WO2019022139A1 - Composition azéotropique, milieu de travail destiné à un cycle thermique et système de cycle thermique - Google Patents

Composition azéotropique, milieu de travail destiné à un cycle thermique et système de cycle thermique Download PDF

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Publication number
WO2019022139A1
WO2019022139A1 PCT/JP2018/027904 JP2018027904W WO2019022139A1 WO 2019022139 A1 WO2019022139 A1 WO 2019022139A1 JP 2018027904 W JP2018027904 W JP 2018027904W WO 2019022139 A1 WO2019022139 A1 WO 2019022139A1
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working medium
composition
azeotropic
azeotrope
tetrafluoropropene
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English (en)
Japanese (ja)
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正人 福島
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Ａｇｃ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention consists of 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) and (Z) -1,3,3,3-tetrafluoropropene (HFO-1234ze (Z))
  • the present invention relates to an azeotrope-like composition, a working medium for thermal cycling using the same, and a thermal cycling system.
  • working media for heat cycle systems such as refrigerants for refrigerators, refrigerants for air conditioners, working media for power generation systems (waste heat recovery power generation etc), working media for latent heat transport devices (heat pipes etc), secondary cooling media etc.
  • chlorofluoromethane chlorofluorocarbons (CFC) such as dichlorodifluoromethane
  • HCFC hydrochlorofluorocarbons
  • CFCs and HCFCs have been pointed out as their effects on the stratospheric ozone layer and are currently subject to regulation.
  • HFC-32 difluoromethane
  • HFC-125 pentafluoroethane
  • HFC-125 Hydrofluorocarbons
  • R410A an azeotrope-like mixed refrigerant having a mass ratio of 1: 1 of HFC-32 and HFC-125
  • HFC has been pointed out as a possible cause of global warming.
  • 1,1,1,2-tetrafluoroethane which is used as a refrigerant for automobile air conditioners, has a large global warming potential of 1430 (100-year value).
  • a car air conditioner there is a high probability that the refrigerant leaks into the atmosphere from the connection hose, the bearing portion and the like.
  • HFC-134a is also used as a working medium for centrifugal refrigerators (also called turbo refrigerators).
  • centrifugal refrigerators the amount of filling of the working medium is larger than that of other refrigerators and heat pumps.
  • a centrifugal refrigerator having a capacity of 500 refrigeration tons about 700 to 800 kg of a working medium is filled.
  • Centrifugal refrigerators are often installed in a machine room in a building, but if a working medium leaks due to an accident etc., a large amount of working medium may be released to the atmosphere .
  • the working medium used in the centrifugal refrigerator is required to have high safety due to low combustibility and the like, and also to have a small global warming potential from the environmental aspect.
  • Hydrofluoro a working medium that has a carbon-carbon double bond and is easily decomposed by OH radicals in the atmosphere in recent years, so it has a low impact on the ozone layer and a low impact on global warming.
  • Expectations are focused on olefins (HFO), hydrochlorofluoroolefins (HCFO) and chlorofluoroolefins (CFO), ie compounds having carbon-carbon double bonds.
  • HFO hydrochlorofluoroolefins
  • CFO chlorofluoroolefins
  • saturated HFC is referred to as HFC and is used separately from HFO.
  • HFC may be specified as a saturated hydrofluorocarbon.
  • HCFO and CFO are compounds in which the flammability is suppressed because the ratio of halogen in one molecule is large. Therefore, it is considered to use HCFO and CFO as a working medium which has little influence on the ozone layer, little influence on global warming, and reduced flammability.
  • a working medium for example, a working medium using HCFO-1224yd (hereinafter referred to as "1224yd”), which is hydrochlorofluoropropene, is known (see, for example, Patent Document 1).
  • the composition containing a plurality of compounds is a non-azeotropic composition
  • the working medium when this is used as a working medium, the working medium is thermally cycled from a pressure vessel housed for storage and transfer.
  • the composition may change when it is filled (transfer-filled) to a refrigeration air conditioner or the like that is a system device, or when it leaks from the refrigeration air conditioner.
  • the composition of the working medium changes, it is difficult to restore the working medium to the initial composition. Therefore, when the non-azeotropic composition is used as a working medium, there is a problem that the controllability of the working medium is inferior.
  • a non-azeotropic composition when using a non-azeotropic composition as a working medium, the subject that a temperature gradient became large also occurred.
  • the present invention uses an azeotrope-like composition that provides a working medium for thermal cycling that has little influence on global warming, a small compositional change, a small temperature gradient, and excellent cycle performance, and the azeotrope-like composition
  • An object of the present invention is to provide a working medium for thermal cycling and a thermal cycling system.
  • the present invention provides an azeotrope-like composition, a working medium for thermal cycling, and a thermal cycling system having the following configurations.
  • An azeotropic or azeotrope-like composition comprising 1-chloro-2,3,3,3-tetrafluoropropene and (Z) -1,3,3,3-tetrafluoropropene.
  • the content ratio of the 1-chloro-2,3,3,3-tetrafluoropropene and the (Z) -1,3,3,3-tetrafluoropropene in the azeotropic or azeotrope-like composition is 1-chloro-2,3,3,3-tetrafluoropropene: (Z) -1,3,3,3-tetrafluoropropene in a mass ratio of 1:99 to 99: 1 [1]
  • the content ratio of the 1-chloro-2,3,3,3-tetrafluoropropene in the azeotropic or azeotropic composition is 30% by mass with respect to the total amount of the azeotropic or azeotropic composition
  • a working medium for thermal cycling comprising the azeotropic or azeotrope-like composition according to any one of [1] to [3].
  • [7] A thermal cycle system using the thermal cycle working medium according to any one of [4] to [6].
  • the heat cycle system according to [7] which is a refrigeration / refrigerator, an air conditioner, a power generation system, a heat transport device, or a secondary cooler.
  • an azeotrope-like composition that provides a working medium for thermal cycling that has little influence on global warming, a small compositional change, a small temperature gradient, and excellent cycle performance, and the azeotrope-like composition
  • the working medium for thermal cycling used can be provided. Further, according to the present invention, it is possible to provide a thermal cycle system which is excellent in cycle performance.
  • FIG. 6 is a cycle diagram in which a change in the state of a working medium for thermal cycling in the refrigeration cycle system is described on a pressure-enthalpy diagram.
  • the azeotropic or azeotrope-like composition of the present invention can be prepared from 1-chloro-2,3,3,3-tetrafluoropropene (1224yd) and (Z) -1,3,3,3-tetrafluoropropene (HFO- 1234ze (Z), hereinafter referred to as "1234ze (Z)".
  • An azeotropic composition is a mixture of two or more substances that behaves as a single substance and is distilled at a defined and predetermined boiling point (constant boiling point).
  • the azeotropic composition has the same composition of the gas phase and the liquid phase in its vapor-liquid equilibrium state, that is, a mixture of two or more substances is evaporated or condensed without composition change.
  • An azeotrope-like composition is a mixture of two or more substances that behaves essentially as a single substance and evaporates at a substantially fixed predetermined boiling point.
  • the azeotrope-like composition exhibits substantially the same behavior as that of the azeotropic composition at the time of vapor-liquid equilibrium.
  • the azeotrope-like composition has substantially the same composition of the gas phase and the liquid phase in its vapor-liquid equilibrium state. That is, when a mixture of two or more substances forms an azeotrope-like composition, they are evaporated or condensed without substantial composition change.
  • the azeotrope-like composition has substantially the same boiling pressure and dew point pressure of the composition at a certain temperature. Since an azeotrope-like composition can be handled equivalently to an azeotropic composition, the azeotrope-like composition is hereinafter described as including an azeotropic composition.
  • the azeotropic composition and the azeotrope-like composition can be determined, for example, by measuring the effect of vapor leakage on the vapor pressure as follows.
  • the initial mixture is contained in a vessel at any temperature, and the initial vapor pressure of the mixture is measured.
  • the mixture is allowed to leak from the vessel while maintaining the temperature constant until 50% by weight of the initial mixture is removed, at which point the vapor pressure of the mixture remaining in the vessel (residual mixture) is measured. At this time, if there is no change in vapor pressure between the initial mixture and the remaining mixture, the initial mixture has an azeotropic composition.
  • the initial mixture is azeotrope-like in composition.
  • the composition is defined as an azeotrope-like composition when is less than 10%.
  • the mixture of 1224yd and 1234ze (Z) has a mass ratio of 1224yd to 1234ze (Z) (1224yd [mass%]: 1234ze (Z) [mass%]) in the range of 1:99 to 99: 1 , Pressure deviation is 0.7% or less. From these results, it can be seen that 1224yd and 1234ze (Z) have an azeotrope-like composition with a pressure deviation of less than 10% in the range of 1 to 99% by mass of 1224yd.
  • 1224 yd and 1224 yd (Z) and 1224 yd (E) can be used without distinction when constituting the azeotrope-like composition described above. That is, 1224yd in the azeotropic or azeotrope-like composition of the present invention is either 1224yd (E) alone, 1224yd (Z) alone, or a mixture of 1224yd (E) and 1224yd (Z) in any proportion. Even if it forms an azeotrope-like composition of the above composition with 1234ze (Z).
  • the temperature gradient is an index reflecting the azeotropic composition, and if the temperature gradient of the mixture is 1.50 or less, it can be said that the mixture is the azeotropic composition.
  • the boiling points of 1224yd and 1234ze (Z) are values measured at a pressure of 1.013 ⁇ 10 5 Pa, and the boiling point of 1224yd (Z) is 15 ° C., and the boiling point of 1224yd (E) is 19 ° C., respectively.
  • the boiling point of 1234ze (Z) is 10 ° C.
  • the azeotrope-like composition consisting of 1224yd and 1234ze (Z) in the present invention has a mass ratio of 1224yd to 1234ze (Z) (1224yd [mass%]) : 1234ze (Z) [mass%]) is a mixture of 1:99 to 99: 1.
  • the azeotrope-like composition of the present invention is suitable as a working fluid for thermal cycling, and a working fluid for thermal cycling having excellent composition stability can be obtained.
  • the compositions of 1224 yd and 1234ze (Z) can be appropriately adjusted within the range of the azeotrope-like composition according to the application.
  • a composition which can make the above pressure deviation 0.6% or less is preferable, and a composition which can make the pressure deviation 0.5% or less Is more preferable, and the composition which can be 0.4% or less is more preferable.
  • the content ratio of 1224yd in the azeotrope-like composition of the present invention is preferably 20% by mass or more based on the total amount of the azeotrope-like composition from the viewpoint of the flammability described below.
  • the content of 1224yd in the azeotropic composition is more preferably 30% by mass or more.
  • 1234ze (Z) is noncombustible under ordinary conditions, it may become flammable when brought to high pressure and high temperature under high concentration of air. At this time, as shown in Examples described later, if the content ratio of 1234ze (Z) in the azeotrope-like composition consisting of 1224yd and 1234ze (Z) is 80% by mass or less, from 1224yd and 1234ze (Z) The resulting azeotrope-like composition has no flammability when mixed with air in any proportion. In order to obtain higher safety, the content of 1234ze (Z) in the azeotropic composition is more preferably 70% by mass or less.
  • the 1224 yd and 1234ze (Z) contained in the azeotrope-like composition of the present invention have a small global warming potential.
  • the global warming potential (GWP) at a 100-year value shown in the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (2013) or measured according to the method is 1224 yd Is 1 or less, and 1234ze (Z) is 1 or less. Therefore, the azeotrope-like composition of the present invention has a very small influence on global warming, and can be suitably used as a working medium for thermal cycling.
  • the working fluid for thermal cycling of the present invention comprises an azeotrope-like composition consisting of 1224yd and 1234ze (Z) described above.
  • the working fluid for thermal cycling of the present invention may optionally contain a compound generally used as a working fluid, as long as the effects of the present invention are not impaired.
  • the working fluid for thermal cycling of the present invention contains the above-described azeotrope-like composition of the present invention, when applied to a thermal cycling system, the composition change upon transfer-filling or leakage from equipment is extremely small. Therefore, extremely stable cycle performance can be obtained in the thermal cycle system. In addition, there is an advantage that management of the thermal cycle working medium is easy, and good cycle performance can be obtained by further increasing the efficiency while maintaining a certain capacity.
  • the thermal cycling working medium of the present invention has an azeotrope-like composition consisting of 1224yd and 1234ze (Z), so the temperature gradient is close to zero. Therefore, as described below, an energy efficient thermal cycle system can be obtained.
  • the "temperature gradient” is one of the indexes for measuring the properties when the mixture is used as a working medium.
  • a temperature gradient is defined as the nature of the start and end temperatures of a heat exchanger, for example of evaporation in an evaporator, or of condensation in a condenser, to be different.
  • FIG. 1 is a schematic block diagram showing an example of the below-mentioned refrigeration cycle system to which the working fluid for thermal cycling of the present invention is applied.
  • the refrigeration cycle system 10 cools and liquefys the working medium vapor B discharged from the compressor 11 by compressing the working medium vapor A into a high temperature and high pressure working medium vapor B, and liquefies it to operate at a low temperature and high pressure A condenser 12 as medium C, an expansion valve 13 expanding the working medium C discharged from the condenser 12 into a low-temperature low-pressure working medium D, and heating the working medium D discharged from the expansion valve 13
  • This system is roughly configured by including an evaporator 14 as a high-temperature low-pressure working medium vapor A, a pump 15 supplying the load fluid E to the evaporator 14, and a pump 16 supplying the fluid F to the condenser 12. is there.
  • the temperature of the working medium rises from the inlet to the outlet of the evaporator 14 during evaporation, and the temperature decreases from the inlet to the outlet of the condenser 12 during condensation.
  • the evaporator 14 and the condenser 12 are configured by performing heat exchange with a heat source fluid such as water or air flowing opposite to a working medium.
  • the heat source fluid is indicated by “E ⁇ E ′” in the evaporator 14 and by “F ⁇ F ′” in the condenser 12 in the refrigeration cycle system 10.
  • the azeotropic composition can be handled almost equally as a working medium of a single composition when used as a working medium because the composition does not change its composition when the composition is repeatedly evaporated and condensed.
  • an azeotrope-like composition has a small compositional fluctuation when evaporation and condensation are repeated, and can be handled as well as an azeotropic composition. Therefore, even when an azeotropic composition or an azeotrope-like composition is used as the working medium, the temperature difference between the outlet temperature and the inlet temperature of the evaporator 14 is substantially constant.
  • the temperature difference is not constant.
  • the inlet temperature becomes lower than 0 ° C., and a problem of frost formation in the evaporator 14 occurs.
  • the larger the temperature gradient the lower the inlet temperature and the greater the possibility of frost formation.
  • the working medium flowing through the heat exchanger such as the evaporator 14 and the condenser 12 always faces the heat source fluid such as water or air. It is devised to improve the heat exchange efficiency by making it flow.
  • the temperature difference between the heat source fluid is small in a stable operation state generally operating for a long time, apart from the start time, the temperature gradient is large in the case of a non-azeotropic composition in which the composition of the gas-liquid phase largely differs. It is difficult to obtain an energy efficient thermal cycle system.
  • an azeotropic composition is used as a working medium, an energy efficient thermal cycle system can be obtained.
  • the azeotrope-like composition having a proportion of 1224 yd of 20% by mass or more with respect to the total amount of 1224 yd and 1234ze (Z) has no flammability. Therefore, the working medium for thermal cycle containing the azeotrope-like composition is extremely safe even when it leaks out of the thermal cycle system. In order to obtain higher safety, the content of 1224yd in the thermal cycle working medium is more preferably 30% by mass or more.
  • the working fluid for thermal cycling of the present invention further comprises an azeotrope-like composition consisting of 1224 yd and 1234ze (Z), the optional ingredient described later
  • the 1234ze (Z) in the working fluid for thermal cycling is When the content ratio is 80% by mass or less, a highly safe working medium for heat cycle can be obtained because it has no combustibility. In order to obtain higher safety, the content of 1234ze (Z) in the working fluid for thermal cycling is more preferably 70% by mass or less.
  • the composition has a combustibility, it can be used in a thermal cycle system by paying careful attention to handling depending on the use conditions.
  • the working medium for thermal cycling of the present invention contains an azeotrope-like composition consisting of 1224yd and 1234ze (Z), it is superior when applied to a thermal cycling system as compared to the working medium for thermal cycling consisting only of 1224yd.
  • Cycle performance coefficient of performance and refrigeration capacity
  • the working medium for thermal cycling of the present invention has an advantage of being able to improve the refrigerating capacity without lowering the coefficient of performance, as compared with the working medium for thermal cycling consisting of only 1224yd.
  • Table 2 shows the coefficient of performance and the refrigerating capacity as the cycle performance as a working medium consisting of each of 1224 yd (Z) and 1234ze (Z).
  • the coefficient of performance and the refrigeration capacity are determined by the method described later (however, evaporation temperature: 5 ° C., condensation completion temperature: 40 ° C., degree of supercooling (SC); 5 ° C., degree of superheat (SH); 5 ° C.).
  • the coefficient of performance and the freezing capacity of each compound are shown as relative values based on 1224 yd (Z) (1.00) (hereinafter referred to as "relative coefficient of performance" or “relative freezing capacity", respectively).
  • the working fluid for thermal cycling of the present invention may optionally contain a compound generally used as a working fluid, in addition to the azeotrope-like composition as long as the effects of the present invention are not impaired.
  • Such optional compounds include, for example, HFC, HFO other than 1234ze (Z), HCFO other than 1224yd, hydrocarbon, carbon dioxide, and other gases such as vaporization and liquefaction with 1224yd and 1234ze (Z) Other ingredients.
  • HFC, HFO other than 1234ze (Z), HCFO other than 1224yd are preferable.
  • a compound which has an action of suppressing the flammability when used in a thermal cycle in combination with 1224yd and 1234ze (Z), and can keep the temperature gradient within an acceptable range while suppressing the GWP low is preferable.
  • the thermal cycle working medium contains such a compound in combination with 1224 yd and 1234ze (Z)
  • better cycle performance can be obtained while suppressing the flammability and keeping the GWP low, and also the influence of the temperature gradient Few.
  • the content of the optional components in total is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less, in the working fluid for thermal cycling (100% by mass). Is more preferred. If the content ratio of the optional components exceeds 10% by mass, the temperature gradient becomes too large, and the composition for the thermal cycle working medium significantly changes if leakage from the thermal cycle equipment occurs in the thermal cycle working medium application Controllability of the working medium may be reduced.
  • HFC HFCs improve the cycle performance of thermal cycling systems.
  • the optional component HFC is preferably selected from the viewpoint of having the effect of suppressing the above-mentioned flammability and keeping the GWP low while keeping the temperature gradient within the allowable range.
  • an HFC having 1 to 5 carbon atoms is preferable in that it has little influence on the ozone layer and little influence on global warming.
  • the HFC may be linear, branched or cyclic.
  • HFC As HFC, HFC-32, difluoroethane, trifluoroethane, tetrafluoroethane, HFC-125, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane and the like can be mentioned.
  • HFC 1,1,2,2-tetrafluoroethane
  • HFC-134a 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc) are more preferable
  • HFC-134a, HFC -245fa and HFC-365mfc are more preferable.
  • One of HFCs may be used alone, or two or more thereof may be used in combination.
  • the content ratio of HFC in the working fluid for thermal cycling (100% by mass) used in the present invention is, for example, as follows.
  • the HFC is HFC-134a
  • the refrigerating capacity is improved in the range of 1 to 10% by mass without causing a large decrease in the coefficient of performance.
  • the coefficient of performance is improved in the range of 1 to 10% by mass without causing a significant decrease in refrigeration capacity.
  • Control of the HFC content can be performed according to the required characteristics of the thermal cycle working medium.
  • HFO other than 1234ze (Z) HFO improves the cycling performance of the thermal cycling system. Also, in the case of HFO, GWP is orders of magnitude lower than HFC. Therefore, GWP can be reduced by using HFO.
  • the HFO is also preferably selected from the viewpoint of keeping the temperature gradient within the allowable range while having the action of suppressing the flammability and suppressing the GWP low similarly to the above-mentioned HFC.
  • HFOs 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf), 1,1,2-triphenyl Fluoropropene (HFO-1243yc), (E) -1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), (Z) -1,2,3,3,3-pentafluoro Propene (HFO-1225ye (Z)), (E) -1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), 3,3,3-trifluoropropene (HFO-1243zf), ( E) -1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (E)), (Z) -1,1,1,4,4,4-hexaf Oro-2-butene (HFO-1336mzz (Z))
  • HFO-1234ze (E), HFO-1234yf, HFO-1336mzz (Z), and HFO-1243zf are preferable, and HFO-1234ze (E), HFO-1234yf, and HFO-1336mzz (Z) are more preferable.
  • the HFO may be used alone or in combination of two or more.
  • the content ratio of HFO in the working fluid for thermal cycling (100% by mass) used in the present invention can be arbitrarily selected according to the required characteristics of the working fluid for thermal cycling. For example, if the content ratio of HFO is 1 to 10% by mass, a thermal cycle system having excellent cycle performance as compared with a working medium composed of an azeotrope-like composition of 1224yd and 1234ze (Z) is provided.
  • the HCFO as an optional component other than 1224 yd also has the action of suppressing the flammability similarly to the above-mentioned HFC, and is preferably selected from the viewpoint of keeping the temperature gradient within the allowable range while suppressing the GWP low.
  • the HCFO's GWP is orders of magnitude lower than that of the HFC. Therefore, GWP can be reduced by containing HCFO.
  • HCFOs other than 1224 yd include 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-dichlorofluoroethylene (HCFO-1121), 1-chloro-2-fluoroethylene (HCFO-1131), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) and 1-chloro-3,3,3-tetrafluoropropene (HCFO-1233zd).
  • HCFO other than 1224yd is preferably HCFO-1233zd from the viewpoint of having high critical temperature and being excellent in durability and coefficient of performance.
  • HCFOs other than 1224 yd may be used alone or in combination of two or more.
  • the content of HCFO other than 1224yd is preferably 1 to 10% by mass, and more preferably 1 to 5% by mass in the working medium for thermal cycling (100% by mass). If the content ratio of HCFO is 1 to 10% by mass, it is possible to provide a thermal cycle system which is superior in cycle performance to a thermal cycle working medium composed of an azeotrope-like composition of 1224yd and 1234ze (Z).
  • the working medium used for the heat cycle system of the present invention may contain carbon dioxide, hydrocarbons, chlorofluoroolefin (CFO), etc. in addition to the above-mentioned optional components.
  • CFO chlorofluoroolefin
  • a component which has less influence on the ozone layer and has less influence on global warming is preferable.
  • hydrocarbon propane, propylene, cyclopropane, butane, isobutane, pentane, isopentane and the like can be mentioned.
  • the hydrocarbon may be used alone or in combination of two or more.
  • the working medium for thermal cycling contains a hydrocarbon
  • the content is less than 10% by mass, preferably 1 to 5% by mass, preferably 3 to 5% by mass, with respect to 100% by mass of the thermal cycling working medium. More preferable. If the hydrocarbon is at least the lower limit value, the solubility of the mineral-based refrigerator oil in the thermal cycle working medium becomes better. If the amount of hydrocarbon is less than or equal to the upper limit value, the influence on combustibility is small.
  • CFO examples include chlorofluoropropene and chlorofluoroethylene.
  • CFO 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214 ya) is preferable because the flammability of the working fluid can be easily suppressed without significantly reducing the cycle performance of the working fluid for thermal cycling.
  • CFO-1214yb 1,3-dichloro-1,2,3,3-tetrafluoropropene
  • CFO-1112 1,2-dichloro-1,2-difluoroethylene
  • the CFO may be used alone or in combination of two or more.
  • the working fluid for thermal cycling contains CFO
  • the content thereof is less than 10% by mass, preferably from 1 to 8% by mass, and more preferably from 2 to 5% by mass, with respect to the total amount of the working fluid for thermal cycling. If the content rate of CFO is more than a lower limit, it will be easy to control the combustibility of the working fluid for thermal cycling. If the content rate of CFO is below an upper limit, favorable cycle performance will be easy to be obtained.
  • the content of the azeotropic composition consisting of 1224 yd and 1234ze (Z) with respect to the total amount of thermal cycling working medium is 90% by mass or more in terms of cycle performance. Preferably, 95% by mass or more is more preferable.
  • the working medium for thermal cycling of the present invention contains an azeotrope-like composition consisting of 1224yd and 1234ze (Z), so that the composition change is extremely small, the temperature gradient is small, and a good cycle performance can be obtained. is there.
  • the working medium can be used as a working medium composition, usually mixed with a lubricating oil, for application to a thermal cycling system.
  • the working vehicle composition may further contain known additives such as stabilizers and leak detection substances in addition to these.
  • the lubricating oil As the lubricating oil, a known lubricating oil used in the working medium composition can be adopted without particular limitation, together with the working medium conventionally composed of halogenated hydrocarbons. Specific examples of the lubricating oil include oxygen-containing synthetic oils (ester-based lubricating oils, ether-based lubricating oils and the like), fluorine-based lubricating oils, mineral-based lubricating oils, hydrocarbon-based synthetic oils and the like.
  • ester-based lubricating oils dibasic acid ester oils, polyol ester oils, complex ester oils, polyol carbonate oils and the like can be mentioned.
  • ether-based lubricating oils examples include polyvinyl ether oils and polyoxyalkylene oils such as polyglycol oils.
  • fluorine-based lubricating oils include compounds in which hydrogen atoms of synthetic oils (mineral oil, poly ⁇ -olefin, alkylbenzene, alkylnaphthalene, etc. described later) are substituted with fluorine atoms, perfluoropolyether oils, fluorinated silicone oils, etc.
  • a mineral-based lubricating oil As a mineral-based lubricating oil, a lubricating oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil is subjected to purification treatment (solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation
  • purifying, clay treatment etc. are mentioned.
  • hydrocarbon synthetic oils examples include poly ⁇ -olefins, alkylbenzenes and alkylnaphthalenes.
  • the lubricating oils may be used alone or in combination of two or more.
  • the lubricating oil is preferably at least one selected from polyol ester oils, polyvinyl ether oils and polyglycol oils from the viewpoint of compatibility with the working medium.
  • the addition amount of the lubricating oil may be in a range that does not significantly reduce the effects of the present invention, and is preferably 10 to 100 parts by mass, and more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the working medium.
  • Stabilizers are components that improve the stability of the working medium against heat and oxidation.
  • the stabilizer there are no particular limitations on known stabilizers conventionally used in thermal cycle systems, such as oxidation resistance improvers, heat resistance improvers, metal deactivators, etc., together with the working medium conventionally made of halogenated hydrocarbons. It can be adopted.
  • N N'-diphenyl phenylene diamine, p-octyl diphenylamine, p, p'-dioctyl diphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine N- (p-dodecyl) phenyl-2-naphthylamine, di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothiazine, 6- (t-butyl) phenol, 2,6-di- (t-butyl) And the like) phenol, 4-methyl-2,6-di- (t-butyl) phenol, 4,4'-methylenebis (2,6-di-t-butylphenol) and the like.
  • the oxidation resistance improver and the heat resistance improver one type may be used alone,
  • metal deactivators examples include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimethylcaptothiadiazole, salicylidine-propylenediamine, pyrazole, benzotriazole, toltriazole, 2-methylbenzamidazole, 3,5- Dimethylpyrazole, methylenebis-benzotriazole, organic acids or their esters, primary, secondary or tertiary aliphatic amines, amine salts of organic acids or inorganic acids, heterocyclic nitrogen-containing compounds, alkyl acid phosphates Amine salts or derivatives thereof.
  • the addition amount of the stabilizer may be within a range not significantly reducing the effects of the present invention, and is preferably 5 parts by mass or less, and more preferably 1 part by mass or less with respect to 100 parts by mass of the working medium.
  • UV fluorescent dye As a leak detection substance, an ultraviolet fluorescent dye, an odor gas, an odor masking agent and the like can be mentioned.
  • Ultraviolet fluorescent dyes are described in U.S. Pat. No. 4,249,412, JP-A-10-502737, JP-A-2007-511645, JP-A-2008-500437, and JP-A-2008-531836.
  • Known ultraviolet fluorescent dyes used in thermal cycle systems, as well as working media conventionally comprising halogenated hydrocarbons such as those described in U.S. Pat.
  • a solubilizer may be used to improve the solubility of the leak detection substance in the working medium.
  • solubilizers examples include those described in JP-A-2007-511645, JP-A-2008-500437, and JP-A-2008-531836.
  • the addition amount of the leak detection substance may be within the range not significantly reducing the effects of the present invention, preferably 2 parts by mass or less and more preferably 0.5 parts by mass or less with respect to 100 parts by mass of the working medium.
  • the thermal cycle system of the present invention is obtained by applying the working medium of the present invention to an apparatus and device for thermal cycling.
  • the working medium may be applied to a thermal cycle system as the working medium composition.
  • a thermal cycle system a thermal cycle system using heat exchangers such as a condenser and an evaporator is used without particular limitation.
  • the thermal cycle system of the present invention may be a heat pump system that utilizes the heat obtained by the condenser, or may be a refrigeration cycle system that utilizes the cold obtained by the evaporator.
  • thermal cycle system of the present invention examples include refrigeration and refrigeration equipment, air conditioners, power generation systems, heat transport devices, secondary coolers and the like.
  • the thermal cycle system of the present invention can stably exhibit thermal cycle performance even in a higher temperature operating environment, and therefore, is preferably used as an air conditioner often installed outdoors.
  • the heat cycle system of this invention is used as a freezing / refrigerating apparatus.
  • the power generation system is preferably a Rankine cycle system power generation system.
  • the working medium is heated by geothermal energy, solar heat, middle to high temperature range waste heat at about 50 to 200 ° C. in an evaporator, and the working medium that has become high-temperature high-pressure steam is expanded
  • An example is a system in which adiabatic expansion is performed in a machine, and a work generated by the adiabatic expansion drives a generator to generate electric power.
  • a latent heat transport device As a heat transport device, a latent heat transport device is preferable.
  • the latent heat transport device include a heat pipe for performing latent heat transport utilizing phenomena such as evaporation, boiling, and condensation of a working medium enclosed in the device, and a two-phase closed thermosyphon device.
  • the heat pipe is applied to a relatively small cooling device such as a cooling device for a semiconductor element or a heat generating portion of an electronic device. Since the two-phase closed thermosyphon does not require a wig and has a simple structure, it is widely used for gas-gas heat exchangers, promoting snow melting on roads, preventing freezing and the like.
  • refrigeration / refrigeration equipment examples include showcases (built-in showcases, separately mounted showcases, etc.), commercial freezers / refrigerators, vending machines, ice makers, and the like.
  • air conditioners specifically, room air conditioners, package air conditioners (package air conditioners for buildings, package air conditioners for buildings, equipment package air conditioners, etc.), heat source equipment chilling units, gas engine heat pumps, train air conditioners, car air conditioners Etc.
  • a heat source equipment chilling unit although a volumetric-compression-type refrigerator and a centrifugal refrigerator are mentioned, for example.
  • the centrifugal refrigerator to be described next is preferable because the effect of the present invention can be more remarkably obtained since the filling amount of the working medium is large.
  • centrifugal refrigerator is a refrigerator using a centrifugal compressor.
  • a centrifugal refrigerator is a type of vapor compression refrigerator, and is generally referred to as a turbo refrigerator.
  • a centrifugal compressor includes an impeller and performs compression by discharging a working medium to the outer peripheral portion by the rotating impeller.
  • Centrifugal refrigerators are used in office buildings, district heating and cooling, heating and cooling in hospitals, semiconductor factories, cold water production plants in the petrochemical industry, and the like.
  • the centrifugal refrigerator may be either a low pressure type or a high pressure type, but is preferably a low pressure type centrifugal refrigerator.
  • the low pressure type is, for example, that of the high pressure gas safety method such as trichlorofluoromethane (CFC-11), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), HFC-245fa.
  • Working medium which does not receive application that is, “a liquefied gas which has a pressure of 0.2 MPa or more at ordinary temperature, a pressure which is actually 0.2 MPa or more, or a temperature when the pressure is 0.2 MPa or more is”
  • a centrifugal refrigerator that uses a working medium that does not correspond to “liquefied gas at 35 ° C. or less”.
  • a refrigeration cycle system which is an example of a thermal cycle system, will be described with reference to FIG.
  • a gaseous working medium is compressed by a compressor and cooled by a condenser to produce a high pressure liquid, and the expansion valve reduces the pressure, and the evaporator vaporizes at a low temperature and removes heat by heat of vaporization.
  • the working medium vapor A discharged from the evaporator 14 is compressed by the compressor 11 to be a high temperature and high pressure working medium vapor B.
  • the working medium vapor B discharged from the compressor 11 is cooled by the fluid F in the condenser 12 and liquefied to form a working medium C of low temperature and high pressure. At this time, the fluid F is heated to become a fluid F ′ and discharged from the condenser 12.
  • the working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to form a low-temperature low-pressure working medium D.
  • the working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to be a high-temperature low-pressure working medium vapor A. At this time, the load fluid E is cooled to be a load fluid E ′ and discharged from the evaporator 14.
  • the state change of the working medium in the refrigeration cycle system 10 can be represented as a trapezoid with vertices A, B, C, and D as shown in FIG. 2 when it is described on a pressure-enthalpy chart.
  • the AB process is a process in which adiabatic compression is performed by the compressor 11 to make the high temperature and low pressure working medium vapor A into a high temperature and high pressure working medium vapor B, which is shown by an AB line in FIG. As described later, the working medium vapor A is introduced into the compressor 11 in a superheated state, and the resulting working medium vapor B is also a superheated vapor.
  • the BC process is a process of performing isobaric cooling in the condenser 12 and making the high temperature / high pressure working medium vapor B into a low temperature / high pressure working medium C, and is shown 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 when the working medium is a non-azeotropic composition is shown as the difference between T 1 and T 2 .
  • the CD process is a process in which isenthalpy expansion is performed by the expansion valve 13 to make the working medium C of low temperature and high pressure into the working medium D of low temperature and low pressure, which is shown by a CD line in FIG. Incidentally, if Shimese the temperature in the working medium C of low temperature and high pressure at T 3, T 2 -T 3 is (i) ⁇ supercooling degree of the working medium in the cycle of (iv) (SC).
  • the DA process is a process in which isobaric heating is performed by the evaporator 14 to return the low-temperature low-pressure working medium D to the high-temperature low-pressure working medium vapor A, which is shown by a DA line in FIG.
  • 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) (SH).
  • T 4 denotes the temperature of the working medium D.
  • the cycle performance of the thermal cycle working medium is, for example, the refrigeration capacity of the thermal cycle working medium (hereinafter referred to as “Q” as required) and the coefficient of performance (hereinafter referred to as “COP” as required)
  • Q and COP of the working medium for thermal cycling are A (high temperature and low pressure after evaporation), B (high temperature and high pressure after compression), C (low temperature and high pressure after condensation) for thermal cycling working medium, D (low temperature after expansion) each enthalpy in each state of the low pressure), h a, h B, h C, the use of h D, the following equation (1), obtained respectively from (2).
  • the compression work indicated by (h B -h A ) corresponds to the output (kW) of the refrigeration cycle, and the Q shown by (h A -h D ) above is required to operate the compressor, for example
  • the amount of power corresponds to the consumed power (kW).
  • Q means the ability to freeze the load fluid, and a higher Q means more work can be done in the same system. In other words, in the case of having a large Q, it indicates that the target performance can be obtained with a small amount of working medium, and the system can be miniaturized.
  • the inclusion of moisture in the thermal cycling system can cause problems, especially when used at low temperatures. For example, there are problems such as freezing in a capillary tube, hydrolysis of a working medium and lubricating oil, material degradation due to the acid component generated thereby, and generation of contamination.
  • the polyalkylene glycol oil, polyol ester oil, etc. mentioned above have extremely high hygroscopicity, are prone to hydrolytic reaction, deteriorate the properties as a refrigerator oil, and are a major cause of impairing the long-term reliability of the compressor. Become.
  • a method using a desiccant (silica gel, activated alumina, zeolite, etc.) can be mentioned.
  • a desiccant a zeolitic desiccant is preferable from the viewpoint of the chemical reactivity between the desiccant and the working fluid for thermal cycling and the moisture absorption capacity of the desiccant.
  • the compound represented by the following formula (3) is a main component from the viewpoint of excellent hygroscopicity.
  • Zeolite based desiccants are preferred.
  • M is an element of Group 1 such as Na and K or an element of Group 2 such as Ca
  • n is a valence of M
  • x and y are values determined by the crystal structure.
  • the pore size can be adjusted by changing M.
  • the pore size and the breaking strength are particularly important in the selection of the desiccant.
  • a desiccant having a pore size larger than the molecular diameter of the thermal cycling working medium is used, the thermal cycling working medium is adsorbed in the desiccant, and as a result, the chemical reaction between the thermal cycling working medium and the desiccant As a result, undesirable phenomena such as generation of non-condensable gas, decrease in strength of desiccant, and decrease in adsorption capacity occur.
  • a zeolite-based desiccant with a small pore size.
  • a sodium-potassium A-type synthetic zeolite having a pore size of 3.5 angstroms or less is preferable.
  • the particle size of the zeolitic desiccant is preferably about 0.5 to 5 mm.
  • the shape is preferably granular or cylindrical.
  • the zeolitic desiccant can be made into an arbitrary shape by solidifying powdered zeolite with a binder (bentonite or the like). Other desiccants (silica gel, activated alumina, etc.) may be used in combination as long as the zeolite-based desiccant is mainly used.
  • the use ratio of the zeolitic desiccant to the thermal cycle working medium is not particularly limited.
  • chlorine concentration The presence of chlorine in the thermal cycle system has undesirable effects, such as formation of deposits due to reaction with metals, wear of bearings, decomposition of a working fluid for thermal cycling and refrigerant oil.
  • the chlorine concentration in the thermal cycle system is preferably 100 ppm or less by mass ratio to the thermal cycle working medium, and particularly preferably 50 ppm or less.
  • non-condensable gas concentration If the non-condensable gas is mixed in the thermal cycle system, it has an adverse effect of poor heat transfer in the condenser and the evaporator and an increase in operating pressure, so it is necessary to suppress the mixing as much as possible.
  • oxygen which is one of the non-condensable gases, reacts with the thermal cycle working medium and refrigerator oil to promote decomposition.
  • the noncondensable gas concentration is preferably 1.5% by volume or less by volume ratio to the thermal cycle working medium in the gas phase portion of the thermal cycle working medium, and particularly preferably 0.5% by volume or less.
  • the system can be miniaturized because the thermal cycle working medium of the present invention is excellent in cycle performance and small in composition change and temperature gradient. Moreover, since the working medium for thermal cycling of the present invention is used, the cycle performance is excellent.
  • Examples 1 to 9 The working media for thermal cycling of Examples 1 to 9 were obtained by mixing 1224yd (Z) and 1234ze (Z) in the predetermined ratio shown in Table 3.
  • the working fluid for thermal cycling of Examples 1 to 9 is an azeotrope-like composition comprising 1224 yd (Z) and 1234ze (Z).
  • the flammability and refrigeration cycle performance were evaluated for each thermal cycle working medium.
  • the flammability evaluation was performed using the equipment specified in ASTM E-681. After evacuating the inside of a 12-liter flask controlled to an internal temperature of 60 ° C. and a relative humidity (Rh) of 50%, the heat cycle working medium of Example 1 and air were sealed to atmospheric pressure. Thereafter, in the gas phase near the center in the flask, discharge ignition was performed at 15 kV and 30 mA for 0.4 seconds, and the spread of the flame was visually confirmed. It was judged as combustible (present) when the angle of the flame spread upward was 90 ° or more, and noncombustible (not) when it was less than 90 °. The flammability was similarly evaluated for the heat cycle working media of Examples 2-9. The results are shown in Table 3.
  • the average evaporation temperature of the heat cycle working medium in the evaporator 14 is 5 ° C.
  • the average condensation temperature of the heat cycle working medium in the condenser 12 is 40 ° C.
  • the degree of subcooling of the heat cycle working medium in the condenser 12 was 5 ° C.
  • the refrigeration capacity and coefficient of performance are as follows: A (evaporation high temperature low pressure after evaporation), B (high temperature high pressure after compression), C (low temperature high pressure after condensation), D (low temperature low pressure after expansion) for thermal cycle working medium It calculated
  • thermodynamic properties required to calculate the refrigeration cycle performance were calculated based on the generalized equation of state (Soave-Redlich-Kwong equation) based on the corresponding state principle, and thermodynamic relations. When characteristic values were not available, calculation was performed using the estimation method based on the group contribution method.
  • the working medium for the heat cycle of the present invention includes a refrigerant for a refrigerator, a refrigerant for an air conditioner, a working fluid for a power generation system (such as waste heat recovery power generation), a working medium for a latent heat transport device (such as a heat pipe), a secondary cooling medium, etc. It is useful as a working medium for a refrigerator, a refrigerant for an air conditioner, a working fluid for a power generation system (such as waste heat recovery power generation), a working medium for a latent heat transport device (such as a heat pipe), a secondary cooling medium, etc. It is useful as a working medium for

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Abstract

L'invention concerne : une composition azéotropique qui fournit un milieu de travail qui est destiné à un cycle thermique et qui présente peu d'impact sur le réchauffement climatique, qui subit peu de changement de composition, qui présente un faible gradient de température et qui présente un excellent rendement de cycle ; un milieu de travail qui est destiné à un cycle thermique et qui utilise la composition azéotropique ; et un système de cycle thermique. L'invention concerne également un azéotrope ou une composition azéotropique qui comprend du 1-chloro-2,3,3,3-tétrafluoropropène et du (Z)-1,3,3,3-tétrafluoropropène. L'invention concerne en outre un milieu de travail qui est destiné à un cycle thermique et qui comporte l'azéotrope ou la composition azéotropique sus-mentionnés.
PCT/JP2018/027904 2017-07-26 2018-07-25 Composition azéotropique, milieu de travail destiné à un cycle thermique et système de cycle thermique WO2019022139A1 (fr)

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CN114316904A (zh) * 2020-10-12 2022-04-12 浙江省化工研究院有限公司 一种环保型传热组合物
US20220162489A1 (en) * 2020-10-22 2022-05-26 Rpl Holdings Limited Thermal pump refrigerants
US11459497B2 (en) 2017-11-27 2022-10-04 Rpl Holdings Limited Low GWP refrigerant blends

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WO2012157763A1 (fr) * 2011-05-19 2012-11-22 旭硝子株式会社 Fluide moteur, et système à cycle thermique
JP2014504675A (ja) * 2011-02-04 2014-02-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 特定のハロオレフィンを含む共沸および共沸混合物様組成物ならびにそれらの使用
WO2016171264A1 (fr) * 2015-04-24 2016-10-27 旭硝子株式会社 Composition à utiliser dans un système de cycle thermique, et système de cycle thermique
WO2016171256A1 (fr) * 2015-04-24 2016-10-27 旭硝子株式会社 Composition à utiliser dans un système de cyclage thermique, et système de cyclage thermique

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JP2014504675A (ja) * 2011-02-04 2014-02-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 特定のハロオレフィンを含む共沸および共沸混合物様組成物ならびにそれらの使用
WO2012157763A1 (fr) * 2011-05-19 2012-11-22 旭硝子株式会社 Fluide moteur, et système à cycle thermique
WO2016171264A1 (fr) * 2015-04-24 2016-10-27 旭硝子株式会社 Composition à utiliser dans un système de cycle thermique, et système de cycle thermique
WO2016171256A1 (fr) * 2015-04-24 2016-10-27 旭硝子株式会社 Composition à utiliser dans un système de cyclage thermique, et système de cyclage thermique

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Publication number Priority date Publication date Assignee Title
US11459497B2 (en) 2017-11-27 2022-10-04 Rpl Holdings Limited Low GWP refrigerant blends
CN114316904A (zh) * 2020-10-12 2022-04-12 浙江省化工研究院有限公司 一种环保型传热组合物
US20220162489A1 (en) * 2020-10-22 2022-05-26 Rpl Holdings Limited Thermal pump refrigerants
WO2022084488A3 (fr) * 2020-10-22 2022-07-07 Rpl Holdings Limited Fluides frigorigènes pour pompe thermique
US11827834B2 (en) * 2020-10-22 2023-11-28 Rpl Holdings Limited Thermal pump refrigerants

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