WO2021184735A1 - 一种替换r290的环保混合制冷剂 - Google Patents

一种替换r290的环保混合制冷剂 Download PDF

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Publication number
WO2021184735A1
WO2021184735A1 PCT/CN2020/120214 CN2020120214W WO2021184735A1 WO 2021184735 A1 WO2021184735 A1 WO 2021184735A1 CN 2020120214 W CN2020120214 W CN 2020120214W WO 2021184735 A1 WO2021184735 A1 WO 2021184735A1
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component
environmentally friendly
mixed refrigerant
friendly mixed
refrigerant
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French (fr)
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雷佩玉
钟权
赵桓
黄宇杰
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Gree Electric Appliances Inc of Zhuhai
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Gree Electric Appliances Inc of Zhuhai
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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
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • 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
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • 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
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • 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
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • 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
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures

Definitions

  • the present invention relates to a refrigeration technology, in particular to an environmentally friendly mixed refrigerant that replaces R290.
  • the Montreal Protocol amendment requires a refrigerant that neither destroys the ozone layer but also has a lower GWP value to replace the current high GWP refrigerant and be effectively used in air conditioning systems middle.
  • R290 has better environmental performance, it is often used in household air conditioning systems, but because it is a Class A3 flammable refrigerant, it has a great lack of safety, so there is an urgent need for a good environmental performance and safety High, thermal performance equivalent to or better than R290 refrigerant to replace.
  • the present invention provides an environmentally friendly mixed refrigerant that replaces R290.
  • the environmentally friendly mixed refrigerant has good environmental performance, not only does not destroy the atmospheric ozone layer, that is, the ODP is zero, but also has a lower GWP (GWP less than 150), which is safe
  • the performance is better than R290, and the thermal performance is not much different from R290 or even better, which solves the technical problem of poor safety performance of the current household air conditioner R290 refrigerant.
  • an environmentally friendly mixed refrigerant that replaces R290, including a first component, a second component, and a third component, wherein: the first component is 1, 1-Difluoroethane (R152a), the second component is 2,3,3,3-tetrafluoropropene (R1234yf), the third component is propane (R290), isobutane (R600a) And one of propylene (R1270), wherein the environmentally friendly mixed refrigerant has a global warming potential (GWP) not greater than 150.
  • the first component is 1, 1-Difluoroethane (R152a)
  • the second component is 2,3,3,3-tetrafluoropropene (R1234yf)
  • the third component is propane (R290), isobutane (R600a) And one of propylene (R1270)
  • GWP global warming potential
  • the first component is 4%-48%
  • the second component is 28%-92%
  • the third component is 4%-28%.
  • the safety performance of the environmentally friendly mixed refrigerant prepared by the formula is better than that of R290, and the thermal performance is equal to or even better than that of R290.
  • the first component is 4%-40%
  • the second component is 56%-84%
  • the third component is 4%-20%.
  • the safety performance of the environmentally friendly mixed refrigerant prepared by the formula is better than that of R290, and the relative thermal performance of R290 is greater than 0.99.
  • the first component is 28%-40%
  • the second component is 56%-68%
  • the third component is 4%-12%.
  • the safety performance of the environmentally friendly mixed refrigerant prepared by the formula is better than that of R290, and the relative thermal performance of R290 is greater than 0.99.
  • the third component is isobutane (R600a).
  • the safety performance of the environmentally friendly mixed refrigerant prepared by the formula is better than that of R290, and the relative thermal performance of R290 is greater than 0.99.
  • the sum of the mole percentages of the first component, the second component and the third component is 100%, wherein: the first component is 4%-48%, The second component is 28%-92%, and the third component is 4%-28%.
  • the flammability of the environmentally friendly mixed refrigerant is A2 or A2L.
  • the present invention also provides a composition comprising a lubricant and an environmentally friendly mixed refrigerant that replaces R290 as described in any one of the above, and the lubricant is 1%-5% by mole percentage.
  • An environmentally friendly mixed refrigerant that replaces R290 is 95%-99%.
  • the lubricant is selected from: silicone oil, polyalkylbenzene (PAB), polyol ester (POE), polyalkylene glycol (PAG), polyalkylene glycol ester (PAG ester) ), at least one of polyvinyl ether (PVE), poly( ⁇ -olefin), or a combination of at least two of them.
  • the present invention also provides a refrigeration system, which uses the environmentally friendly mixed refrigerant or the composition described in any one of the above.
  • the present invention also provides a refrigeration equipment, which adopts the above-mentioned refrigeration system.
  • the refrigeration equipment is any one of a central air conditioner, a heat pump air conditioner, and a household air conditioner.
  • the environmentally friendly mixed refrigerant in the present invention has obvious environmental advantages.
  • the heat transfer composition has good thermal performance, its GWP is lower than 150, and its ODP is 0; and after being applied in a refrigeration system, it is relatively
  • the refrigeration capacity per unit volume and relative efficiency COP are equal to or better than that of refrigeration systems using R290 refrigerant, and the safety performance is better than R290, which can replace R290 in refrigeration systems.
  • the components of the present invention are commercially available, or can be prepared by methods already in the art.
  • the content ratio of each component in the present invention is obtained through a large amount of screening, which is a condition for ensuring the excellent performance of the environmentally friendly mixed refrigerant.
  • the preparation method of the environmentally friendly mixed refrigerant used in the refrigeration system of the present invention is to combine 1,1-difluoroethane (R152a), 3,3,3-tetrafluoropropene (R1234yf), propane (R290), isobutane ( R600a) and propylene (R1270) and other components are physically mixed in a liquid phase state at room temperature and pressure according to different molar ratios according to the above technical scheme, and form an environmentally friendly mixed refrigerant after being evenly mixed.
  • the basic parameters of each component material are shown in Table 1.
  • the ratios of the components are all molar ratios, and the sum of the molar ratios of the component substances of each environmentally friendly mixed refrigerant is 100%.
  • the components are physically mixed in a liquid phase state at room temperature and pressure at a fixed molar ratio, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
  • Example 1 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propane (R290) were pressed at 24: The molar ratio of 72:4 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 2 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propane (R290) were pressed 28: The mol ratio of 68:4 is physically mixed, and the mixing is uniform to obtain an environmentally friendly mixed refrigerant.
  • Example 3 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propane (R290) were pressed at room temperature and pressure in the liquid phase according to 32: The molar ratio of 64:4 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 4 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propane (R290) were pressed 36: The 60:4 molar ratio is physically mixed, and the mixing is uniform to obtain an environmentally friendly mixed refrigerant.
  • Example 5 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propane (R290) were pressed at room temperature and pressure in the liquid phase according to 48: Physical mixing is carried out at a molar ratio of 48:4, and the mixing is uniform to obtain an environmentally friendly mixed refrigerant.
  • Example 6 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The 20:72:8 molar ratio is physically mixed and evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 7 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The molar ratio of 24:68:8 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 8 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The mol ratio of 28:68:4 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 9 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The molar ratio of 32:64:4 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 10 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The mol ratio of 36:60:4 is physically mixed and evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 11 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The mol ratio of 40:56:4 is physically mixed and evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 12 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase Physical mixing is carried out at a molar ratio of 44:28:28 and evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 13 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were adjusted according to 4: The molar ratio of 92:4 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 14 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were pressed at room temperature and pressure in the liquid phase according to 8: The molar ratio of 88:4 is physically mixed, and the mixing is uniform to obtain an environmentally friendly mixed refrigerant.
  • Example 15 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were subjected to 12:
  • the molar ratio of 84:4 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 16 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were pressed at room temperature and pressure in the liquid phase according to 16: The mol ratio of 80:4 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 17 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were pressed 20: The molar ratio of 76:4 is physically mixed, and the mixing is uniform to obtain an environmentally friendly mixed refrigerant.
  • Example 18 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were pressed at room temperature and pressure in the liquid phase according to 24: The molar ratio of 72:4 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 19 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were pressed 48: Physical mixing is carried out at a molar ratio of 48:4, and the mixing is uniform to obtain an environmentally friendly mixed refrigerant.
  • Example 20 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The molar ratio of 4:84:12 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 21 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The molar ratio of 8:72:20 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 22 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The molar ratio of 8:80:12 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Example 23 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The molar ratio of 12:68:20 is physically mixed, and the mixture is evenly mixed to obtain an environmentally friendly mixed refrigerant.
  • Comparative Example 1 the three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propane (R290) were pressed at room temperature and pressure in the liquid phase according to 32: The molar ratio of 4:64 is physically mixed, and the mixture is evenly mixed to obtain a mixed refrigerant.
  • Comparative Example 3 Three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and isobutane (R600a) were pressed at room temperature and pressure in the liquid phase The molar ratio of 2:70:28 is physically mixed, and the mixture is evenly mixed to obtain a mixed refrigerant.
  • Comparative example 4 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propane (R290) three components at room temperature and pressure liquid phase according to 50: The 28:22 molar ratio is physically mixed, and the mixture is evenly mixed to obtain a mixed refrigerant.
  • Comparative Example 5 The three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propane (R290) were pressed into the liquid phase at room temperature and pressure at 48: The molar ratio of 24:28 is physically mixed, and the mixture is evenly mixed to obtain a mixed refrigerant.
  • Comparative Example 6 The three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were adjusted according to 4: The molar ratio of 94:2 is physically mixed, and the mixture is evenly mixed to obtain a mixed refrigerant.
  • Comparative Example 7 The three components of 1,1-difluoroethane (R152a), 2,3,3,3-tetrafluoropropene (R1234yf) and propylene (R1270) were subjected to 42: Physical mixing is carried out at a molar ratio of 28:30, and the mixing is uniform to obtain a mixed refrigerant.
  • Table 2 compares the basic parameters such as molecular weight, critical temperature, and environmental performance of the above examples and comparative examples with R290.
  • the flammability is calculated according to the theoretical model in the paper published by the NIST organization in 2019. The theoretical calculation result is The flammability decreases in the order of A3, A2, and A2L.
  • This embodiment also provides a composition comprising a lubricant and an environmentally friendly mixed refrigerant that replaces R290 in any of the above embodiments, and the lubricant is 1%-5% by mole percentage, a replacement The environmentally friendly mixed refrigerant of R290 is 95%-99%.
  • the lubricant is selected from silicone oil, polyalkylbenzene (PAB), polyol ester (POE), polyalkylene glycol (PAG), polyalkylene glycol ester (PAG ester), polyethylene At least one substance among ether (PVE) and poly( ⁇ -olefin) or a combination of at least two substances.
  • the refrigeration system using the composition not only has good refrigeration effect and environmental protection effect, but also reduces the abrasion of compressor components in the refrigeration system such as the motor, crankshaft and connecting rod device during rotation, and makes the rotation of the components more flexible.
  • This embodiment also provides a refrigeration equipment.
  • the refrigeration equipment is any of a central air conditioner, a heat pump air conditioner, and a household air conditioner.
  • the refrigeration system used in the refrigeration equipment uses any environmentally friendly mixed refrigerant or composition in the foregoing embodiments. Further preferably, the refrigeration system adopts the environmentally friendly mixed refrigerant of any one of the embodiments.
  • the ternary refrigerant provided in this embodiment and the comparative example is used in a household air-conditioning system, where it exchanges heat, is compressed, and throttles in an air-conditioning unit, instead of R290 refrigerant.
  • Table 3 compares the environmentally friendly mixed refrigerant in the above embodiment and the mixed refrigerant in the comparative example under cooling conditions (the evaporator outlet temperature is 283.15K, the condenser outlet temperature is 313.15K, and the gas phase at the evaporator outlet is overheated. , The superheat is 5K, the liquid phase at the outlet of the condenser is supercooled, the supercooling is 5K, the adiabatic efficiency of the compressor is 0.75), calculated according to isentropic compression, the above embodiment and the thermal parameters of R290 (ie compression ratio And exhaust temperature) and relative thermal performance (ie, relative unit volume refrigeration capacity and relative efficiency COP).
  • R290 ie compression ratio And exhaust temperature
  • relative thermal performance ie, relative unit volume refrigeration capacity and relative efficiency COP
  • the mixed environmental protection refrigerant provided by the present invention through the synergy between the first component, the second component and the third component, makes its GWP less than 150, which is environmentally friendly and has the flammability of all refrigerants. All are A2L/A2, and the safety performance is better than R290.
  • the third component is preferably isobutane (R600a), and the environmentally friendly mixed refrigerant with this component has lower flammability than R290, and is relatively COP is better than the third component, which is one of propane (R290) and propylene (R1270); further analysis shows that when the third component is isobutane (R600a), preferably, it is calculated by mole percentage , 1,1-difluoroethane (R152a) is 4%-40%, 2,3,3,3-tetrafluoropropene (R1234yf) is 56%-84%, isobutane (R600a) is 4%- The relative COP of the mixed environmentally friendly refrigerant prepared with 20% of the formula is greater than 0.9; further analysis shows that it is further preferred that 1,1-difluoroethane (R152a) is 28%-40% by mole percentage, 2 ,3,3,3-Tetrafluoropropene (R
  • 1,1-difluoroethane (R152a): 2,3,3,3-tetrafluoropropene (R1234yf): isobutane (R600a) is a formula of 40:56:4
  • the relative COP of the prepared environmentally friendly mixed refrigerant is up to 1.003, which is the optimal formula.
  • the environmentally friendly mixed refrigerant that replaces R290 provided by this embodiment not only has the environmental protection characteristics of GWP lower than 150 and ODP of zero, but also has lower flammability than R290, safety performance better than R290, and thermal performance equivalent to R290 refrigerant. Even better, it can completely replace R290 in refrigeration settings, especially in household air conditioners.
  • the present invention provides an environmentally friendly mixed refrigerant that replaces R290, which includes a first component, a second component, and a third component, wherein: the first component is 1,1-difluoroethane (R152a ), the second component is 2,3,3,3-tetrafluoropropene (R1234yf), and the third component is one of propane (R290), isobutane (R600a) and propylene (R1270), among which environmental protection
  • the mixed refrigerant has a global warming potential (GWP) not greater than 150; and the ODP is zero, and the flammability is lower than R290, the safety performance is better than R290, and the thermal performance is equal to or better than R290 refrigerant, and it can completely replace R290 It is used in refrigeration settings especially in household air conditioners.
  • GWP global warming potential

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Abstract

一种替换R290的环保混合制冷剂，其包括第一组分、第二组分和第三组分，其中：第一组分为1,1-二氟乙烷(R152a)，第二组分为2,3,3,3-四氟丙烯(R1234yf)，第三组分为丙烷(R290)、异丁烷(R600a)以及丙烯(R1270)中的一种，其中环保混合制冷剂具有不大于150的全球变暖潜力(GWP)；且ODP为零，而且可燃性低于R290，安全性能优于R290，热力性能也与R290制冷剂相当甚至更优，完全可以替代R290在制冷设置尤其是在家用空调上使用。

Description

一种替换R290的环保混合制冷剂 技术领域
本发明涉及一种制冷技术，尤其涉及一种替换R290的环保混合制冷剂。
背景技术
随着环保趋势的日益严重，对于HFCs的“温室效应”，蒙特利尔议定书修订案要求一种既不破坏臭氧层又具有较低GWP值的制冷剂来替代目前高GWP制冷剂，并有效应用于空调系统中。由于自然工质R290的环保性能比较好，常被用来在家用空调系统中使用，但是由于其是A3类可燃制冷剂，安全性方面有很大不足，因此急需一种环保性能好，安全性高，热力性能与R290相当甚至更好的制冷剂进行替代。
发明内容
鉴于此，本发明提供了一种替换R290的环保混合制冷剂，该环保混合制冷剂环保性能好，不仅不破坏大气臭氧层即ODP为零，而且具有较低的GWP(GWP低于150)，安全性能优于R290，同时热力性能与R290相差不大甚至更优，解决目前家用空调R290制冷剂安全性能差的技术问题。
本发明为实现上述目的，采用的技术方案是：一种替换R290的环保混合制冷剂，包括第一组分、第二组分和第三组分，其中：所述第一组分为1,1-二氟乙烷(R152a)，所述第二组分为2,3,3,3-四氟丙烯(R1234yf)，所述第三组分为丙烷(R290)、异丁烷(R600a)以及丙烯(R1270)中的一种，其中所述环保混合制冷剂具有不大于150的全球变暖潜力(GWP)。
进一步可选地，以摩尔百分比计，所述第一组分为4％-48％，所述第二组分为28％-92％，所述第三组分为4％-28％。该配方制备得到的环保混合制冷剂的安全性能优于R290，且热力性能与R290相当甚至更优。
进一步可选地，以摩尔百分比计，所述第一组分为4％-40％，所述第二组分为56％-84％，所述第三组分为4％-20％。该配方制备得到的环保混合制冷剂的安全性能优于R290，且相对R290的热力性能大于0.99。
进一步可选地，以摩尔百分比计，所述第一组分为28％-40％，所述第二组分为56％-68％，所述第三组分为4％-12％。该配方制备得到的环保混合制冷剂的安全性能优于R290，且相对R290的热力性能大于0.99。
进一步可选地，所述第三组分为异丁烷(R600a)。该配方制备得到的环保混合制冷剂的安全性能优于R290，且相对R290的热力性能大于0.99。
进一步可选地，以摩尔百分比计，所述第一组分、第二组分和第三组分的摩尔百分比之和为100％，其中：所述第一组分为4％-48％，所述第二组分为28％-92％，所述第三组分为4％-28％。
进一步可选地，所述环保混合制冷剂的可燃性为A2或A2L。
本发明还提供了一种组合物，其包含润滑剂和上述任一项所述的一种替换R290的环保混合制冷剂，以摩尔百分比计，所述润滑剂为1％-5％，所述一种替换R290的环保混合制冷剂为95％-99％。
进一步可选地，其中所述润滑剂选自：硅油、多烷基苯(PAB)、多元醇酯(POE)、聚亚烷基二醇(PAG)、聚亚烷基二醇酯(PAG酯)、聚乙烯醚(PVE)、聚(α-烯烃)的中至少一种物质或至少两种物质的组合。
本发明还提供一种制冷系统，其使用上述任一项所述的环保混合制冷剂或所述的组合物。
本发明还提供一种制冷设备，所述制冷设备采用上述的制冷系统。
进一步可选地，所述制冷设备为中央空调、热泵空调和家用空调中的任一种。
本发明中的环保混合制冷剂相比R290制冷剂，具备明显的环保优势，热传递组合物具备良好的热力性能，其GWP低于150，ODP为0；且应用于制冷系统中后，其相对单位容积制冷量和相对效率COP与使用R290制冷剂的制冷系统相当甚至更优，同时安全性能优于R290，能够替代R290在制冷系统中使用。
本发明中各组分可商购获得，或可由本领域已经的方法制得。本发明中各组分的含量配比经由大量筛选获得，是保证对环保混合制冷剂优良性能的条件。
具体实施方式
本发明的制冷系统使用的环保混合制冷剂的制备方法是将1,1-二氟乙烷(R152a)，3,3,3-四氟丙烯(R1234yf)，丙烷(R290)，异丁烷(R600a)以及丙烯(R1270)等多种组分，根据上述技术方案按不同的摩尔配比在常温常压液相状态下进行物理混合成，混合均匀后形成环保混合制冷剂。各组分物质的基本参数见表1。
表1环保混合制冷剂中各组分物质的基本参数
Figure PCTCN2020120214-appb-000001
下面给出多个具体实施例和对比例，其中组分的比例均为摩尔比，每种环保混合制冷剂的组分物质的摩尔比之和为100％。每种实施例中都是将各组分常温常压液相状态下按固定的摩尔比进行液相物理混合，混合均匀得到一种环保混合制冷剂。
实施例1，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烷(R290)三种组分在常温常压液相下按24:72:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例2，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烷(R290)三种组分在常温常压液相下按28:68:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例3，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烷(R290)三种组分在常温常压液相下按32:64:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例4，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烷(R290)三种组分在常温常压液相下按36:60:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例5，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烷(R290)三种组分在常温常压液相下按48:48:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例6，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按20:72:8的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例7，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按24:68:8的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例8，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按28:68:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例9，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按32:64:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例10，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按36:60:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例11，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按40:56:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例12，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按44:28:28的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例13，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按4:92:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例14，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按8:88:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例15，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按12:84:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例16，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按16:80:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例17，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按20:76:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例18，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按24:72:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例19，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按48:48:4的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例20，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按4:84:12的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例21，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按8:72:20的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例22，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按8:80:12的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
实施例23，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按12:68:20的摩尔比进行物理混合，混合均匀得到一种环保混合制冷剂。
对比例1，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烷(R290)三种组分在常温常压液相下按32:4:64的摩尔比进行物理混合，混合均匀得到一种混合制冷剂。
对比例2，将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按20:12:68的摩尔比进行物理混合，混合均匀得到一种混合制冷剂。
对比例3：将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和异丁烷(R600a)三种组分在常温常压液相下按2:70:28的摩尔比进行物理混合，混合均匀得到一种混合制冷剂。
对比例4：将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烷(R290)三种组分在常温常压液相下按50:28:22的摩尔比进行物理混合，混合均匀得到一种混合制冷剂。
对比例5：将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烷(R290)三种组分在常温常压液相下按48:24:28的摩尔比进行物理混合，混合均匀得到一种混合制冷剂。
对比例6：将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按4:94:2的摩尔比进行物理混合，混合均匀得到一种混合制冷剂。
对比例7：将1,1-二氟乙烷(R152a)、2,3,3,3-四氟丙烯(R1234yf)和丙烯(R1270)三种组分在常温常压液相下按42:28:30的摩尔比进行物理混合，混合均匀得到一种混合制冷剂。
表2比较了上述实施例和对比例与R290的分子量、临界温度及环境性能等基本参数，其中可燃性是根据NIST机构于2019年发表论文中的理论模型进行计算得到的，其中理论计算结果中可燃性按照A3，A2，A2L的顺序降低。
表2混合制冷剂的基本参数
Figure PCTCN2020120214-appb-000002
本实施还提供一种组合物，其包含润滑剂和上述任一项的实施例中的一种替换R290的环保混合制冷剂，以摩尔百分比计，润滑剂为1％-5％，一种替换R290的环保混合制冷剂为95％-99％。优选的，其中润滑剂选自：硅油、多烷基苯(PAB)、多元醇酯(POE)、聚亚烷基二 醇(PAG)、聚亚烷基二醇酯(PAG酯)、聚乙烯醚(PVE)、聚(α-烯烃)的中至少一种物质或至少两种物质的组合。使用该组合物的制冷系统不仅有良好的的制冷效果和环保效果，且减少制冷系统中压缩机的机件如电动机、曲轴和连杆装置转动时的磨损，使机件的转动更加灵活。
本实施例还提供一制冷设备该制冷设备中央空调、热泵空调和家用空调中的任一种，其采用了的制冷系统使用上述实施例中任一种环保混合制冷剂或组合物。进一步优选的，该制冷系统采用实施例中任一项的环保混合制冷剂。
本实施例和对比例提供的三元制冷剂应用于家用空调系统中的，在空调机组中换热、被压缩、节流，替代R290制冷剂。
表3比较了上述实施例中的环保混合制冷剂和对比例的混合制冷剂在制冷工况下(蒸发器出口温度为283.15K，冷凝器出口温度为313.15K，蒸发器出口的气相为过热状态，过热度为5K，冷凝器出口的液相为过冷状态，过冷度为5K，压缩机的绝热效率为0.75)，按照等熵压缩计算，上述实施例与R290的热力参数(即压缩比和排气温度)及相对热力性能(即相对单位容积制冷量和相对效率COP)。
表3混合制冷剂与R290的性能对比结果
Figure PCTCN2020120214-appb-000003
结合表2和表3分析可知本实施例中的环保混合制冷剂与对比例中的混合制冷剂相比，通过各组分之间的协同作用，使制备的环保混合制冷剂的可燃性，GWP，相对容积制冷量等性能保持在一个良好的状态。
通过对比例1和对比例2不难发现，当配方中的第二组分和第三组分的摩尔百分比不在本发明提供的数值范围即第二组分低于本发明提供的最低值28％，第三组分超出本发明给出的摩尔百分比28％，制备得到的混合制冷剂具有强可燃性为A3制冷剂，且相对于与R290制冷剂来说，其热力性能几乎没有任何提升，特别是对比例2，相对容积制冷量仅有R290制冷剂的50％，因此，不能作为替代R290制冷剂的优选替代制冷剂。
通过对比例3-7可以发现，当配方中的第一组分、第二组分和第三组分中的任一种物质的摩尔百分比不在本发明提供的数值范围即超过或低于本发明提供的范围，制备得到的混合制冷剂的可燃性相对于R290而言，有进一步的降低，但是相对R290制冷剂的能效有较大幅度的降低，最高只能达到R290的87％，热力性能较差。因此，也不能作为R290制冷剂的优选替代制冷剂。
因此本发明提供的混合环保制冷剂，通过第一组分、第二组分和第三组分的之间的协同作用，使其GWP均小于150，环保性好，并且所有制冷剂的可燃性均为A2L/A2，安全性能优于R290。
由表2和3可知，本实施例提供的环保混合制冷剂的容积制冷量虽然只有R290的77％左右，但是COP值与R290相当，甚至更优，可成为替代R290的环保制冷剂。从实施例6-11，实施例20-23分析得出，第三组分优选为异丁烷(R600a)，具有该组分的环保混合制冷剂的可燃性低于R290的前提下，且相对COP优于第三组分为丙烷(R290)和丙烯(R1270)中的一种；更进一步分析出，在第三组分为异丁烷(R600a)的配方下，优选的，以摩尔百分比计，1,1-二氟乙烷(R152a)为4％-40％，2,3,3,3-四氟丙烯(R1234yf)为56％-84％，异丁烷(R600a)为4％-20％的配方制备得到的混合环保制冷剂的相对COP大于0.9；再进步分析出，进一步优选的，以摩尔百分比计，1,1-二氟乙烷(R152a)为28％-40％，2,3,3,3-四氟丙烯(R1234yf)为56％-68％，异丁烷(R600a)为4％-12％的配方制备得到的环保混合制冷剂的相对COP由于R290，即大于0.99。进一步优选的，以摩尔百分比计，1,1-二氟乙烷(R152a)：2,3,3,3-四氟丙烯(R1234yf)：异丁烷(R600a)为40:56:4的配方制备得到环保混合制冷剂的相对COP最高为1.003，为最优的配方。
本实施例提供的一种替换R290的环保混合制冷剂，不仅具有GWP低于150，ODP为零的环保特性，而且可燃性低于R290，安全性能优于R290，热力性能也与R290制冷剂相当甚至更优，完全可以替代R290在制冷设置尤其是在家用空调上使用。
综上，本发明提供一种替换R290的环保混合制冷剂，其包括第一组分、第二组分和第三组分，其中：第一组分为1,1-二氟乙烷(R152a)，第二组分为2,3,3,3-四氟丙烯(R1234yf)，第三组分为丙烷(R290)、异丁烷(R600a)以及丙烯(R1270)中的一种，其中环保混合制冷剂具有不大于150的全球变暖潜力(GWP)；且ODP为零，而且可燃性低于R290，安全性能 优于R290，热力性能也与R290制冷剂相当甚至更优，完全可以替代R290在制冷设置尤其是在家用空调上使用。
以上具体地示出和描述了本公开的示例性实施例。应可理解的是，本公开不限于这里描述的详细结构、设置方式或实现方法；相反，本公开意图涵盖包含在所附权利要求的精神和范围内的各种修改和等效设置。

Claims (12)

  1. 一种替换R290的环保混合制冷剂，其特征在于，包括第一组分、第二组分和第三组分组成，其中：所述第一组分为1,1-二氟乙烷，所述第二组分为2,3,3,3-四氟丙烯，所述第三组分为丙烷、异丁烷以及丙烯中的一种，其中所述环保混合制冷剂具有不大于150的全球变暖潜力。
  2. 如权利要求1所述的一种替换R290的环保混合制冷剂，其特征在于，以摩尔百分比计，所述第一组分为4％-48％，所述第二组分为28％-92％，所述第三组分为4％-28％。
  3. 如权利要求2所述的一种替换R290的环保混合制冷剂，其特征在于，以摩尔百分比计，所述第一组分为4％-40％，所述第二组分为56％-84％，所述第三组分为4％-20％。
  4. 如权利要求2所述的一种替换R290的环保混合制冷剂，其特征在于，以摩尔百分比计，所述第一组分为28％-40％，所述第二组分为56％-68％，所述第三组分为4％-12％。
  5. 如权利要求2所述的一种替换R290的环保混合制冷剂，其特征在于，所述第三组分为异丁烷。
  6. 如权利要求1所述的一种替换R290的环保混合制冷剂，其特征在于，以摩尔百分比计，所述第一组分、第二组分和第三组分的摩尔百分比之和为100％，其中：所述第一组分为4％-48％，所述第二组分为28％-92％，所述第三组分为4％-28％。
  7. 如权利要求1-6任一项所述的一种替换R290的环保混合制冷剂，其特征在于，所述环保混合制冷剂的可燃性为A2或A2L。
  8. 一种组合物，其特征在于，包含润滑剂和权利要求1-7任一项所述的一种替换R290的环保混合制冷剂，以摩尔百分比计，所述润滑剂为1％-5％,所述一种替换R290的环保混合制冷剂为95％-99％。
  9. 如权利要求8所述的组合物，其特征在于，其中所述润滑剂选自：硅油、多烷基苯、多元醇酯、聚亚烷基二醇、聚亚烷基二醇酯、聚乙烯醚、聚(α-烯烃)的中至少一种物质或至少两种物质的组合。
  10. 一种制冷系统，其特征在于，使用权利要求1-7中任一项所述的环保混合制冷剂或8-9任一项所述的组合物。
  11. 一种制冷设备，其特征在于，所述制冷设备采用权利要求10所述的制冷系统。
  12. 如权利要求11所述的制冷设备，其特征在于，所述制冷设备为中央空调、热泵空调和家用空调中的任一种。
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