WO2015125880A1 - 熱サイクルシステム用組成物および熱サイクルシステム - Google Patents
熱サイクルシステム用組成物および熱サイクルシステム Download PDFInfo
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- WO2015125880A1 WO2015125880A1 PCT/JP2015/054651 JP2015054651W WO2015125880A1 WO 2015125880 A1 WO2015125880 A1 WO 2015125880A1 JP 2015054651 W JP2015054651 W JP 2015054651W WO 2015125880 A1 WO2015125880 A1 WO 2015125880A1
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
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- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
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- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
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Definitions
- the present invention relates to a composition for a heat cycle system and a heat cycle system using the composition.
- CFC chlorofluorocarbons
- HCFC hydrochlorofluorocarbons
- HFC-32 difluoromethane
- HFC-125 pentafluoroethane
- HFC-125 hydrofluorocarbons
- R410A a pseudo-azeotropic mixture of HFC-32 and HFC-125 having a mass ratio of 1: 1 is a refrigerant that has been widely used.
- HFC may cause global warming.
- R410A has been widely used for ordinary air-conditioning equipment called so-called package air conditioners and room air conditioners because of its high refrigerating capacity.
- GWP global warming potential
- the global warming potential (GWP) is as high as 2088, and therefore development of a low GWP working medium is required.
- R410A is simply replaced and the devices that have been used so far continue to be used.
- HFO olefins
- HFC saturated HFC
- HFC is referred to as HFC, and is used separately from HFO.
- HFC is specified as a saturated hydrofluorocarbon.
- Patent Document 1 discloses a technique related to a working medium using trifluoroethylene (HFO-1123) that has the above-described characteristics and provides excellent cycle performance. Patent Document 1 further attempts to use HFO-1123 in combination with various HFCs and HFOs for the purpose of improving the nonflammability and cycle performance of the working medium.
- HFO-1123 trifluoroethylene
- HFO-1123 is a compound containing an unsaturated bond in the molecule and has a very short life in the atmosphere. Therefore, under conditions where compression and heating are repeated in a thermal cycle, conventional HFC and It is inferior in stability to saturated hydrofluorocarbons such as HCFC and hydrochlorofluorocarbons, and the lubricity may be reduced in the thermal cycle system.
- the present invention has been made from the above viewpoint, and in a composition for a thermal cycle system containing trifluoroethylene (HFO-1123), the low global warming potential and excellent cycle performance of HFO-1123 are sufficiently obtained.
- a composition for a thermal cycle system that makes HFO-1123 more stably lubricable while utilizing it, and has a high cycle performance with little impact on global warming using the composition, and further for thermal cycle use It is an object of the present invention to provide a thermal cycle system with improved working medium lubricity.
- the present invention provides a working medium for heat cycle, a composition for heat cycle system, and a heat cycle system having the configurations described in [1] to [15] below.
- a composition for a heat cycle system comprising a working medium for heat cycle containing trifluoroethylene and a refrigerating machine oil.
- the refrigerating machine oil is at least one selected from an ester refrigerating machine oil, an ether refrigerating machine oil, a polyglycol based refrigerating machine oil, and a hydrocarbon refrigerating machine oil.
- composition for a heat cycle system according to any one of [1] to [8], wherein the working medium for heat cycle further contains a hydrofluorocarbon having a carbon-carbon double bond other than trifluoroethylene.
- the hydrofluorocarbon having a carbon-carbon double bond is at least one selected from 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene.
- the composition for thermal cycle systems as described in. [11] The composition for a heat cycle system according to any one of [1] to [10], wherein the content of trifluoroethylene is 10% by mass or more with respect to 100% by mass of the working medium for heat cycle.
- composition for a heat cycle system according to [11], wherein the content of trifluoroethylene is 20 to 80% by mass with respect to 100% by mass of the working medium for heat cycle.
- the working medium for heat cycle further includes difluoromethane, and the content of difluoromethane with respect to 100% by weight of the working medium for heat cycle is 20% by weight or more.
- Composition for thermal cycle system [14] A thermal cycle system using the composition for thermal cycle system according to any one of [1] to [13].
- a composition for a heat cycle system containing trifluoroethylene contains HFO-1123 while fully utilizing the low global warming potential and excellent cycle performance of HFO-1123.
- a composition for a heat cycle system that can more stably lubricate the working medium for heat cycle can be provided.
- the thermal cycle system of the present invention is a thermal cycle system that has little influence on global warming, has high cycle performance, and further improves the lubrication characteristics of the working medium for thermal cycle.
- FIG. 2 is a cycle diagram in which a change in state of a working medium in the refrigeration cycle system of FIG. 1 is described on a pressure-enthalpy diagram.
- composition for thermal cycle system includes a working medium for heat cycle containing HFO-1123 and refrigeration oil.
- a heat cycle system using a heat exchanger such as a condenser or an evaporator is used without particular limitation.
- a heat cycle system for example, a refrigeration cycle
- a gas working medium is compressed by a compressor, cooled by a condenser to produce a high-pressure liquid, the pressure is reduced by an expansion valve, and vaporized at a low temperature by an evaporator. It has a mechanism that takes heat away with heat.
- HFO-1123 When HFO-1123 is used as a working medium in such a thermal cycle system, HFO-1123 may become unstable depending on temperature conditions and pressure conditions, and self-decomposition may occur, thereby reducing the function of the working medium for thermal cycles. .
- the composition for a heat cycle system of the present invention it is possible to enhance the lubricity of HFO-1123 as a heat cycle working medium and exhibit efficient cycle performance by coexisting refrigeration oil.
- each component which the composition for thermal cycle systems of this invention contains is demonstrated.
- the composition for a heat cycle system of the present invention contains HFO-1123 as a working medium.
- the working medium according to the present invention may contain an optional component described later, if necessary.
- the content of HFO-1123 with respect to 100% by mass of the working medium is preferably 10% by mass or more, more preferably 20 to 80% by mass, still more preferably 40 to 80% by mass, and further preferably 40 to 60% by mass.
- HFO-1123 The characteristics of HFO-1123 as a working medium are shown in Table 1 particularly in a relative comparison with R410A (a pseudo-azeotropic 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 shown as relative values (hereinafter referred to as relative performance coefficient and relative refrigerating capacity) with R410A as the 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.
- IPCC Intergovernmental Panel on climate Change
- the working medium used in the present invention 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.
- 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 vaporize and liquefy together with HFO-1123 other than these, etc. Is mentioned.
- HFO other than HFC and HFO-1123 HFC having a carbon-carbon double bond
- a compound capable of keeping 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 when used in a heat cycle in combination with HFO-1123 is preferable.
- 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.
- thermo gradient When the working medium contains an optional component, it has a considerable temperature gradient except when the 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.
- 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.
- Temperature gradient is generally used as an index for measuring the possibility of using the mixture in the working medium.
- a temperature gradient is defined as the nature of heat exchangers, such as evaporation in an evaporator or condensation in a condenser, with different start and end temperatures. 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.
- the inlet temperature in the evaporator decreases, which increases the possibility of frost formation, which is a problem.
- 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 heat 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.
- HFC is known to have higher GWP than HFO-1123. Therefore, the HFC 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
- 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.
- HFC examples include fluorides of alkanes having 1 to 5 carbon atoms, such as trifluoromethane, HFC-32, difluoroethane, trifluoroethane, tetrafluoroethane, HFC-125, trifluoroiodomethane, pentafluoropropane. , Hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane and the like are preferable.
- HFC 1,1-difluoroethane
- HFC-152a 1,1,1-trifluoroethane
- HFC-125 1,1,2,2-tetrafluoroethane
- HFC-132, 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.
- 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.
- 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 obtained working medium low, the HFC-32 is most preferable as an optional HFC.
- HFO-1123 and HFC-32 can form a pseudo-azeotropic mixture close to azeotropy in a composition range of 99: 1 to 1:99 by mass ratio. The temperature gradient is close to zero. Also in this respect, HFC-32 is advantageous as an HFC combined with HFO-1123.
- the content of HFC-32 with respect to 100% by mass of the working medium is specifically preferably 20% by mass or more, and 20 to 80% by mass. % Is more preferable, and 40 to 60% by mass is further preferable.
- HFO other than HFO-1123 HFO as an optional component other than HFO-1123 is also preferably selected from the same viewpoint as HFC.
- GWP is much lower than HFC. Therefore, as HFOs other than HFO-1123 combined with HFO-1123, it is particularly noted that the cycle performance as the working medium is improved and the temperature gradient is kept within an appropriate range rather than considering GWP. These are preferably selected as appropriate.
- HFO other than HFO-1123 examples include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf), 1, 1,2-trifluoropropene (HFO-1243yc), (E) -1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), (Z) -1,2,3,3 , 3-pentafluoropropene (HFO-1225ye (Z)), (E) -1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), (Z) -1,3,3,3 -Tetrafluoropropene (HFO-1234ze (Z)), 3,3,3-trifluoropropene (HFO-1243zf) and the like.
- 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.
- the coefficient of performance improves when the content of HFO-1234yf or HFO-1234ze is in the range of 1 to 99% by mass.
- composition range (S) 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).
- the abbreviation of each compound indicates the ratio (% by mass) of the compound with respect to the total amount of HFO-1123, HFO-1234yf, and other components (such as HFC-32). .
- the working medium in the composition range (S) has an extremely low GWP and a small temperature gradient.
- refrigeration cycle performance that can be substituted for the conventional R410A can be expressed.
- 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 more preferably 50 to 85% by mass. % Is particularly preferable, and 60 to 85% by mass is most preferable.
- the total content of HFO-1123 and HFO-1234yf in 100% by mass of the working medium is more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
- the working medium used in the present invention may be a combination of HFO-1123, HFC, and HFO other than HFO-1123.
- the working medium is preferably composed of HFO-1123, HFC-32, and HFO-1234yf, and the ratio of each compound to the total amount of the working medium is preferably in the following range. 10% by mass ⁇ HFO-1123 ⁇ 80% by mass 10 mass% ⁇ HFC-32 ⁇ 75 mass% 5% by mass ⁇ HFO-1234yf ⁇ 60% by mass
- composition range (P) a preferred composition range (P) is shown below.
- 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.
- R composition range
- L composition range
- M composition range
- the total amount of HFO-1123, HFO-1234yf, and HFC-32 specifically described is more than 90% by mass and less than 100% by mass with respect to the total amount of the working medium for heat cycle. Preferably there is.
- 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 defects possessed by each are suppressed.
- 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.
- More preferable composition of the working medium used in the present invention is 30 to 70% by mass of HFO-1123 and 4 to 40% by mass of HFO-1234yf with respect to the total amount of HFO-1123, HFO-1234yf and HFC-32.
- 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.
- the content of HFC-32 is preferably 5% by mass or more, and more preferably 8% by mass or more.
- 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 is 70 mol% or less.
- the self-decomposition reaction of HFO-1123 is suppressed, and a highly durable working medium can be 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 defects possessed by each 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.
- 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 defects possessed by 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.
- composition range (R) a more preferred composition range (L) is shown below.
- the composition range (M) is more preferable.
- 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 drawbacks of the working medium are suppressed.
- 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.
- 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. Further, HFO-1234yf ⁇ 35 mass% is more preferable from the viewpoint of high relative refrigeration capacity.
- composition range (T) A preferred composition range when the working medium used in the present invention contains HFO-1123 and HFO-1234ze (E) is shown below as a composition range (T).
- T a composition range
- the abbreviation of each compound is the ratio of the compound to the total amount of HFO-1123, HFO-1234ze (E) and other components (HFC-32, etc.) (mass%) ).
- the working medium in the composition range (T) has an extremely low GWP and a small temperature gradient.
- refrigeration cycle performance that can be substituted for the conventional R410A can be expressed.
- the ratio of HFO-1123 to the total amount of HFO-1123 and HFO-1234ze (E) is more preferably 40 to 95% by mass, further preferably 50 to 90% by mass, Is particularly preferably from 85 to 85% by weight, most preferably from 60 to 85% by weight.
- the total content of HFO-1123 and HFO-1234ze (E) in 100% by mass of the working medium is more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass. Particularly preferred.
- the working medium used in the present invention may be a combination of HFO-1123, HFC, and HFO other than HFO-1123.
- the working medium is preferably composed of HFO-1123, HFC-32, and HFO-1234ze (E), and the ratio of each compound in the total amount of the working medium is preferably in the following range. 10% by mass ⁇ HFO-1123 ⁇ 80% by mass 10 mass% ⁇ HFC-32 ⁇ 75 mass% 5% by mass ⁇ HFO-1234ze (E) ⁇ 60% by mass
- the working medium used in the present invention contains HFO-1123, HFO-1234ze (E) and HFC-32
- the preferred composition range (Q) is shown below.
- the abbreviation of each compound indicates the ratio (mass%) of the compound with respect to the total amount of HFO-1123, HFO-1234ze (E), and HFC-32.
- the total amount of HFO-1123, HFO-1234ze (E), and HFC-32 specifically described exceeds 90% by mass with respect to the total amount of the working medium for heat cycle and is 100% by mass. % Or less is preferable.
- the working medium having the above composition is a working medium in which the characteristics of HFO-1123, HFO-1234ze (E), and HFC-32 are exhibited in a well-balanced manner, and the disadvantages of each of them are suppressed.
- 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.
- More preferable composition of the working medium used in the present invention is 30 to 70% by mass of HFO-1123 and HFO-1234ze (E) with respect to the total amount of HFO-1123, HFO-1234ze (E) and HFC-32. 4 to 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.
- the content of HFC-32 is preferably 5% by mass or more, and more preferably 8% by mass or more.
- the working medium used in the present invention contains HFO-1123, HFO-1234ze (E) and HFC-32
- another preferred composition is shown, but the content of HFO-1123 with respect to the total amount of the working medium is 70 mol%.
- the self-decomposition reaction of HFO-1123 is suppressed, and a highly durable working medium can be obtained.
- a more preferable composition range (U) is shown below. ⁇ Composition range (U)> 10% by mass ⁇ HFO-1123 ⁇ 70% by mass 0% by mass ⁇ HFO-1234ze (E) ⁇ 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-1234ze (E), 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.
- composition range (U) preferred ranges are shown below. 20% by mass ⁇ HFO-1123 ⁇ 70% by mass 0% by mass ⁇ HFO-1234ze (E) ⁇ 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-1234ze (E), 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.
- composition range (U) a more preferred composition range (K) is shown below.
- the composition range (N) is more preferable.
- the working medium having the composition range (N) is a working medium in which the characteristics of the HFO-1123, HFO-1234ze (E), and HFC-32 are exhibited in a particularly well-balanced manner, and the disadvantages of the working medium are suppressed. .
- 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.
- 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-1234ze (E) is more preferable. Further, HFO-1234ze (E) ⁇ 35 mass% is more preferable from the viewpoint of high relative refrigeration capacity.
- 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.
- CFO chlorofluoroolefin
- HCFO hydrochlorofluoroolefin
- the other optional component a component that has little influence on the ozone layer and little influence on global warming is preferable.
- hydrocarbon examples 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.
- the working medium contains a hydrocarbon
- the content thereof is less than 10% by weight with respect to 100% by weight of the working medium, preferably 1 to 5% by weight, and more preferably 3 to 5% by weight. If a hydrocarbon is more than a lower limit, the solubility of the mineral refrigeration oil to a working medium will become more favorable.
- CFO examples include chlorofluoropropene and chlorofluoroethylene.
- 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.
- CFO-1214yb 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.
- the working medium contains CFO
- the content thereof is less than 10% by weight with respect to 100% by weight of the working medium, preferably 1 to 8% by weight, and more preferably 2 to 5% by weight. 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.
- HCFO examples include hydrochlorofluoropropene and hydrochlorofluoroethylene.
- HCFO 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd)
- 1-chloro can be 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.
- the content of HCFO in 100% by mass of the working medium is less than 10% by mass, preferably 1 to 8% by mass, and more preferably 2 to 5% by mass. 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.
- the total content of the other optional components in the working medium is 10% by mass with respect to 100% by mass of the working medium. %, Preferably 8% by mass or less, more preferably 5% by mass or less.
- the composition for a heat cycle system of the present invention comprises a refrigerating machine oil capable of improving the lubricating properties of the working medium containing HFO-1123 in addition to the above working medium.
- refrigerating machine oil used in the present invention examples include ester-based refrigerating machine oil, ether-based refrigerating machine oil, polyglycol-based refrigerating machine oil, hydrocarbon-based refrigerating machine oil, and the like.
- an oxygen-containing synthetic refrigerating machine oil such as an ester refrigerating machine oil, an ether refrigerating machine oil, or a polyglycol based refrigerating machine oil is preferable. More preferred are system refrigerating machine oil and ether type refrigerating machine oil.
- the kinematic viscosity at 40 ° C. of the refrigeration oil does not decrease the lubricity and the hermeticity of the compressor, and is satisfactory in compatibility with the working medium under low temperature conditions. From the viewpoint of sufficient heat exchange in the evaporator, 1 to 750 mm 2 / s is preferable, and 1 to 400 mm 2 / s is more preferable.
- the kinematic viscosity at 100 ° C. is preferably 1 to 100 mm 2 / s, more preferably 1 to 50 mm 2 / s from the viewpoint of maintaining power consumption and wear resistance within an appropriate range.
- carbon atoms and oxygen atoms are typically cited as the atoms constituting the refrigerating machine oil. If the ratio of carbon atoms to oxygen atoms (carbon / oxygen molar ratio) is too small, the hygroscopicity is increased, and if it is too large, the compatibility with the working medium is lowered. From this viewpoint, the ratio of carbon atoms to oxygen atoms in the refrigerating machine oil is suitably 2 to 7.5 in terms of molar ratio.
- hydrocarbon-based refrigeration oil is required to circulate both the working medium and the refrigeration oil in the heat cycle system. It is most preferable that the refrigerating machine oil dissolves in the working medium. However, if a refrigerating machine oil that can circulate the refrigerating machine oil and the working medium in the heat cycle system is selected, a refrigerating machine oil having a low solubility (for example, in Japanese Patent No. 2803451).
- the refrigerating machine oils described can be used as one component of the composition for a thermal cycle system of the present invention.
- the refrigerating machine oil is required to have a low kinematic viscosity.
- the kinematic viscosity of the hydrocarbon refrigerating machine oil is preferably 1 to 50 mm 2 / s at 40 ° C., particularly preferably 1 to 25 mm 2 / s.
- These refrigerating machine oils may contain a stabilizer in order to prevent deterioration of the working medium and refrigerating machine oil.
- Additives include oxidation resistance improvers, heat resistance improvers, and metal deactivators, and the content of the stabilizer may be in a range that does not significantly reduce the effect of the present invention. In (100 mass%), it is 5 mass% or less normally, and 3 mass% or less is preferable.
- ester-based refrigerating machine oil in terms of chemical stability, dibasic acid ester-based refrigerating machine oil of dibasic acid and monohydric alcohol, polyol ester refrigerating machine oil of polyol and fatty acid, or polyol and polyvalent base
- the base oil component include complex ester type refrigerating machine oil and polyol carbonate type refrigerating machine oil of acid and monohydric alcohol (or fatty acid).
- Dibasic acid ester refrigerating machine oils include dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.
- divalent acids having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and monovalent monovalent C 1-15 having a linear or branched alkyl group
- Esters with alcohols methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc.
- alcohols methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecan
- dibasic ester refrigerating machine oil examples include ditridecyl glutarate, di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, di (3-ethylhexyl) sebacate and the like.
- the polyol ester refrigerating machine oil is an ester synthesized from a polyhydric alcohol and a fatty acid (carboxylic acid), and has a carbon / oxygen molar ratio of 2 to 7.5, preferably 3.2 to 5.8. Is.
- polyhydric alcohol constituting the polyol ester type refrigerating machine oil examples include diols (ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3 -Propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2- Propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.), polyol having
- the fatty acid constituting the polyol ester type refrigerating machine oil is not particularly limited, but usually those having 1 to 24 carbon atoms are used. Straight chain fatty acids and branched fatty acids are preferred. Linear fatty acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid , Heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, oleic acid, linoleic acid, linolenic acid, etc., and the hydrocarbon group bonded to the carboxyl group may be all saturated hydrocarbons or unsaturated
- branched fatty acids include 2-methylpropanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid 2,2-dimethylbutanoic acid, 2,3-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2 , 2-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 3,4-dimethylpentanoic acid, 4,4-dimethylpentanoic acid, 2-ethyl Pentanoic acid, 3-ethylpentanoic acid, 2,2,3-trimethylbutanoic acid
- the polyol constituting the ester may be one kind or a mixture of two or more kinds.
- the fatty acid constituting the ester may be a single component or an ester with two or more fatty acids. Each of the fatty acid and the fatty acid may be one kind or a mixture of two or more kinds.
- the polyol ester refrigerating machine oil may have a free hydroxyl group.
- Specific polyol ester refrigerating machine oils include neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (penta More preferred are esters of hindered alcohols such as erythritol), tri- (pentaerythritol), and even more esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol, di- (pentaerythritol).
- the fatty acid may be only a fatty acid having a linear alkyl group or may be selected from fatty acids having a branched structure. Moreover, the mixed ester of a linear and branched fatty acid may be sufficient. Furthermore, the fatty acid which comprises ester may use 2 or more types chosen from the said fatty acid.
- the molar ratio of the linear fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms is 15:85 to 90:10, preferably 15:85 to 85:15, more preferably 20:80 to 80:20, still more preferably 25:75 to 75:25, and most preferably 30:70. ⁇ 70: 30.
- the total ratio of the straight chain fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms in the total amount of fatty acids constituting the polyhydric alcohol fatty acid ester is 20 mol% or more.
- the fatty acid composition should be selected in consideration of sufficient compatibility with the working medium and compatibility with the viscosity required for refrigerating machine oil.
- the ratio of the fatty acid here is a value based on the total amount of fatty acids constituting the polyhydric alcohol fatty acid ester contained in the refrigerating machine oil.
- the complex ester refrigerating machine oil is an ester of a fatty acid and a dibasic acid, a monohydric alcohol and a polyol.
- fatty acid, dibasic acid, monohydric alcohol, and polyol the same ones as described above can be used.
- fatty acid As fatty acid, what was shown with the fatty acid of the said polyol ester is mentioned.
- dibasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.
- polyol examples include those shown as the polyhydric alcohol of the above polyol ester.
- Complex esters are esters of these fatty acids, dibasic acids, and polyols, and each may be a single component or an ester composed of a plurality of components.
- the polyol carbonate type refrigerating machine oil is an ester of carbonic acid and polyol.
- Polyols include polyglycols (polyalkylene glycols, ether compounds thereof, modified compounds thereof, etc.) obtained by homopolymerization or copolymerization of diols (same as above), polyols (same as above), polyols and polyglycols. And the like added.
- polyalkylene glycol examples include those obtained by polymerizing C 2-4 alkylene oxide (ethylene oxide, propylene oxide, etc.) using water or alkali hydroxide as an initiator. Moreover, what etherified the hydroxyl group of polyalkylene glycol may be used.
- the oxyalkylene units in the polyalkylene glycol may be the same in one molecule, or two or more oxyalkylene units may be included. It is preferable that at least an oxypropylene unit is contained in one molecule.
- the polyol carbonate refrigerating machine oil may be a ring-opening polymer of cyclic alkylene carbonate.
- ether refrigerating machine oil examples include polyvinyl ether refrigerating machine oil and polyalkylene glycol refrigerating machine oil.
- Polyvinyl ether refrigerating machine oil Polyvinyl ether refrigerating machine oils obtained by polymerizing vinyl ether monomers, those obtained by copolymerizing vinyl ether monomers and hydrocarbon monomers having an olefinic double bond, and polyvinyl ether and alkylene glycol Or there are polyalkylene glycols or their copolymers with monoethers.
- the carbon / oxygen molar ratio of the polyvinyl ether refrigerating machine oil is 2 or more and 7.5 or less, preferably 2.5 or more and 5.8 or less. If the carbon / oxygen molar ratio is less than this range, the hygroscopicity is high, and if it exceeds this range, the compatibility is lowered.
- the weight average molecular weight of polyvinyl ether is preferably 200 or more and 3000 or less, more preferably 500 or more and 1500 or less.
- Kinematic viscosity at 40 ° C. it is preferably 1 ⁇ 750mm 2 / s kinematic viscosity at 40 °C, 1 ⁇ 400mm 2 / s is more preferable.
- the kinematic viscosity at 100 ° C. is preferably 1 to 100 mm 2 / s, and more preferably 1 to 50 mm 2 / s.
- the vinyl ether monomer may be used alone or in combination of two or more.
- hydrocarbon monomers having an olefinic double bond include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, ⁇ -methylstyrene, various alkyl-substituted styrenes, etc. Is mentioned.
- the hydrocarbon monomer which has an olefinic double bond may be used individually by 1 type, and may be used in combination of 2 or more type.
- the polyvinyl ether copolymer may be either a block or a random copolymer.
- One type of polyvinyl ether refrigerating machine oil may be used alone, or two or more types may be used in combination.
- the polyvinyl ether refrigerating machine oil preferably used has a structural unit represented by the following general formula (1).
- R 1 , R 2 and R 3 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; R 4 is a divalent carbon atom having 1 to 10 carbon atoms
- R 2 represents a hydrogen group or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms
- R 5 represents a hydrocarbon group having 1 to 20 carbon atoms
- m represents an average value of m for the polyvinyl ether.
- R 1 to R 5 may be the same or different for each structural unit, and when m is 2 or more in one structural unit, a plurality of R 4 O may be the same or different.
- R 1 , R 2 and R 3 is preferably a hydrogen atom, particularly preferably a hydrogen atom.
- M in the general formula (1) is 0 or more and 10 or less, particularly 0 or more and 5 or less, and more preferably 0.
- R 5 in the general formula (1) represents a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, and various hexyl groups.
- Examples include an alkyl group, a cycloalkyl group, a phenyl group, an aryl group, an arylalkyl group, and the like, and an alkyl group, particularly an alkyl group having 1 to 5 carbon atoms is preferable.
- the polyvinyl ether refrigerating machine oil in the present embodiment is a copolymer composed of two or more kinds of structural units, even if the structural unit represented by the general formula (1) is the same homopolymer. Also good.
- the copolymer may be a block copolymer or a random copolymer.
- the polyvinyl ether refrigerating machine oil according to the present embodiment may be composed only of the structural unit represented by the general formula (1), but the structural unit represented by the following general formula (2) Further, a copolymer may be included. In this case, the copolymer may be a block copolymer or a random copolymer.
- R 6 to R 9 may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- vinyl ether monomer examples include compounds represented by the following general formula (3). (Wherein, R 1, R 2, R 3, R 4, R 5 and m is, R 1, R 2, R 3, R 4, identical to R 5 and m in the definition of each in the general formula (1) Show contents.)
- polyvinyl ether compounds there are various types corresponding to the above-mentioned polyvinyl ether compounds.
- the polyvinyl ether compound which has the structural unit represented by the said General formula (1) used as refrigerating machine oil in the composition for thermal cycle systems of this invention is the method which shows the terminal to this indication example, and It can be converted into a desired structure by a known method.
- Examples of the group to be converted include saturated hydrocarbons, ethers, alcohols, ketones, amides, and nitriles.
- the polyvinyl ether compound used as the refrigerating machine oil in the composition for a heat cycle system of the present invention preferably has a terminal structure represented by the following formulas (4) to (8).
- R 11 , R 21 and R 31 may be the same or different from each other and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms;
- R 41 is a divalent divalent having 1 to 10 carbon atoms;
- R 51 represents a hydrocarbon group having 1 to 20 carbon atoms, and
- m represents an average value of m for polyvinyl ether of 0
- the plurality of R 41 Os may be the same or different.
- R 61 , R 71 , R 81 and R 91 may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- R 12 , R 22 and R 32 may be the same as or different from each other, each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 42 is a divalent divalent hydrocarbon having 1 to 10 carbon atoms.
- R 2 represents a hydrocarbon group or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms
- R 52 represents a hydrocarbon group having 1 to 20 carbon atoms
- m represents an average value of m for polyvinyl ether is 0.
- the plurality of R 42 Os may be the same or different.
- R 62 , R 72 , R 82 and R 92 may be the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- R 13 , R 23 and R 33 may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
- the polyvinyl ether refrigerating machine oil in the present embodiment can be produced by radical polymerization, cationic polymerization, radiation polymerization or the like of the above-described monomer. After completion of the polymerization reaction, a polyvinyl ether compound having the target structural unit represented by the general formula (1) can be obtained by subjecting to an ordinary separation / purification method as necessary.
- polyalkylene glycol refrigerating machine oil examples include those obtained by a method of polymerizing alkylene oxide (ethylene oxide, propylene oxide, etc.) having 2 to 4 carbon atoms using water or alkali hydroxide as an initiator. Moreover, what etherified the hydroxyl group of polyalkylene glycol may be used.
- the oxyalkylene units in the polyalkylene glycol refrigerating machine oil may be the same in one molecule, or two or more oxyalkylene units may be included. It is preferable that at least an oxypropylene unit is contained in one molecule.
- R 101 As specific polyoxyalkylene glycol type refrigerating machine oil, for example, the following general formula (9) R 101 -[(OR 102 ) k -OR 103 ] l (9) (Wherein R 101 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding parts, R 102 Is an alkylene group having 2 to 4 carbon atoms, R 103 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, l is an integer of 1 to 6, and k is an average value of k ⁇ l Is a number from 6 to 80.).
- the alkyl group in R 101 and R 103 may be linear, branched or cyclic.
- Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Cyclopentyl group, cyclohexyl group and the like. When the number of carbon atoms of the alkyl group exceeds 10, compatibility with the working medium is lowered, and rough separation may occur.
- the alkyl group preferably has 1 to 6 carbon atoms.
- the alkyl group portion of the acyl group in R 101 and R 103 may be linear, branched or cyclic.
- various groups having 1 to 9 carbon atoms exemplified as specific examples of the alkyl group can be exemplified.
- compatibility with the working medium may be reduced and phase separation may occur.
- a preferred acyl group has 2 to 6 carbon atoms.
- R 101 and R 103 are both alkyl groups or acyl groups, R 101 and R 103 may be the same or different from each other. Further, when l is 2 or more, a plurality of R 103 in one molecule may be the same or different.
- R 101 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding sites
- the aliphatic hydrocarbon group may be a chain or a cyclic one. Also good.
- Examples of the aliphatic hydrocarbon group having two binding sites include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, cyclopentylene group, and cyclohexylene. Group and the like.
- Examples of the aliphatic hydrocarbon group having 3 to 6 binding sites include trimethylolpropane, glycerin, pentaerythritol, sorbitol; 1,2,3-trihydroxycyclohexane; 1,3,5-trihydroxycyclohexane. Examples thereof include a residue obtained by removing a hydroxyl group from a polyhydric alcohol.
- the compatibility with the working medium is lowered, and phase separation may occur.
- a preferred carbon number is 2-6.
- R 102 in the general formula (9) is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
- the oxyalkylene groups in one molecule may be the same or two or more oxyalkylene groups may be contained, but those containing at least an oxypropylene unit in one molecule are preferred, and in particular, oxyalkylene units. Those containing 50 mol% or more of oxypropylene units are preferred.
- l is an integer of 1 to 6, and is determined according to the number of R 101 binding sites.
- R 101 is an alkyl group or an acyl group
- l is 1, and when R 101 is an aliphatic hydrocarbon group having 2, 3, 4, 5, and 6 binding sites, l is 2, 3 respectively. , 4, 5 and 6.
- k is a number with an average value of k ⁇ l of 6 to 80, and if the average value of k ⁇ l deviates from the above range, the object of the present invention cannot be sufficiently achieved.
- polyalkylene glycol is such that polypropylene glycol dimethyl ether represented by the following general formula (10) and poly (oxyethyleneoxypropylene) glycol dimethyl ether represented by the following general formula (11) are economical and have the aforementioned effects.
- a polypropylene glycol monobutyl ether represented by the following general formula (12), a polypropylene glycol monomethyl ether represented by the following general formula (13), and a polyglycol represented by the following general formula (14) (Oxyethyleneoxypropylene) glycol monomethyl ether, poly (oxyethyleneoxypropylene) glycol monobutyl ether represented by the following general formula (15), polypropylene glycol diacetate represented by the following general formula (16), It is preferable in terms of gender, and the like.
- Kinematic viscosity at 40 ° C. of polyalkylene glycol represented by the above general formula (9) is preferably 1 ⁇ 750mm 2 / s kinematic viscosity at 40 °C, 1 ⁇ 400mm 2 / s is more preferable.
- the kinematic viscosity at 100 ° C. is preferably 1 to 100 mm 2 / s, and more preferably 1 to 50 mm 2 / s.
- Alkylbenzene can be used as the hydrocarbon refrigerating machine oil.
- alkylbenzene branched alkylbenzene synthesized using propylene polymer and benzene as raw materials using a catalyst such as hydrogen fluoride, and linear alkylbenzene synthesized using normal paraffin and benzene as raw materials using the same catalyst can be used.
- the number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 4 to 20, from the viewpoint of achieving a viscosity suitable as a lubricating base oil.
- the number of alkyl groups contained in one molecule of alkylbenzene is preferably 1 to 4, more preferably 1 to 3, in order to keep the viscosity within a set range depending on the number of carbon atoms of the alkyl group.
- the refrigeration oil is required to circulate in the heat cycle system together with the working medium. It is most preferable that the refrigerating machine oil dissolves with the working medium, but if a refrigerating machine oil that can circulate the refrigerating machine oil and the working medium in the heat cycle system is selected, the refrigerating machine oil with low solubility is used as the refrigerating machine oil composition of the present invention. Can be used.
- the refrigerating machine oil is required to have a low kinematic viscosity.
- the kinematic viscosity of alkylbenzene at 40 ° C. is preferably 1 to 50 mm 2 / s, particularly preferably 1 to 25 mm 2 / s.
- These refrigeration oils may be used alone or in combination of two or more.
- These refrigerating machine oils are preferably mixed with a working medium and used as a composition for a heat cycle system.
- the blending ratio of the refrigerating machine oil is desirably 5 to 60% by mass and more preferably 10 to 50% by mass with respect to the total amount of the composition for a heat cycle system.
- composition for thermal cycle systems can contain known optional components as long as the effects of the present invention are not impaired.
- an optional component include a leak detection substance, and examples of the optional leak detection substance include an ultraviolet fluorescent dye, an odor gas, an odor masking agent, and the like.
- the ultraviolet fluorescent dyes are described in U.S. Pat. No. 4,249,412, JP-T-10-502737, JP-T 2007-511645, JP-T 2008-500437, JP-T 2008-531836.
- odor masking agent examples include known fragrances used in heat cycle systems, together with working media composed of halogenated hydrocarbons, such as those described in JP-T-2008-500337 and JP-A-2008-531836. Can be mentioned.
- a solubilizing agent that improves the solubility of the leak detection substance in the working medium may be used.
- solubilizer examples include those described in JP-T 2007-511645, JP-T 2008-500337, JP-T 2008-531836.
- the content of the leak detection substance in the composition for a heat cycle system may be in a range that does not significantly reduce the effect of the present invention, and is preferably 2 parts by mass or less, based on 100 parts by mass of the working medium, and 0.5 mass. Part or less is more preferable.
- the thermal cycle system of the present invention is a system using the composition for a thermal cycle system of the present invention.
- the heat cycle system of the present invention may be a heat pump system that uses warm heat obtained by a condenser, or may be a refrigeration cycle system that uses cold heat obtained by an evaporator.
- thermal cycle system of the present invention examples include refrigeration / refrigeration equipment, air conditioning equipment, power generation systems, heat transport devices, and secondary coolers.
- the thermal cycle system of the present invention can exhibit thermal cycle performance efficiently even in a higher temperature operating environment, it is preferably used as an air conditioner that is often installed outdoors.
- the thermal cycle system of the present invention is also preferably used as a refrigeration / refrigeration apparatus.
- air conditioners include room air conditioners, packaged air conditioners (store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, etc.), gas engine heat pumps, train air conditioners, automobile air conditioners, and the like.
- refrigeration / refrigeration equipment include showcases (built-in showcases, separate showcases, etc.), commercial freezers / refrigerators, vending machines, ice makers, and the like.
- a power generation system using a Rankine cycle system is preferable.
- the working medium is heated by geothermal energy, solar heat, waste heat in the middle to high temperature range of about 50 to 200 ° C in the evaporator, and the working medium turned into high-temperature and high-pressure steam is expanded.
- An example is a system in which power is generated by adiabatic expansion by a machine, and a generator is driven by work generated by the adiabatic expansion.
- the heat cycle system of the present invention may be a heat transport device.
- a latent heat transport device is preferable.
- the latent heat transport device include a heat pipe and a two-phase sealed thermosyphon device that transport latent heat using phenomena such as evaporation, boiling, and condensation of a working medium enclosed in the device.
- the heat pipe is applied to a relatively small cooling device such as a cooling device for a heat generating part of a semiconductor element or an electronic device. Since the two-phase closed thermosyphon does not require a wig and has a simple structure, it is widely used for a gas-gas heat exchanger, for promoting snow melting on roads, and for preventing freezing.
- the refrigeration cycle system is a system that uses cold heat obtained by an evaporator.
- a refrigeration cycle system 10 shown in FIG. 1 cools and liquefies a compressor 11 that compresses the working medium vapor A into a high-temperature and high-pressure working medium vapor B and the working medium vapor B discharged from the compressor 11.
- the condenser 12 as a low-temperature and high-pressure working medium C
- the expansion valve 13 that expands the working medium C discharged from the condenser 12 to form a low-temperature and low-pressure working medium D
- the working medium D discharged from the expansion valve 13 Is composed of an evaporator 14 that heats the working medium vapor A to a high-temperature and low-pressure working medium vapor A, a pump 15 that supplies a load fluid E to the evaporator 14, and a pump 16 that supplies a fluid F to the condenser 12.
- the working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to obtain a low-temperature and low-pressure working medium D (hereinafter referred to as “CD process”).
- the working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to obtain high-temperature and low-pressure working medium vapor A. At this time, the load fluid E is cooled to become the load fluid E ′ and discharged from the evaporator 14 (hereinafter referred to as “DA process”).
- the refrigeration cycle system 10 is a cycle system including adiabatic / isoentropic change, isoenthalpy change, and isopressure change.
- the state change of the working medium is described on the pressure-enthalpy line (curve) diagram shown in FIG. 2, it can be expressed as a trapezoid having A, B, C, and D as apexes.
- the AB process is a process in which adiabatic compression is performed by the compressor 11 to convert the high-temperature and low-pressure working medium vapor A into a high-temperature and high-pressure working medium vapor B, which is indicated by an AB line in FIG.
- the BC process is a process in which the condenser 12 performs isobaric cooling to convert the high-temperature and high-pressure working medium vapor B into a low-temperature and high-pressure working medium C, and is indicated by a BC line in FIG.
- the pressure at this time is the condensation pressure.
- Pressure - an intersection T 1 of the high enthalpy side condensing temperature of the intersection of the enthalpy and BC line, the low enthalpy side intersection T 2 is the condensation boiling temperature.
- the temperature gradient in the case where HFO-1123 is a mixed medium with another working medium and is a non-azeotropic mixed medium is shown as a difference between T 1 and T 2 .
- the CD process is a process in which isenthalpy expansion is performed by the expansion valve 13 and the low-temperature and high-pressure working medium C is used as the low-temperature and low-pressure working medium D, and is indicated by a CD line in FIG.
- T 2 -T 3 is (i) ⁇ supercooling degree of the working medium in the cycle of (iv) (hereinafter, optionally in the "SC" It is shown.)
- the DA process is a process of performing isobaric heating in the evaporator 14 to return the low-temperature and low-pressure working medium D to the high-temperature and low-pressure working medium vapor A, and is indicated by a DA line in FIG.
- T 6 The pressure at this time is the evaporation pressure.
- Pressure - intersection T 6 of the high enthalpy side of the intersection of the enthalpy and DA line is evaporating temperature. If Shimese the temperature of the working medium vapor A in T 7, T 7 -T 6 is (i) ⁇ superheat of the working medium in the cycle of (iv) a (hereinafter,. Indicated by "SH", if necessary) .
- T 4 indicates the temperature of the working medium D.
- the cycle performance of the working medium is evaluated by, for example, the refrigerating capacity of the working medium (hereinafter, indicated as “Q” as necessary) and the coefficient of performance (hereinafter, indicated as “COP” as necessary).
- Q and COP of the working medium in each state of A after evaporation, high temperature and low pressure
- B after compression, high temperature and high pressure
- C after condensation, low temperature and high pressure
- D after expansion, low temperature and low pressure.
- COP means efficiency in the refrigeration cycle system. The higher the COP value, the smaller the input, for example, the amount of power required to operate the compressor, and the larger the output, for example, Q can be obtained. It represents what you can do.
- Q means the ability to freeze the load fluid, and the higher Q means that more work can be done in the same system.
- a large Q indicates that the target performance can be obtained with a small amount of working medium, and the system can be miniaturized.
- both the Q and COP are high, that is, equivalent to R410A, while keeping the global warming coefficient much lower. It is possible to set a level higher than that.
- the composition that keeps the temperature gradient of the working medium contained in the composition for the heat cycle system to be a certain value or less, in which case, the composition change when filling from the pressure vessel to the refrigeration air conditioner, A change in the refrigerant composition in the refrigeration air conditioner when the refrigerant leaks from the refrigeration air conditioner can be suppressed to a low level.
- the lubricating properties of HFO-1123 contained in the working medium contained therein can be improved. Therefore, the heat cycle system using the composition is more efficient than the conventional working medium. The system can be maintained in a stable state and the system can be operated stably.
- a method for controlling the moisture concentration in the thermal cycle system a method using a moisture removing means such as a desiccant (silica gel, activated alumina, zeolite, etc.) can be mentioned.
- the desiccant is preferably brought into contact with the liquid thermal cycle system composition in terms of dehydration efficiency. For example, it is preferable to place a desiccant at the outlet of the condenser 12 or the inlet of the evaporator 14 to contact the composition for the thermal cycle system.
- a zeolitic desiccant is preferable from the viewpoint of chemical reactivity between the desiccant and the composition for the heat cycle system and the moisture absorption capacity of the desiccant.
- the main component is a compound represented by the following formula (C) because it has a high hygroscopic capacity.
- Zeolite desiccants are preferred.
- M is a Group 1 element such as Na or K, or a Group 2 element such as Ca
- n is the valence of M
- x and y are values determined by the crystal structure.
- pore diameter and breaking strength are important.
- the working medium or the desiccant having a pore size larger than the molecular diameter of the refrigerating machine oil contained in the composition for the heat cycle system is used, the working medium or the refrigerating machine oil is adsorbed in the desiccant, and as a result, the working medium or A chemical reaction occurs between the refrigerating machine oil and the desiccant, and undesired phenomena such as generation of non-condensable gas, a decrease in the strength of the desiccant, and a decrease in adsorption capacity occur.
- a zeolitic desiccant having a small pore size as the desiccant.
- a sodium / potassium A type synthetic zeolite having a pore diameter of 3.5 angstroms or less is preferable.
- sodium / potassium type A synthetic zeolite having a pore size smaller than the molecular diameter of the working medium or refrigerating machine oil only the water in the heat cycle system is selectively absorbed without adsorbing the working medium or refrigerating machine oil. Can be removed by adsorption. In other words, the adsorption of the working medium and the refrigerating machine oil to the desiccant is unlikely to occur, so that thermal decomposition is difficult to occur.
- the size of the zeolitic desiccant is preferably about 0.5 to 5 mm because if it is too small, it will cause clogging of valves and piping details of the heat cycle system, and if it is too large, the drying ability will be reduced.
- the shape is preferably granular or cylindrical.
- the zeolitic desiccant can be formed into an arbitrary shape by solidifying powdery zeolite with a binder (such as bentonite).
- a binder such as bentonite
- Other desiccants silicon gel, activated alumina, etc.
- the use ratio of the zeolitic desiccant with respect to the composition for a heat cycle system is not particularly limited.
- non-condensable gas when non-condensable gas is mixed in the heat cycle system, it adversely affects heat transfer in the condenser and the evaporator and increases in operating pressure. Therefore, it is necessary to suppress mixing as much as possible.
- oxygen which is one of non-condensable gases, reacts with the working medium and refrigerating machine oil to promote decomposition.
- the non-condensable gas concentration is preferably 1.5% by volume or less, particularly preferably 0.5% by volume or less in terms of volume ratio to the working medium in the gas phase part of the working medium.
- the composition for the thermal cycle system of the present invention described above, by using the composition for the thermal cycle system of the present invention, the lubrication characteristics are good, and the practically sufficient cycle performance is suppressed while suppressing the influence on global warming. Is obtained, and there is almost no problem with the temperature gradient.
- Examples 1 to 40 Example 55 to 158, Examples 185 to 292, Examples 320 to 415
- conventional examples Examples 41 to 44
- comparative examples Examples 45 to 54, Examples 159 to 184, Examples 293 to 319, and Examples 416 to 439.
- 50 g of refrigerating machine oil was mixed and dissolved in 50 g of the working medium in the combinations shown in Tables 4 to 43 to produce a composition for a heat cycle system. Therefore, the composition for a heat cycle system in this example is composed of 50% by mass of a working medium and 50% by mass of refrigerating machine oil.
- Refrigerating machine oil 1 Refrigerating machine oil mainly composed of polyol ester (trade name: Ze-GLES RB-68, product of JX Nippon Oil & Energy Corporation)
- Refrigerator oil 2 Refrigerator oil mainly composed of polyvinyl ether (trade name: Daphne Hermetic Oil FVC68D, a product of Idemitsu Kosan Co., Ltd.)
- Refrigerating machine oil 3 Refrigerating machine oil mainly composed of polyalkylene glycol (trade name: ND-8, DENSO Corporation product)
- Refrigerating machine oil 4 Refrigerating machine oil mainly composed of alkylbenzene (trade name: Atmos N22, JX Nippon Mining & Energy Corporation product; kinematic viscosity at 40 ° C. is 21.5 mm 2 / s)
- Refrigerator oil 5 High-grade naphthenic refrigeration oil (trade name: Suniso 4GS, a product of Idemitsu Kosan Co., Ltd.)
- the composition for a heat cycle system obtained in each example was put into the heat cycle system 10 shown in FIG. 1, and the heat cycle system was continuously operated.
- a part of the flow path from the evaporator 14 to the compressor 11 in the heat cycle system was made into glass piping.
- the inside of the glass pipe was observed to evaluate the circulation state of the composition for the heat cycle system in the heat cycle system.
- the circulation state was visually evaluated according to the following criteria. ⁇ : Refrigerating machine oil circulation was confirmed. ⁇ : Refrigerating machine oil is circulated, but the circulation rate is insufficient. X: Refrigerating machine oil circulation cannot be confirmed.
- the sealed pressure vessel was then stored in a thermostatic chamber (Perfect Oven PHH-202, manufactured by ESPEC Corporation) at 175 ° C. for 14 days.
- the acid content of the working medium was measured, the hue of the refrigerating machine oil was observed, and the catalyst The appearance change was observed.
- Test piece of cold-rolled steel sheet for general steel (as defined in JIS G3141, symbol type SPCC-SB), 30 mm ⁇ 25 mm ⁇ thickness 3.2 mm
- Copper Tough pitch copper (as defined in JIS H3100, alloy number C1100, symbol C1100P) test piece, 30 mm ⁇ 25 mm ⁇ thickness 2 mm
- Aluminum Test piece of pure aluminum (as defined in JIS H4000, alloy number 1050, symbol A1050P), 30 mm ⁇ 25 mm ⁇ thickness 2 mm
- the acid content of the working medium after the test was measured according to JIS K1560 (1,1,1,2-tetrafluoroethane (HFC-134a)).
- the pressure vessel after the test was allowed to stand until it reached room temperature. 100 ml of pure water was put in each of four absorption bottles, and a series of pipes connected in series was prepared. Connect a pressure vessel at room temperature to which an absorption bottle containing pure water is connected, and gradually open the valve of the pressure vessel to introduce refrigerant gas into the water in the absorption bottle. Minutes were extracted.
- the water in the absorption bottle after extraction was added with 1 drop of an indicator (BTB: bromothymol blue) for the 1st and 2nd bottles, and titrated with 1/100 N-NaOH alkaline standard solution.
- BTB bromothymol blue
- the third and fourth water in the absorption bottle were combined and titrated in the same manner to obtain a measurement blank. From these measurement values and measurement blank values, the acid content in the refrigerant after the test was determined as the HCl concentration.
- Examples 1 to 40, Examples 55 to 158, Examples 185 to 292, and Examples 320 to 415 which are examples of the present invention, are equivalent to the compositions of the prior art in all the compositions for thermal cycle systems. It has been found that it has properties and is suitable as a composition for thermal cycling systems.
- the composition for a heat cycle system of the present invention and the heat cycle system using the composition are refrigeration / refrigeration equipment (built-in showcase, separate-type showcase, commercial refrigeration / refrigerator, vending machine, ice maker, etc.) , Air conditioners (room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.), power generation systems (waste heat recovery power generation, etc.), heat transport It can be used for equipment (heat pipe, etc.).
- refrigeration / refrigeration equipment built-in showcase, separate-type showcase, commercial refrigeration / refrigerator, vending machine, ice maker, etc.
- Air conditioners room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.
- power generation systems waste heat recovery power generation, etc.
- heat transport It can be used for equipment (heat pipe, etc.).
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Abstract
Description
従来、冷凍機用冷媒、空調機器用冷媒、発電システム(廃熱回収発電等)用作動媒体、潜熱輸送装置(ヒートパイプ等)用作動媒体、二次冷却媒体等の熱サイクルシステム用の作動媒体としては、クロロトリフルオロメタン、ジクロロジフルオロメタン等のクロロフルオロカーボン(CFC)、クロロジフルオロメタン等のヒドロクロロフルオロカーボン(HCFC)が用いられてきた。しかし、CFCおよびHCFCは、成層圏のオゾン層への影響が指摘され、現在、規制の対象となっている。
[2]前記冷凍機油が、エステル系冷凍機油、エーテル系冷凍機油、ポリグリコール系冷凍機油、炭化水素系冷凍機油から選ばれる少なくとも1種である、[1]に記載の熱サイクルシステム用組成物。
[3]前記冷凍機油が、二塩基酸エステル、ポリオールエステル、コンプレックスエステル、ポリオール炭酸エステル、ポリビニルエーテル、ポリアルキレングリコールおよびアルキルベンゼンから選ばれる少なくとも1種である、[2]に記載の熱サイクルシステム用組成物。
[4]前記冷凍機油の40℃における動粘度が1~750mm2/sである、[1]~[3]のいずれかに記載の熱サイクルシステム用組成物。
[5]前記冷凍機油の100℃における動粘度が1~100mm2/sである、[1]~[4]のいずれかに記載の熱サイクルシステム用組成物。
[6]前記冷凍機油の炭素原子と酸素原子の比率(炭素/酸素モル比)が2~7.5である、[1]~[5]のいずれかに記載の熱サイクルシステム用組成物。
[7]前記熱サイクル用作動媒体がさらに飽和のヒドロフルオロカーボンを含む、[1]~[6]のいずれかに記載の熱サイクルシステム用組成物。
[8]前記飽和のヒドロフルオロカーボンがジフルオロメタン、1,1-ジフルオロエタン、1,1,1,2-テトラフルオロエタンおよびペンタフルオロエタンから選ばれる少なくとも1種である、[7]に記載の熱サイクルシステム用組成物。
[10]前記炭素-炭素二重結合を有するヒドロフルオロカーボンが、1,3,3,3-テトラフルオロプロペンおよび2,3,3,3-テトラフルオロプロペンから選ばれる少なくとも1種である、[9]に記載の熱サイクルシステム用組成物。
[11]前記熱サイクル用作動媒体の100質量%に対するトリフルオロエチレンの含有量が10質量%以上である、[1]~[10]のいずれかに記載の熱サイクルシステム用組成物。
[12]前記熱サイクル用作動媒体の100質量%に対するトリフルオロエチレンの含有量が20~80質量%である、[11]に記載の熱サイクルシステム用組成物。
[13]前記熱サイクル用作動媒体がさらにジフルオロメタンを含み、前記熱サイクル用作動媒体の100質量%に対するジフルオロメタンの含有量が20質量%以上である、[11]または[12]に記載の熱サイクルシステム用組成物。
[14][1]~[13]のいずれかに記載の熱サイクルシステム用組成物を用いた、熱サイクルシステム。
[15]前記熱サイクルシステムが、冷凍・冷蔵機器、空調機器、発電システム、熱輸送装置または二次冷却機である、[14]に記載の熱サイクルシステム。
[熱サイクルシステム用組成物]
熱サイクルシステム用組成物は、HFO-1123を含む熱サイクル用作動媒体と、冷凍機油とを含む。
以下、本発明の熱サイクルシステム用組成物が含有する各成分を説明する。
本発明の熱サイクルシステム用組成物は作動媒体として、HFO-1123を含有する。本発明に係る作動媒体は、HFO-1123に加えて、必要に応じて、後述する任意成分を含んでいてもよい。作動媒体の100質量%に対するHFO-1123の含有量は、10質量%以上が好ましく、20~80質量%がより好ましく、40~80質量%がより一層好ましく、40~60質量%がさらに好ましい。
HFO-1123の作動媒体としての特性を、特に、R410A(HFC-32とHFC-125の質量比1:1の擬似共沸混合物)との相対比較において表1に示す。サイクル性能は、後述する方法で求められる成績係数と冷凍能力で示される。HFO-1123の成績係数と冷凍能力は、R410Aを基準(1.000)とした相対値(以下、相対成績係数および相対冷凍能力という)で示す。地球温暖化係数(GWP)は、気候変動に関する政府間パネル(IPCC)第4次評価報告書(2007年)に示される、または該方法に準じて測定された100年の値である。本明細書において、GWPは特に断りのない限りこの値をいう。作動媒体が混合物からなる場合、後述するとおり温度勾配は、作動媒体を評価する上で重要なファクターとなり、値は小さい方が好ましい。
本発明に用いる作動媒体は、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。
作動媒体が任意成分を含有する場合、HFO-1123と任意成分が共沸組成である場合を除いて相当の温度勾配を有する。作動媒体の温度勾配は、任意成分の種類およびHFO-1123と任意成分との混合割合により異なる。
任意成分のHFCとしては、上記観点から選択されることが好ましい。ここで、HFCは、HFO-1123に比べてGWPが高いことが知られている。したがって、HFO-1123と組合せるHFCとしては、上記作動媒体としてのサイクル性能を向上させ、かつ温度勾配を適切な範囲にとどめることに加えて、特にGWPを許容の範囲にとどめる観点から、適宜選択されることが好ましい。
HFCは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
HFO-1123以外の任意成分としてのHFOについても、上記HFCと同様の観点から選択されることが好ましい。なお、HFO-1123以外であってもHFOであれば、GWPはHFCに比べて桁違いに低い。したがって、HFO-1123と組合せるHFO-1123以外のHFOとしては、GWPを考慮するよりも、上記作動媒体としてのサイクル性能を向上させ、かつ温度勾配を適切な範囲にとどめることに特に留意して、適宜選択されることが好ましい。
なお、組成範囲(S)を示す各式において、各化合物の略称は、HFO-1123とHFO-1234yfと他の成分(HFC-32等)の合計量に対する当該化合物の割合(質量%)を示す。
HFO-1123+HFO-1234yf≧70質量%
95質量%≧HFO-1123/(HFO-1123+HFO-1234yf)≧35質量%
10質量%≦HFO-1123≦80質量%
10質量%≦HFC-32≦75質量%
5質量%≦HFO-1234yf≦60質量%
なお、組成範囲(P)を示す各式において、各化合物の略称は、HFO-1123とHFO-1234yfとHFC-32の合計量に対する当該化合物の割合(質量%)を示す。組成範囲(R)、組成範囲(L)、組成範囲(M)においても同様である。また、以下に記載の組成範囲では、具体的に記載したHFO-1123とHFO-1234yfとHFC-32の合計量が、熱サイクル用作動媒体全量に対して90質量%を超え100質量%以下であることが好ましい。
70質量%≦HFO-1123+HFO-1234yf
30質量%≦HFO-1123≦80質量%
0質量%<HFO-1234yf≦40質量%
0質量%<HFC-32≦30質量%
HFO-1123/HFO-1234yf≦95/5質量%
さらに好ましい組成範囲(R)を、以下に示す。
<組成範囲(R)>
10質量%≦HFO-1123<70質量%
0質量%<HFO-1234yf≦50質量%
30質量%<HFC-32≦75質量%
20質量%≦HFO-1123<70質量%
0質量%<HFO-1234yf≦40質量%
30質量%<HFC-32≦75質量%
<組成範囲(L)>
10質量%≦HFO-1123<70質量%
0質量%<HFO-1234yf≦50質量%
30質量%<HFC-32≦44質量%
20質量%≦HFO-1123<70質量%
5質量%≦HFO-1234yf≦40質量%
30質量%<HFC-32≦44質量%
この範囲にあると温度勾配の上限が下がり、相対成績係数×相対冷凍能力の下限が上がる。相対成績係数が大きい点から8質量%≦HFO-1234yfがより好ましい。また、相対冷凍能力が大きい点からHFO-1234yf≦35質量%がより好ましい。
なお、組成範囲(T)を示す各式において、各化合物の略称は、HFO-1123とHFO-1234ze(E)と他の成分(HFC-32等)の合計量に対する当該化合物の割合(質量%)を示す。
HFO-1123+HFO-1234ze(E)≧70質量%
95質量%≧HFO-1123/(HFO-1123+HFO-1234ze(E)≧35質量%
10質量%≦HFO-1123≦80質量%
10質量%≦HFC-32≦75質量%
5質量%≦HFO-1234ze(E)≦60質量%
なお、組成範囲(Q)を示す各式において、各化合物の略称は、HFO-1123とHFO-1234ze(E)とHFC-32の合計量に対する当該化合物の割合(質量%)を示す。組成範囲(U)、組成範囲(K)、組成範囲(N)においても同様である。また、以下に記載の組成範囲では、具体的に記載したHFO-1123とHFO-1234ze(E)とHFC-32の合計量が、熱サイクル用作動媒体全量に対して90質量%を超え100質量%以下であることが好ましい。
70質量%≦HFO-1123+HFO-1234ze(E)
30質量%≦HFO-1123≦80質量%
0質量%<HFO-1234ze(E)≦40質量%
0質量%<HFC-32≦30質量%
HFO-1123/HFO-1234ze(E)≦95/5質量%
さらに好ましい組成範囲(U)を、以下に示す。
<組成範囲(U)>
10質量%≦HFO-1123<70質量%
0質量%<HFO-1234ze(E)≦50質量%
30質量%<HFC-32≦75質量%
20質量%≦HFO-1123<70質量%
0質量%<HFO-1234ze(E)≦40質量%
30質量%<HFC-32≦75質量%
<組成範囲(K)>
10質量%≦HFO-1123<70質量%
0質量%<HFO-1234ze(E)≦50質量%
30質量%<HFC-32≦44質量%
20質量%≦HFO-1123<70質量%
5質量%≦HFO-1234ze(E)≦40質量%
30質量%<HFC-32≦44質量%
この範囲にあると温度勾配の上限が下がり、相対成績係数×相対冷凍能力の下限が上がる。相対成績係数が大きい点から8質量%≦HFO-1234ze(E)がより好ましい。また、相対冷凍能力が大きい点からHFO-1234ze(E)≦35質量%がより好ましい。
本発明の熱サイクルシステム用組成物に用いる作動媒体は、上記任意成分以外に、二酸化炭素、炭化水素、クロロフルオロオレフィン(CFO)、ヒドロクロロフルオロオレフィン(HCFO)等を含有してもよい。他の任意成分としてはオゾン層への影響が少なく、かつ地球温暖化への影響が小さい成分が好ましい。
炭化水素は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
CFOは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
HCFOは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本発明の熱サイクルシステム用組成物には、上記作動媒体に加え、HFO-1123を含む作動媒体の潤滑特性を改善可能な冷凍機油を含んでなる。
その中でも、本発明の必須の作動媒体成分であるトリフルオロエチレンとの相溶性の観点からエステル系冷凍機油、エーテル系冷凍機油、ポリグリコール系冷凍機油等の含酸素系合成冷凍機油が好ましく、エステル系冷凍機油、エーテル系冷凍機油がより好ましい。
エステル系冷凍機油としては、化学的な安定性の面で、二塩基酸と1価アルコールとの二塩基酸エステル系冷凍機油、ポリオールと脂肪酸とのポリオールエステル系冷凍機油、またはポリオールと多価塩基酸と1価アルコール(又は脂肪酸)とのコンプレックスエステル系冷凍機油、ポリオール炭酸エステル系冷凍機油等が基油成分として挙げられる。
二塩基酸エステル系冷凍機油としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸等の二塩基酸、特に、炭素数5~10の二塩基酸(グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等)と、直鎖または分岐アルキル基を有する炭素数1~15の一価アルコール(メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、ウンデカノール、ドデカノール、トリデカノール、テトラデカノール、ペンタデカノール等)とのエステルが好ましい。この二塩基酸エステル系冷凍機油としては、具体的には、グルタル酸ジトリデシル、アジピン酸ジ(2-エチルヘキシル)、アジピン酸ジイソデシル、アジピン酸ジトリデシル、セバシン酸ジ(3-エチルヘキシル)等が挙げられる。
ポリオールエステル系冷凍機油とは、多価アルコールと脂肪酸(カルボン酸)とから合成されるエステルであり、炭素/酸素モル比が2以上7.5以下、好ましくは3.2以上5.8以下のものである。
コンプレックスエステル系冷凍機油とは、脂肪酸および二塩基酸と、一価アルコールおよびポリオールとのエステルである。脂肪酸、二塩基酸、一価アルコール、ポリオールとしては、上述と同様のものを用いることができる。
二塩基酸としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸等が挙げられる。
ポリオール炭酸エステル系冷凍機油とは、炭酸とポリオールとのエステルである。
ポリオールとしては、ジオール(上述と同様のもの)を単独重合または共重合したポリグリコール(ポリアルキレングリコール、そのエーテル化合物、それらの変性化合物等)、ポリオール(上述と同様のもの)、ポリオールにポリグリコールを付加したもの等が挙げられる。
エーテル系冷凍機油としては、ポリビニルエーテル系冷凍機油、ポリアルキレングリコール系冷凍機油等が挙げられる。
ポリビニルエーテル系冷凍機油としては、ビニルエーテルモノマーを重合して得られたもの、ビニルエーテルモノマーとオレフィン性二重結合を有する炭化水素モノマーとを共重合して得られたもの、およびポリビニルエーテルと、アルキレングリコールもしくはポリアルキレングリコール、またはそれらのモノエーテルとの共重合体がある。
ビニルエーテルモノマーは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。オレフィン性二重結合を有する炭化水素モノマーとしては、エチレン、プロピレン、各種ブテン、各種ペンテン、各種ヘキセン、各種ヘプテン、各種オクテン、ジイソブチレン、トリイソブチレン、スチレン、α-メチルスチレン、各種アルキル置換スチレン等が挙げられる。オレフィン性二重結合を有する炭化水素モノマーは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ビニルエーテル系モノマーとしては、下記一般式(3)の化合物が挙げられる。
本発明の熱サイクルシステム用組成物に冷凍機油として用いられる上記一般式(1)で表される構成単位を有するポリビニルエーテル系化合物は、その末端を本開示例に示す方法及び公知の方法により、所望の構造に変換することができる。変換する基としては、飽和の炭化水素,エーテル,アルコール,ケトン,アミド,ニトリルなどを挙げることができる。
本実施形態におけるポリビニルエーテル系冷凍機油は、上記したモノマーをラジカル重合、カチオン重合、放射線重合などによって製造することができる。重合反応終了後、必要に応じて通常の分離・精製方法を施すことにより、目的とする一般式(1)で表される構造単位を有するポリビニルエーテル系化合物が得られる。
ポリアルキレングリコール系冷凍機油としては、炭素数2~4のアルキレンオキシド(エチレンオキシド、プロピレンオキシド等)を、水や水酸化アルカリを開始剤として重合させる方法等により得られたものが挙げられる。また、ポリアルキレングリコールの水酸基をエーテル化したものであってもよい。ポリアルキレングリコール系冷凍機油中のオキシアルキレン単位は、1分子中において同一であってもよく、2種以上のオキシアルキレン単位が含まれていてもよい。1分子中に少なくともオキシプロピレン単位が含まれることが好ましい。
R101-[(OR102)k-OR103]l …(9)
(式中、R101は水素原子、炭素数1~10のアルキル基、炭素数2~10のアシル基又は結合部2~6個を有する炭素数1~10の脂肪族炭化水素基、R102は炭素数2~4のアルキレン基、R103は水素原子、炭素数1~10のアルキル基又は炭素数2~10のアシル基、lは1~6の整数、kはk×lの平均値が6~80となる数を示す。)で表される化合物が挙げられる。
さらにlが2以上の場合には、1分子中の複数のR103は同一であってもよいし、異なっていてもよい。
(式中、hは6~80の数を表す。)
CH3O-(C2H4O)i-(C3H6O)j-CH3 …(11)
(式中、iおよびjはそれぞれ1以上であり且つiとjとの合計が6~80となる数を表す。)
C4H9O-(C3H6O)h-H …(12)
(式中、hは6~80の数を示す。)
CH3O-(C3H6O)h-H …(13)
(式中、hは6~80の数を表す。)
(式中、iおよびjはそれぞれ1以上であり且つiとjとの合計が6~80となる数を表す。)
C4H9O-(C2H4O)i-(C3H6O)j-H …(15)
(式中、iおよびjはそれぞれ1以上であり且つiとjとの合計が6~80となる数を表す。)
CH3COO-(C3H6O)h-COCH3 …(16)
(式中、hは6~80の数を表す。)
このポリオキシアルキレングリコール類は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
炭化水素系冷凍機油としては、アルキルベンゼンを用いることができる。
これらの冷凍機油は、作動媒体と混合して熱サイクルシステム用組成物として使用することが好ましい。このとき、冷凍機油の配合割合は、熱サイクルシステム用組成物全量に対して5~60質量%が望ましく、10~50質量%がより好ましい。
熱サイクルシステム用組成物は、その他、本発明の効果を阻害しない範囲で公知の任意成分を含有できる。このような任意成分としては、例えば、漏れ検出物質が挙げられ、この任意に含有する漏れ検出物質としては、紫外線蛍光染料、臭気ガスや臭いマスキング剤等が挙げられる。
本発明の熱サイクルシステムは、本発明の熱サイクルシステム用組成物を用いたシステムである。本発明の熱サイクルシステムは、凝縮器で得られる温熱を利用するヒートポンプシステムであってもよく、蒸発器で得られる冷熱を利用する冷凍サイクルシステムであってもよい。
冷凍・冷蔵機器として、具体的には、ショーケース(内蔵型ショーケース、別置型ショーケース等)、業務用冷凍・冷蔵庫、自動販売機、製氷機等が挙げられる。
発電システムとして、具体的には、蒸発器において地熱エネルギー、太陽熱、50~200℃程度の中~高温度域廃熱等により作動媒体を加熱し、高温高圧状態の蒸気となった作動媒体を膨張機にて断熱膨張させ、該断熱膨張によって発生する仕事によって発電機を駆動させ、発電を行うシステムが例示される。
潜熱輸送装置としては、装置内に封入された作動媒体の蒸発、沸騰、凝縮等の現象を利用して潜熱輸送を行うヒートパイプおよび二相密閉型熱サイフォン装置が挙げられる。ヒートパイプは、半導体素子や電子機器の発熱部の冷却装置等、比較的小型の冷却装置に適用される。二相密閉型熱サイフォンは、ウィッグを必要とせず構造が簡単であることから、ガス-ガス型熱交換器、道路の融雪促進および凍結防止等に広く利用される。
(i)蒸発器14から排出された作動媒体蒸気Aを圧縮機11にて圧縮して高温高圧の作動媒体蒸気Bとする(以下、「AB過程」という。)。
(ii)圧縮機11から排出された作動媒体蒸気Bを凝縮器12にて流体Fによって冷却し、液化して低温高圧の作動媒体Cとする。この際、流体Fは加熱されて流体F’となり、凝縮器12から排出される(以下、「BC過程」という。)。
(iii)凝縮器12から排出された作動媒体Cを膨張弁13にて膨張させて低温低圧の作動媒体Dとする(以下、「CD過程」という。)。
(iv)膨張弁13から排出された作動媒体Dを蒸発器14にて負荷流体Eによって加熱して高温低圧の作動媒体蒸気Aとする。この際、負荷流体Eは冷却されて負荷流体E’となり、蒸発器14から排出される(以下、「DA過程」という。)。
BC過程は、凝縮器12で等圧冷却を行い、高温高圧の作動媒体蒸気Bを低温高圧の作動媒体Cとする過程であり、図2においてBC線で示される。この際の圧力が凝縮圧である。圧力-エンタルピ線とBC線の交点のうち高エンタルピ側の交点T1が凝縮温度であり、低エンタルピ側の交点T2が凝縮沸点温度である。ここで、HFO-1123が他の作動媒体との混合媒体であって非共沸混合媒体である場合の温度勾配はT1とT2の差として示される。
DA過程は、蒸発器14で等圧加熱を行い、低温低圧の作動媒体Dを高温低圧の作動媒体蒸気Aに戻す過程であり、図2においてDA線で示される。この際の圧力が蒸発圧である。圧力-エンタルピ線とDA線の交点のうち高エンタルピ側の交点T6は蒸発温度である。作動媒体蒸気Aの温度をT7で示せば、T7-T6が(i)~(iv)のサイクルにおける作動媒体の過熱度(以下、必要に応じて「SH」で示す。)となる。なお、T4は作動媒体Dの温度を示す。
COP=Q/圧縮仕事=(hA-hD)/(hB-hA) …(B)
M2/nO・Al2O3・xSiO2・yH2O …(C)
ただし、Mは、Na、K等の1族の元素またはCa等の2族の元素であり、nは、Mの原子価であり、x、yは、結晶構造にて定まる値である。Mを変化させることにより細孔径を調整できる。
熱サイクルシステム用組成物が含有する作動媒体や冷凍機油の分子径よりも大きい細孔径を有する乾燥剤を用いた場合、作動媒体や冷凍機油が乾燥剤中に吸着され、その結果、作動媒体や冷凍機油と乾燥剤との化学反応が生じ、不凝縮性気体の生成、乾燥剤の強度の低下、吸着能力の低下等の好ましくない現象を生じることとなる。
熱サイクルシステム用組成物に対するゼオライト系乾燥剤の使用割合は、特に限定されない。
冷凍機油2:ポリビニルエーテルを主成分とする冷凍機油(商品名:ダフニーハーメチックオイルFVC68D、出光興産株式会社製品)
冷凍機油3:ポリアルキレングリコールを主成分とする冷凍機油(商品名:ND-8、株式会社デンソー社製品)
冷凍機油4:アルキルベンゼンを主成分とする冷凍機油(商品名:アトモスN22、JX日鉱日石エネルギー株式会社製品;40℃の動粘度が21.5mm2/s)
冷凍機油5:ナフテン系高級冷凍機油(商品名:スニソ4GS、出光興産株式会社製品)
図1に示した熱サイクルシステム10に、各例で得られた熱サイクルシステム用組成物を入れ、熱サイクルシステムの連続運転を行った。熱サイクルシステム用組成物の循環状態を評価するために、熱サイクルシステムにおける蒸発器14から圧縮機11への流路の一部をガラス配管とした。このガラス配管から内部を観察して熱サイクルシステム内の熱サイクルシステム用組成物の循環状態を評価した。循環状態は、目視にて以下の基準により評価した。
○:冷凍機油の循環が確認できた。
△:冷凍機油の循環は見られるが循環量が不十分。
×:冷凍機油の循環が確認できない。
安定性試験は、循環状態が良好な例1~44、例55~158、例185~292、例320~415の熱サイクルシステム用組成物に対して、JIS K 2211に記された「冷媒と冷凍機油の化学的安定性試験方法(オートクレーブ)」に準拠して実施した。
例1~44、例55~158、例185~292、例320~415で得られた熱サイクルシステム用組成物を、内部に150mlのガラス筒を入れた200mlのステンレス製の耐圧容器に、それぞれ入れ、さらに触媒として、1つの耐圧容器に鉄、銅およびアルミニウムの試験片を入れ、密閉した。次いで、密閉した耐圧容器を恒温槽(パーフェクトオーブンPHH-202、エスペック株式会社製)中に175℃で14日間保存し、次のように作動媒体の酸分量測定、冷凍機油の色相観察および触媒の外観変化観察を行った。
a)鉄一般用冷間圧延鋼板(JIS G3141に定められたもの、記号の種類SPCC-SB)の試験片,30mm×25mm×厚さ3.2mm
b)銅 タフピッチ銅(JIS H3100に定められたもの、合金番号C1100、記号C1100P)の試験片、30mm×25mm×厚さ2mm
c)アルミニウム 純アルミニウム(JIS H4000に定められたもの、合金番号1050、記号A1050P)の試験片、30mm×25mm×厚さ2mm
試験後の作動媒体の酸分量測定は、JIS K1560(1,1,1,2-テトラフルオロエタン(HFC-134a))に準拠して試験を実施した。
試験後の耐圧容器を室温になるまで静置した。
吸収瓶4本にそれぞれ純水を100ml入れ、導管で直列に連結したものを準備した。
室温になった耐圧容器に、純水を加えた吸収瓶を連結したものをつなぎ、徐々に耐圧容器の弁を開放して、冷媒ガスを吸収瓶の水中に導入し、冷媒ガスに含まれる酸分を抽出した。
抽出後の吸収瓶の水は、1本目と2本目を合わせて指示薬(BTB:ブロモチモールブルー)を1滴加え、1/100N-NaOHアルカリ標準液を用いて滴定した。同時に、吸収瓶の3本目および4本目の水を合わせて同様に滴定し、測定ブランクとした。これら測定値と測定ブランクの値から、試験後の冷媒に含まれる酸分をHCl濃度として求めた。
酸分量測定後、作動媒体を抜き出した圧力容器に残った冷凍機油を取り出し、ASTM-D156に準拠して冷凍機油の色相を評価した。ここで、L値は数値が大きいほど着色度合いが大きいため、数値が低いほど好ましい。ここではL3.5以下が好ましく、L3.0以下がより好ましく、L2.5以下がさらに好ましい。
触媒の外観変化は、上記試験後の触媒金属の外観を目視で確認し、以下の基準により評価した。
○:変化なし、×:光沢なしまたは黒く変色
光沢なしまたは黒く変色の場合は、上記安定性試験により熱サイクルシステム用組成物が劣化したことを示す。
なお、2014年2月20日に出願された日本特許出願2014-030857号、2014年6月20日に出願された日本特許出願2014-127744号、2014年7月18日に出願された日本特許出願2014-148347号および2014年9月12日に出願された日本特許出願2014-187002号の明細書、特許請求の範囲、要約書および図面の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (15)
- トリフルオロエチレンを含む熱サイクル用作動媒体と冷凍機油とを含む熱サイクルシステム用組成物。
- 前記冷凍機油が、エステル系冷凍機油、エーテル系冷凍機油、ポリグリコール系冷凍機油、炭化水素系冷凍機油から選ばれる少なくとも1種である、請求項1に記載の熱サイクルシステム用組成物。
- 前記冷凍機油が、二塩基酸エステル、ポリオールエステル、コンプレックスエステル、ポリオール炭酸エステル、ポリビニルエーテル、ポリアルキレングリコールおよびアルキルベンゼンから選ばれる少なくとも1種である、請求項2に記載の熱サイクルシステム用組成物。
- 前記冷凍機油の40℃における動粘度が1~750mm2/sである、請求項1~3のいずれか1項に記載の熱サイクルシステム用組成物。
- 前記冷凍機油の100℃における動粘度が1~100mm2/sである、請求項1~4のいずれか1項に記載の熱サイクルシステム用組成物。
- 前記冷凍機油の炭素原子と酸素原子の比率(炭素/酸素モル比)が2~7.5である、請求項1~5のいずれか1項に記載の熱サイクルシステム用組成物。
- 前記熱サイクル用作動媒体がさらに飽和のヒドロフルオロカーボンを含む、請求項1~6のいずれか1項に記載の熱サイクルシステム用組成物。
- 前記飽和のヒドロフルオロカーボンがジフルオロメタン、1,1-ジフルオロエタン、1,1,1,2-テトラフルオロエタンおよびペンタフルオロエタンから選ばれる少なくとも1種である、請求項7に記載の熱サイクルシステム用組成物。
- 前記熱サイクル用作動媒体がさらにトリフルオロエチレン以外の炭素-炭素二重結合を有するヒドロフルオロカーボンを含む、請求項1~8のいずれか1項に記載の熱サイクルシステム用組成物。
- 前記炭素-炭素二重結合を有するヒドロフルオロカーボンが、1,3,3,3-テトラフルオロプロペンおよび2,3,3,3-テトラフルオロプロペンから選ばれる少なくとも1種である、請求項9に記載の熱サイクルシステム用組成物。
- 前記熱サイクル用作動媒体の100質量%に対するトリフルオロエチレンの含有量が10質量%以上である、請求項1~10のいずれか1項に記載の熱サイクルシステム用組成物。
- 前記熱サイクル用作動媒体の100質量%に対するトリフルオロエチレンの含有量が20~80質量%である、請求項11に記載の熱サイクルシステム用組成物。
- 前記熱サイクル用作動媒体がさらにジフルオロメタンを含み、前記熱サイクル用作動媒体の100質量%に対するジフルオロメタンの含有量が20質量%以上である、請求項11または12に記載の熱サイクルシステム用組成物。
- 請求項1~13のいずれか1項に記載の熱サイクルシステム用組成物を用いた、熱サイクルシステム。
- 前記熱サイクルシステムが、冷凍・冷蔵機器、空調機器、発電システム、熱輸送装置または二次冷却機である、請求項14に記載の熱サイクルシステム。
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US10358591B2 (en) | 2019-07-23 |
US20160347982A1 (en) | 2016-12-01 |
CN110776874B (zh) | 2021-12-17 |
CN110776874A (zh) | 2020-02-11 |
EP3109298A4 (en) | 2017-09-27 |
US20190322916A1 (en) | 2019-10-24 |
JPWO2015125880A1 (ja) | 2017-03-30 |
CN106029850B (zh) | 2019-12-10 |
CN106029850A (zh) | 2016-10-12 |
EP3109298A1 (en) | 2016-12-28 |
EP3109298B1 (en) | 2023-11-29 |
US10851276B2 (en) | 2020-12-01 |
JP6520915B2 (ja) | 2019-05-29 |
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