WO2009081673A1 - Réfrigérant à mélange d'hydrocarbures, système et procédé de congélation et réfrigération ou de conditionnement d'air, et procédé de production de système de congélation et réfrigération ou conditionnement d'air - Google Patents

Réfrigérant à mélange d'hydrocarbures, système et procédé de congélation et réfrigération ou de conditionnement d'air, et procédé de production de système de congélation et réfrigération ou conditionnement d'air Download PDF

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WO2009081673A1
WO2009081673A1 PCT/JP2008/071084 JP2008071084W WO2009081673A1 WO 2009081673 A1 WO2009081673 A1 WO 2009081673A1 JP 2008071084 W JP2008071084 W JP 2008071084W WO 2009081673 A1 WO2009081673 A1 WO 2009081673A1
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Prior art keywords
refrigerant
air conditioning
formula
conditioning system
refrigeration
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PCT/JP2008/071084
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English (en)
Japanese (ja)
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Naoyuki Yada
Hiroyoshi Hosomura
Yoshinobu Shinkawa
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E.R.D.Co., Ltd.
Mitsui & Co., Ltd.
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Application filed by E.R.D.Co., Ltd., Mitsui & Co., Ltd. filed Critical E.R.D.Co., Ltd.
Priority to JP2009546988A priority Critical patent/JP5633088B2/ja
Priority to KR1020107015808A priority patent/KR101205442B1/ko
Priority to CN2008801231171A priority patent/CN101918507B/zh
Publication of WO2009081673A1 publication Critical patent/WO2009081673A1/fr
Priority to HK11106069.0A priority patent/HK1152068A1/xx

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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
    • 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
    • C09K5/042—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 compounds containing carbon and hydrogen only
    • 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

  • refrigerants such as carbon dioxide, ammonia, and hydrocarbons have been used as refrigerants that replace HCFCs and HFCs.
  • hydrocarbon refrigerant for example, isobutane is used as a refrigerant for a domestic refrigerator in Japan.
  • propane or a refrigerant mixed with the same number of moles of propane and isobutane shows air conditioning performance equivalent to HFC of an air conditioner, but since the required refrigerant charging amount is greatly increased than a domestic refrigerator, Advanced refrigerant flammability countermeasures on the equipment side and a reduction in refrigerant charge amount are major issues for practical application.
  • there is an urgent need for power saving measures for refrigeration air-conditioning equipment as a measure against global warming.
  • Patent Documents 1 and 2 as a hydrocarbon mixed refrigerant that can replace Freon R12, which was difficult to replace with a hydrocarbon simple substance refrigerant, a physical property that approximates Freon R12 in terms of evaporation and condensation temperature under pressure when a sufficient amount is filled.
  • a mixed refrigerant of propane and butane so as to have a specific characteristic, or the use of a mixed refrigerant of propane, butane and ethane so as to have a vapor pressure curve approximating that of Freon R12 is described.
  • these mixed refrigerants have a problem that a sufficient refrigerating and air-conditioning function cannot be obtained to replace the above-mentioned substitute CFCs.
  • Patent Document 3 describes a refrigerant containing ethane, propane, isobutane, n-butane, isopentane, and n-pentane, but its purpose is a problem that the ignition point of the propane and butane refrigerant is as low as about 400 ° C. There is a problem that a sufficient refrigeration and air-conditioning function cannot be obtained to replace alternative chlorofluorocarbons such as HCFC and HFC.
  • An object of the present invention is to replace a substitute chlorofluorocarbon (HCFC, HFC) having a lower boiling point and higher vapor pressure than chlorofluorocarbon (CFC) with a hydrocarbon refrigerant of a natural refrigerant, thereby enabling non-fluorocarbons using a hydrocarbon refrigerant of a natural refrigerant. It is to contribute to the prevention of global warming by reducing alternative chlorofluorocarbons, which are greenhouse gases, and saving energy in refrigeration air conditioners. More specifically, a hydrocarbon mixed refrigerant that contributes to power saving of refrigeration air-conditioning equipment, and that can reduce the refrigerant charge amount and facilitate measures for flammability of equipment, and an air-conditioning system using the same. And providing an air conditioning method.
  • HCFC substitute chlorofluorocarbon
  • CFC chlorofluorocarbon
  • the hydrocarbon mixed refrigerant of the present invention contains propane, has a saturated vapor pressure at 7 ° C. of 0.3 to 1 MPa, and a saturated vapor pressure at 35 ° C. of 0.6 to 2.2 MPa. .
  • hydrocarbon mixed refrigerant according to a preferred embodiment of the present invention is characterized by further containing n-butane and isobutane.
  • hydrocarbon mixed refrigerant of a desirable aspect of the present invention is characterized by further containing ethane.
  • the hydrocarbon mixed refrigerant of a desirable aspect of the present invention is characterized in that the boiling point is ⁇ 20 ° C. or lower.
  • the hydrocarbon mixed refrigerant according to a preferred embodiment of the present invention is characterized in that the total of n-butane and isobutane is 39 mol% or less.
  • the hydrocarbon mixed refrigerant according to a preferred embodiment of the present invention is such that the total of n-butane and isobutane is 24 mol% or less, n-butane is 19 mol% or less, isobutane is 12 mol% or less, and ethane is 3 mol% or more. It is characterized by being.
  • the hydrocarbon mixed refrigerant according to a preferred embodiment of the present invention is characterized in that the refrigerant theory COP R satisfies one or more of the conditions (a) to (c).
  • the hydrocarbon mixed refrigerant according to a preferred embodiment of the present invention is characterized by satisfying one or more of the formulas (V) to (IX).
  • Formula (V) [In the formula, COP RC (7 ° C./35° C.): Theoretical cooling performance coefficient ⁇ L (7 ° C.) of a refrigeration cycle having an evaporation temperature of 7 ° C. and a condensation temperature of 35 ° C .: 7 ° C.
  • the hydrocarbon mixed refrigerant includes 55 to 98 mol% of propane (in a hydrocarbon mixed refrigerant), methane, ethane, ethylene, n-butane, isobutane, propyne, cyclopropane, butene, and It contains at least one selected from isobutene.
  • the freezing refrigeration or air conditioning air conditioning system of the present invention is characterized by using the hydrocarbon mixed refrigerant described above.
  • the hydrocarbon mixed refrigerant according to any one of the above is placed in the refrigerant flow path of the refrigeration / refrigeration / cooling / air conditioning system using an alternative chlorofluorocarbon refrigerant.
  • the refrigeration or cooling / heating / air conditioning system is operated by filling to satisfy (II).
  • Formula (I) [In formula, A: Saturated vapor pressure of alternative CFC refrigerant at 7 ° C.
  • the freezing refrigeration or the air conditioning air conditioning method of the desirable aspect of this invention is characterized by filling with hydrocarbon mixed refrigerant
  • P Mass of filling of hydrocarbon mixed refrigerant
  • Q In an air-conditioning system in which an alternative chlorofluorocarbon refrigerant is used or has been used, it means a filling mass of the alternative chlorofluorocarbon refrigerant.
  • the freezing refrigeration or the air conditioning air conditioning method of a desirable aspect of the present invention is characterized in that the filling of the hydrocarbon mixed refrigerant satisfies the formula (IV).
  • Q ⁇ (R / 2S) ⁇ P ⁇ Q ⁇ (R / S) (formula (IV)) [Wherein P, Q, R and S have the same contents as above]
  • the hydrocarbon mixed refrigerant according to any one of the above is used in a refrigerant flow path of a refrigeration / refrigeration / cooling / air conditioning system using an alternative chlorofluorocarbon refrigerant. It is characterized in that the system is filled so as to satisfy (III) and the refrigeration or air conditioning system is operated.
  • the hydrocarbon mixed refrigerant according to any one of the above is used in a refrigerant flow path of a refrigeration / refrigeration / cooling / air conditioning system using an alternative chlorofluorocarbon refrigerant. It is filled with satisfying (IV), and the freezing refrigeration or the air conditioning air conditioning system is operated.
  • Q ⁇ (R / 2S) ⁇ P ⁇ Q ⁇ (R / S) (formula (IV)) [Wherein P, Q, R and S have the same contents as above]
  • the refrigeration / refrigeration / cooling / air conditioning method according to a preferred aspect of the present invention is the refrigeration / refrigeration / cooling / air conditioning method according to any one of the above, wherein the refrigeration / refrigeration / cooling / air conditioning system is operated exclusively for cooling.
  • the freezing refrigeration or air conditioning air conditioning method of a desirable aspect of the present invention is the freezing refrigeration or air conditioning air conditioning method according to any of the above, wherein the inside of the refrigerant flow path of the freezing refrigeration or air conditioning air conditioning system is a pattern (a). Or the pattern (b) or the pattern (c).
  • b) A pattern in which the existing chlorofluorocarbon refrigerant that has been filled is removed
  • the method for producing a refrigeration / cooling / heating / air-conditioning system includes a hydrocarbon mixed refrigerant according to any one of the above formulas (I) in a refrigerant flow path of a refrigeration / refrigeration / cooling / air-conditioning system using an alternative chlorofluorocarbon-based refrigerant. ) And formula (II) are satisfied.
  • (C ⁇ D) ⁇ 1 MPa Formula (II) [Wherein C and D have the same contents as above]
  • the manufacturing method of the freezing / refrigeration or the air conditioning system of the desirable aspect of this invention is characterized by filling with hydrocarbon mixed refrigerant
  • the manufacturing method of the freezing / refrigeration or the air conditioning air conditioning system of the desirable aspect of this invention is characterized by filling with hydrogen mixed refrigerant
  • the manufacturing method of the freezing refrigerating or air-conditioning air conditioning system of the desirable aspect of this invention WHEREIN: The hydrocarbon mixed refrigerant in any one of the above in the inside of the refrigerant
  • the manufacturing method of the freezing refrigerating or air-conditioning air conditioning system of the desirable aspect of this invention WHEREIN: The hydrocarbon mixed refrigerant in any one of the above in the inside of the refrigerant
  • a method for manufacturing a refrigeration / refrigeration / cooling / air conditioning system is characterized in that the refrigeration / refrigeration / cooling / air conditioning system operated exclusively for cooling is filled with the hydrocarbon mixed refrigerant.
  • the manufacturing method of the freezing / refrigeration or air conditioning air conditioning system of the desirable aspect of this invention performs pattern (a) inside the refrigerant
  • pattern in which the existing chlorofluorocarbon refrigerant that has been filled is removed
  • an alternative chlorofluorocarbon having a boiling point lower than that of chlorofluorocarbon and having a high vapor pressure can be replaced with a natural refrigerant, reducing the chlorofluorocarbon alternative chlorofluorocarbon, and energy saving of refrigeration and air conditioning equipment. Can contribute to the prevention of global warming.
  • the hydrocarbon mixed refrigerant of the present invention can be used as it is in a conventional refrigeration / cooling / heating / air-conditioning system (refrigeration / air-conditioning equipment) in which an alternative chlorofluorocarbon-based refrigerant has been used. For this reason, it is not necessary to install a new device, and by using the hydrocarbon mixed refrigerant of the present invention with respect to the previous device, the greenhouse gas can be reduced extremely quickly and energy can be saved. Can contribute to the prevention of global warming in various ways. Further, by using the hydrocarbon mixed refrigerant of the present invention, an energy-saving air conditioner can be manufactured in a short period of time by using the technology and design of a conventional refrigeration air conditioner of an alternative chlorofluorocarbon refrigerant.
  • the refrigerant disposal cost can be greatly reduced as compared with that of a conventional alternative chlorofluorocarbon.
  • the hydrocarbon mixed refrigerant of the present invention is used, higher refrigeration and air conditioning performance can be obtained than propane, which is conventionally known in refrigeration and air conditioning equipment using alternative chlorofluorocarbon refrigerant, or a hydrocarbon refrigerant in which propane and isobutane are mixed in the same number of moles. Therefore, it is possible to reduce the refrigerant charge amount and facilitate the measures against the refrigerant flammability of the equipment.
  • the hydrocarbon mixed refrigerant of the embodiment (1) contains propane, may further contain n-butane and isobutane, and may further contain ethane. These hydrocarbon mixed refrigerants have a saturated vapor pressure at 7 ° C. of 0.3 to 1 MPa, preferably 0.35 to 0.9 MPa, and a saturated vapor pressure at 35 ° C. of 0.6 to 2.2 Pa, preferably 0.8. It is mixed so that the condition is -2.2 MPa, more preferably 1.3-1.5 MPa. If the saturated vapor pressure at 7 ° C. of the hydrocarbon mixed refrigerant is less than 0.3 MPa, sufficient refrigerating and air conditioning performance cannot be obtained, and if it exceeds 1 MPa, sufficient energy saving effect cannot be obtained. Further, when the saturated vapor pressure at 35 ° C. of the hydrocarbon mixed refrigerant is less than 0.6 MPa, sufficient refrigerating and air conditioning performance cannot be obtained, and when the value exceeds 2.2 MPa, sufficient energy saving effect cannot be obtained.
  • the blending ratio of propane with respect to the entire hydrocarbon mixed refrigerant is 50 to 97 mol%, more preferably 60 to 93 mol%. By setting it as this range, the saturated vapor pressure of the refrigerant at 7 ° C. and 35 ° C. can be adjusted to a preferable value.
  • the blending ratio of n-butane and isobutane is 39 mol% or less in total, preferably 0.2 to 39 mol%, more preferably 1.0 to 24 mol%. By setting this range, various alternative CFCs can be replaced.
  • the compounding ratio of n-butane is 19 mol% or less, preferably 0.1 to 19 mol%, and the compounding ratio of isobutane is 12 mol% or less, preferably 0.1 to 12 mol%. By setting it as this range, the saturated vapor pressure of the refrigerant at 7 ° C. and 35 ° C. can be finely adjusted to a preferable value.
  • the boiling point of the hydrocarbon mixed refrigerant of embodiment (1) is preferably ⁇ 20 ° C. or lower. This is because the pressure of the hydrocarbon mixed refrigerant is increased to increase the refrigerant capacity, thereby making it possible to replace HCFCs and HFCs with high refrigeration capacity.
  • the term “refrigerant” is used not only for a medium used for cooling but also for heating. This is because if the refrigerant is compressed, heat is generated and the heat can be used for heating.
  • FIG. 7 is a graph for cooling showing the relationship between the measured COP and the refrigerant theory COP R of the inverter heat pump air conditioner
  • FIG. 8 is a graph for heating. That is, when the measured COP is taken on the vertical axis and (refrigerant theory COP R ) / ⁇ saturated liquid density ⁇ L kg / l ⁇ (1 / saturated vapor density ⁇ V mol-kg / m 3 ) ⁇ is taken on the horizontal axis, FIG. As shown in FIG. 8, it has been found that there is a substantially proportional relationship. Measured COP was made by Nippon Pemac Co., Ltd., using air heat source heat pump unit AEP22B.
  • refrigerant theory COP R is obtained from the relationship between the evaporating temperature and condensing temperature of the refrigeration cycle, the refrigerant pressure and the enthalpy by the method described in "Refrigeration and Air Conditioning Technology Elementary Text" (published by the Japan Refrigeration Association, 1991). Calculated from each enthalpy difference defined as refrigeration capacity and theoretical required compression power.
  • the hydrocarbon refrigerant of the present invention is non-azeotropic, the isotherm will deviate from the isobaric line even in the gas-liquid coexistence state, so set the evaporation temperature and condensation temperature with the saturated vapor line and change the isobaric pressure.
  • the liquid side enthalpy was calculated.
  • Various state equations and empirical equations have been proposed to calculate the thermodynamic properties such as the enthalpy of the refrigerant in the refrigeration cycle necessary to calculate this enthalpy, but the initial method differs from the measured value.
  • the refrigerant theory COP R and (refrigerant theory COP R ) / ⁇ saturated liquid density ⁇ (1 / saturated vapor density) ⁇ obtained from the relationship with the measured COP are large, and can be replaced with chlorofluorocarbon alternatives.
  • the components of the hydrocarbon mixed refrigerant having high performance were found from the thermodynamic property value simulation by REFPROP8.0 of the combination of propane and 23 kinds of hydrocarbons and the findings from the above experiments. The results are shown in the calculation examples shown in Tables 2 and 3 in the Examples section and FIGS.
  • the refrigerant provided by the present invention has a coefficient of performance [refrigerant theory COP R (7 ° C./35° C.)] of the theoretical refrigeration cycle having an evaporation temperature of 7 ° C. and a condensation temperature of 35 ° C. of 8.4. As described above, it is preferably 8.5 or more from the viewpoint of obtaining air conditioning and air conditioning performance from an alternative chlorofluorocarbon refrigerant or a conventional hydrocarbon refrigerant in an air conditioner such as a room air conditioner.
  • the coefficient of performance of the theoretical refrigeration cycle with an evaporation temperature of 0 ° C. and a condensation temperature of 50 ° C. is 3.9 or more, preferably 4.0 or more. It is preferable from the viewpoint of obtaining air conditioning and air conditioning and refrigeration performance from alternative chlorofluorocarbon refrigerants and conventional hydrocarbon refrigerants in air conditioning and refrigeration equipment such as air conditioners, vending machines and refrigerators.
  • COP R ( ⁇ 15 ° C./30° C.)
  • COP R ( ⁇ 15 ° C./30° C.)
  • the refrigerant of the present invention is one of the formulas (V), (VI), (VII), (VIII), and (IX) at the evaporation temperature and the condensation temperature.
  • the refrigerant of the present invention is one of the formulas (V), (VI), (VII), (VIII), and (IX) at the evaporation temperature and the condensation temperature.
  • COP RC (7 ° C./35° C.) / ⁇ L (7 ° C.) ⁇ (1 / ⁇ V (7 ° C.)) ⁇ ⁇ 4.6 ....
  • the refrigerant component of the present invention is mainly composed of propane having a thermodynamic property close to a relatively high-pressure alternative chlorofluorocarbon such as R410A in order to satisfy the above-mentioned thermodynamic properties, and is a C1 hydrocarbon, C2 hydrocarbon, C3 hydrocarbon, It contains at least one hydrocarbon selected from C4 hydrocarbons and has a high refrigerant theory COP and (COP R ) / ⁇ saturated liquid density ⁇ L ⁇ (1 / saturated vapor density ⁇ V) ⁇ .
  • propane is 55 to 98 mol% (in the hydrocarbon mixed refrigerant), preferably 60 to 96 mol%, more preferably 70 to 95 mol%, and methane, ethylene, ethane, n -It can contain at least one selected from butane, isobutane, propyne, cyclopropane, butene and isobutene.
  • the refrigerant theoretical COP shows a maximum value in the range of 5 to 35 mol% and improves. Therefore, in the case of a mixed refrigerant of propane and methane, methane is 5 to 40 Considering the deviation of mol%, saturated vapor pressure, and isotherm and isobaric line in the coexisting state of gas and liquid, 5 to 25 mol% is more preferable from the viewpoint of obtaining refrigeration and air conditioning performance than alternative CFC refrigerants and conventional hydrocarbon refrigerant . In the case of a mixed refrigerant of propane and ethylene, it is more preferable from the same viewpoint that ethylene is 5 to 35 mol%.
  • ethane is 5 to 25 mol% from the same viewpoint, and considering that the effect of improving the refrigerant theoretical COP is relatively small, 10 to 15 mol close to the maximum value. % Is more preferable.
  • propyne and cyclopropane have the effect of improving the refrigerant theoretical COP, but tend to be flat.
  • propyne is 5 to 30 mol%. Is more preferable from the same viewpoint.
  • cyclopropane is more preferably 5 to 40 mol% from the same viewpoint.
  • mixing with C3 hydrocarbon has an advantage that the deviation between the isotherm and the isobar in the gas-liquid coexistence state is reduced.
  • n-butane and isobutane do not improve the refrigerant theory COP unless mixed at 30 mol% or higher.
  • n-butane is preferably 15 mol% or more because the refrigerant theoretical COP can be improved, but considering the decrease in vapor pressure, it is more preferably 25 mol% or less from the same viewpoint. preferable.
  • isobutane is 5 mol% or more because the theoretical COP of the refrigerant can be improved, but considering a decrease in vapor pressure, it is more preferably 30 mol% or less from the same viewpoint.
  • isobutene is 25 to 35 mol%.
  • butene is more preferably 25 to 35% from the same viewpoint.
  • a more preferable aspect of the hydrocarbon mixed refrigerant of the present invention is a propane ternary hydrocarbon mixed refrigerant in which C1 or C2 hydrocarbon and C4 hydrocarbon are combined and mixed, and the refrigerant is more refrigerant than the binary hydrocarbon mixed refrigerant.
  • the theoretical COP can be improved.
  • One specific embodiment contains 70 to 85 mol% propane, 10 to 25 mol% ethane, and 5 to 10 mol% isobutane.
  • Another embodiment contains 60 to 85 mol% propane, 10 to 30 mol% ethylene, and 5 to 15 mol% isobutane.
  • Yet another embodiment contains 50-90 mol% propane, 5-25 mol% methane, 5-20 mol% isobutane.
  • An even more preferred embodiment of the hydrocarbon mixed refrigerant of the present invention is a propane multi-component hydrocarbon mixed refrigerant in which at least one selected from ethane, ethylene and methane is mixed with propane, isobutane and n-butane.
  • (COP R ) / ⁇ saturated liquid density ⁇ L ⁇ (1 / saturated vapor density ⁇ V) ⁇ can be easily improved from the ternary hydrocarbon mixed refrigerant.
  • Propane multi-component hydrocarbon mixed refrigerant contains propane 55 to 96 mol%, n-butane 0.2 to 28 mol%, isobutane 0.812 mol%, and ethane 2 to 111 mol%.
  • ethane may contain up to 25 mol%
  • ethylene can contain 2 to 30 mol%
  • methane can contain 2 to 25 mol%.
  • the content of other hydrocarbons is desirably 0.1 mol% or less.
  • the refrigeration / refrigeration or air conditioning air conditioning method of the embodiment (1) uses an alternative chlorofluorocarbon refrigerant such as HCFC or HFC, or has used such an alternative chlorofluorocarbon refrigerant, or has used such an alternative chlorofluorocarbon. Applies to refrigeration or air-conditioning systems without In these refrigeration / refrigeration or air conditioning systems, the refrigerant flow path is filled with the above-described hydrocarbon mixed refrigerant so as to satisfy the expressions (I) and (II). More specifically, there are the following three modes.
  • a refrigerant mixed refrigerant satisfying the formulas (I) and (II) is filled in and operated in a refrigeration / refrigeration or heating / air conditioning system that does not use an alternative chlorofluorocarbon refrigerant or has never used an alternative chlorofluorocarbon refrigerant. To do.
  • Formulas (I) and (II) of the embodiment (1) are as follows. That is, (AB) ⁇ 0.5 MPa Formula (I) [In formula, A: Saturated vapor pressure of alternative CFC refrigerant at 7 ° C. B: Saturated vapor pressure of hydrocarbon mixed refrigerant at 7 ° C.] (C ⁇ D) ⁇ 1 MPa Formula (II) [In the formula, C: saturated vapor pressure of alternative CFC refrigerant at 35 ° C. D: saturated vapor pressure of hydrocarbon mixed refrigerant at 35 ° C.]
  • the hydrocarbon mixed refrigerant satisfies the formula (III).
  • the filling amount satisfies the formula (III)
  • sufficient refrigeration / refrigeration or air conditioning capability and energy saving effect can be achieved simultaneously when replacing HCFC and HFC.
  • the optimum mass of the alternative chlorofluorocarbon refrigerant changes the variables assumed by those skilled in the art such as the filling amount of the alternative chlorofluorocarbon, the frequency of the inverter of the air conditioner, and / or the degree of opening and closing of the expansion valve in the air conditioning system,
  • This is the filling amount of CFC substitutes for which the measured COP (see (Note 2) in Table 1) is the maximum value when the cooling test is performed according to the method of JIS B8615-1.
  • the significance of the upper limit value and the lower limit value of the formula (III) means a numerical value that the filling mass P of the embodiment (1) is preferably between the upper limit value and the lower limit value of the formula (III) as a result.
  • the manufacturing method of the freezing refrigeration or the air conditioning air conditioning system of embodiment (1) is performed by filling the inside of a refrigerant flow path with a hydrocarbon mixed refrigerant so as to satisfy the above-mentioned formulas (I) and (II). . That is, the alternative chlorofluorocarbon refrigerant in the refrigeration / refrigeration or air conditioning system using the alternative chlorofluorocarbon refrigerant is removed, replaced with the alternative chlorofluorocarbon refrigerant, and filled with the hydrocarbon mixed refrigerant satisfying the formulas (I) and (II). .
  • a refrigerant mixed refrigerant satisfying the formulas (I) and (II) is filled into a refrigeration / refrigeration / cooling / air-conditioning system using the alternative CFC-based refrigerant from which the CFC-based refrigerant has already been removed.
  • a hydrocarbon mixed refrigerant satisfying the formulas (I) and (II) is filled in a refrigeration / refrigeration system that does not use an alternative chlorofluorocarbon refrigerant or has never used an alternative chlorofluorocarbon refrigerant.
  • the embodiment (2) is applied in addition to the filling conditions of the formula (I) and the formula (II) in place of the formula (III) in the freezing / refrigeration or air conditioning air conditioning method of the embodiment (1). be able to.
  • the refrigerated refrigeration or air conditioning air conditioning system of the above-described embodiment uses the hydrocarbon mixed refrigerant described above.
  • the conventional air conditioner using the alternative chlorofluorocarbon is used as it is or by slightly adjusting the frequency of the air conditioner inverter or the opening / closing degree of the expansion valve. can do.
  • the present invention is not limited to this, and a freezing / refrigeration or cooling / heating air conditioning system dedicated to the hydrocarbon mixed refrigerant of the embodiment may be constructed.
  • the saturated vapor pressure is measured by filling a sample container with a known internal volume with a sample (refrigerant) and measuring the temperature and pressure while keeping the sample container under a predetermined temperature condition.
  • FIG. 1 shows a sample container, (a) is a plan view, (b) is a front view, and (c) is a left side view.
  • 2A and 2B show another sample container, in which FIG. 2A is a side view and FIG. 2B is a cross-sectional view in the aa direction.
  • FIG. 3 shows a saturated vapor pressure measuring apparatus that performs measurement using the sample container of FIG.
  • the sample container 1 is, for example, a SUS304 container having an internal volume of about 70 cm 3 as shown in FIG. A structure in which the density distribution in the height direction due to the weight of the sample is kept as small as possible, and a thick cylinder whose shape and external force are axisymmetric so as to achieve uniform deformation and pressure due to internal pressure, and these are crossed It has become. Further, as the sample container 10, for example, a container made of SUS304 having an internal volume of about 600 cm 3 can be used as shown in FIG. There is a transparent portion at the center of the sample container 10 where the presence of a liquid meniscus (gas-liquid interface) can be confirmed.
  • the sample container 10 is mainly used for measuring the critical point of the sample. In the figure, 12 is a sapphire glass, 13 is an O-ring, and 14 is a backup ring. The sample container body 15 is sandwiched and fixed by a central member 16.
  • the inside of the sample container 1 is evacuated to 3 ⁇ 10 ⁇ 3 Pa or less with an air-cooled turbo molecular pump, and then the sample is filled.
  • the filling amount of the sample is determined in consideration of (internal volume) ⁇ (saturation density).
  • the sample container 1 is installed in the thermostat 7 every 5 minutes, and the saturated vapor pressure of the sample is measured.
  • the pressure when the temperature and pressure do not fluctuate and become a constant value is the saturated vapor pressure. This operation is performed by setting a thermostat at 7 ° C. and 35 ° C.
  • refrigerants A and B After removing R410A from the air conditioner, the respective refrigerants are filled and operated, and the charge amount is changed in two cases two by refrigerant A in Examples 2 and 3 and refrigerant B in Example 4. It was set to 5. For each refrigerant, the refrigerant filling amount, the inverter frequency, and the air volume were changed, and the conditions under which the measured COP value (see (Note 2) in Table 1) was the optimum value were determined.
  • the cooling operation was performed under the conditions shown in Table 1, and the measured COP was calculated.
  • the indoor suction dry bulb temperature is 26.98 to 27.00 ° C.
  • the indoor suction wet bulb temperature is 18.96 to 18.99 ° C.
  • the outdoor suction dry bulb temperature is 34.95 to 35.07.
  • the outdoor suction wet bulb temperature was maintained at 22.07-24.03 ° C.
  • the measured COP value was the optimum value
  • the air volume of the refrigerant A was 7.64 m 3 / min
  • the air volume of the refrigerant B was 7.31 m 3 / min.
  • COP RC (7/35 °C) calculated by the method, COP RC (7/35 °C ) / ⁇ L (7 °C) ⁇ (1 / ⁇ V (7 °C) ⁇ , COP RC (0/50 °C ), COP RC (0/50 ° C.) / ⁇ L (0 ° C.) ⁇ (1 / ⁇ V (0 ° C.) ⁇ , COP RC ( ⁇ 15 / 30 ° C.), and COP RC ( ⁇ 15 / 30 ° C.) / ⁇ ⁇ L ( ⁇ 15 ° C.) ⁇ (1 / ⁇ V ( ⁇ 15 ° C.) ⁇ is shown in Table 1.
  • the outdoor suction wet bulb was maintained at 5.96 to 6.00 ° C. Air flow of the refrigerant A when measured COP value is the optimum value is 7.95m 3 / min, air volume of the refrigerant B was 8.10m 3 / min.
  • COP RH (7/35 °C) calculated by the method, COP RH (7/35 °C ) / ⁇ L (35 °C) ⁇ (1 / ⁇ V (35 °C) ⁇ , COP RH (0/50 °C ) And COP RH (0/50 ° C.) / ⁇ L (50 ° C.) ⁇ (1 / ⁇ V (50 ° C.) ⁇ are shown in Table 1.
  • the air conditioning capacity of the air conditioner was measured by the indoor air enthalpy method. That is, it was calculated by (1) measurement of temperature / humidity with a dry bulb / wet bulb thermometer installed outside and inside the laboratory, and (2) measurement of the air volume at the air outlet of the air conditioner in the laboratory.
  • refrigerant R22 was replaced with refrigerant B (approximately 12Kg), and the freezer was operated from November 22, 2006 to January 22, 2007, and the power consumption per 24 hours was measured (implementation) Example 10). Also, the temperature inside the cabinet was -20 ° C to -25 ° C except on the day when business was stopped.
  • Fig. 4 shows the transition of power consumption of R22 and refrigerant B obtained in the test.
  • the graph in black is Example 10.
  • the average power consumption amount of R22 and refrigerant B is 124.6 kWh / day when R22 is used as a refrigerant, and the average power consumption when refrigerant B is used is 284.6 kWh / day.
  • the value was 81.7 kWh / day, which was a value less than about 40 kWh per day.
  • the power consumption of R22 is 100%
  • the power consumption of the refrigerant B is 65.6%.
  • By replacing refrigerant B in a refrigerator designed with R22 as the refrigerant almost the same cooling capacity was obtained with about 2/3 of the conventional power consumption. From this, it has been found that not only the air conditioner for home use but also the commercial refrigerator can greatly contribute to energy saving by changing the refrigerant from R22 to refrigerant B without changing the existing equipment.
  • refrigerant R134a which is an HFC-based refrigerant
  • refrigerant B was filled (Example 11).
  • a freezing and refrigeration test using refrigerant R134a was conducted with a container MOLU55446957 (container A, 20 feet) manufactured by Nippon Full Half Co., Ltd. equipped with LXE5C-1 manufactured by Daikin Industries, Ltd. as a refrigerator (Comparative Example 4). .
  • Test Example 5 ⁇ Freezing and refrigeration test> As the refrigerator used in Test Example 4, a container MOLU5544039 (container B) manufactured by Nippon Full Half Co., Ltd. equipped with LXE5C-1 manufactured by Daikin Industries, Ltd. was used. A test was conducted (Example 12).
  • Both containers were set at 5 ° C and operated simultaneously.
  • the container temperature and power consumption were measured.
  • the results are shown in FIG. In FIG. 6, the hatched graph is the power consumption of Example 12.
  • the characteristic curve P is the container internal temperature of Example 8
  • the characteristic curve Q is the container internal temperature of Comparative Example 5.
  • the temperature inside the container was lower in the refrigerant A, and the power consumption was slightly lower in the refrigerant A. As a result, it was confirmed that the refrigerant A could be used in place of the refrigerant 134a.
  • the present invention can replace the substitute chlorofluorocarbon with a natural refrigerant, reduce the substitute chlorofluorocarbon, which is a greenhouse gas, and save energy in the refrigeration and refrigeration and air-conditioning air conditioning equipment. It contributes to the prevention of global warming by both energy saving and can be used for freezing and refrigeration and air conditioning with air conditioning.

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Abstract

L'invention porte sur un réfrigérant à hydrocarbures naturel destiné à remplacer les fluorocarbones de remplacement des chlorofluorocarbones (HCFC et HFC) afin d'éliminer l'utilisation de ces derniers. L'invention permet de réduire les fluorocarbones de remplacement et de réaliser des économies d'énergie dans les réfrigérateurs et les appareils de conditionnement d'air. Le réfrigérant à mélange d'hydrocarbures selon l'invention contient du propane et possède une pression de vapeur saturée à 7°C comprise entre 0,3 et 1 MPa et une pression de vapeur saturée à 35°C comprise entre 0,6 et 2,2 MPa. Le réfrigérant précité peut en outre contenir du n-butane, de l'isobutane et de l'éthane. Le réfrigérant à mélange d'hydorcarbures possède de préférence un point d'ébulliton inférieur ou égal à -20°C.
PCT/JP2008/071084 2007-12-26 2008-11-20 Réfrigérant à mélange d'hydrocarbures, système et procédé de congélation et réfrigération ou de conditionnement d'air, et procédé de production de système de congélation et réfrigération ou conditionnement d'air WO2009081673A1 (fr)

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JP2009546988A JP5633088B2 (ja) 2007-12-26 2008-11-20 炭化水素混合冷媒、冷凍冷蔵又は冷暖房空調方法
KR1020107015808A KR101205442B1 (ko) 2007-12-26 2008-11-20 탄화수소혼합냉매, 냉동냉장 또는 냉난방 공조시스템, 냉동냉장 또는 냉난방 공조방법, 및 냉동냉장 또는 냉난방 공조시스템의 제조방법
CN2008801231171A CN101918507B (zh) 2007-12-26 2008-11-20 烃类混合制冷剂、冷冻/冷藏或制冷/制热空调系统、冷冻/冷藏或制冷/制热空调方法、以及冷冻/冷藏或制冷/制热空调系统的制造方法
HK11106069.0A HK1152068A1 (en) 2007-12-26 2011-06-14 Hydrocarbon mixture refrigerant, freezing/refrigerating or air-conditioning system, freezing/refrigerating or air-conditioning method, and process for producing freezing/refrigerating or air-conditioning system

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JP2007335382 2007-12-26
JP2007-335382 2007-12-26
PCT/JP2008/070999 WO2009081672A1 (fr) 2007-12-26 2008-11-19 Fluide frigorigène à base d'un mélange d'hydrocarbures, système et procédé de congélation/réfrigération ou conditionnement d'air, et procédé de production d'un système de congélation/réfrigération ou conditionnement d'air
JPPCT/JP2008/070999 2008-11-19

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PCT/JP2008/071084 WO2009081673A1 (fr) 2007-12-26 2008-11-20 Réfrigérant à mélange d'hydrocarbures, système et procédé de congélation et réfrigération ou de conditionnement d'air, et procédé de production de système de congélation et réfrigération ou conditionnement d'air

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JP2015529705A (ja) * 2012-07-16 2015-10-08 タッツェッティ ソシエタ ペル アチオニ 冷媒混合物
US10712073B2 (en) 2017-03-01 2020-07-14 Haier Us Appliance Solutions, Inc. Ternary natural refrigerant mixture that improves the energy efficiency of a refrigeration system

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WO2011132306A1 (fr) * 2010-04-23 2011-10-27 Shinkawa Yoshinobu Procédé de production d'un réfrigérant mixte hydrocarboné
CN102656246A (zh) * 2010-12-14 2012-09-05 爱斯信托控股有限公司 碳氢化合物制冷剂和清洁剂组合物
CN102453468B (zh) * 2011-10-10 2015-03-11 周应斌 一种混合烷烃及其应用和制冷方法
KR101754225B1 (ko) * 2013-11-12 2017-07-19 최창균 탄화수소 혼합 냉매 및 이것의 조성비를 결정하기 위한 시뮬레이션 장치
CN103881659B (zh) * 2014-03-28 2015-07-08 深圳市美可达科技有限公司 一种混合烷烃及其应用和制冷方法
CN105018037A (zh) * 2015-07-07 2015-11-04 黑龙江盛大科技有限公司 用于热交换循环系统的一种冷媒合成制剂
KR20210022940A (ko) * 2019-08-21 2021-03-04 엘지전자 주식회사 비공비혼합냉매 및 그 냉매를 사용하는 냉장고

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JP2015529705A (ja) * 2012-07-16 2015-10-08 タッツェッティ ソシエタ ペル アチオニ 冷媒混合物
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US10712073B2 (en) 2017-03-01 2020-07-14 Haier Us Appliance Solutions, Inc. Ternary natural refrigerant mixture that improves the energy efficiency of a refrigeration system

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HK1152068A1 (en) 2012-02-17
KR20100108385A (ko) 2010-10-06
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MY152742A (en) 2014-11-28
CN101918507A (zh) 2010-12-15
JP2014051668A (ja) 2014-03-20
KR101205442B1 (ko) 2012-11-27
JP5849339B2 (ja) 2016-01-27
CN101918507B (zh) 2013-11-27
WO2009081672A1 (fr) 2009-07-02
JP5849338B2 (ja) 2016-01-27
JP5633088B2 (ja) 2014-12-03

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