HEAT TRANSPORT DEVICE AND HEAT TRANSPORT METHOD USING SAME

Abstract

The present invention provides a heat transport device in which a hydrohaloolefin-containing refrigerant is enclosed in a circulation route, and the heat transport device is capable of reducing the influence of oxygen entrapped in the circulation route. The present invention also provides a heat transport method using the heat transport device. In the heat transport device 1, a refrigerant comprising at least one of hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), or hydrochloroolefins (HCOs) is enclosed in a circulation route, and a stabilizer container comprising an acid scavenger and/or an antioxidant is disposed in the circulation route. The antioxidant is at least one member selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines, and phthalates, and the acid scavenger is at least one member selected from the group consisting of aliphatic alcohols, polyhydric alcohols, amines, terpenes, alkyl epoxides, and alkenyl tolyls.

Claims

1. A heat transport device comprising a circulation route enclosing a refrigerant containing at least one of hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), or hydrochloroolefins (HCOs), the circulation route comprising a stabilizer container containing an acid scavenger and/or an antioxidant, the antioxidant being at least one member selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines, and phthalates; and the acid scavenger being at least one member selected from the group consisting of aliphatic alcohols, polyhydric alcohols, amines, terpenes, alkyl epoxides, and alkenyl tolyls.

2. The heat transport device according to claim 1, wherein the stabilizer container is disposed between a condenser and an evaporator in the circulation route.

3. The heat transport device according to claim 1, wherein the stabilizer container is composed of a drier.

4. The heat transport device according to claim 1, wherein the refrigerant comprises 1-chloro-3,3,3-trifluoropropene.

5. The heat transport device according to claim 1, wherein the circulation route comprises refrigerant oil in addition to the refrigerant, and the amount of the refrigerant oil is 5 parts by weight or less per 100 parts by weight of the refrigerant.

6. The heat transport device according to claim 5, wherein a bearing that supports an axis of a motor driving a compressor part that compresses the refrigerant in a compressor is a magnetic bearing, ceramic bearing, or air bearing.

7. The heat transport device according to claim 1, wherein a turbo compressor is disposed in the circulation route.

8. The heat transport device according to claim 1, wherein the device is operated at 3.0 MPa or less.

9. A heat transport method comprising circulating the refrigerant in the circulation route of the heat transport device according to claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0018] FIG. 1 shows an embodiment of a refrigerant circulation route in an air conditioner, which is one embodiment of the heat transport device according to the present invention.

[0019] FIG. 2 shows an embodiment of a refrigerant circulation route in a turbo refrigerating machine, which is another embodiment of the heat transport device according to the present invention.

DESCRIPTION OF EMBODIMENTS

Heat Transport Device of the Present Invention

[0020] In the heat transport device of the present invention, a refrigerant (hereinbelow a refrigerant mixture is also abbreviated as “refrigerant”) comprising at least one of hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), or hydrochloroolefins (HCOs) is enclosed in the refrigerant circulation route in the device, and heat is transferred by passing through each device disposed in the circulation route.

[0021] The purpose of the heat transport device is not limited. A wide variety of applications include air conditioners (mobile air conditioners, domestic air conditioners, and air conditioners for business use), refrigerating machines, refrigerators, coolers (chillers), container refrigerating apparatus, and heat transport apparatus, such as hot-water supply systems. A specific example of the heat transport device of the present invention is explained below with reference to the air conditioner (see FIG. 1) or the turbo refrigerating machine (see FIG. 2), which is one of the compression heat transport devices.

[0022] Embodiments of the heat transport device of the present invention are explained below.

[0023] The heat transport device according to the embodiment of the present invention is a heat transport device in which a refrigerant comprising at least one of hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), or hydrochloroolefins (HCOs) is enclosed in the circulation route. A stabilizer container comprising an acid scavenger and/or an antioxidant is disposed in the circulation route. The antioxidant is at least one member selected from the group consisting of alkylcatechols, alkoxyphenols, benzoquinones, phenothiazines, and phthalates, and the acid scavenger is at least one member selected from the group consisting of aliphatic alcohols, polyhydric alcohols, amines, terpenes, alkyl epoxides, and alkenyl tolyls.

[0024] The refrigerant comprises at least one of HFOs, HCFOs, or HCOs. Examples of HFOs include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3-tetrafluoropropene (HFO-1234ye), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 1,1,1,2,4,4,5,5,5-nonafluoropentene (HFO-1429myz), etc.

[0025] Examples of HCFOs include 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 1,2,3-trichloro-3,3-difluoropropene (HCFO-1222xd), 2,3,3-trichloro-3-fluoropropene (HCFO-1231xf), etc.

[0026] Examples of HCOs include 1,3,3,3-tetrachloropropene (HCO-1230zd), 1,1,2,3-tetrachloropropene (HCO-1230xa), 1,1,3,3-tetrachloropropene (HCO-1230za), 2,3,3,3-tetrachloropropene (HCO-1230xf), etc.

[0027] These HFOs, HCFOs, and HCOs can be used singly or as a mixture of two or more. It is possible to mix refrigerants other than HFOs, HCFOs, and HCOs. In this case, adjusting the total amount of HFOs, HCFOs, and HCOs in the refrigerant mixture to 50 wt % or more is preferable. In the present invention, the refrigerant or refrigerant mixture is preferably composed of at least one of HFOs, HCFOs, or HCOs.

[0028] FIG. 1 shows an embodiment of the refrigerant circulation route when the air conditioner 1 is used as a heat transport device. The air conditioner 1 mainly consists of a compressor 2, a four-way switching valve 3, an outdoor heat exchanger 4, an expansion mechanism 5, and an indoor heat exchanger 6. In FIG. 1, the solid arrow indicates the refrigerant circulation direction during cooling while the dotted arrow indicates the refrigerant circulation direction during heating. The refrigerant circulation direction can be controlled by allowing the refrigerant discharged from the compressor 2 to select the outdoor heat exchanger 4 direction or indoor heat exchanger 6 direction using the four-way switching valve 3.

[0029] The refrigeration cycle of the air conditioner 1 during cooling is explained. First, the compressor 2 compresses a low-pressure gas refrigerant and discharges a high-pressure gas refrigerant. The refrigerant discharged from the compressor 2 passes through the four-way switching valve 3 and is supplied to the outdoor heat exchanger 4. The outdoor heat exchanger 4 condenses a high-pressure gas refrigerant and discharges a high-pressure liquid refrigerant. The refrigerant discharged from the outdoor heat exchanger 4 passes through the expansion valve of the expansion mechanism 5 and becomes a refrigerant in the low-pressure gas-liquid mixing state. The refrigerant is then supplied to the indoor heat exchanger 6. The indoor heat exchanger 6 allows the refrigerant in the low-pressure gas-liquid mixing state to evaporate, and discharges a low-pressure gas refrigerant. The low-pressure gas refrigerant discharged from the indoor heat exchanger 6 is supplied to the compressor 2. This refrigeration cycle can cool a room.

[0030] During cooling, the outdoor heat exchanger 4 functions as a condenser and the indoor heat exchanger 6 functions as an evaporator. Specifically, evaporative latent heat of a refrigerant generated in the indoor heat exchanger 6 cools a room. On the other hand, during heating, by switching the four-way switching valve 3, the outdoor heat exchanger 4 functions as an evaporator and the indoor heat exchanger 6 functions as a condenser. Specifically, condensed latent heat of a refrigerant generated in the indoor heat exchanger 4 heats a room.

[0031] The air conditioner 1 includes a stabilizer container 7 present in the refrigerant circulation route. The stabilizer container 7 includes an acid scavenger and/or an antioxidant by storing a solid acid scavenger and/or antioxidant inside the container as a stabilizer. The antioxidant prevents oxidative degradation of the refrigerant. The acid scavenger scavenges acids such as fluoric acid generated by oxidative degradation of the refrigerant to inhibit degradation of refrigerant oil or metallic corrosion of the apparatus caused by the acids. The stabilizer container 7 is disposed in the circulation route in a manner such that the refrigerant flowing in the circulation route passes inside the stabilizer container 7 and is returned to the circulation route again. Because the refrigerant mixes the acid scavenger and/or the antioxidant when passing inside the stabilizer container 7, oxidative degradation of the refrigerant caused by oxygen entrapped in the circulation route is prevented and/or acids generated in the circulation route are scavenged.

[0032] Examples of the antioxidant include at least one member selected from the group consisting of alkyl catechols, alkoxy phenols, benzoquinones, phenothiazins, and phthalates.

[0033] Examples of alkylcatechols include pyrocatechol compounds represented by Formula (1):

##STR00001##

wherein R.sup.1 is alkyl and n is an integer of 1 to 4.

[0034] Examples of alkyl groups represented by R.sup.1 include C.sub.1 to C.sub.10 linear, branched, or cyclic alkyl groups. Specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Tert-butyl is preferable.

[0035] n is preferably 1 or 2, and is more preferably 1. When n is an integer of 2 to 4, the groups represented by R.sup.1 may be the same or different. Although R.sup.1 may be bonded to any position on the benzene ring, R.sup.1 is preferably bonded to the 4- or 5-position.

[0036] A preferable example of alkylcatechol is 4-tert-butylpyrocatechol.

[0037] Examples of alkoxyphenols include phenolic compounds represented by Formula (2):

##STR00002##

wherein R.sup.2 is an alkyl group, and m is an integer of 1 to 5.

[0038] Examples of the alkyl group represented by R.sup.2 include C.sub.1 to C.sub.10 linear, branched, or cyclic alkyl groups. Specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Methyl, ethyl, isopropyl, and tert-butyl are preferable. m is preferably 1 or 2, and more preferably 1. When n is an integer of 2 to 4, the groups represented by R.sup.2O may be the same or different. Although R.sup.2O may be bonded to any position on the benzene ring, R.sup.2O is preferably bonded to the p-position (4-position).

[0039] A preferable example of alkoxyphenol is 4-methoxyphenol.

[0040] Examples of benzoquinones include quinone compounds represented by Formula (3):

##STR00003##

wherein R.sup.3 is an alkyl group, and p is an integer of 1 to 4.

[0041] Examples of alkyl groups represented by R.sup.3 include C.sub.1 to C.sub.10 linear, branched, or cyclic alkyl groups. Specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Methyl, ethyl, isopropyl, and tert-butyl are preferable.

[0042] p is preferably 0, 1, or 2, and more preferably 0. When n is an integer of 2 to 4, groups represented by R.sup.3 may be the same or different. R.sup.3 may be bonded to any position on the ring.

[0043] A preferable example of benzoquinone is 1,4-benzoquinone.

[0044] Examples of phenothiazines include phenothiazine compounds represented by Formula (4):

##STR00004##

wherein R.sup.4 is a hydrogen atom or an alkyl group, the groups represented by R.sup.5 or the groups represented by R.sup.6 may be the same or different, and each represents a hydrogen atom or an alkyl group, q and r may be the same or different, and each represents an integer of 1 to 4.

[0045] Examples of alkyl groups represented by R.sup.4 include C.sub.1 to C.sub.10 linear, branched, or cyclic alkyl groups. Specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Methyl, ethyl, isopropyl, and tert-butyl are preferable. R.sup.4 is preferably a hydrogen atom.

[0046] Alkyl groups represented by R.sup.5 and RE can be suitably selected from those represented by R.sup.4. Preferably, both R.sup.5 and R.sup.6 are hydrogen atoms.

[0047] q and r are preferably 0, 1, or 2, and more preferably 0. When q is an integer of 2 to 4, the groups represented by R.sup.5 may be the same or different. When r is an integer of 2 to 4, the groups represented by R.sup.6 may be the same or different. R.sup.5 and R.sup.6 may be bonded to any position on the ring.

[0048] A preferable example of phenothiazine is a phenothiazine.

[0049] Examples of phthalates include mono- or di-alkali metal salts of phthalic acid. Mono-alkali metal salts of phthalic acid are preferable. Specific examples thereof include potassium hydrogen phthalate and sodium hydrogen phthalate. Potassium hydrogen phthalate is preferable.

[0050] As the antioxidant, alkyl catechols, alkoxy phenols, benzoquinones, phenothiazins, and phthalates can be used alone or as a mixture of two or more.

[0051] As an acid scavenger, at least one member selected from the group consisting of aliphatic alcohols, polyhydric alcohols, amines, terpenes, alkyl epoxides, and alkenyl tolyls can be used.

[0052] Examples of aliphatic alcohols (monovalent) include C.sub.1 to C.sub.4 linear or branched alcohols. The alkyl group of alcohol may include an ether bond. Specific examples thereof include methanol, ethanol, (n-, iso-)propyl alcohol, (n-, sec-, tert-)butanol, etc. Methanol, isopropyl alcohol, sec-butanol, and tert-butanol are preferable.

[0053] Examples of polyhydric alcohols include C.sub.2 to C.sub.4 alcohols having 2 to 4 hydroxy groups. The hydrocarbon chain in the alcohol may include an ether bond. Specific examples thereof include ethylene glycol, propylene glycol, glycerol, erythritol, etc. Ethylene glycol is preferable.

[0054] Examples of amines include primary, secondary, and tertiary amine compounds substituted with a C.sub.2 to C.sub.5 alkyl group or phenyl. Specific examples thereof include triethylamine, tributylamine, aniline, and diphenylamine. Triethylamine and aniline are preferable.

[0055] Examples of terpenes include isoprene, myrcene, allo-ocimene, beta ocimene, terpene, d-limonene, retinal, pinene, menthol, etc. Isoprene and d-limonene are preferable.

[0056] Examples of alkyl epoxides include epoxy compounds substituted with a C.sub.4 to C.sub.5 alkyl group. Specific examples thereof include 1,2-butylene oxide, 1,2-isobutyleneoxide, 1,2-pentyloxide, 1,2-isopentyloxide, and 1,2-tert-pentyloxide. 1,2-Butylene oxide is preferable.

[0057] Examples of alkenyl tolyls include tolyl compounds in which one C.sub.2 to C.sub.4 alkenyl group is substituted. Specific examples include 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propenyltoluene, 4-isopropenyl toluene, etc. 4-Isopropenyl toluene is preferable.

[0058] As an acid scavenger, aliphatic alcohols, polyhydric alcohols, amines, terpenes, alkyl epoxides, and alkenyl tolyls can be used singly or as a mixture of two or more.

[0059] The amount of the antioxidant is usually 0.1 to 5.0 parts by weight and preferably 0.3 to 3.0 parts by weight, per 100 parts by weight of the total amount of HFOs, HCFOs, and HCOs. The amount of the acid scavenger is usually 0.005 to 5 parts by weight and preferably 0.01 to 1 part by weight, per 100 parts by weight of the total amount of HFOs, HCFOs, and HCOs.

[0060] The position of the stabilizer container 7 in the circulation route is not limited. The stabilizer container 7 is preferably disposed between the evaporator and the condenser between which the refrigerant flows in the circulation route as a liquid refrigerant. Specifically, the stabilizer container 7 is preferably disposed between the outdoor heat exchanger 4 and the expansion mechanism 5 or between the indoor heat exchanger 6 and the expansion mechanism 5. During cooling, the outdoor heat exchanger 4 functions as a condenser and the indoor heat exchanger 6 functions as an evaporator. During heating, the outdoor heat exchanger 4 functions as an evaporator and the indoor heat exchanger 6 functions as a condenser. In either case of cooling or heating, the liquid refrigerant is present between the expansion mechanism 5 and the outdoor heat exchanger 4 or between the expansion mechanism 5 and the indoor heat exchanger 6. Thus, as the liquid refrigerant passes through the stabilizer container 7, oxidation of the refrigerant can be efficiently prevented and acids in the circulation route can be efficiently scavenged.

[0061] The stabilizer container 7 may be disposed between the outdoor heat exchanger 4 and the expansion mechanism 5 or between the indoor exchanger 6 and the expansion mechanism 5. When one stabilizer container 7 is disposed in the circulation route, it is preferable to store both an acid scavenger and an antioxidant in the stabilizer container 7. Alternatively, as the stabilizer container 7, two stabilizer containers, i.e., one including an acid scavenger and the other including an antioxidant, can be disposed in the circulation route.

[0062] In FIG. 1 mentioned above, the air conditioner 1 is used as an example of the heat transport device; however, a turbo refrigerating machine 1′ shown in FIG. 2 can be used as the heat transport device. FIG. 2 shows an embodiment of a refrigerant circulation route in the turbo refrigerating machine 1′. The turbo refrigerating machine 1′ mainly consists of a compressor 2′, a condenser 4′, an expansion mechanism 5′, and an evaporator 6′.

[0063] The solid arrow in FIG. 2 shows the refrigerant circulation direction. Specifically, the compressor 2′ compresses a low-pressure gas refrigerant and discharges a high-pressure gas refrigerant. The refrigerant discharged from the compressor 2′ is supplied to the condenser 4′. The condenser 4′ condenses a high-pressure gas refrigerant and discharges a high-pressure liquid refrigerant. The refrigerant discharged from the condenser 4′ passes through the expansion valve of the expansion mechanism 5′ and becomes a refrigerant in the low-pressure gas-liquid mixing state. The refrigerant is then supplied to the evaporator 6′. The evaporator 6′ allows the refrigerant in the low-pressure gas-liquid mixing state to evaporate and discharges a low-pressure gas refrigerant. The low-pressure gas refrigerant discharged from the evaporator 6′ is supplied to the compressor 2′. Cool wind formed of cool water generated by this refrigeration cycle is used for cooling a large-scale space.

[0064] The turbo refrigerating machine 1′ also includes the stabilizer container 7′ present in the refrigerant circulation route. Since the stabilizer container 7′ is as explained above, detailed explanation is omitted here. The position of the stabilizer container 7′ in the circulation route is not limited. The stabilizer container is preferably disposed between the evaporator 4′ and the condenser 6′ between which the refrigerant flows in the circulation route as a liquid refrigerant. Specifically, the stabilizer container 7′ is preferably disposed between the condenser 4′ and the expansion mechanism 5′ or between the evaporator 6′ and the expansion mechanism 5′. Thus, the liquid refrigerant passes through the stabilizer container 7′, the oxidation of the refrigerant can be efficiently prevented and acids in the circulation route can be efficiently scavenged.

[0065] When the circulation route includes an injection line 8 (dashed line in FIG. 2) and an economizer (not shown), the stabilizer container 7 may be disposed on the injection line 8 from the condenser 4′ to the compressor 2′.

[0066] The stabilizer container 7′ may be disposed between the condenser 4′ and the expansion mechanism 5′, between the evaporator 6′ and the expansion mechanism 5′, or at any position on the injection line 8. When one stabilizer container 7′ is disposed in the circulation route, it is preferable to store both an acid scavenger and an antioxidant in the stabilizer container 7′. As the stabilizer container 7′, two stabilizer containers, i.e., one including an acid scavenger and the other including an antioxidant, can be disposed in the circulation route.

[0067] In either of the embodiments shown above, the stabilizer container 7 or 7′ may be a special device containing an acid scavenger and/or an antioxidant as the stabilizer. A drier or the like can be used as a stabilizer container containing an acid scavenger and/or an antioxidant by storing a solid acid scavenger and/or antioxidant in a drying device (drier) provided in the refrigerant circulation route of a known heat transport device, or by immersing a liquid acid scavenger and/or antioxidant in a drying agent in the drier.

[0068] In the heat transport device according to an embodiment of the present invention, valves are provided before and after the stabilizer container 7 or 7′, and the stabilizer container 7 or 7′ is removably mounted on the circulation route so that the acid scavenger or antioxidant in the stabilizer container 7 or 7′ is easily removed or exchanged. Both manual and electric valves can be used as long as the valves are provided in the circulation route in a manner such that the flow of the refrigerant against the stabilizer container 7 or 7′ can be controlled. Manual and electric valves are both usable.

[0069] The embodiments of the heat transport device of the present invention are explained above; however, the heat transport device of the present invention is not limited to these embodiments. Various modifications are possible as long as the gist of the present invention is not deviated from.

[0070] For example, the heat transport device of the present invention can be operated at a low pressure of 3.0 MPa or less, and preferably 1.0 MPa or less.

[0071] The heat transport device of the present invention can use a magnetic bearing, a ceramic bearing, or an air bearing as a bearing that supports the axis of a motor driving the compression part compressing the refrigerant in the compressor. Thereby, an oil-free heat transport device in which the amount of the refrigerant oil to be used is limited to 5 parts by weight or less per 100 parts by weight of the refrigerant can be attained, and a turbo compressor for use in chillers can be provided. The above bearing does not require refrigerant oil for improving lubricity of the bearing in addition to the refrigerant, and the amount of the refrigerant oil can be substantially set to 0 parts by weight. However, considering oil (grease etc.) entrapped during the construction of the heat transport device, the amount of the refrigerant oil is preferably 5 parts by weight or less.

Heat Transport Method of the Present Invention

[0072] The heat transport method of the present invention can be performed by circulating the refrigerant in the refrigerant circulation route of the heat transport device according to the present invention.

EXAMPLES

[0073] The present invention is explained in detail below with reference to Examples and Comparative Examples. However, the present invention is not limited to the Examples.

Examples 1 to 36 and Comparative Examples 1 and 2

Preparation of Refrigerant

[0074] HCFO-1233zd (E) was used as a refrigerant. 100 g of a stabilizer was used per 100 kg of the refrigerant. In Examples 1 to 6, an antioxidant alone was used as a stabilizer and in Examples 7 to 36, an antioxidant and an acid scavenger were used as a stabilizer. Of Examples 7 to 36 in which an antioxidant and an acid scavenger were used as a stabilizer, the weight ratio of the antioxidant and the acid scavenger (i) was 9:1 in Examples 7 to 12 and 25 to 30, while the weight ratio of the antioxidant, acid scavenger (i), and acid scavenger (ii) was 8:1:1 in Examples 13 to 18 and 31 to 36. The antioxidants and acid scavengers used in the Examples are shown in Table 1 below.

[0075] 5 kg of refrigerant oil mainly consisting of a polyvinyl ether-based compound having a constitutional unit represented by Formula (5) below and having a kinematic viscosity at 40° C. of about 70 mm.sup.2/s was prepared as refrigerant oil.

##STR00005##

TABLE-US-00001 TABLE 1 Acid scavenger Antioxidant (i) (ii) Comparative — — — Example 1 Comparative — — — Example 2 Example 1 2,6-Di-tert-butyl-4- — — methylphenol Example 2 4-Tert-butylcatechol — — Example 3 4-Methoxyphenol — — Example 4 1,4-Benzoquinone — — Example 5 Phenothiazine — — Example 6 Potassium hydrogen — — phthalate Example 7 2,6-Di-tert-butyl-4- Isopropanol — methylphenol Example 8 4-Tert-butylcatechol p-Isopropenyltoluene — Example 9 4-Methoxyphenol d-Limonene — Example 10 1,4-Benzoquinone 1,2-Butylene oxide — Example 11 Phenothiazine Ethylene glycol — Example 12 Potassium hydrogen Isopropanol — phthalate Example 13 2,6-Di-tert-buty1-4- p-Isopropenyltoluene Triethylamine methylphenol Example 14 4-Tert-butylcatechol p-Isopropenyltoluene Triethylamine Example 15 4-Methoxyphenol p-Isopropenyltoluene Triethylamine Example 16 1,4-Benzoquinone p-Isopropenyltoluene Triethylamine Example 17 Phenothiazine p-Isopropenyltoluene Triethylamine Example 18 Potassium hydrogen p-Isopropenyltoluene Triethylamine phthalate Example 19 2,6-Di-tert-butyl-4- — — methylphenol Example 20 4-Tert-butylcatechol — — Example 21 4-Methoxyphenol — — Example 22 1,4-Benzoquinone — — Example 23 Phenothiazine — — Example 24 Potassium hydrogen — — phthalate Example 25 2,6-Di-tert-butyl-4- Isopropanol — methylphenol Example 26 4-Tert-butylcatechol p-Isopropenyltoluene — Example 27 4-Methoxyphenol d-Limonene — Example 28 1,4-Benzoquinone 1,2-Butylene oxide — Example 29 Phenothiazine Ethylene glycol — Example 30 Potassium hydrogen Isopropanol — phthalate Example 31 2,6-Di-tert-butyl-4- p-Isopropenyltoluene Triethylamine methylphenol Example 32 4-Tert-butylcatechol p-Isopropenyltoluene Triethylamine Example 33 4-Methoxyphenol p-Isopropenyltoluene Triethylamine Example 34 1,4-Benzoquinone p-Isopropenyltoluene Triethylamine Example 35 Phenothiazine p-Isopropenyltoluene Triethylamine Example 36 Potassium hydrogen p-Isopropenyltoluene Triethylamine phthalate

[0076] A total of 38 kinds (Examples 1 to 36 and Comparative Examples 1 and 2) of refrigerants shown in Table 1 were individually enclosed in the circulation route of the turbo refrigerating machine shown in FIG. 2, and stabilizers were stored in a stabilizer container. The turbo refrigerating machine was operated for a certain period of time (Examples 1 to 18 and Comparative Example 1: 330 hours; Examples 19 to 36 and Comparative Example 2: 1000 hours). The refrigerants after operation were taken as samples, and the total acid numbers of gases and oil refrigerants were measured by a neutralization titration method. Table 2 shows the measurement results.

TABLE-US-00002 TAN (mg .Math. KOH/g) Gas Oil Comparative 0.95 1.40 Example 1 Comparative 3.10 4.65 Example 2 Example 1 0.10 0.15 Example 2 0.10 0.14 Example 3 0.14 0.15 Example 4 0.24 0.30 Example 5 0.10 0.35 Example 6 0.15 0.21 Example 7 0.01 0.07 Example 8 0.02 0.08 Example 9 0.05 0.10 Example 10 0.04 0.15 Example 11 0.10 0.15 Example 12 0.01 0.018 Example 13 0.02 0.08 Example 14 0.01 0.09 Example 15 0.01 0.08 Example 16 0.10 0.15 Example 17 0.04 0.15 Example 18 0.01 0.07 Example 19 0.45 0.70 Example 20 0.46 0.93 Example 21 0.78 0.94 Example 22 1.09 1.40 Example 23 0.78 1.63 Example 24 0.60 0.94 Example 25 0.15 0.48 Example 26 0.14 0.47 Example 27 0.30 0.95 Example 28 0.47 0.93 Example 29 0.62 0.25 Example 30 0.15 0.46 Example 31 0.14 0.24 Example 32 0.16 0.33 Example 33 0.14 0.42 Example 34 0.46 1.16 Example 35 0.30 0.83 Example 36 0.16 0.36

[0077] A comparison between Comparative Example 1 and Examples 1 to 18 indicates that the total acid number was reduced to about 1/20 or less when the operation time was 330 hours. A comparison between Comparative Example 2 and Examples 19 to 36 indicates that the total acid number was reduced to about 1/10 or less when the operation time was 1000 hours. This indicates that the stabilizer container exhibits inhibitory effects. Further, Examples 1 to 6 and Examples 7 to 18, and Examples 19 to 24 and Examples 25 to 36 were compared. Specifically, Examples using the same kind of antioxidant were compared between the case in which the antioxidant alone was used as the stabilizer and the case in which the antioxidant and acid scavenger(s) were used as the stabilizer. The results indicate that the total acid number was substantially reduced when the antioxidant and the acid scavenger(s) were used as the stabilizer. This indicates that the use of the antioxidant and the acid scavenger(s) as the stabilizer attained higher inhibitory effects of the stabilizer container.

[0078] The above results confirmed that by the stabilizer, a refrigerant containing a hydrohaloolefin, such as 1-chloro-3,3,3-trifluoro propene, can exhibit stability against oxygen even in the presence of air (oxygen). Accordingly, the present invention is found to be useful as a heat transport device and a heat transport method that exhibit the stability equivalent to that of conventional HEC refrigerants, and exert very little effect on the global environment.

DESCRIPTION OF REFERENCE NUMERALS

[0079] 1 Air conditioner (Heat transport device) [0080] 1′ Turbo refrigerating machine (Heat transport device) [0081] 2 Compressor [0082] 2′ Compressor [0083] 3 Four-way switching valve [0084] 4 Outdoor heat exchanger [0085] 4′ Condenser [0086] 5 Expansion mechanism [0087] 5′ Expansion mechanism [0088] 6 Indoor heat exchanger [0089] 6′ Evaporator [0090] 7 Stabilizer container [0091] 7′ Stabilizer container