flow path of the refrigeration cycle.

  The inlet 52 and the outlet 53 are an inlet and an outlet for the refrigerant, and are both ends connected to the pipe 60. That is, the inlet 52 and the outlet 53 of the deoxygenation unit 50 are connected in series to the pipe 60, and the deoxygenation unit 50 constitutes a part of the flow path of the refrigeration cycle.

  The inlet-side flow surface 54 and the outlet-side flow surface 55 are a pair of surfaces configured to allow the working medium to flow, and are provided to be joined to the inner peripheral surface of the tubular member 51. The inlet-side flow surface 54 and the outlet-side flow surface 55 have a shape that allows the working medium to flow, and are configured to have openings in a mesh shape such as a mesh shape or a lattice shape.

  A space between the inlet-side flow surface 54 and the outlet-side flow surface 55 is configured as an oxygen scavenger holding unit 56. The oxygen scavenger holding unit 56 is a region that holds the oxygen scavenger 57. Therefore, the opening forming the mesh of the inlet side flow surface 54 and the outlet side flow surface 55 is larger than the particle size of the oxygen absorber 57 so that the oxygen absorber 57 can be held in the region inside the oxygen absorber holding portion 55. Is preferably configured as an opening having a small size.

  The oxygen scavenger 57 is a particulate medicine for removing oxygen in the refrigerant. As the oxygen scavenger 57, various oxygen scavengers 57 can be used as long as oxygen in the refrigerant can be removed. As the oxygen scavenger 57, for example, iron powder may be used.

  As described above, the oxygen scavenger 57 may use a desiccant. As the desiccant, various desiccants can be used as long as water in the refrigerant can be removed. As the desiccant, for example, anhydrous calcium sulfide, calcium chloride, barium oxide, phosphorus pentoxide, activated alumina, silica gel, and molecular sieves can be used. In this case, the oxygen scavenger holding unit 56 becomes the desiccant holding unit 56. The oxygen scavenger holding unit 56 and the desiccant holding unit 56 may be collectively referred to as a drug holding unit 56.

  In addition to the oxygen scavenger 57, a hydrogen fluoride scavenger that removes hydrogen fluoride in the working medium may be used. Any hydrogen fluoride scavenger may be used as long as it reacts with hydrogen fluoride, but the byproduct of the hydrogen fluoride scavenging reaction is less likely to adversely affect the refrigeration cycle. Is preferred. Among these, it is preferable to use one or a combination of calcium carbonate, calcium oxide and calcium hydroxide that does not react with hydrogen fluoride to cause a reverse reaction.

  Further, the inlet-side flow surface 54 and the outlet-side flow surface 55 are configured in a mesh shape, and if the working medium can be passed, a permeable member that allows the working medium to pass therethrough, a fiber structure, or the like. There may be.

  FIG. 3 is a view showing an example of the deoxygenation unit 50a having a configuration different from that in FIG. The deoxygenation part 50a is the same as the deoxygenation part 50 according to FIG. 2 in that it includes a tubular member 51, an inlet 52, an outlet 53, an inlet-side flow surface 54, and a deoxygenating agent 57. It differs from the deoxidation part 50 which concerns on FIG. 2 by the point which does not have the surface 55 but has the bag-shaped deoxidation agent holding | maintenance part 56a. As described above, the oxygen scavenger holding part 56a may be configured in a bag shape and the oxygen scavenger 57 may be held in the bag. In this case, the oxygen scavenger holding part 56a may have a cloth shape or a mesh shape.

  3 shows an example in which the outlet-side flow surface 55 is not provided, but the outlet-side flow surface 55 may be further provided in the configuration of FIG.

  Note that the oxygen scavenger 57 may be used as the desiccant, as described with reference to FIGS.

  FIG. 4 is a diagram showing an example of the deoxygenating unit 50b having a configuration different from those in FIGS. The oxygen scavenging part 50b is the same as the oxygen scavenging part 50 according to FIG. 2 in that it includes the inlet 52, the outlet 53, the oxygen scavenger holding part 56, and the oxygen scavenger 57, but the tubular member 51a and the inlet side passage are provided. The structures of the flow surface 54a and the outlet-side flow surface 55a are different from those of the deoxygenation unit 50 according to FIG. Moreover, it differs from the deoxidation part 50 which concerns on FIG. 2 also in the point in which the strainer mesh 58 was newly provided in the tubular member 51a.

  First, the tubular member 51a includes an upstream tubular member 51b and a downstream tubular member 51c having different tube diameters. The upstream tubular member 51b has a larger pipe diameter than the downstream tubular member 51c. The downstream end of the upstream tubular member 51b and the upstream end of the downstream tubular member 51c are connected to form the tubular member 51a integrally.

  The downstream tubular member 51c is provided with an inlet-side flow surface 54a and an outlet-side flow surface 55a, and an oxygen scavenger holding portion is provided between the inlet-side flow surface 54a and the outlet-side flow surface 55a. 56 is formed, and the oxygen scavenger 57 is held in the oxygen scavenger holding part 56. This point is the same as the oxygen scavenging part 50 according to FIG. The oxygen removal part 50b which concerns on FIG. 4 differs from the oxygen removal part 50 which concerns on FIG. 2 by the point by which the inlet side flow surface 54a and the outlet side flow surface 55a are comprised by the strainer mesh. The strainer mesh constituting the inlet-side flow surface 54a and the outlet-side flow surface 55a is similar to the inlet-side flow surface 54 and the outlet-side flow surface 55 of the deoxygenation unit 50 shown in FIG. Since it has a role to fix, it is preferable not to make the mesh roughness extremely fine but to use a strainer mesh of about 100 mesh, for example.

  On the other hand, the upstream tubular member 51b is also provided with a strainer mesh 58, but the strainer mesh 58 is configured to be a finer mesh than the strainer mesh constituting the inlet-side flow surface 54a and the outlet-side flow surface 55a. It is preferable to configure so that sludge can be captured upstream. Since the tube diameter of the upstream tubular member 51b is larger than the tube diameter of the downstream tubular member 51c, the area of the strainer mesh 58 is larger than the inlet-side flow surface 54a and the outlet-side flow surface 55a. Therefore, even when the strainer mesh 58 is clogged with sludge, the clogging remains partial, and the entire surface of the strainer mesh 58 is hardly clogged. Therefore, the strainer mesh 58 can play a role of trapping sludge, and sludge can be prevented from adhering to the surface of the oxygen scavenger 57.

  As described above, the inlet-side flow surface 54a and the outlet-side flow surface 55a may be configured as a strainer mesh, and a strainer mesh 58 for capturing sludge may be provided further upstream.

  Further, the inlet-side flow surface 54 and the outlet-side flow surface 55 of the deoxygenating unit 50 according to FIG. 2 are provided in the downstream tubular member 51c of FIG. 4 without providing the strainer mesh 58 on the upstream side. You may comprise a strainer mesh like the side flow surface 54a and the exit side flow surface 55a.

  Further, in any configuration of the oxygen scavenging sections 50, 50a, 50b, a desiccant may be used in place of the oxygen scavenger 57, as described above.

  As described above, the deoxygenating units 50, 50a, and 50b can have various configurations as long as the working medium can be brought into contact with the deoxidizing agent 57 or the desiccant. Also, considering whether the working medium is gaseous or liquid, an appropriate configuration may be adopted in accordance with it, or a configuration that can handle both the liquid working medium and the gaseous working medium. Also good. The configuration shown in FIGS. 2 to 4 can be applied to both a liquid working medium and a gaseous working medium.

  As described above, the refrigeration cycle apparatus according to the present embodiment includes the deoxygenation unit 50 in the refrigeration cycle, thereby removing water and oxygen in the refrigeration cycle and suppressing generation of sludge. Thereby, even if it uses HFO which is easy to melt | dissolve with water and oxygen as a refrigerant | coolant, generation | occurrence | production of sludge can be suppressed.

  Moreover, the refrigeration cycle apparatus according to the present embodiment can be used in a heat cycle system such as an air conditioner. Hereinafter, the compressor 10 of the refrigeration cycle system according to FIG. 1 is the compressor 10a, the condenser 20 is the indoor heat exchanger 20a, the decompression mechanism 30 is the expansion valve 30a, the evaporator 40 is the outdoor heat exchanger 40a, and the deoxygenating unit 50. An example in which the air conditioner 150 is configured by applying the above to the deoxygenation unit 50c will be described.

  FIG. 5 is a diagram illustrating an example of an air conditioner 150 that is an example of a thermal cycle system according to an embodiment of the present invention.

  As shown in FIG. 5, the air conditioner 150 has an outdoor unit 150a and an indoor unit 150b, a compressor 10a as a compression mechanism provided in the outdoor unit 150a, a four-way switching valve 154, an expansion unit An expansion valve 30a, a release valve 159, an outdoor heat exchanger 40a, and an indoor heat exchanger 20a provided in the indoor unit 150b are connected by a pipe 60a to form a refrigerant circulation path 61. ing. Moreover, between the indoor heat exchanger 20a and the expansion valve 30a, the deoxidation part 50c is provided in the outdoor unit 150a. The oxygen scavenging part 50 c may contain a desiccant or may contain an oxygen scavenger 57. Further, the configuration may be the configuration of the deoxidation units 50, 50a, and 50b shown in FIGS. 2 to 4, or other configurations. By providing the deoxygenation part 50c in a heat cycle system, decomposition | disassembly of HFO in a heat cycle can be suppressed, and generation | occurrence | production of sludge can be suppressed.

  The outdoor heat exchanger 40 a is provided with a fan 160, and the indoor unit 150 b is provided with a fan 161, and each unit is cooled by blowing air from the fans 160 and 161. The release valve 159 is provided on the outdoor unit 150a side, and is an emergency valve that can discharge the refrigerant circulating in the path 61 to the outdoor unit 150a (outside the apparatus).

  The air conditioner 150 can reverse the refrigerant circulation direction by the switching operation of the four-way switching valve 154, and can perform an air conditioning operation. That is, in the air conditioner 150, the compressor 10a, the outdoor heat exchanger 40a of the outdoor unit 150a (heat source side), the expansion valve 30a, and the indoor heat exchanger 20a of the indoor unit 150b (use side) are sequentially connected. Thus, a working medium path 61 in which the working medium circulation is reversible is configured.

  The air conditioner 150 also includes a control device 170, various sensors S1 to S8 disposed on the path 61 or in each unit, and power such as an inverter power source that supplies power to the compressor 10a by power supply from the AC power source 171. Supply device 172.

  Sensors S <b> 1 and S <b> 2 are sensors that detect (detect) leakage of the refrigerant outside the path 61. The sensor S1 is provided inside the outdoor unit 150a. The sensor S2 is provided inside the indoor unit 150b.

  The sensor S3 is a sensor that detects the temperature of the working medium flowing through the discharge pipe of the compressor 10a. The sensor S4 is a sensor that detects the temperature of the working medium flowing through the pipe 60a between the heat exchanger 40a on the heat source side and the expansion valve 30a. The sensor S5 is a sensor that detects the opening degree of the expansion valve 30a. The sensor S6 is a sensor that detects the temperature of a motor (not shown) that is a drive unit of the compressor 10a. Sensors S7 and S8 are arranged before and after the expansion valve 30a (input end and output end), and are sensors for detecting the flow rate of the working medium circulating in the path 61 (in the pipe 60a).

  Based on the detection information detected by the various sensors S1 to S8, the control device 170 uses the above devices (compressor 10a, four-way switching valve 154, expansion valve 30a, release valve 159, outdoor heat exchanger 40a, indoor heat exchanger). 20a, fans 160 and 161) are controlled. Specifically, the control device 170 drives the compressor 10a by performing drive control on the power supply device 172 that supplies power to the motor of the compressor 10a. The release valve 159 is provided in a pipe 58 extending from the path 61 to the outside of the unit so as to be openable / closable, and is normally closed. The release valve 159 is opened by the control device 170 during the avoidance operation.

  Here, a schematic operation of the air conditioner 150 will be described.

  In the heating operation, the four-way switching valve 154 is set as shown by a solid line in FIG. When the compressor 10a is operated in this state, the indoor heat exchanger 20a becomes the condenser 20 in FIG. 1, and the outdoor heat exchanger 40a becomes the evaporator 40 to perform the refrigeration cycle.

  The high-pressure refrigerant discharged from the compressor 10a passes through the four-way switching valve 154 (point d2 in FIG. 5), flows into the indoor heat exchanger 20a, radiates heat to the indoor air, and condenses (point d3 in FIG. 5). At this time, the condensed high-pressure refrigerant passes through the deoxygenation part 50c, and the oxygen component in the high-pressure refrigerant is removed. The high-pressure refrigerant that has passed through the deoxygenation unit 50c flows into the expansion valve 30a, is decompressed by the expansion valve 30a, becomes low-pressure refrigerant (point d4 in FIG. 5), and flows into the outdoor heat exchanger 40a.

  The low-pressure refrigerant that has flowed into the outdoor heat exchanger 40a absorbs heat from the outdoor air and evaporates. The evaporated low-pressure refrigerant passes through the four-way switching valve 154 and is sucked into the compressor 10a through the point d1 in FIG. The sucked low-pressure refrigerant is compressed and discharged again as a high-pressure refrigerant. By repeating this operation, heating operation of the air conditioner 150 is performed.

  In the air conditioner 150, in both the indoor heat exchanger 20a and the outdoor heat exchanger 40a, the working medium flow during the cooling operation and the working medium flow during the heating operation are in opposite directions. For example, in the cooling operation, the indoor heat exchanger 20a and the outdoor heat exchanger 40a are heated when the working medium inflow side becomes an air outlet side and the working medium outflow side becomes a so-called counterflow with the air inlet side. During operation, the working medium inflow side is the air inlet side, and the working medium outflow side is the air outlet side. In that case, another deoxygenation part 50c may be provided between the outdoor heat exchanger 40a and the expansion valve 30a, and the deoxygenation part 50c can be applied not only to the liquid refrigerant but also to a gaseous working medium. And you may make it dry or deoxygenate from a gaseous working medium in the deoxidation part 50c between the indoor heat exchanger 20a and the expansion valve 30a. In FIG. 5, the example in which the deoxygenation part 50c is provided between the indoor heat exchanger 20a and the expansion valve 30a has been described. However, the deoxygenation part 50c is provided at an arbitrary location in the thermal cycle. be able to.

  Thus, by providing the deoxidation part 50c in thermal cycle systems, such as the air conditioning apparatus 150, the oxygen component in a thermal cycle system can be removed and generation | occurrence | production of the sludge in a thermal cycle can be suppressed.

  Next, the refrigerant used in the refrigeration cycle apparatus and the thermal cycle system according to the embodiment of the present invention will be described.

  As described above, the working medium used in the refrigeration cycle apparatus and the thermal cycle system according to the embodiment of the present invention includes hydrofluoroolefin (HFO). Examples of HFO include trifluoroethylene (HFO-1123), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf). ), 1,1,2-trifluoropropene (HFO-1243yc), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), cis-1,2,3,3 , 3-pentafluoropropene (HFO-1225ye (Z)), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)), 3,3,3-trifluoropropene (HFO-1243zf) and the like. HFO-1234yf, preferably comprising HFO-1234ze (E) or HFO-1234ze (Z), more preferably containing HFO-1234yf or HFO-1123, it is particularly preferred that it include a HFO-1123.

The working medium used in the present invention preferably contains HFO-1123, and may further contain an optional component described later, if necessary. 10 mass% or more is preferable, as for content of HFO-1123 with respect to 100 mass% of a working medium, 20-80 mass% is more preferable, 40-80 mass% is more preferable, 40-60 mass% is further more preferable.
(HFO-1123)
The characteristics of HFO-1123 as a working medium are shown in Table 1 in a relative comparison with R410A (a pseudo-azeotropic refrigerant mixture of HFC-32 and HFC-125 having a mass ratio of 1: 1). The cycle performance is indicated by a coefficient of performance and a refrigerating capacity obtained by a method described later. The coefficient of performance and the refrigerating capacity of HFO-1123 are expressed as relative values (hereinafter referred to as relative performance coefficient and relative refrigerating capacity) with R410A as a reference (1.000). The global warming potential (GWP) is a value of 100 years indicated in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (2007) or measured according to the method. In this specification, GWP refers to this value unless otherwise specified. When the working medium is composed of a mixture, the temperature gradient is an important factor in evaluating the working medium as described later, and a smaller value is preferable.

［任意成分］
本発明で用いる作動媒体はＨＦＯ−１１２３を含むことが好ましく、本発明の効果を損なわない範囲でＨＦＯ−１１２３以外に、通常作動媒体として用いられる化合物を任意に含有してもよい。このような任意の化合物（任意成分）としては、例えば、ＨＦＣ、ＨＦＯ−１１２３以外のＨＦＯ（炭素−炭素二重結合を有するＨＦＣ）、これら以外のＨＦＯ−１１２３とともに気化、液化する他の成分等が挙げられる。任意成分としては、ＨＦＣ、ＨＦＯ−１１２３以外のＨＦＯ（炭素−炭素二重結合を有するＨＦＣ）が好ましい。

[Optional ingredients]
The working medium used in the present invention preferably contains HFO-1123, and may optionally contain a compound used as a normal working medium in addition to HFO-1123 as long as the effects of the present invention are not impaired. Examples of such an arbitrary compound (optional component) include HFO other than HFC and HFO-1123 (HFC having a carbon-carbon double bond), other components that are vaporized and liquefied together with HFO-1123 other than these, etc. Is mentioned. As an optional component, HFO other than HFC and HFO-1123 (HFC having a carbon-carbon double bond) is preferable.

As an optional component, for example, when used in a heat cycle in combination with HFO-1123, there is a compound that can keep the GWP and temperature gradient within an allowable range while having the effect of further increasing the relative coefficient of performance and the relative refrigeration capacity. preferable. When the working medium contains such a compound in combination with HFO-1123, a better cycle performance can be obtained while keeping the GWP low, and the influence of the temperature gradient is small.
(Temperature gradient)
When the working medium contains, for example, HFO-1123 and an optional component, it has a considerable temperature gradient except when HFO-1123 and the optional component have an azeotropic composition. The temperature gradient of the working medium varies depending on the type of the optional component and the mixing ratio of HFO-1123 and the optional component.

  When a mixture is used as the working medium, usually an azeotropic or pseudo-azeotropic mixture such as R410A is preferably used. Non-azeotropic compositions have the problem of causing composition changes when filled from a pressure vessel to a refrigeration air conditioner. Furthermore, when refrigerant leakage from the refrigeration air conditioner occurs, the refrigerant composition in the refrigeration air conditioner is very likely to change, and it is difficult to restore the refrigerant composition to the initial state. On the other hand, the above problem can be avoided if the mixture is azeotropic or pseudo-azeotropic.

  In general, a “temperature gradient” is used as an index for measuring the availability of the mixture in the working medium. A temperature gradient is defined as the property of the start and end temperatures of a heat exchanger, for example, evaporation in an evaporator or condensation in a condenser, differing. In the azeotrope, the temperature gradient is 0, and in the pseudoazeotrope, the temperature gradient is very close to 0, for example, the temperature gradient of R410A is 0.2.

If the temperature gradient is large, for example, the inlet temperature in the evaporator decreases, which increases the possibility of frost formation. Furthermore, in a heat cycle system, in order to improve heat exchange efficiency, it is common to make the working medium flowing through the heat exchanger and a heat source fluid such as water or air counter flow, and in a stable operation state Since the temperature difference of the heat source fluid is small, it is difficult to obtain an energy efficient thermal cycle system in the case of a non-azeotropic mixed medium having a large temperature gradient. For this reason, when a mixture is used as a working medium, a working medium having an appropriate temperature gradient is desired.
(HFC)
The optional HFC is preferably selected from the above viewpoint. Here, HFC is known to have higher GWP than HFO-1123. Therefore, the HFC to be combined with HFO-1123 is appropriately selected from the viewpoint of improving the cycle performance as the working medium and keeping the temperature gradient within an appropriate range, and particularly keeping the GWP within an allowable range. It is preferred that

  Specifically, an HFC having 1 to 5 carbon atoms is preferable as an HFC that has little influence on the ozone layer and has little influence on global warming. The HFC may be linear, branched, or cyclic.

  Examples of the HFC include HFC-32, difluoroethane, trifluoroethane, tetrafluoroethane, HFC-125, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane and the like.

  Among these, HFC-32, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC) have a small influence on the ozone layer and excellent refrigeration cycle characteristics as HFC. -143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), and HFC-125 are preferred, HFC-32, HFC -152a, HFC-134a, and HFC-125 are more preferred.

  One HFC may be used alone, or two or more HFCs may be used in combination.

  The content of HFC in the working medium (100% by mass) can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium composed of HFO-1123 and HFC-32, the coefficient of performance and the refrigerating capacity are improved when the content of HFC-32 is in the range of 1 to 99% by mass. In the case of a working medium composed of HFO-1123 and HFC-134a, the coefficient of performance improves when the content of HFC-134a is in the range of 1 to 99% by mass.

  The preferred HFC GWP is 675 for HFC-32, 1430 for HFC-134a, and 3500 for HFC-125. From the viewpoint of keeping the GWP of the resulting working medium low, the HFC-32 is most preferable as the optional component HFC.

  Moreover, HFO-1123 and HFC-32 can form a pseudo-azeotropic mixture close to azeotropic in a composition range of 99: 1 to 1:99 by mass ratio, and the mixture of both does not choose the composition range almost. The temperature gradient is close to zero. Also in this respect, HFC-32 is advantageous as an HFC combined with HFO-1123.

  In the working medium used in the present invention, when HFC-32 is used together with HFO-1123, the content of HFC-32 with respect to 100% by mass of the working medium is preferably 20% by mass or more, and preferably 20 to 80% by mass. % Is more preferable, and 40 to 60% by mass is more preferable.

  In the working medium used in the present invention, for example, when HFO-1123 is included, HFO other than HFO-1123 has a high critical temperature and is excellent in durability and coefficient of performance, so that HFO-1234yf (GWP = 4), HFO-1234ze (E), HFO-1234ze (Z) (GWP = 6 for both (E) and (Z) isomers) are preferred, and HFO-1234yf and HFO-1234ze (E) are more preferred. HFOs other than HFO-1123 may be used alone or in combination of two or more. The content of HFO other than HFO-1123 in the working medium (100% by mass) can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium composed of HFO-1123 and HFO-1234yf or HFO-1234ze, the coefficient of performance improves when the content of HFO-1234yf or HFO-1234ze is in the range of 1 to 99% by mass.

  A preferred composition range in the case where the working medium used in the present invention contains HFO-1123 and HFO-1234yf is shown below as a composition range (S).

In each formula showing the composition range (S), the abbreviation of each compound is the ratio (mass%) of the compound with respect to the total amount of HFO-1123, HFO-1234yf, and other components (such as HFC-32). Show.
<Composition range (S)>
HFO-1123 + HFO-1234yf ≧ 70% by mass
95% by mass ≧ HFO-1123 / (HFO-1123 + HFO-1234yf) ≧ 35% by mass
The working medium in the composition range (S) has a very low GWP and a small temperature gradient. In addition, from the viewpoint of coefficient of performance, refrigeration capacity, and critical temperature, refrigeration cycle performance that can be substituted for the conventional R410A can be expressed.

  In the working medium having the composition range (S), the ratio of HFO-1123 to the total amount of HFO-1123 and HFO-1234yf is more preferably 40 to 95% by mass, further preferably 50 to 90% by mass, and 50 to 85%. Mass% is particularly preferable, and 60 to 85 mass% is most preferable.

  Further, the total content of HFO-1123 and HFO-1234yf in 100% by mass of the working medium is more preferably from 80 to 100% by mass, further preferably from 90 to 100% by mass, and particularly preferably from 95 to 100% by mass. .

  Moreover, it is preferable that the working medium used for this invention contains HFO-1123, HFC-32, and HFO-1234yf, and the preferable composition range in the case of containing HFO-1123, HFO-1234yf, and HFC-32 (P ) Is shown below.

In each formula showing the composition range (P), the abbreviation of each compound indicates the ratio (mass%) of the compound with respect to the total amount of HFO-1123, HFO-1234yf, and HFC-32. The same applies to the composition range (R), composition range (L), and composition range (M). Moreover, in the composition range described below, the total amount of HFO-1123, HFO-1234yf, and HFC-32 specifically described exceeds 90% by mass and 100% by mass or less with respect to the total amount of the working medium for heat cycle. It is preferable that
<Composition range (P)>
70% by mass ≦ HFO-1123 + HFO-1234yf
30% by mass ≦ HFO-1123 ≦ 80% by mass
0% by mass <HFO-1234yf ≦ 40% by mass
0% by mass <HFC-32 ≦ 30% by mass
HFO-1123 / HFO-1234yf ≦ 95/5% by mass
The working medium having the above composition is a working medium in which the characteristics of HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a well-balanced manner, and the disadvantages of each of them are suppressed. In other words, this working medium is a working medium that has a very low GWP, has a small temperature gradient, and has a certain capacity and efficiency when used in a thermal cycle, and can obtain good cycle performance. Here, the total amount of HFO-1123 and HFO-1234yf with respect to the total amount of HFO-1123, HFO-1234yf, and HFC-32 is preferably 70% by mass or more.

  Moreover, as a more preferable composition of the working medium used for this invention, 30-70 mass% of HFO-1123 and HFO-1234yf are 4-4 with respect to the total amount of HFO-1123, HFO-1234yf, and HFC-32. Examples include a composition containing 40% by mass and HFC-32 in a proportion of 0 to 30% by mass, and the content of HFO-1123 with respect to the total amount of the working medium is 70 mol% or less. The working medium in the above range is a highly durable working medium in which the above effect is enhanced and the self-decomposition reaction of HFO-1123 is suppressed. From the viewpoint of the relative coefficient of performance, the content of HFC-32 is preferably 5% by mass or more, and more preferably 8% by mass or more.

  Moreover, although another preferable composition is shown when the working medium used in the present invention contains HFO-1123, HFO-1234yf and HFC-32, the content of HFO-1123 with respect to the total amount of the working medium should be 70 mol% or less. For example, the self-decomposition reaction of HFO-1123 is suppressed, and a highly durable working medium is obtained.

A more preferred composition range (R) is shown below.
<Composition range (R)>
10% by mass ≦ HFO-1123 <70% by mass
0% by mass <HFO-1234yf ≦ 50% by mass
30% by mass <HFC-32 ≦ 75% by mass
The working medium having the above composition is a working medium in which the characteristics of HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a well-balanced manner, and the disadvantages of each of them are suppressed. That is, it is a working medium in which good cycle performance can be obtained by having a low temperature gradient and high performance and efficiency when used in a thermal cycle after GWP is kept low and durability is ensured.

  In the working medium of the present invention having the composition range (R), preferred ranges are shown below.

20% by mass ≦ HFO-1123 <70% by mass
0% by mass <HFO-1234yf ≦ 40% by mass
30% by mass <HFC-32 ≦ 75% by mass
The working medium having the above composition is a working medium in which the characteristics of HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a particularly well-balanced manner, and the disadvantages of each of them are suppressed. That is, it is a working medium in which GWP is kept low and durability is ensured, and when used in a thermal cycle, the temperature gradient is smaller and the cycle performance is higher by having higher capacity and efficiency. is there.

In the working medium of the present invention having the composition range (R), a more preferred composition range (L) is shown below. The composition range (M) is more preferable.
<Composition range (L)>
10% by mass ≦ HFO-1123 <70% by mass
0% by mass <HFO-1234yf ≦ 50% by mass
30% by mass <HFC-32 ≦ 44% by mass
<Composition range (M)>
20% by mass ≦ HFO-1123 <70% by mass
5 mass% ≦ HFO-1234yf ≦ 40 mass%
30% by mass <HFC-32 ≦ 44% by mass
The working medium having the composition range (M) is a working medium in which the characteristics of the HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a particularly well-balanced manner, and the disadvantages of the working medium are suppressed. In other words, this working medium has a GWP with an upper limit of 300 or less, and durability is ensured, and when used in a heat cycle, the temperature gradient is less than 5.8, and the relative coefficient of performance and relative This is a working medium having a refrigerating capacity close to 1 and good cycle performance.

  Within this range, the upper limit of the temperature gradient is lowered, and the lower limit of the relative coefficient of performance x the relative refrigeration capacity is raised. From the viewpoint of a large relative coefficient of performance, 8% by mass ≦ HFO-1234yf is more preferable. Moreover, HFO-1234yf <= 35 mass% is more preferable from the point with a large relative freezing capacity.

  Moreover, it is preferable that another working medium used for this invention contains HFO-1123, HFC-134a, HFC-125, and HFO-1234yf, and the combustibility of a working medium is suppressed by this composition.

  More preferably, it includes HFO-1123, HFC-134a, HFC-125, and HFO-1234yf, and the ratio of the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf to the total amount of the working medium is 90. The ratio of HFO-1123 to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 3% by mass or more and 35% by mass or less, and HFC-134a. Is preferably 10% by mass to 53% by mass, HFC-125 is preferably 4% by mass to 50% by mass, and HFO-1234yf is preferably 5% by mass to 50% by mass. By using such a working medium, the working medium is non-flammable and excellent in safety, has less influence on the ozone layer and global warming, and has better cycle performance when used in a thermal cycle system. It can be set as the working medium which has these.

Most preferably, it contains HFO-1123, HFC-134a, HFC-125, and HFO-1234yf, and the ratio of the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf to the total amount of the working medium is 90. The ratio of HFO-1123 to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 6% by mass or more and 25% by mass or less, and HFC-134a. It is more preferable that the ratio of HFC-125 is 20% by mass to 35% by mass, the ratio of HFC-125 is 8% by mass to 30% by mass, and the ratio of HFO-1234yf is 20% by mass to 50% by mass. By using such a working medium, the working medium is non-flammable, and is more excellent in safety, has less influence on the ozone layer and global warming, and is even better when used in a heat cycle system. The working medium having a high cycle performance can be obtained.
(Other optional ingredients)
The working medium used in the composition for a heat cycle system of the present invention may contain carbon dioxide, hydrocarbon, chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO) and the like in addition to the above optional components. Other optional components are preferably components that have little influence on the ozone layer and little influence on global warming.

  Examples of the hydrocarbon include propane, propylene, cyclopropane, butane, isobutane, pentane, isopentane and the like.

  A hydrocarbon may be used individually by 1 type and may be used in combination of 2 or more type.

  When the said working medium contains a hydrocarbon, the content is less than 10 mass% with respect to 100 mass% of a working medium, 1-5 mass% is preferable and 3-5 mass% is more preferable. If a hydrocarbon is more than a lower limit, the solubility of the mineral refrigeration oil to a working medium will become more favorable.

  Examples of CFO include chlorofluoropropene and chlorofluoroethylene. As the CFO, 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1 is easy to suppress the flammability of the working medium without greatly reducing the cycle performance of the working medium. , 3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb) and 1,2-dichloro-1,2-difluoroethylene (CFO-1112) are preferred.

  One type of CFO may be used alone, or two or more types may be used in combination.

  When a working medium contains CFO, the content is less than 10 mass% with respect to 100 mass% of a working medium, 1-8 mass% is preferable, and 2-5 mass% is more preferable. If the CFO content is at least the lower limit value, it is easy to suppress the combustibility of the working medium. If the content of CFO is not more than the upper limit value, good cycle performance can be easily obtained.

  Examples of HCFO include hydrochlorofluoropropene and hydrochlorofluoroethylene. As HCFO, 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 1-chloro is easily used because flammability of the working medium can be easily suppressed without greatly reducing the cycle performance of the working medium. -1,2-difluoroethylene (HCFO-1122) is preferred.

  HCFO may be used alone or in combination of two or more.

  When the said working medium contains HCFO, content of HCFO in 100 mass% of working media is less than 10 mass%, 1-8 mass% is preferable and 2-5 mass% is more preferable. If the content of HCFO is equal to or higher than the lower limit value, it is easy to suppress the combustibility of the working medium. If the content of HCFO is not more than the upper limit value, good cycle performance can be easily obtained.

  When the working medium used in the present invention contains other optional components as described above, the total content of other optional components in the working medium is less than 10% by mass with respect to 100% by mass of the working medium, and 8% by mass. % Or less is preferable, and 5 mass% or less is more preferable.

  According to the refrigeration cycle apparatus and the thermal cycle system 150 according to the embodiment of the present invention, sludge generation in the refrigeration cycle is prevented and stable refrigeration can be achieved even with such a working refrigerant that is susceptible to self-decomposition. Cycle operation can be performed.

  Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on January 12, 2016 (Japanese Patent Application No. 2016-3873), the contents of which are incorporated herein by reference.

10, 10a Compressor 20, 20a Condenser 30, 30a Decompression mechanism 40, 40a Evaporator 50, 50a, 50b, 50c Deoxygenation part 51, 51a, 51b, 51c Tubular member 52 Inlet 53 Outlet 54, 54a Inlet side flow Surface 55, 55a Outlet side flow surface 56, 56a Oxygen absorber holding part 57 Oxygen absorber 58 Strainer mesh 150 Thermal cycle system

Claims (12)

A refrigeration cycle apparatus using a working medium containing hydrofluoroolefin (HFO) by connecting a compressor, a condenser, a decompression mechanism and an evaporator with piping to constitute a refrigeration cycle,
A refrigeration cycle apparatus in which a deoxygenation unit for bringing the working medium into contact with a desiccant or a deoxidizer is provided at any location in the refrigeration cycle.   The refrigeration cycle apparatus according to claim 1, wherein the deoxygenation unit is provided between the condenser and the decompression mechanism. The deoxygenation part is configured as a tubular member having both ends connected to the pipe in the refrigeration cycle,
An inlet-side flow surface through which refrigerant flows,
The refrigeration cycle apparatus according to claim 1, further comprising: a medicine holding unit that is provided on the downstream side of the inlet-side flow surface and holds the desiccant or the oxygen scavenger.   The refrigeration cycle apparatus according to claim 3, wherein the inlet-side flow surface is configured in a mesh shape. An outlet side flow surface through which the working medium flows;
The refrigeration cycle apparatus according to claim 3 or 4, wherein the medicine holding unit is provided between the inlet-side flow surface and the outlet-side flow surface.   The refrigeration cycle apparatus according to claim 5, wherein the outlet-side flow surface is configured in a mesh shape.   The refrigeration cycle apparatus according to any one of claims 3 to 6, wherein the medicine holding unit is configured in a bag shape.   The refrigeration cycle apparatus according to any one of claims 3 to 7, wherein a strainer mesh for capturing sludge is provided on the upstream side of the inlet-side flow surface.   The refrigeration cycle apparatus according to claim 8, wherein an area of the strainer mesh is larger than an area of the inlet-side flow surface.   The refrigeration cycle apparatus according to any one of claims 1 to 9, wherein the HFO includes HFO-1123.   The working medium is a single refrigerant of HFO-1123, a mixed refrigerant of HFO-1123 and HFC-32, a mixed refrigerant of HFO-1123 and HFO-1234yf, or HFO-1123, HFO-1234yf, and HFC-32. The refrigeration cycle apparatus according to claim 10, which is a mixed refrigerant.   The thermal cycle system by which the refrigeration cycle apparatus as described in any one of Claims 1 thru | or 11 was mounted.

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